Transparent conductive layer and transparent conductive film

Abstract

The transparent conductive layer 1 contains krypton atoms. The ratio of the integrated intensity of the peak of X-ray diffraction of the (440) plane to the integrated intensity of the peak of X-ray diffraction of the (222) plane is 0.130 or more.(440)

Description

Technical Field

[0001] This invention relates to transparent conductive layers and transparent conductive films. More specifically, it relates to transparent conductive layers and transparent conductive films having the same transparent conductive layer. Background Technology

[0002] Optical films, such as transparent conductive films, are known to be used in optical applications such as touch panels.

[0003] As such a transparent conductive film, a transparent conductive film having an organic polymer film substrate and a transparent conductive film sequentially has been proposed (see, for example, Patent Document 1).

[0004] In addition, this transparent conductive film is obtained by sputtering and forming a transparent conductive film on the surface of an organic polymer film substrate in the presence of argon gas.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2014-157814 Summary of the Invention

[0008] The problem the invention aims to solve

[0009] On the other hand, it is required to have high transmittance and low resistivity compared to the transparent conductive film in Patent Document 1.

[0010] The present invention provides a transparent conductive layer with high transmittance and low resistivity, and a transparent conductive film having the transparent conductive layer.

[0011] Solution for solving the problem

[0012] The present invention [1] is a transparent conductive layer containing krypton atoms, wherein the ratio of the integrated intensity of the X-ray diffraction peak of the (440) plane of the transparent conductive layer to the integrated intensity of the X-ray diffraction peak of the (222) plane is 0.130 or more.

[0013] The present invention [2] includes the transparent conductive layer described in [1] above, which contains indium tin composite oxide.

[0014] The present invention [3] includes the transparent conductive layer described in [1] or [2] above, having a resistivity of less than 2.3 × 10⁻⁶. -4 Ω·cm.

[0015] The present invention [4] includes any one of the above [1] to [3] transparent conductive layer having a patterned shape.

[0016] The present invention [5] includes a transparent conductive film having a substrate layer and a transparent conductive layer as described in any one of [1] to [4] sequentially on one side facing the thickness direction.

[0017] The effects of the invention

[0018] The transparent conductive layer of the present invention contains krypton atoms, and the ratio of the integrated intensity of the X-ray diffraction peak of the (440) plane to the integrated intensity of the X-ray diffraction peak of the (222) plane is 0.130 or higher. Therefore, it is possible to improve transmittance and reduce resistivity.

[0019] The transparent conductive film of the present invention includes the transparent conductive layer of the present invention. Therefore, it is possible to improve transmittance and reduce resistivity. Attached Figure Description

[0020] Figure 1 This is a schematic diagram illustrating a first embodiment of the transparent conductive layer of the present invention.

[0021] Figure 2 This is a schematic diagram illustrating a first embodiment of the transparent conductive film of the present invention.

[0022] Figure 3 This is a schematic diagram illustrating a first embodiment of the manufacturing method of the transparent conductive layer and the transparent conductive film of the present invention. Figure 3 The A in the first process refers to the process of preparing the transparent substrate. Figure 3 The B indicates the process of applying a hard coating to one side of the transparent substrate in the thickness direction during the first process. Figure 3 The C in the second process indicates the fourth process in which a krypton-containing transparent conductive layer is disposed on one side in the thickness direction of the substrate layer. Figure 3 D represents the fifth step in which an argon-containing transparent conductive layer is disposed on one face in the thickness direction of the krypton-containing transparent conductive layer in the second step. Figure 3 The letter E indicates the third step of heating the transparent conductive layer.

[0023] Figure 4 This is a graph showing the relationship between the resistivity of an amorphous transparent conductive layer and the amount of oxygen introduced.

[0024] Figure 5 This is a schematic diagram illustrating a second embodiment of the transparent conductive layer of the present invention.

[0025] Figure 6 This is a schematic diagram illustrating a second embodiment of the transparent conductive film of the present invention.

[0026] Figure 7 This is a schematic diagram illustrating a second embodiment of the manufacturing method of the transparent conductive layer and the transparent conductive film of the present invention. Figure 7 A represents the first step in preparing the substrate layer. Figure 7 B indicates the second step of configuring a transparent conductive layer on one side of the substrate layer in the thickness direction. Figure 7 The C in the figure represents the third step of heating the transparent conductive layer.

[0027] Figure 8 This is a schematic diagram illustrating one embodiment of an article having a transparent conductive film.

[0028] Figure 9 This is a schematic diagram illustrating one embodiment of an article with a transparent conductive layer. Detailed Implementation

[0029] <Transparent Conductive Layer>

[0030] The transparent conductive layer 1 is in the shape of a thin film (including a sheet) with a specified thickness. The transparent conductive layer 1 extends along a plane direction orthogonal to the thickness direction. The transparent conductive layer 1 has a flat upper surface and a flat lower surface.

[0031] The transparent conductive layer 1 is a transparent layer exhibiting excellent conductivity. The transparent conductive layer 1 contains crystalline material, preferably formed from crystalline material.

[0032] The transparent conductive layer 1 contains krypton atoms. In other words, the transparent conductive layer 1 has a krypton-containing transparent conductive layer 10 (sometimes called KrITO) containing krypton atoms.

[0033] Alternatively, the transparent conductive layer 1 may have a krypton-free transparent conductive layer 11 that does not contain krypton atoms, while also having a krypton-containing transparent conductive layer 10.

[0034] Hereinafter, we will describe the first embodiment in which the transparent conductive layer 1 is provided with a krypton-containing transparent conductive layer 10 and a krypton-free transparent conductive layer 11 in sequence, and the second embodiment in which the transparent conductive layer 1 is formed by the krypton-containing transparent conductive layer 10.

[0035] 1. First Implementation Method

[0036] like Figure 1 As shown, the transparent conductive layer 1 sequentially comprises a krypton-containing transparent conductive layer 10 and a krypton-free transparent conductive layer 11. More specifically, the transparent conductive layer 1 comprises a krypton-containing transparent conductive layer 10 and a krypton-free transparent conductive layer 11 disposed on the upper surface (one side in the thickness direction) of the krypton-containing transparent conductive layer 10. Preferably, the transparent conductive layer 1 comprises only the krypton-containing transparent conductive layer 10 and the krypton-free transparent conductive layer 11.

[0037] The krypton-containing transparent conductive layer 10 comprises a metal oxide and trace amounts of krypton atoms. The krypton-containing transparent conductive layer 10 is preferably formed of a metal oxide and trace amounts of krypton atoms. Specifically, in the krypton-containing transparent conductive layer 10, trace amounts of krypton atoms are present in the metal oxide matrix.

[0038] The metal oxide is, for example, an oxide of at least one metal and / or half-metal selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. Specifically, indium-containing oxides and antimony-containing oxides can be listed as metal oxides. Examples of indium-containing oxides include, for example, indium tin oxide (ITO), indium gallium oxide (IGO), indium zinc oxide (IZO), and indium gallium zinc oxide (IGZO). Examples of antimony-containing oxides include, for example, antimony tin oxide (ATO).

[0039] As a metal oxide, indium oxides are preferred, and indium tin oxide (ITO) is more preferred. In other words, the krypton-containing transparent conductive layer 10 (transparent conductive layer 1) preferably contains indium tin oxide (ITO). If the krypton-containing transparent conductive layer 10 (transparent conductive layer 1) contains indium tin oxide (ITO), the resistivity of the transparent conductive layer 1 can be reduced.

[0040] When the metal oxide is indium tin oxide (ITO), the proportion of tin oxide relative to the total amount of tin oxide and indium oxide is, for example, 0.5% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, especially preferably 9% by mass or more, and in addition, for example, 20% by mass or less, preferably 15% by mass or less, more preferably 12% by mass or less.

[0041] If the tin oxide content is above the lower limit mentioned above, it will promote low resistance. If the tin oxide content is below the upper limit mentioned above, the krypton-containing transparent conductive layer 10 exhibits excellent heating stability.

[0042] In addition, the krypton-containing transparent conductive layer 10 contains krypton atoms.

[0043] The krypton atoms originate from krypton gas, which is used as a sputtering gas as described later. In other words, as described later, in the sputtering process, krypton gas, which is used as a sputtering gas, enters the krypton-containing transparent conductive layer 10.

[0044] The krypton atom content in the krypton-containing transparent conductive layer 10 is, for example, 1.0 atomic% or less, more preferably 0.7 atomic% or less, further preferably 0.5 atomic% or less, especially preferably 0.3 atomic% or less, most preferably 0.2 atomic% or less, and further less than 0.1 atomic%, and, for example, 0.0001 atomic% or more.

[0045] The content of krypton atoms can be determined using, for example, Rutherford backscattering spectroscopy. Alternatively, the presence of krypton atoms can be confirmed using, for example, fluorescence X-ray analysis. In the krypton-containing transparent conductive layer 10, when the content of krypton atoms is too low (specifically, when the content of krypton atoms is not above the detection limit (lower limit) of Rutherford backscattering analysis), it is sometimes impossible to quantify the content of krypton atoms using Rutherford backscattering analysis. However, in this application, even in this case, when the presence of krypton atoms is identified using fluorescence X-ray analysis, the content of krypton atoms is determined to be at least 0.0001 atomic%.

[0046] In addition, the krypton-containing transparent conductive layer 10 contains crystalline material, preferably formed from crystalline material.

[0047] If the krypton-containing transparent conductive layer 10 is crystalline, its resistivity can be reduced.

[0048] The crystallinity of the krypton-containing transparent conductive layer 10 can be determined, for example, by observing the cross-section of the krypton-containing transparent conductive layer 10 using FE-TEM and confirming the presence of grains. The magnification of the FE-TEM observation is not limited as long as the presence of grains can be confirmed, for example, 200,000x. Furthermore, in observations at higher magnifications (e.g., 2 millionx or higher), even if a lattice structure is confirmed in the krypton-containing transparent conductive layer 10, that portion can be identified as crystalline.

[0049] The krypton-containing transparent conductive layer 10 is preferably a post-crystalline layer (post-crystalline film). A post-crystalline film refers to a film that is amorphous during the film formation process and immediately after film formation (e.g., within 10 hours after film formation), and subsequently transforms into a crystalline film through processes such as heating. If the krypton-containing transparent conductive layer 10 is a post-crystalline layer, it is easy to obtain a transparent conductive layer 1 with low resistivity and excellent appearance quality, as well as a transparent conductive thin film 20 described later.

[0050] The krypton-free transparent conductive layer 11 does not contain krypton atoms. As described later, the krypton-free transparent conductive layer 11 contains atoms derived from sputtering gases (such as argon or xenon) containing rare gases other than krypton.

[0051] Examples of krypton-free transparent conductive layers 11 include argon-containing transparent conductive layers (sometimes called ArITO).

[0052] The argon-containing transparent conductive layer contains the aforementioned metal oxides and trace amounts of argon atoms.

[0053] As metal oxides, indium-containing oxides are preferred, and indium-tin oxide (ITO) is even more preferred.

[0054] When the metal oxide is indium tin oxide (ITO), the proportion of tin oxide relative to the total amount of tin oxide and indium oxide is, for example, 0.5% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, especially preferably 9% by mass or more, and in addition, for example, 20% by mass or less, preferably 15% by mass or less, more preferably 12% by mass or less.

[0055] In addition, the argon-containing transparent conductive layer contains argon atoms.

[0056] Argon atoms originate from argon gas, which is used as the sputtering gas as described later. In other words, as detailed later, in the sputtering process, argon gas, as the sputtering gas, enters the argon-containing transparent conductive layer.

[0057] The content of argon atoms in the argon-containing transparent conductive layer is, for example, 0.8 atomic% or less, preferably 0.5 atomic% or less, more preferably 0.2 atomic% or less, and even more preferably 0.1 atomic% or less, and in addition, for example, 0.0001 atomic% or more.

[0058] The argon atom content can be determined using, for example, Rutherford backscattering spectroscopy.

[0059] In addition, the argon-containing transparent conductive layer contains crystalline material, preferably formed from crystalline material.

[0060] If the argon-containing transparent conductive layer is crystalline, it can reduce resistivity.

[0061] The crystallinity of the argon-containing transparent conductive layer can be confirmed using the same method as that used for the krypton-containing transparent conductive layer 10.

[0062] Furthermore, the ratio of the integrated intensity of the X-ray diffraction peak of the (440) plane of the transparent conductive layer 1 to the integrated intensity of the X-ray diffraction peak of the (222) plane (integrated intensity of the X-ray diffraction peak of the (440) plane / integrated intensity of the X-ray diffraction peak of the (222) plane) (hereinafter sometimes referred to as the integrated intensity ratio) is 0.130 or more, preferably 0.160 or more, more preferably 0.180 or more, and for example, 0.250 or less, preferably 0.200 or less.

[0063] If the integral intensity ratio of the transparent conductive layer 1 is above the lower limit, then from the viewpoint of reducing light absorption, the transmittance can be improved.

[0064] Specifically, the total light transmittance of the transparent conductive layer 1 (JIS K 7375-2008) is, for example, 60% or more, preferably 80% or more, and more preferably 85% or more.

[0065] On the other hand, if the ratio is less than the lower limit, then from the perspective of increasing light absorption, the transmittance cannot be improved.

[0066] Furthermore, if the ratio mentioned above is above the lower limit, then from the viewpoint of improving mobility, resistivity can be reduced.

[0067] Specifically, the resistivity of the transparent conductive layer 1 is, for example, less than 2.3 × 10⁻⁶. -4 Ω·cm, preferably less than 2.2×10 -4 Ω·cm, more preferably 2.0×10 -4 Below Ω·cm, more preferably 1.7×10 -4 Ω·cm or less, especially preferably 1.5×10 -4 Below Ω·cm, and for example, 0.01×10 -4 Ω·cm or higher, preferably 0.05×10 -4 Ω·cm or more, more preferably 0.1×10 -4 Ω·cm or higher, more preferably 0.5×10 -4 Ω·cm or higher, especially preferably 1.0×10 -4 Ω·cm or higher, with a particularly preferred value of 1.01×10⁻⁶. -4 Ω·cm or higher.

[0068] It should be noted that the resistivity can be obtained by multiplying the surface resistance value measured according to JIS K7194 and using the four-terminal method with the thickness of the transparent conductive layer 1.

[0069] The surface resistance of the transparent conductive layer 1 is, for example, 200 Ω / □ or less, preferably 80 Ω / □ or less, more preferably 60 Ω / □ or less, even more preferably 50 Ω / □ or less, particularly preferably 30 Ω / □ or less, most preferably 20 Ω / □ or less, and usually more than 0 Ω / □, and more than 1 Ω / □.

[0070] It should be noted that the surface resistivity value can be measured according to JIS K7194 using the four-terminal method.

[0071] On the other hand, if the ratio is less than the lower limit, then from the perspective of reducing mobility, it is impossible to reduce resistivity.

[0072] It should be noted that the method for measuring X-ray diffraction is described in detail in the examples described later.

[0073] As described above, since the integral intensity ratio of the transparent conductive layer 1 is 0.130 or higher, the transmittance can be improved and the resistivity can be reduced.

[0074] Furthermore, the ratio of the total transmittance of the transparent conductive layer 1 to the resistivity of the transparent conductive layer 1 (total transmittance of the transparent conductive layer 1 / resistivity of the transparent conductive layer 1) is, for example, 45% / 10.-4 Ω·cm or higher, preferably 50% / 10 -4 Ω·cm or more, more preferably 55% / 10 -4 Ω·cm or higher, more preferably 55% / 10 -4 Ω·cm or higher, especially preferably 57% / 10 -4 Ω·cm or higher, and for example, 70% / 10 -4 Below Ω·cm.

[0075] If the ratios mentioned above are within the range, then both high transmittance and low resistivity can be achieved.

[0076] Furthermore, the thickness of the transparent conductive layer 1 is, for example, 10 nm or more, preferably 40 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more. In addition, it is, for example, 1000 nm or less, preferably 500 nm or less, more preferably less than 300 nm, even more preferably 280 nm or less, especially preferably 200 nm or less, particularly preferably 170 nm or less, most preferably 150 nm or less, and even more preferably 148 nm or less.

[0077] Furthermore, in the transparent conductive layer 1, the thickness of the krypton-containing transparent conductive layer 10 is, for example, 1 nm or more, preferably 10 nm or more, more preferably 40 nm or more, and even more preferably 60 nm or more. Additionally, it is, for example, 800 nm or less, preferably less than 300 nm, more preferably 200 nm or less, even more preferably less than 150 nm, particularly preferably less than 100 nm, especially preferably less than 100 nm, and most preferably less than 90 nm. Furthermore, the thickness of the krypton-free transparent conductive layer 11 is, for example, 1 nm or more, preferably 10 nm or more, more preferably 40 nm or more. Additionally, it is, for example, 500 nm or less, preferably less than 200 nm, more preferably less than 100 nm, and even more preferably less than 60 nm.

[0078] The thickness of the krypton-containing transparent conductive layer 10 relative to the thickness of the transparent conductive layer 1 is, for example, 1% or more, preferably 20% or more, more preferably 30% or more, further preferably 50% or more, especially preferably 60% or more, and in addition, for example, 99% or less, preferably 80% or less, more preferably 70% or less.

[0079] If the thickness of the krypton-containing transparent conductive layer 10 is above the lower limit and below the upper limit, the transmittance can be increased and the resistivity can be reduced.

[0080] It should be noted that the thickness of the transparent conductive layer 1 can be determined, for example, by observing the cross-section of the transparent conductive film 20 using a transmission electron microscope. It should be noted that in Figure 1In the diagram, the boundary between the krypton-containing transparent conductive layer 10 and the krypton-free transparent conductive layer 11 is drawn with a solid line, but sometimes it is not possible to clearly distinguish the boundary between the krypton-containing transparent conductive layer 10 and the krypton-free transparent conductive layer 11.

[0081] Additionally, the transparent conductive layer 1 is contained in the (222) plane, for example as follows: The above, preferred The above, or more preferably The above, further preferred The above, especially preferred The above, and for example, is The following are preferred The following, more preferably The following are further preferred options The following microcrystals. Additionally, those contained in the (440) plane, for example, are... The above, preferred The above, or more preferably The above, further preferred The above, especially preferred The above, and for example, is The following are preferred The following, more preferably The following are further preferred options The following are microcrystals. It should be noted that the method for determining the crystal grain size (microcrystal size) is detailed in the examples described later.

[0082] <Transparent Conductive Film>

[0083] like Figure 2 As shown, the transparent conductive film 20 has a film shape (sheet-like) with a specified thickness. The transparent conductive film 20 extends along a plane direction orthogonal to the thickness direction. The transparent conductive film 20 has a flat upper surface and a flat lower surface.

[0084] The transparent conductive film 20 has a substrate layer 2 and a transparent conductive layer 1 sequentially disposed on the side facing the thickness direction. More specifically, the transparent conductive film 20 has a substrate layer 2 and a transparent conductive layer 1 disposed on the upper surface (one side in the thickness direction) of the substrate layer 2. Preferably, the transparent conductive film 20 has only a substrate layer 2 and a transparent conductive layer 1.

[0085] More specifically, the transparent conductive film 20 comprises, on its thickness-direction side, a substrate layer 2, a krypton-containing transparent conductive layer 10, and a krypton-free transparent conductive layer 11. More specifically, the transparent conductive film 20 comprises, on its thickness-direction side, a substrate layer 2, a krypton-containing transparent conductive layer 10 disposed on the upper surface (thickness-direction side) of the substrate layer 2, and a krypton-free transparent conductive layer 11 disposed on the upper surface (thickness-direction side) of the krypton-containing transparent conductive layer 10.

[0086] The transparent conductive film 20 is, for example, a component of a touch panel substrate or electromagnetic wave shielding device included in an image display device; that is, it is not an image display device itself. In other words, the transparent conductive film 20 is a component used to manufacture image display devices, etc., and it does not contain image display elements such as OLED modules. It is a device that can be distributed independently as a component and utilized industrially.

[0087] The thickness of the transparent conductive film 20 is, for example, 1000 μm or less, preferably 500 μm or less, more preferably 250 μm or less, and also, for example, 1 μm or more, preferably 20 μm or more, more preferably 50 μm or more.

[0088] <Substrate Layer>

[0089] The substrate layer 2 is a transparent substrate used to ensure the mechanical strength of the transparent conductive film 20.

[0090] The substrate layer 2 has a thin film shape. The substrate layer 2 is disposed on the entire lower surface of the transparent conductive layer 1 in such a way that it contacts the lower surface of the transparent conductive layer 1.

[0091] The substrate layer 2 has a transparent substrate 3 and a functional layer 4.

[0092] Specifically, the substrate layer 2 has a transparent substrate 3 and a functional layer 4 sequentially on one side facing the thickness direction. Specifically, the substrate layer 2 has a transparent substrate 3 and a functional layer 4, with the functional layer 4 disposed on one surface of the transparent substrate 3 in the thickness direction.

[0093] <Transparent substrate>

[0094] The transparent substrate 3 has a thin film shape.

[0095] Examples of materials that can be used as transparent substrate 3 include olefin resins, polyester resins, (meth)acrylic resins (acrylic resins and / or methacrylic resins), polycarbonate resins, polyethersulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, and polystyrene resins. Examples of olefin resins include polyethylene, polypropylene, and cyclic olefin polymers. Examples of polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of (meth)acrylic resins include polymethacrylate. Although it has poor heat resistance and is not resistant to high-temperature (e.g., above 200°C) heating processes, from the viewpoint of easily obtaining a transparent conductive layer 1 and a transparent conductive film 20 with excellent smoothness, low resistivity, and high transmittance, the materials for the transparent substrate 3 can include olefin resins, (meth)acrylic resins, polycarbonate resins, melamine resins, and polyester resins, and more preferably polyethylene terephthalate (PET).

[0096] The transparent substrate 3 is transparent. Specifically, the total light transmittance (JIS K7375-2008) of the transparent substrate 3 is, for example, 60% or more, preferably 80% or more, and more preferably 85% or more.

[0097] The thickness of the transparent substrate 3 is, for example, 1 μm or more, preferably 10 μm or more, preferably 30 μm or more, and also, for example, 1000 μm or less, preferably 500 μm or less, more preferably 250 μm or less, further preferably 200 μm or less, especially preferably 100 μm or less, and most preferably 60 μm or less.

[0098] <Functional Layer>

[0099] The functional layer 4 is disposed on one surface of the transparent substrate 3 in the thickness direction.

[0100] Functional layer 4 has a thin film shape.

[0101] As functional layer 4, examples include hard coating.

[0102] In this case, the substrate layer 2 has a transparent substrate 3 and a hard coating layer on the side facing the thickness direction.

[0103] The following explanation focuses on the case where functional layer 4 is a hard coating.

[0104] The hard coating is a protective layer used to suppress damage to the transparent conductive film 20.

[0105] Hard coatings are formed, for example, from hard coating compositions.

[0106] The hard coating composition comprises a resin and, if desired, particles. In other words, the hard coating layer comprises a resin and, if desired, particles.

[0107] Examples of resins include thermoplastic resins and curable resins. Examples of thermoplastic resins include polyolefin resins.

[0108] Examples of curable resins include, for example, active energy ray-curable resins that cure by irradiation with active energy rays (e.g., ultraviolet rays and electron rays) and thermosetting resins that cure by heating. Active energy ray-curable resins are preferred examples of curable resins.

[0109] Examples of UV-curable resins include (meth)acrylic resins, urethane resins, melamine resins, alkyd resins, siloxane polymers, and organosilane condensates. (meth)acrylic resins are preferably examples of UV-curable resins.

[0110] In addition, the resin may contain, for example, a reactive diluent as described in Japanese Patent Application Publication No. 2008-88309. Specifically, the resin may contain polyfunctional (meth)acrylates.

[0111] Resins can be used alone or in combination of two or more.

[0112] Examples of particulate matter include, for example, metal oxide particles and organic particles. Examples of metal oxide particles include, for example, silicon dioxide, aluminum oxide, titanium dioxide, zirconium oxide, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. Examples of organic particles include, for example, polymethyl methacrylate, silicone, polystyrene, polyurethane, acrylic-styrene copolymers, benzoguanamine, melamine, and polycarbonate.

[0113] The granules can be used alone or in combination of two or more types.

[0114] In addition, the hard coating composition can be formulated with thixotropic agents, photopolymerization initiators, fillers (e.g., organoclay), and leveling agents in appropriate proportions as needed. Furthermore, the hard coating composition can be diluted using known solvents.

[0115] In addition, to form a hard coating, as detailed below, a diluted solution of the hard coating composition is applied to one side of the temporary support 2 in the thickness direction and dried by heating as needed. After drying, the hard coating composition is cured by, for example, irradiation with active energy rays.

[0116] This forms a hard coating.

[0117] The thickness of the hard coating is, for example, 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, and also, for example, 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less.

[0118] <Manufacturing Methods of Transparent Conductive Layers and Transparent Conductive Films>

[0119] The manufacturing method of the transparent conductive layer 1 and the transparent conductive film 20 includes the following steps: a first step of preparing the substrate layer 2; a second step of depositing the transparent conductive layer 1 on one side of the substrate layer 2 in the thickness direction; and a third step of heating the transparent conductive layer 1. Furthermore, in this manufacturing method, each layer is deposited sequentially using, for example, a roll-to-roll method.

[0120] <First Process>

[0121] In the first process, substrate layer 2 is prepared.

[0122] To prepare substrate layer 2, such as Figure 3 As shown in Figure A, prepare a transparent substrate 3.

[0123] Next, as Figure 3 As shown in Figure B, a diluted solution of the hard coating composition is applied to one side of the transparent substrate 3 in the thickness direction. After drying, the hard coating composition is cured by ultraviolet irradiation or heating. Thus, a hard coating layer (functional layer 4) is formed on one side of the transparent substrate 3 in the thickness direction. This prepares the substrate layer 2.

[0124] <Second Process>

[0125] In the second process, a transparent conductive layer 1 is disposed on one side of the substrate layer 2 (hard coating) in the thickness direction.

[0126] When manufacturing the transparent conductive layer of the first embodiment and the transparent conductive film having the transparent conductive layer, the second step includes: a fourth step of disposing a krypton-containing transparent conductive layer 10 on one side in the thickness direction of the substrate layer 2, and a fifth step of disposing a krypton-free transparent conductive layer 11.

[0127] In the fourth process, such as Figure 3 As shown in Figure C, a krypton-containing transparent conductive layer 10 is disposed on one side of the substrate layer 2 in the thickness direction.

[0128] Specifically, in the sputtering apparatus, sputtering is performed in the presence of krypton gas while one side of the substrate layer 2 in the thickness direction is facing a target formed of a material containing the krypton transparent conductive layer 10. Furthermore, during sputtering, the substrate layer 2 is tightly adhered along the circumferential direction of the film-forming roller. Additionally, in addition to krypton gas, reactive gases such as oxygen may also be present.

[0129] The partial pressure of krypton gas in the sputtering apparatus is, for example, 0.05 Pa or more, preferably 0.1 Pa or more, and also, for example, 10 Pa or less, preferably 5 Pa or less, and more preferably 1 Pa or less.

[0130] like Figure 4 As shown, the amount of reactive gas introduced can be estimated based on the surface resistance of the amorphous krypton-containing transparent conductive layer 10. Specifically, the film quality (surface resistance) of the amorphous krypton-containing transparent conductive layer 10 changes depending on the amount of reactive gas introduced into the amorphous krypton-containing transparent conductive layer 10; therefore, the amount of reactive gas introduced can be adjusted based on the target surface resistance of the amorphous krypton-containing transparent conductive layer 10. It should be noted that, in order to obtain a crystalline krypton-containing transparent conductive layer 10 by heating the amorphous krypton-containing transparent conductive layer 10, it is possible to... Figure 4 By adjusting the amount of reactive gas introduced within region X, an amorphous krypton-containing transparent conductive layer 10 is obtained.

[0131] Specifically, the resistivity of the amorphous krypton-containing transparent conductive layer 10 is, for example, 8.0 × 10⁻⁶. -4 Below Ω·cm, preferably 7.0×10 -4 Below Ω·cm, and for example, 2.0 × 10 -4 Ω·cm or higher, preferably 4.0×10 -4 Ω·cm or higher, more preferably 5.0×10 -4 The reactive gas is introduced in a manner that is above Ω·cm.

[0132] The pressure inside the sputtering device is essentially the total pressure of the partial pressure of krypton and the partial pressure of the reactive gas.

[0133] The power supply can be any of the following: DC power supply, AC power supply, MF power supply, and RF power supply. Alternatively, a combination of them can also be used.

[0134] The discharge output power value with respect to the long side of the target is, for example, 0.1 W / mm or more, preferably 0.5 W / mm or more, more preferably 1 W / mm or more, and even more preferably 5 W / mm or more. It is also, for example, 30 W / mm or less, preferably 15 W / mm or less. It should be noted that the direction of the long side of the target is, for example, the direction orthogonal to the conveying direction (TD direction) in a roll-to-roll sputtering apparatus.

[0135] Furthermore, the material of the krypton-containing transparent conductive layer 10 ejected from the target by sputtering will fall onto the substrate layer 2 to form a film. At this time, heat energy is generated. Therefore, during the film formation of the krypton-containing transparent conductive layer 10, the krypton-containing transparent conductive layer 10 is cooled by the substrate layer 2 using a film forming roller to suppress the crystallization of the krypton-containing transparent conductive layer 10.

[0136] Specifically, the temperature of the film-forming roller is, for example, -50°C or higher, preferably -30°C or higher, more preferably -20°C or higher, and also, for example, 20°C or lower, preferably 15°C or lower, more preferably 10°C or lower, further preferably 5°C or lower, and even more preferably 0°C or lower. Within the above temperature range, the substrate layer 2 can be sufficiently cooled, and the crystallization of the amorphous krypton-containing transparent conductive layer 10 can be reliably achieved. Furthermore, degassing (water, organic solvents) from the substrate layer 2 is less likely to occur, reducing impurity components within the krypton-containing transparent conductive layer 10, resulting in excellent low resistivity and high transmittance of the krypton-containing transparent conductive layer 10.

[0137] Therefore, an amorphous krypton-containing transparent conductive layer 10 is disposed on one side of the substrate layer 2 in the thickness direction.

[0138] In addition, as mentioned above, since krypton gas is used as the sputtering gas, krypton atoms originating from the krypton gas will enter the krypton-containing transparent conductive layer 10.

[0139] In the fifth process, such as Figure 3 As shown in Figure D, a krypton-free transparent conductive layer 11 is disposed on one side of the krypton-containing transparent conductive layer 10 in the thickness direction.

[0140] It should be noted that the following description focuses on the case where the transparent conductive layer 11 without krypton is an argon-containing transparent conductive layer.

[0141] In the fifth step, sputtering is performed in the sputtering apparatus with one side of the krypton-containing transparent conductive layer 10 in the thickness direction facing a target formed of a material containing an argon-containing transparent conductive layer, while in the presence of argon gas. Furthermore, during sputtering, the substrate layer 2 (the substrate layer 2 having the krypton-containing transparent conductive layer 10) is brought into contact with the film-forming roller along its circumferential direction. Additionally, in addition to argon gas, reactive gases such as oxygen may also be present at this time.

[0142] The partial pressure of argon gas in the sputtering apparatus is, for example, 0.1 Pa or more, preferably 0.3 Pa or more, and also, for example, 10 Pa or less, preferably 5 Pa or less, and more preferably 1 Pa or less.

[0143] The amount of reactive gas introduced is the same as that introduced in the fourth step described above.

[0144] The pressure inside the sputtering device is essentially the sum of the partial pressures of argon and the reactive gases. The power supply is the same as that in the fourth step described above. The discharge output power relative to the long side of the target is the same as that in the fourth step described above.

[0145] Furthermore, the argon-containing transparent conductive layer material ejected from the target by sputtering will fall onto the krypton-containing transparent conductive layer 10 to form a film. At this time, heat energy is generated. Therefore, during the film formation of the argon-containing transparent conductive layer, the argon-containing transparent conductive layer is cooled by the cooling of the krypton-containing transparent conductive layer 10 (substrate layer 2) using a film forming roller, thereby suppressing the crystallization of the argon-containing transparent conductive layer.

[0146] The temperature of the film-forming roller is the same as that of the film-forming roller in the fourth process described above.

[0147] Therefore, an amorphous argon-containing transparent conductive layer is disposed on one side of the krypton-containing transparent conductive layer 10 in the thickness direction.

[0148] In addition, as mentioned above, since argon is used as the sputtering gas, argon atoms originating from argon gas can enter the argon-containing transparent conductive layer.

[0149] As described above, through the fourth and fifth processes, an amorphous krypton-containing transparent conductive layer 10 and an amorphous argon-containing transparent conductive layer are sequentially disposed on one side of the substrate layer 2 in the thickness direction. Thus, an amorphous transparent conductive layer 1 (an amorphous krypton-containing transparent conductive layer 10 and an amorphous argon-containing transparent conductive layer) is disposed on one side of the substrate layer 2 in the thickness direction.

[0150] <Third Process>

[0151] In the third step, the amorphous transparent conductive layer 1 is heated. For example, the amorphous transparent conductive layer 1 is heated using a heating device (e.g., an infrared heater and a hot air oven).

[0152] The heating temperature is, for example, 80°C or higher, preferably 110°C or higher, and also, for example, less than 200°C, preferably less than 180°C. The heating time is, for example, 1 minute or more, preferably 10 minutes or more, more preferably 30 minutes or more, and also, for example, 24 hours or less, preferably 4 hours or less, more preferably 2 hours or less.

[0153] Therefore, as Figure 3 As shown in E, the amorphous transparent conductive layer 1 crystallizes to form a crystalline transparent conductive layer 1.

[0154] Thus, while obtaining the transparent conductive layer 1, a transparent conductive film 20 having a substrate layer 2 and the transparent conductive layer 1 in sequence is also obtained.

[0155] Subsequently, the transparent conductive layer 1 can also be patterned. Patterning is carried out using, for example, etching.

[0156] If the transparent conductive layer 1 is patterned, then the transparent conductive layer 1 has a patterned shape. If the transparent conductive layer 1 has a patterned shape, then the patterned shape can be designed freely.

[0157] 2. Second Implementation Method

[0158] <Transparent Conductive Layer>

[0159] like Figure 5 As shown, the transparent conductive layer 1 is formed from a krypton-containing transparent conductive layer 10.

[0160] The krypton-containing transparent conductive layer 10 is the same as the krypton-containing transparent conductive layer 10 in the first embodiment described above.

[0161] The integral intensity ratio of the transparent conductive layer 1 is the same as that of the first embodiment described above.

[0162] The total transmittance, resistivity, surface resistance, and thickness of the transparent conductive layer 1 are the same as those of the first embodiment described above.

[0163] <Transparent Conductive Film>

[0164] like Figure 6 As shown, the transparent conductive film 20 sequentially comprises a substrate layer 2 and a transparent conductive layer 1 (krypton-containing transparent conductive layer 10) on one side facing the thickness direction. More specifically, the transparent conductive film 20 comprises a substrate layer 2 and a transparent conductive layer 1 (krypton-containing transparent conductive layer 10) disposed on the upper surface (one side in the thickness direction) of the substrate layer 2. Preferably, the transparent conductive film 20 comprises only a substrate layer 2 and a transparent conductive layer 1 (krypton-containing transparent conductive layer 10).

[0165] <Manufacturing Methods of Transparent Conductive Layers and Transparent Conductive Films>

[0166] The manufacturing method of the transparent conductive layer 1 and the transparent conductive film 20 includes the following steps: a first step of preparing the substrate layer 2; a second step of disposing the transparent conductive layer 1 on one side of the substrate layer 2 in the thickness direction; and a third step of heating the transparent conductive layer 1.

[0167] <First Process>

[0168] In the first process, such as Figure 7 As shown in A, the substrate layer 2 is prepared using the same method as in the first embodiment described above.

[0169] <Second Process>

[0170] In the second process, a transparent conductive layer 1 is disposed on one side of the substrate layer 2 (hard coating) in the thickness direction.

[0171] When manufacturing the transparent conductive layer and the transparent conductive film having the transparent conductive layer according to the second embodiment described above, the fifth step of configuring the krypton-free transparent conductive layer 11 is not performed in the second step. In other words, only the fourth step of configuring the krypton-containing transparent conductive layer 10 is performed in the second step.

[0172] In the fourth process, such as Figure 7 As shown in Figure B, using the same method as in the first embodiment described above, a krypton-containing transparent conductive layer 10 is disposed on one side of the substrate layer 2 in the thickness direction. Thus, a transparent conductive layer 1 is disposed on one side of the substrate layer 2 in the thickness direction.

[0173] <Third Process>

[0174] In the third process, such as Figure 7 As shown in Figure C, the amorphous transparent conductive layer 1 is heated using the same method as in the first embodiment described above. As a result, the amorphous transparent conductive layer 1 crystallizes, forming a crystalline transparent conductive layer 1.

[0175] Thus, while obtaining the transparent conductive layer 1, a transparent conductive film 20 having a substrate layer 2 and the transparent conductive layer 1 are obtained in sequence.

[0176] 3. Effects

[0177] The transparent conductive layer 1 contains krypton atoms, and the ratio of the integrated intensity of the X-ray diffraction peak of the (440) plane to the integrated intensity of the X-ray diffraction peak of the (222) plane is greater than 0.130. Therefore, there is a tendency for the light absorption rate to decrease. As a result, the transmittance can be increased, and the resistivity can be reduced.

[0178] Furthermore, the transparent conductive film 20 includes a transparent conductive layer 1. Therefore, it is possible to improve transmittance and reduce resistivity.

[0179] In particular, when the transparent substrate 3 is an organic polymer film (e.g., a film formed from the material of the transparent substrate 3 described above), the transparent conductive layer 1 cannot crystallize at high temperatures. In addition, sometimes the crystallization of the transparent conductive layer 1 is hindered by gases absorbed by the organic polymer film. Therefore, it is sometimes difficult to achieve high transmittance and low resistivity.

[0180] On the other hand, the transparent conductive layer 1 contains krypton atoms, and the ratio of the integrated intensity of the X-ray diffraction peak of the (440) plane to the integrated intensity of the X-ray diffraction peak of the (222) plane is 0.130 or higher. Therefore, even if the transparent substrate 3 is an organic polymer film, the transmittance can be improved and the resistivity can be reduced.

[0181] Furthermore, in the manufacturing method of transparent conductive layer 1 and transparent conductive film 20, in the fourth step of the second process, an amorphous transparent conductive layer 1 (krypton-containing transparent conductive layer 10) is configured by sputtering in the presence of krypton gas.

[0182] Typically, when amorphous transparent conductive layer 1 is configured using sputtering, sputtering gas enters the amorphous transparent conductive layer 1.

[0183] However, using this method, krypton, which has a larger atomic weight than argon, is used instead of the commonly used argon as the sputtering gas. Therefore, it is possible to suppress the entry of krypton atoms into the amorphous transparent conductive layer 1.

[0184] Furthermore, this amorphous transparent conductive layer 1 is transformed into a crystalline transparent conductive layer 1 in the third process.

[0185] Although the crystalline transparent conductive layer 1 (krypton-containing transparent conductive layer 10) contains krypton atoms, the amount of krypton atoms introduced is suppressed as described above. Therefore, when the amorphous transparent conductive layer 1 is heated, the crystal growth of the transparent conductive layer 1 is particularly excellent. If this is done, the aforementioned integral intensity ratio of the transparent conductive layer 1 can be set to a specified range. As a result, it is possible to manufacture a transparent conductive layer 1 with high transmittance and low resistivity, and a transparent conductive thin film 20.

[0186] 4. Items with transparent conductive films and items with transparent conductive layers

[0187] By disposing the transparent conductive film 20 on one side of the component 31 in the thickness direction, it is also possible to obtain an article 30 with a transparent conductive film.

[0188] like Figure 8 As shown, the article 30 with a transparent conductive film sequentially includes a component 31 and a transparent conductive film 20 on its thickness side. Specifically, the article 30 with a transparent conductive film sequentially includes a component 31, a substrate layer 2, and a transparent conductive layer 1 on its thickness side.

[0189] It should be noted that, Figure 8 An article 30 with a transparent conductive film having a transparent conductive layer 1 according to the second embodiment is shown.

[0190] As for item 30, without particular limitation, examples include elements, components, and devices. More specifically, as elements, examples include dimming elements and photoelectric conversion elements. As dimming elements, examples include current-driven dimming elements and electric field-driven dimming elements. As current-driven dimming elements, examples include electrochromic (EC) dimming elements. As electric field-driven dimming elements, examples include PDLC (polymer dispersed liquid crystal) dimming elements, PNLC (polymer network liquid crystal) dimming elements, and SPD (suspended particle device) dimming elements. As photoelectric conversion elements, examples include solar cells. As solar cells, examples include organic thin-film solar cells, perovskite solar cells, and pigment-sensitized solar cells. As components, examples include electromagnetic wave shielding components, hot wire control components, heater components, lighting and antenna components. As devices, examples include contact sensor devices and image display devices.

[0191] An article 30 with a transparent conductive film can be obtained, for example, by bonding the component 31 to the substrate layer 2 in the transparent conductive film 20 using a fixing functional layer.

[0192] Examples of fixed functional layers include adhesive layers and bonding layers.

[0193] As a fixing functional layer, any material can be used without restriction as long as it is transparent. The fixing functional layer is preferably formed of resin. Examples of resins include acrylic resins, silicone resins, polyester resins, polyurethane resins, polyamide resins, polyvinyl ether resins, vinyl acetate / vinyl chloride copolymers, modified polyolefin resins, epoxy resins, fluoropolymers, natural rubber, and synthetic rubber. In particular, from the viewpoint of excellent optical transparency, moderate wettability, cohesive and adhesive properties, as well as excellent weather resistance and heat resistance, acrylic resins are preferred.

[0194] To suppress corrosion and migration of the transparent conductive layer 3, known corrosion inhibitors and anti-migration agents (such as the materials disclosed in Japanese Patent Application Publication No. 2015-022397) can be added to the fixing functional layer (the resin forming the fixing functional layer). Furthermore, to suppress the deterioration of the article 30 with the transparent conductive film during outdoor use, known ultraviolet absorbers can be added to the fixing functional layer (the resin forming the fixing functional layer). Examples of ultraviolet absorbers include, for instance, benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxaloyl aniline compounds, cyanoacrylate compounds, and triazine compounds.

[0195] Alternatively, a cover layer may be disposed on the upper surface of the transparent conductive layer 1 in the article 30 with the transparent conductive film.

[0196] The capping layer is a layer that covers the transparent conductive layer 1, which can improve the reliability of the transparent conductive layer 1 and suppress functional degradation caused by damage.

[0197] The capping layer is preferably a dielectric. The capping layer is formed from a mixture of resin and inorganic material. Examples of resins used in fixed functional layers can be cited as resins. The inorganic material is, for example, composed of inorganic oxides such as silicon dioxide, titanium dioxide, niobium oxide, aluminum oxide, zirconium dioxide, and calcium oxide, and fluorides such as magnesium fluoride.

[0198] In addition, from the same point of view as the aforementioned fixed functional layer, preservatives, anti-migration agents, and ultraviolet absorbers can also be added to the coating layer (a mixture of resin and inorganic materials).

[0199] In addition, although not shown in the figure, an article 30 with a transparent conductive film can also be obtained by bonding the component 31 to the transparent conductive layer 1 in the transparent conductive film 20 with the help of a fixing functional layer.

[0200] The article 30 with a transparent conductive film includes a transparent conductive film 20. Therefore, it is possible to improve transmittance and reduce resistivity.

[0201] Alternatively, by placing the transparent conductive layer 1 on one side of the component 31 in the thickness direction, an article 40 with a transparent conductive layer can also be obtained.

[0202] like Figure 9 As shown, the article 40 with the transparent conductive layer has a component 31 and a transparent conductive layer 1 sequentially on the side facing the thickness direction. Specifically, the article 40 with the transparent conductive layer has a component 31, a krypton-containing transparent conductive layer 10, and a krypton-free transparent conductive layer 11 sequentially on the side facing the thickness direction.

[0203] It should be noted that, Figure 9 This refers to an article 40 having a transparent conductive layer 1 according to the second embodiment.

[0204] The article 40 with the transparent conductive layer is obtained by sputtering the transparent conductive layer 1 onto one side of the component 31 in the thickness direction, or by transferring the transparent conductive layer 1 from the transparent conductive film 20 to one side of the component 31 in the thickness direction.

[0205] Alternatively, the component 31 can be bonded to the transparent conductive layer 1 using the aforementioned fixing functional layer.

[0206] Alternatively, a cover layer may be disposed on the upper surface of the transparent conductive layer 1 in the article 40 with the transparent conductive layer.

[0207] The article 40 with the transparent conductive layer has the transparent conductive layer 1. Therefore, it is possible to improve transmittance and reduce resistivity.

[0208] 5. Variations

[0209] In the variations, the same reference numerals are used to mark the same components and processes as in the first and second embodiments, and their detailed descriptions are omitted. Furthermore, unless specifically described otherwise, the variations can achieve the same effects as the first and second embodiments. Moreover, the first embodiment, the second embodiment, and their variations can be appropriately combined.

[0210] The above description focuses on the case where functional layer 4 is a hard coating layer, but functional layer 4 can also be an optical adjustment layer.

[0211] The optical adjustment layer is a layer that adjusts the optical properties (e.g., refractive index) of the conductive film 10 to suppress visual recognition of the pattern of the transparent conductive layer 1 or to suppress reflection at the interface within the transparent conductive film 20, and to ensure the excellent transparency of the transparent conductive film 20.

[0212] The optical adjustment layer is formed, for example, from an optical adjustment composition.

[0213] Optical adjustment compositions may contain, for example, resins and particles. Examples of resins listed in the above-described hard coating compositions include those listed above. Examples of particles are also listed above. The optical adjustment composition may be a resin monomer or an inorganic monomer. Examples of resins listed in the above-described hard coating compositions include those listed above. Additionally, examples of inorganic substances include, for instance, half-metal oxides and / or metal oxides such as silicon oxide, aluminum oxide, titanium dioxide, zirconium oxide, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. The half-metal oxides and / or metal oxides may or may not be stoichiometric in composition.

[0214] The thickness of the optical adjustment layer is, for example, 1 nm or more, preferably 5 nm or more, more preferably 10 nm or more, and also, for example, 200 nm or less, preferably 100 nm or less. The thickness of the optical adjustment layer can be calculated based on, for example, the wavelength of the interference spectrum observed using an instantaneous multi-functional photometry system. Alternatively, the thickness can be determined by observing the cross-section of the optical adjustment layer using an FE-TEM.

[0215] In addition, as functional layer 4, hard coating and optical adjustment layer (including multiple layers including hard coating and optical adjustment layer) can also be used in combination.

[0216] In the above description, in the first embodiment, the transparent conductive film 20 sequentially comprises a substrate layer 2, a krypton-containing transparent conductive layer 10, and a krypton-free transparent conductive layer 11 on one side facing the thickness direction. However, the order of the krypton-containing transparent conductive layer 10 and the krypton-free transparent conductive layer 11 is not particularly limited. More specifically, the transparent conductive film 20 may also sequentially comprise a substrate layer 2, a krypton-free transparent conductive layer 11, and a krypton-containing transparent conductive layer 10 on one side facing the thickness direction. To manufacture this transparent conductive film 20, in the second process, the fourth process is performed after the fifth process.

[0217] In the above description, the krypton-containing transparent conductive layer 10 comprises a metal oxide and trace amounts of krypton atoms. However, the krypton-containing transparent conductive layer 10 may further comprise trace amounts of rare gases other than krypton atoms (e.g., argon, xenon). In this case, for the krypton-containing transparent conductive layer 10, trace amounts of krypton atoms and rare gases other than krypton atoms are present in the metal oxide matrix. This krypton-containing transparent conductive layer 10 can be manufactured, for example, by combining krypton gas and rare gases other than krypton atoms as sputtering gases.

[0218] In the above description, in the third process, the transparent conductive layer 1 is crystallized by heating the amorphous transparent conductive layer 1. However, the amorphous transparent conductive layer 1 can also be crystallized by standing at a temperature below room temperature (e.g., below 40°C) for a long period of time (e.g., more than 5 days).

[0219] In the above description, the article 30 with a transparent conductive film has a component 31, a substrate layer 2 and a transparent conductive layer 1 sequentially on the side facing the thickness direction. However, the article 30 with a transparent conductive film may also have a substrate layer 2, a transparent conductive layer 1 and a component 31 sequentially on the side facing the thickness direction.

[0220] In the above description, the article 40 with a transparent conductive layer has a component 31, a krypton-containing transparent conductive layer 10 and a krypton-free transparent conductive layer 11 sequentially on the side facing the thickness direction. However, the article 40 with a transparent conductive layer may also have a krypton-containing transparent conductive layer 10, a krypton-free transparent conductive layer 11 and a component 31 sequentially on the side facing the thickness direction.

[0221] Example

[0222] The specific values ​​of mixing ratios (including proportions), physical property values, parameters, etc. used in the following description can be replaced with the corresponding upper limit values ​​(defined in the form of "less than" or "less than") or lower limit values ​​(defined in the form of "more than" or "exceeding") of the mixing ratios (including proportions), physical property values, parameters, etc., described in the "Specific Embodiments" above. Furthermore, unless otherwise specified, "parts" and "%" in the following description refer to mass measurements.

[0223] 1. Fabrication of transparent conductive layers and transparent conductive films

[0224] Example 1

[0225] <First Process>

[0226] A coating film is formed by applying a hard coating composition (a UV-curable resin containing acrylic resin) to one side of a strip of PET film (50 μm thick, manufactured by Toray Industries, Inc.) in the thickness direction, which serves as a transparent substrate. The coating film is then cured by UV irradiation. This forms a hard coating layer (2 μm thick). This prepares the substrate layer.

[0227] <Second Process>

[0228] Next, using reactive sputtering, an amorphous transparent conductive layer (krypton-containing transparent conductive layer) with a thickness of 130 nm is deposited on one side of the substrate layer (hard coating) in the thickness direction. In the reactive sputtering method, a sputtering film deposition apparatus (DC magnetron sputtering apparatus) capable of performing the film deposition process using a roll-to-roll method is used.

[0229] Specifically, a sintered body of indium oxide and tin oxide (tin oxide concentration of 10% by mass) is used as the target. A DC power supply is used as the power source for applying voltage to the target. The horizontal magnetic field strength on the target is set to 90 mT. In the sputtering apparatus, the substrate layer is brought into close contact with the film-forming roller along its circumference. The temperature of the film-forming roller is set to -5°C. Furthermore, vacuum exhaust is performed inside the sputtering apparatus until the vacuum level in the film-forming chamber of the sputtering apparatus reaches 0.8 × 10⁻⁶ m³ / s. -4 The pressure is set to 0.2 Pa. Then, krypton gas as the sputtering gas and oxygen gas as the reactive gas are introduced into the sputtering film deposition apparatus, and the gas pressure inside the sputtering film deposition apparatus is set to 0.2 Pa. The ratio of the amount of oxygen introduced into the sputtering film deposition apparatus to the total amount of krypton and oxygen introduced is approximately 2.5% of the flow rate. Figure 4 As shown, the resistivity of the amorphous krypton-containing transparent conductive layer, located in region X of the resistivity-oxygen induction curve, is 6.6 × 10⁻⁶. -4 The oxygen delivery rate is adjusted using the Ω·cm method. Figure 4 The resistivity-oxygen introduction curve shown can be fabricated by prior investigation of the oxygen introduction dependence of the resistivity of the amorphous krypton-containing transparent conductive layer when forming the amorphous krypton-containing transparent conductive layer using reactive sputtering under the same conditions as described above, except for the oxygen introduction amount.

[0230] <Third Process>

[0231] The amorphous transparent conductive layer is crystallized by heating in a hot air oven. The heating temperature is set to 165℃ and the heating time is set to 1 hour.

[0232] Thus, a transparent conductive layer and a transparent conductive film are obtained simultaneously.

[0233] Example 2

[0234] The same procedure as in Example 1 was followed to obtain a transparent conductive layer and a transparent conductive film.

[0235] The second process is modified as follows.

[0236] <Second Process>

[0237] In the second process, the fourth and fifth processes are carried out in sequence.

[0238] <Fourth Process>

[0239] In the fourth step, the same operation as the second step in Example 1 is performed, and a krypton-containing transparent conductive layer is disposed on one side of the substrate layer in the thickness direction.

[0240] The oxygen introduction amount is expressed as 6.5 × 10⁻⁶ for the resistivity of the amorphous krypton-containing transparent conductive layer. -4 The adjustment was made in Ω·cm (the ratio of oxygen introduction to the total krypton and oxygen introduction was approximately 2.6% flow rate). Additionally, the thickness of the amorphous krypton-containing transparent conductive layer was varied according to Table 1.

[0241] <Fifth Process>

[0242] In the fifth step, the same operation as the second step is performed, and a krypton-free transparent conductive layer (containing an argon transparent conductive layer) is disposed on one side in the thickness direction of the krypton-containing transparent conductive layer.

[0243] Specifically, the sputtering gas was changed to argon, and the gas pressure inside the sputtering film deposition apparatus was changed to 0.4 Pa. Additionally, the thickness of the amorphous argon-containing transparent conductive layer was changed according to Table 1.

[0244] Example 3

[0245] The same procedure as in Example 2 was followed to obtain a transparent conductive layer and a transparent conductive film.

[0246] Specifically, the krypton-containing transparent conductive layer and the argon-containing transparent conductive layer are modified according to Table 1.

[0247] Example 4

[0248] The same procedure as in Example 2 was followed to obtain a transparent conductive layer and a transparent conductive film.

[0249] In the second process, the fifth and fourth processes are performed in sequence. Furthermore, the thicknesses of the amorphous krypton-containing transparent conductive layer and the amorphous argon-containing transparent conductive layer are varied according to Table 1.

[0250] Example 5

[0251] The same procedure as in Example 1 was followed to obtain a transparent conductive layer and a transparent conductive film.

[0252] The sputtering gas used was a mixture of krypton and argon (90% krypton and 10% argon), and the oxygen introduction amount was such that the resistivity of the amorphous krypton-containing transparent conductive layer was 5.8 × 10⁻⁶. -4 The adjustment is made in Ω·cm. Additionally, the thickness of the amorphous krypton-containing transparent conductive layer is varied according to Table 1.

[0253] Comparative Example 1

[0254] The same procedure as in Example 1 was followed to obtain a transparent conductive layer and a transparent conductive film.

[0255] In the second step, the sputtering gas is changed to argon. Additionally, the gas pressure inside the sputtering film deposition apparatus is changed to 0.4 Pa.

[0256] 2. Evaluation

[0257] <Thickness of the transparent conductive layer>

[0258] The thickness of the transparent conductive layer in each embodiment and comparative example was determined by FE-TEM observation. Specifically, cross-sectional observation samples of the transparent conductive layer in each embodiment and comparative example were first prepared using the FIB microsampling method. In the FIB microsampling method, an FIB apparatus (trade name "FB2200", manufactured by Hitachi) was used, and the accelerating voltage was set to 10 kV. Next, the thickness of the transparent conductive layer in the cross-sectional observation sample was determined by FE-TEM observation. In the FE-TEM observation, an FE-TEM apparatus (trade name "JEM-2800", manufactured by JEOL) was used, and the accelerating voltage was set to 200 kV.

[0259] Furthermore, in Examples 2 and 3, before the argon-containing transparent conductive layer was deposited on one side in the thickness direction of the krypton-containing transparent conductive layer, a cross-sectional observation sample was prepared from the krypton-containing transparent conductive layer, and the thickness of the krypton-containing transparent conductive layer was determined by FE-TEM observation of the sample. Additionally, the thickness of the argon-containing transparent conductive layer was calculated by subtracting the thickness of the krypton-containing transparent conductive layer from the thickness of the transparent conductive layer.

[0260] Furthermore, in Example 4, before the krypton-containing transparent conductive layer was deposited on one side in the thickness direction of the argon-containing transparent conductive layer, a cross-sectional observation sample was prepared from the argon-containing transparent conductive layer, and the thickness of the argon-containing transparent conductive layer was determined by FE-TEM observation of the sample. Additionally, the thickness of the krypton-containing transparent conductive layer was calculated by subtracting the thickness of the argon-containing transparent conductive layer from the thickness of the transparent conductive layer.

[0261] The integrated intensity I of the X-ray diffraction peak on the (440) plane (440) The integrated intensity I of the X-ray diffraction peak relative to the (222) plane (222) The ratio (I) (440) / I (222 and crystal grain size >

[0262] The X-ray diffraction peaks of the transparent conductive layers in each embodiment and each comparative example were obtained by X-ray diffraction measurement using a horizontal X-ray diffraction apparatus (trade name "SmartLab", manufactured by Rigaku Corporation) under the measurement conditions described below. Furthermore, the X-ray peak curves were set to the values ​​obtained by subtracting the background from the PET film (PET film heated under the same conditions as the transparent conductive layers in each embodiment and each comparative example) in each embodiment and each comparative example. Subsequently, using analysis software (software name "SmartLab StudioII"), curves of X-ray diffraction peaks corresponding to the (222) plane were generated with a 2θ range of 29.5° to 31.5°. Additionally, curves of X-ray diffraction peaks corresponding to the (440) plane were generated with a 2θ range of 49.8° to 51.8°. The curves of each X-ray diffraction peak were obtained by fitting the X-ray diffraction peaks (peak shape: segmented Pearson VII function, background type: B-spline, fitting condition: automatic) to obtain the integral intensity I of the X-ray diffraction peaks of the (222) plane. (222) (Unit: Count°), Integrated intensity I of the X-ray diffraction peak on the (440) plane (440) (Unit: Count°), (222) crystal grain size (crystal size, unit: Crystal grain size (crystal size, unit: ) and (440) planes Furthermore, the integrated intensity I of the X-ray diffraction peak on the (440) plane was calculated. (440) The integrated intensity I of the X-ray diffraction peak relative to the (222) plane (222) The ratio (I) (440) / I (222 The results are shown in Table 1.

[0263] [Measurement Conditions]

[0264] Parallel beam optical configuration

[0265] Light source: CuKα rays (wavelength: )

[0266] Output: 45kV, 200mA

[0267] Incident-side slit system: Soler slit 5.0°

[0268] Entrance slit: 1.000mm

[0269] Light-receiving slit: 20.100mm

[0270] Light-receiving slit: Parallel slit beam splitter (PSA) 0.114deg.

[0271] Detector: Hypix-3000 Multi-Dimensional Pixel Detector

[0272] Sample stage: The test object, which is obtained by attaching glass to a transparent substrate with a transparent conductive film using an adhesive layer, is placed on the sample plate (4-inch wafer sample plate).

[0273] Scanning axis: 2θ / θ (out-of-plane measurement)

[0274] Step interval: 0.02°

[0275] Measurement speed: 0.8° / minute

[0276] Measurement range: 10°~90°

[0277] <Resistivity>

[0278] The resistivity of the transparent conductive layer in each embodiment and comparative example was measured. Specifically, the surface resistance of the transparent conductive layer was measured using the four-terminal method based on JIS K7194 (1994). Subsequently, the resistivity (Ω·cm) was calculated by multiplying the surface resistance value by the thickness of the transparent conductive layer. The results are shown in Table 1.

[0279] Total transmittance

[0280] For the transparent conductive films of each embodiment and comparative example, the total transmittance was measured using a haze meter (Suga Test Instruments, device name "HGM-2DP"). The results are shown in Table 1.

[0281] <Confirmation of Kr atoms within the transparent conductive layer>

[0282] The presence of Kr atoms in each transparent conductive layer in each embodiment can be confirmed as follows: First, using a scanning fluorescence X-ray analysis device (trade name "ZSX PrimusIV", manufactured by Rigaku Corporation), five fluorescence X-ray analyses were repeatedly performed under the following measurement conditions. The average value of each scanning angle was calculated to generate an X-ray spectrum. Furthermore, a peak was observed near a scanning angle of 28.2° in the generated X-ray spectrum, thus confirming the presence of Kr atoms in the transparent conductive layer.

[0283] [Measurement Conditions]

[0284] Spectrum: Kr-KA

[0285] Diameter measured: 30mm

[0286] Atmosphere: Vacuum

[0287] Target: Rh

[0288] Tube voltage: 50kV

[0289] Tube current: 60mA

[0290] Primary filter: Ni40

[0291] Scanning angle (deg): 27.0~29.5

[0292] Step size (deg): 0.020

[0293] Speed ​​(deg / minute): 0.75

[0294] Attenuator: 1 / 1

[0295] Slit: S2

[0296] Spectroscopic crystal: LiF(200)

[0297] Detector: SC

[0298] PHA: 100-300

[0299] [Table 1]

[0300]

[0301] It should be noted that the above-described invention is provided as an exemplary embodiment of the present invention, but it is merely an example and not intended to be limiting. Variations of the invention that will be apparent to those skilled in the art are included in the above claims.

[0302] Industrial availability

[0303] The transparent conductive layer and transparent conductive film of the present invention can be suitably used in, for example, electromagnetic wave shielding components, hot wire control components, heater components, lighting, antenna components, contact sensor devices, and image display devices.

[0304] Explanation of reference numerals in the attached figures

[0305] 1 Transparent conductive layer

[0306] 2 Substrate layer

[0307] 20 Transparent conductive film

Claims

1. A transparent conductive layer comprising krypton atoms, The transparent conductive layer comprises microcrystals with a crystal grain size of 350 Å or larger on the (222) facet, or microcrystals with a crystal grain size of 400 Å or larger on the (440) facet. The ratio of the integrated intensity of the X-ray diffraction peak of the (440) plane of the transparent conductive layer to the integrated intensity of the X-ray diffraction peak of the (222) plane is 0.130 or higher.

2. The transparent conductive layer according to claim 1, comprising indium tin composite oxide.

3. The transparent conductive layer according to claim 1 or 2, wherein the resistivity is less than 2.3 × 10⁻⁶. -4 Ω・cm.

4. The transparent conductive layer according to any one of claims 1 to 3, having a patterned shape.

5. A transparent conductive film, wherein a substrate layer and a transparent conductive layer according to any one of claims 1 to 4 are sequentially provided on one side facing the thickness direction.

Images