Transparent Conductive Film, Method for Manufacturing Transparent Conductive Film, and Intermediate

Abstract

The present invention provides a transparent conductive film having excellent adhesion between a conductor layer and a transparent conductive layer, a method for manufacturing the transparent conductive film, and an intermediate used in the method for manufacturing the transparent conductive film. The transparent conductive film (1) sequentially includes a transparent substrate (2) and a conductive layer (3) in the thickness direction. The conductive layer (3) includes a visual recognition area (10) and a border area (11) disposed on the outer peripheral edge of the visual recognition area (10). The visual recognition area (10) includes a transparent conductive layer (4). The border area (11) includes: a conductor layer (5), a transparent conductive layer (4), and a conductive adhesion layer (6) disposed therebetween and used to achieve adhesion between the conductor layer (5) and the transparent conductive layer (4). The transparent conductive layer (4) contains metal nanowires.

Description

Technical Field

[0001] The present invention relates to a transparent conductive film, a method for manufacturing the transparent conductive film, and an intermediate. More specifically, the present invention relates to a transparent conductive film suitable for optical applications, a method for manufacturing the transparent conductive film, and an intermediate used in the method for manufacturing the transparent conductive film. Background Art

[0002] Conventionally, a transparent conductive film obtained by forming a transparent conductive layer containing metal nanowires into a desired electrode pattern has been used in optical applications such as touch panels.

[0003] As such a transparent conductive film, the following touch input sensor has been proposed, which includes: a transparent substrate, a first photosensitive resin layer, a transparent conductive film layer containing silver nanowires, a metal thin film layer, and a second photosensitive resin layer (for example, refer to Patent Document 1).

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2017-27231 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] However, for the touch input sensor of Patent Document 1, since the adhesion between the metal thin film layer and the transparent conductive layer containing metal nanowires is low, there is a problem such as peeling of the transparent conductive layer.

[0009] An object of the present invention is to provide a transparent conductive film having excellent adhesion between a conductor layer and a transparent conductive layer, a method for manufacturing the transparent conductive film, and an intermediate used in the method for manufacturing the transparent conductive film.

[0010] Solutions for Solving the Problems

[0011] The present invention [1] is a transparent conductive film, which sequentially includes a transparent substrate and a conductive layer in the thickness direction. The conductive layer includes a visual recognition region and a border region disposed at the outer peripheral edge of the visual recognition region. The visual recognition region includes a transparent conductive layer, and the border region includes: a conductor layer, the transparent conductive layer, and a conductive adhesion layer disposed between them and used to achieve the adhesion between the conductor layer and the transparent conductive layer. The transparent conductive layer contains metal nanowires.

[0012] The present invention [2] includes the transparent conductive film described in [1] above, wherein the foregoing frame region sequentially includes the foregoing conductor layer, the foregoing conductive adhesion layer, and the foregoing transparent conductive layer toward one side in the thickness direction.

[0013] The present invention [3] includes the transparent conductive film described in [1] or [2] above, wherein the foregoing conductive layer is disposed on both sides of the foregoing transparent substrate.

[0014] The present invention [4] includes the transparent conductive film described in any one of [1] to [3] above, wherein the foregoing metal nanowire is a silver nanowire.

[0015] The present invention [5] includes the transparent conductive film described in any one of [1] to [4] above, wherein the foregoing conductor layer is a copper layer.

[0016] The present invention [6] includes the transparent conductive film described in any one of [1] to [5] above, wherein the foregoing conductive adhesion layer includes one or more selected from the group consisting of chromium, nickel, silicon oxide, and aluminum-doped zinc oxide.

[0017] The present invention [7] includes the transparent conductive film described in any one of [1] to [6] above, which is used for photolithography or wet etching.

[0018] The present invention [8] is a method for manufacturing a transparent conductive film, which includes: a first step of preparing a transparent substrate; and a second step of disposing a conductive layer having a visual recognition region and a frame region disposed on the outer peripheral edge of the foregoing visual recognition region on the foregoing transparent substrate. In the second step, a transparent conductive layer is disposed on the foregoing visual recognition region, and a conductor layer, a transparent conductive layer, and a conductive adhesion layer disposed between them and used to achieve the adhesion of the foregoing conductor layer and the foregoing transparent conductive layer are disposed on the foregoing frame region. The foregoing transparent conductive layer includes metal nanowires.

[0019] The present invention [9] includes an intermediate used in the method for manufacturing the transparent conductive film described in [8] above. The intermediate sequentially includes the foregoing transparent substrate, the foregoing conductor layer, and the foregoing conductive adhesion layer toward one side in the thickness direction, or sequentially includes the foregoing transparent substrate, the foregoing transparent conductive layer, and the foregoing conductive adhesion layer toward one side in the thickness direction.

[0020] Effects of the Invention

[0021] In the transparent conductive film of the present invention, the frame region includes: a conductor layer, a transparent conductive layer, and a conductive adhesion layer disposed between them and used to achieve the adhesion of the conductor layer and the transparent conductive layer.

[0022] Therefore, the adhesion between the conductor layer and the transparent conductive layer is excellent.

[0023] The manufacturing method of the transparent conductive film of the present invention includes a step of disposing a conductor layer, a transparent conductive layer, and a conductive adhesion layer disposed between them and used to achieve the adhesion between the conductor layer and the transparent conductive layer in a border region.

[0024] Therefore, a transparent conductive film with excellent adhesion between the conductor layer and the transparent conductive layer can be obtained.

[0025] The intermediate of the present invention is used in the manufacturing method of the transparent conductive film of the present invention.

[0026] Therefore, by using this intermediate, a transparent conductive film with excellent adhesion between the conductor layer and the transparent conductive layer can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 A cross-sectional view showing an embodiment of the transparent conductive film of the present invention.

[0028] Figure 2 An embodiment of the manufacturing method of the transparent conductive film of the invention is shown. Figure 2 A in it shows the first step of preparing a transparent substrate. Figure 2 B in it shows the step of disposing a conductor layer on one surface in the thickness direction of the transparent substrate in the second step. Figure 2 C in it shows the step of disposing a conductive adhesion layer on one surface in the thickness direction of the conductor layer in the second step. Figure 2 D in it shows the step of forming a pattern on the conductor layer and the conductive adhesion layer in the second step, thereby forming a visual recognition region and a border region. Figure 2 E in it shows the step of disposing a transparent conductive layer on one surface in the thickness direction of the visual recognition region and one surface in the thickness direction of the border region in the second step.

[0029] Figure 3 Shows Figure 1 A cross-sectional view of a modified example of the transparent conductive film shown (the case where a conductive layer is disposed on both sides of the transparent substrate).

[0030] Figure 4 Shows Figure 1 A cross-sectional view of a modified example of the transparent conductive film shown (the case where a hard coat is provided).

[0031] Explanation of Reference Signs

[0032] 1 Transparent conductive film

[0033] 2 Transparent substrate

[0034] 3 Conductive layer

[0035] 4 Transparent conductive layer

[0036] 5 Conductor layer

[0037] 6 Conductive bonding layer

[0038] 10 Visual recognition area

[0039] 11 Frame area

[0040] 12 Intermediate body Detailed implementation manners

[0041] Refer to Figure 1 , and an embodiment of the transparent conductive film of the present invention will be described.

[0042] Figure 1 In [reference], the up-down direction on the paper surface is the up-down direction (thickness direction), the upper side of the paper surface is the upper side (one side in the thickness direction), and the lower side of the paper surface is the lower side (the other side in the thickness direction). In addition, the left-right direction and the depth direction on the paper surface are the plane directions orthogonal to the up-down direction. Specifically, it is based on the direction arrows in each figure.

[0043] 1. Transparent conductive film

[0044] The transparent conductive film 1 has a film shape (including a sheet shape) with a specified thickness, and has a flat upper surface and a flat lower surface extending in a plane direction orthogonal to the thickness direction. The transparent conductive film 1 is, for example, a component such as a substrate for a touch panel or an electromagnetic wave shield provided in an image display device, that is, it is not an image display device. That is, the transparent conductive film 1 is a component for manufacturing an image display device or the like, and is a device that does not include an image display element such as an OLED module, circulates as a component itself, and is industrially available.

[0045] Specifically, as shown in Figure 1 , the transparent conductive film 1 sequentially includes a transparent substrate 2 and a conductive layer 3 toward one side in the thickness direction. More specifically, the transparent conductive film 1 includes a transparent substrate 2 and a conductive layer 3 disposed on the upper surface (one surface in the thickness direction) of the transparent substrate 2.

[0046] The thickness of the transparent conductive film 1 is, for example, 200 μm or less, preferably 150 μm or less. In addition, for example, it is 20 μm or more, preferably 30 μm or more.

[0047] 2. Transparent substrate

[0048] The transparent substrate 2 is a transparent substrate for ensuring the mechanical strength of the transparent conductive film 1.

[0049] The transparent substrate 2 has a film shape. The transparent substrate 2 is disposed on the entire lower surface of the conductive layer 3 in contact with the lower surface of the conductive layer 3.

[0050] The transparent substrate 2 is, for example, a polymer film having transparency.

[0051] Examples of the material of the transparent substrate 2 include olefin resins such as polyethylene, polypropylene, and norbornene polymers; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; (meth)acrylic resins (acrylic resins and / or methacrylic resins) such as polymethacrylate; polycarbonate resins, polyethersulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, polystyrene resins, and the like.

[0052] The transparent substrate 2 can be used alone or in combination of two or more kinds.

[0053] As the material of the transparent substrate 2, norbornene polymers are preferably exemplified. That is, the transparent substrate 2 is preferably a norbornene-based film formed of a norbornene polymer.

[0054] The norbornene-based polymer is a polymer obtained by polymerizing norbornene monomers and having an alicyclic structure in the repeating units of the main chain. The norbornene-based resin is preferably an amorphous norbornene-based resin.

[0055] Examples of the norbornene-based polymer include norbornene homopolymers formed of norbornene monomers and norbornene copolymers formed of copolymers of norbornene monomers and olefins such as ethylene.

[0056] Examples of the norbornene monomer include polycyclic olefins such as norbornene, methylnorbornene, dimethylnorbornene, ethylidenenorbornene, butylnorbornene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, and tricyclopentadiene; monocyclic olefins such as cyclobutene, cyclopentene, cyclooctadiene, and cyclooctatriene. Polycyclic olefins are preferably exemplified. These norbornene monomers can be used alone or in combination of two or more kinds.

[0057] Regarding the thickness of the transparent substrate 2, from the viewpoints of mechanical strength and the like, for example, it is 2 μm or more, preferably 15 μm or more. In addition, for example, it is 300 μm or less, preferably 150 μm or less. From the viewpoints of thinning and flexibility, it is more preferably less than 50 μm. The thickness of the transparent substrate 2 can be measured using, for example, a microgauge type thickness gauge.

[0058] 3. Conductive layer

[0059] The conductive layer 3 is a layer for imparting conductivity to the transparent conductive film 1.

[0060] The conductive layer 3 is disposed on the entire upper surface of the transparent substrate 2 in contact with the upper surface (one surface in the thickness direction) of the transparent substrate 2.

[0061] The conductive layer 3 has a visual recognition area 10 and a border area 11 disposed on the outer peripheral edge of the visual recognition area 10.

[0062] The visual recognition area 10 is, for example, a touch input area of a touch panel and has a transparent conductive layer 4.

[0063] The border area 11 is an area for forming a wiring pattern (not shown) and has a conductor layer 5, a transparent conductive layer 4, and a conductive adhesion layer 6 disposed therebetween.

[0064] Specifically, for the border area 11, the conductor layer 5, the conductive adhesion layer 6, and the transparent conductive layer 4 are sequentially provided on one side in the thickness direction, or the transparent conductive layer 4, the conductive adhesion layer 6, and the conductor layer 5 are sequentially provided on one side in the thickness direction. From the viewpoint of a narrow border, it is preferable that the border area 11 has the conductor layer 5, the conductive adhesion layer 6, and the transparent conductive layer 4 sequentially on one side in the thickness direction.

[0065] In the following description, the case where the border area 11 has the conductor layer 5, the conductive adhesion layer 6, and the transparent conductive layer 4 sequentially on one side in the thickness direction will be described in detail.

[0066] In such a case, the transparent conductive film 1 has a transparent substrate 2 in the visual recognition area 10 and a transparent conductive layer 4 disposed on the upper surface (one surface in the thickness direction) of the transparent substrate 2.

[0067] In addition, the transparent conductive film 1 has, in the border area 11: a transparent substrate 2, a conductor layer 5 disposed on the upper surface (one surface in the thickness direction) of the transparent substrate 2, a conductive adhesion layer 6 disposed on the upper surface (one surface in the thickness direction) of the conductor layer 5, and a transparent conductive layer 4 disposed on the upper surface (one surface in the thickness direction) of the conductive adhesion layer 6.

[0068] In addition, the transparent conductive layer 4 is the uppermost layer in the transparent conductive film 1, and the transparent conductive layer 4 is disposed across the visual recognition area 10 and the border area 11 in such a manner that it continuously covers the entire upper surface (one surface in the thickness direction) of the transparent substrate 2 in the visual recognition area 10, the upper surface (one surface in the thickness direction) of the conductive adhesion layer 6 in the border area 11, and the inner side surfaces of the conductor layer 5 and the conductive adhesion layer 6 at the boundary between the visual recognition area 10 and the border area 11.

[0069] 4. Transparent Conductive Layer

[0070] The transparent conductive layer 4 is a transparent layer that exhibits excellent conductivity.

[0071] The transparent conductive layer 4 is formed of a transparent conductive composition.

[0072] The transparent conductive composition contains metal nanowires and a binder resin. That is, the transparent conductive layer 4 contains metal nanowires.

[0073] When the transparent conductive layer 4 contains metal nanowires, the metal nanowires form a mesh shape, so that even a small amount of metal nanowires can form a good conduction path and the resistivity can be reduced. In addition, by forming the metal nanowires into a mesh shape, openings are formed in the gaps of the mesh, thereby improving the light transmittance.

[0074] The metal nanowires are, for example, conductive substances having an outer diameter of about 10 nm on average and having a needle-like or filamentous shape.

[0075] Examples of the metal constituting the metal nanowires include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, lead, or alloys thereof, etc. Silver is preferably exemplified.

[0076] That is, the metal nanowires are preferably silver nanowires.

[0077] When the metal nanowires are silver nanowires, the resistivity of the transparent conductive layer 4 can be reduced.

[0078] The binder resin is not particularly limited, and examples thereof include acrylic resins, epoxy resins, amide resins, alkyd resins, phenolic resins, urethane resins, cellulose derivatives, etc.

[0079] Moreover, the transparent conductive composition can be obtained by mixing the binder resin and the metal nanowires.

[0080] The compounding ratio of the binder resin is, for example, 75% by mass or more with respect to the transparent conductive composition.

[0081] In addition, the compounding ratio of the metal nanowires is, for example, 0.1% by mass or more with respect to the transparent conductive composition.

[0082] In addition, the transparent conductive composition can be diluted with a solvent as needed.

[0083] In addition, from the viewpoints of corrosion prevention, etc., the transparent conductive composition can be compounded with known additives such as antioxidants and ultraviolet absorbers as needed.

[0084] The transparent conductive layer 4 is formed by the method described below.

[0085] The thickness of the transparent conductive layer 4 is, for example, 10 nm or more, preferably 30 nm or more, more preferably 40 nm or more, and, for example, 80 nm or less.

[0086] It should be noted that the thickness of the transparent conductive layer 4 can be measured, for example, by observing the cross-section of the transparent conductive film 1 using a transmission electron microscope.

[0087] The surface resistance value of the transparent conductive layer 4 is, for example, 70 Ω / square or less, preferably 30 Ω / square or less.

[0088] When the surface resistance value of the transparent conductive layer 4 is below the above upper limit, excellent electrical characteristics can be exhibited when the transparent conductive layer 4 is patterned and used as an electrode.

[0089] There is no particular limitation on the lower limit of the surface resistance value of the transparent conductive layer 4. For example, the surface resistance value of the transparent conductive layer 4 generally exceeds 0 Ω / square, and is also 1 Ω / square or more.

[0090] It should be noted that the surface resistance value can be measured by the four-terminal method in accordance with JIS K 7194.

[0091] 4. Conductor layer

[0092] The conductor layer 5 is a layer for connecting to a wiring pattern (not shown) in the frame region 11.

[0093] The conductor layer 5 has a frame shape when viewed from above.

[0094] Examples of the material of the conductor layer 5 include metals such as copper, silver, gold, nickel, or their alloys.

[0095] The materials of the conductor layer 5 can be used alone or in combination of two or more.

[0096] From the viewpoint of conductivity and the like, examples of the preferred material of the conductor layer 5 include copper.

[0097] That is, the conductor layer 5 is preferably a copper layer.

[0098] It should be noted that when the conductor layer 5 is made of a material such as copper that is easily oxidized, the surface of the conductor layer 5 can be oxidized. Specifically, when the conductor layer 5 is a copper layer, the conductor layer 5 can be a copper layer having copper oxide on a part or all of the surface.

[0099] The conductor layer 5 is formed by the method described later.

[0100] The thickness of the conductor layer 5 is, for example, 40 nm or more, preferably 100 nm or more, and is also, for example, 400 nm or less.

[0101] It should be noted that the thickness of the conductor layer 5 can be measured, for example, by observing the cross-section of the transparent conductive film 1 using a transmission electron microscope.

[0102] 5. Conductive adhesion layer

[0103] The conductive bonding layer 6 is a layer for achieving the bonding of the conductor layer 5 and the transparent conductive layer 4.

[0104] The conductive bonding layer 6 has a frame shape when viewed from above.

[0105] Examples of the material of the conductive bonding layer 6 include chromium, nickel, silicon oxide (SiO x , (0 < x < 2)), copper-nickel-titanium (Cu-Ni-Ti) alloy, and aluminum-doped zinc oxide (AZO), etc.

[0106] The materials of the conductive bonding layer 6 can be used alone or in combination of two or more kinds.

[0107] Examples of the material of the conductive bonding layer 6, from the viewpoint of the bonding property between the transparent conductive layer 4 and the conductor layer 5, preferably include chromium, copper-nickel-titanium (Cu-Ni-Ti) alloy, silicon oxide (SiO x ), and aluminum-doped zinc oxide (AZO). More preferably, examples include chromium, silicon oxide (SiO x ), and aluminum-doped zinc oxide (AZO). Further preferably, examples include chromium, silicon oxide (SiO x ). Particularly preferably, examples include silicon oxide (SiO x ).

[0108] That is, from the viewpoint of the bonding property between the transparent conductive layer 4 and the conductor layer 5, the conductive bonding layer 6 preferably contains one or more selected from the group consisting of chromium (preferably chromium contained in the copper-nickel-titanium (Cu-Ni-Ti) alloy), nickel, silicon oxide, and aluminum-doped zinc oxide.

[0109] The conductive bonding layer 6 is formed by the method described below.

[0110] The thickness of the conductive bonding layer 6 is, for example, 1 nm or more, and for example, 10 nm or less.

[0111] In particular, when the material of the conductive bonding layer 6 is any one of chromium, silicon oxide (SiO x ), and aluminum-doped zinc oxide (AZO), the thickness of the conductive bonding layer 6 is, for example, 1 nm or more, and for example, 10 nm or less, preferably 5 nm or less, and more preferably 3 nm or less.

[0112] In addition, when the material of the conductive bonding layer 6 is any one of nickel and copper-nickel-titanium (Cu-Ni-Ti) alloy, the thickness of the conductive bonding layer 6 is, for example, 1 nm or more, preferably 5 nm or more, and for example, 10 nm or less.

[0113] 5. Method for manufacturing a transparent conductive thin film

[0114] Next, a method for manufacturing the transparent conductive film 1 will be described.

[0115] The method for manufacturing the transparent conductive film 1 includes: a first step of preparing a transparent substrate 2, and a second step of disposing a conductive layer 3 on the transparent substrate 2. In addition, in this manufacturing method, for example, each layer is sequentially disposed in a roll-to-roll manner.

[0116] In the first step, as shown in Figure 2 A of, a transparent substrate 2 is prepared.

[0117] In the second step, the conductive layer 3 is disposed on the transparent substrate 2. Specifically, the conductive layer 3 is disposed on one surface in the thickness direction of the transparent substrate 2.

[0118] More specifically, in the second step, a transparent conductive layer 4 is disposed in the visual recognition area 10, and a conductor layer 5, a conductive adhesion layer 6, and a transparent conductive layer 4 are sequentially disposed on one side in the thickness direction of the frame area 11.

[0119] Hereinafter, a detailed description will be given specifically.

[0120] In the second step, first, as shown in Figure 2 B of, the conductor layer 5 is disposed on the entire surface of one surface in the thickness direction of the transparent substrate 2.

[0121] As a method for disposing the conductor layer 5 on the entire surface of one surface in the thickness direction of the transparent substrate 2, for example, vacuum evaporation, sputtering, lamination, plating, ion plating, etc. can be mentioned, and sputtering is preferably mentioned.

[0122] For sputtering, the target and the transparent substrate 2 are disposed opposite to each other in a vacuum chamber, a gas is supplied and a voltage is applied by a power source, thereby accelerating the gas ions and irradiating them onto the target, ejecting the target material from the target surface, and laminating the target material on the surface of the transparent substrate 2.

[0123] As the gas, for example, an inert gas such as Ar can be mentioned. In addition, if necessary, a reactive gas such as oxygen can be used in combination. When a reactive gas is used in combination, the flow rate ratio (sccm) of the reactive gas is not particularly limited, and is, for example, 0.1% by flow rate or more and 5% by flow rate or less with respect to the total flow rate ratio of the sputtering gas and the reactive gas.

[0124] The gas pressure during sputtering is, for example, 0.1 Pa or more, and is, for example, 1.0 Pa or less, preferably 0.7 Pa or less.

[0125] The power source can be, for example, any one of a DC power source, an AC power source, an MF power source, and an RF power source, and can also be a combination thereof.

[0126] Thus, the conductor layer 5 is disposed over the entire surface on one side in the thickness direction of the transparent substrate 2.

[0127] Next, in the second step, as Figure 2 shown in C of FIG., the conductive adhesion layer 6 is disposed over the entire surface on one side in the thickness direction of the conductor layer 5.

[0128] As a method of disposing the conductive adhesion layer 6 over the entire surface on one side in the thickness direction of the conductor layer 5, for example, a sputtering method, a plating method, a vacuum evaporation method, etc. can be cited, and preferably, the sputtering method can be cited.

[0129] The sputtering conditions (flow ratio of reactive gas and gas pressure during sputtering) are the same as those of the sputtering of the above-mentioned conductor layer 5.

[0130] Thus, the conductive adhesion layer 6 is disposed over the entire surface on one side in the thickness direction of the conductor layer 5. In addition, an intermediate 12 (described later) is obtained which sequentially includes the transparent substrate 2, the conductor layer 5, and the conductive adhesion layer 6 in the thickness direction.

[0131] Next, in the second step, as Figure 2 shown in D of FIG., the conductor layer 5 and the conductive adhesion layer 6 are patterned, thereby forming (defining) the visual recognition area 10 and the frame area 11.

[0132] As a method of patterning the conductor layer 5 and the conductive adhesion layer 6, a known etching method can be cited.

[0133] Specifically, the conductor layer 5 and the conductive adhesion layer 6 are patterned to be frame-shaped in a top view. In other words, the conductor layer 5 and the conductive adhesion layer 6 in the central portion 20 in the top view of the conductor layer 5 and the conductive adhesion layer 6 are removed, and the conductor layer 5 and the conductive adhesion layer 6 at the outer peripheral edge portion 21 of the central portion 20 are left to form a pattern.

[0134] Thus, the above-mentioned central portion 20 becomes the visual recognition area 10, and the outer peripheral edge portion 21 becomes the frame area 11.

[0135] That is, the area where the conductor layer 5 and the conductive adhesion layer 6 are disposed is the frame area 11, and the area where the conductor layer 5 and the conductive adhesion layer 6 are not disposed is the visual recognition area 10.

[0136] Next, in the second step, as Figure 2 shown in E of FIG., a transparent conductive layer 4 is disposed on one side in the thickness direction of the visual recognition area 10, on one side in the thickness direction of the frame area 11, and on the inner side surfaces of the conductor layer 5 and the conductive adhesion layer 6 at the boundary between the visual recognition area 10 and the frame area 11.

[0137] Specifically, the transparent conductive layer 4 is disposed so as to straddle the visual recognition area 10 and the frame area 11. In detail, the transparent conductive layer 4 is disposed on one side in the thickness direction of the transparent substrate 2 in the visual recognition area 10. In addition, the transparent conductive layer 4 is disposed on one side in the thickness direction of the conductive adhesion layer 6 in the frame area 11, and is disposed on the inner side surfaces of the conductor layer 5 and the conductive adhesion layer 6 at the boundary between the visual recognition area 10 and the frame area 11. Moreover, the transparent conductive layer 4 in the visual recognition area 10, the transparent conductive layer 4 in the frame area 11, and the transparent conductive layer 4 at the boundary between the visual recognition area 10 and the frame area 11 are continuously formed.

[0138] When disposing the transparent conductive layer 4, a diluent of a transparent conductive composition is coated on one side in the thickness direction of the visual recognition area 10 (one side in the thickness direction of the transparent substrate 2), one side in the thickness direction of the frame area 11 (one side in the thickness direction of the conductive adhesion layer 6), and the inner side surfaces of the conductor layer 5 and the conductive adhesion layer 6 at the boundary between the visual recognition area 10 and the frame area 11, and then dried.

[0139] Thereby, the transparent conductive layer 4 is disposed on one side in the thickness direction of the visual recognition area 10, one side in the thickness direction of the frame area 11, and the inner side surfaces of the conductor layer 5 and the conductive adhesion layer 6 at the boundary between the visual recognition area 10 and the frame area 11.

[0140] As described above, through such a second process, the transparent conductive layer 4 is disposed in the visual recognition area 10. In addition, in the frame area 11, the conductor layer 5, the conductive adhesion layer 6, and the transparent conductive layer 4 are sequentially disposed toward the thickness direction side.

[0141] Thereby, the transparent conductive film 1 having the transparent substrate 2 and the conductive layer 3 sequentially toward the thickness direction side is obtained.

[0142] Moreover, the transparent conductive layer 4 of the transparent conductive film 1 can also be patterned by a known patterning method such as photolithography or wet etching.

[0143] Preferably, the transparent conductive layer 4 is patterned by photolithography and wet etching.

[0144] That is, the transparent conductive film 1 is suitable for photolithography or wet etching.

[0145] 6. Function and effect

[0146] In the transparent conductive film 1, in the frame area 11, the conductor layer 5, the conductive adhesion layer 6, and the transparent conductive layer 4 are sequentially provided toward the thickness direction side.

[0147] That is, the conductive adhesion layer 6 is provided between the conductor layer 5 and the transparent conductive layer 4.

[0148] Therefore, the adhesion between the conductor layer 5 and the transparent conductive layer 4 is excellent.

[0149] In particular, when the transparent conductive layer 4 of the transparent conductive thin film 1 is patterned by photolithography, since the adhesion between the conductor layer 5 and the transparent conductive layer 4 containing metal nanowires is low, there is a case where the transparent conductive layer 4 peels off.

[0150] On the other hand, in this transparent conductive thin film 1, a conductive adhesion layer 6 is provided between the conductor layer 5 and the transparent conductive layer 4, so the adhesion between the conductor layer 5 and the transparent conductive layer 4 is excellent. As a result, peeling of the transparent conductive layer 4 can also be suppressed when forming a pattern by photolithography.

[0151] In the manufacturing method of the transparent conductive thin film 1, in the second step, the conductor layer 5, the conductive adhesion layer 6, and the transparent conductive layer 4 are sequentially provided on one side in the thickness direction of the frame region 11.

[0152] Therefore, a transparent conductive thin film 1 with excellent adhesion between the conductor layer 5 and the transparent conductive layer 4 can be obtained.

[0153] 7. Intermediate

[0154] The intermediate 12 is a component that can be used in the manufacturing method of the transparent conductive thin film 1.

[0155] The intermediate 12 sequentially includes a transparent substrate 2, a conductor layer 5, and a conductive adhesion layer 6 on one side in the thickness direction, or sequentially includes a transparent substrate 2, a transparent conductive layer 4, and a conductive adhesion layer 6 on one side in the thickness direction.

[0156] In particular, as described above, when the conductor layer 5, the conductive adhesion layer 6, and the transparent conductive layer 4 are sequentially provided on one side in the thickness direction of the frame region 11, as shown in Figure 2 C of, the intermediate 12 sequentially includes a transparent substrate 2, a conductor layer 5, and a conductive adhesion layer 6 on one side in the thickness direction.

[0157] Using such an intermediate 12, a transparent conductive thin film 1 with excellent adhesion between the conductor layer 5 and the transparent conductive layer 4 can be obtained.

[0158] 8. Variation

[0159] In the variation, the same reference numerals are used for the same components and processes as in an embodiment, and their detailed descriptions are omitted. In addition, unless otherwise specified, the variation can exhibit the same effects as an embodiment. Furthermore, an embodiment and its variation can be appropriately combined.

[0160] In the above description, the border region 11 successively includes a conductor layer 5, a conductive bonding layer 6, and a transparent conductive layer 4 on one side in the thickness direction. However, the border region 11 may also successively include a transparent conductive layer 4, a conductive bonding layer 6, and a conductor layer 5 on one side in the thickness direction.

[0161] In such a case, in the second step of the method for manufacturing the transparent conductive film, first, the transparent conductive layer 4 is disposed on the entire surface of one side in the thickness direction of the transparent substrate 2. Next, the conductive bonding layer 6 is disposed on the entire surface of one side in the thickness direction of the transparent conductive layer 4. Next, the transparent conductive layer 4 and the conductive bonding layer 6 are patterned to form the visual recognition region 10 and the border region 11. Then, the conductor layer 5 is disposed on one side in the thickness direction of the border region 11 (one side in the thickness direction of the conductive bonding layer 6).

[0162] In addition, in such a case, the intermediate 12 successively includes a transparent substrate 2, a transparent conductive layer 4, and a conductive bonding layer 6 on one side in the thickness direction.

[0163] In addition, in the above description, the conductive layer 3 is disposed on one side in the thickness direction of the transparent substrate 2. However, as Figure 3 shown, the conductive layer 3 may also be disposed on both sides of the transparent substrate 2 (one side in the thickness direction and the other side in the thickness direction).

[0164] In such a case, the transparent conductive film 1 successively includes a conductive layer 3, a transparent substrate 2, and a conductive layer 3 on one side in the thickness direction. Specifically, the transparent conductive film 1 successively includes a transparent conductive layer 4, a transparent substrate 2, and a transparent conductive layer 4 on one side in the thickness direction in the visual recognition region 10, and successively includes a transparent conductive layer 4, a conductive bonding layer 6, a conductor layer 5, a transparent substrate 2, a conductor layer 5, a conductive bonding layer 6, and a transparent conductive layer 4 on one side in the thickness direction in the border region 11.

[0165] When the conductive layer 3 is disposed on both sides of the transparent substrate 2, there are advantages such as film thinning based on the common use of the transparent substrate 2 and improved positional accuracy of the pattern wiring.

[0166] In addition, in the above description, the conductive layer 3 is disposed on the upper surface (one side in the thickness direction) of the transparent substrate 2. However, a hard coat 7 may also be disposed on the upper surface (one side in the thickness direction) of the transparent substrate 2.

[0167] In such a case, as Figure 4 shown, the transparent conductive film 1 includes: a transparent substrate 2, a hard coat 7 disposed on the upper surface (one side in the thickness direction) of the transparent substrate 2, and a conductive layer 3 disposed on the upper surface (one side in the thickness direction) of the hard coat 7.

[0168] The hard coat layer 7 is a protective layer for suppressing damage to the transparent substrate 2 during the production of the transparent conductive film 1. In addition, the hard coat layer 7 is an anti-scratch layer for suppressing scratches on the transparent conductive layer 4 when the transparent conductive films 1 are laminated.

[0169] The hard coat layer 7 is formed from a hard coat composition.

[0170] The hard coat composition contains a resin and particles.

[0171] Examples of the resin include curable resins, thermoplastic resins (e.g., polyolefin resins), etc., and curable resins are preferably cited.

[0172] Examples of the curable resin include energy ray curable resins that are cured by irradiation with active energy rays (specifically, ultraviolet rays, electron beams, etc.), thermosetting resins that are cured by heating, etc., and energy ray curable resins are preferably cited.

[0173] Examples of the energy ray curable resin include polymers containing functional groups having polymerizable carbon-carbon double bonds in the molecule. Examples of such functional groups include vinyl, (meth)acryloyl (methacryloyl and / or acryloyl), etc.

[0174] Specific examples of the energy ray curable resin include (meth)acrylic ultraviolet curable resins such as urethane acrylate and epoxy acrylate.

[0175] In addition, examples of curable resins other than energy ray curable resins include thermosetting resins such as urethane resins, melamine resins, alkyd resins, silicone-based polymers, and organosilane condensates.

[0176] The resin can be used alone or in combination of two or more.

[0177] Examples of the particles include inorganic particles such as silica particles and zirconia particles, and organic particles such as crosslinked acrylic particles.

[0178] The average particle size of the particles is, for example, 10 nm or more, and, for example, 3000 nm or less, preferably 1000 nm or less, more preferably 100 nm or less, and still more preferably 50 nm or less.

[0179] Moreover, the hard coat composition is obtained by mixing the resin and the particles.

[0180] In addition, known additives such as leveling agents, thixotropic agents, and antistatic agents can be blended in the hard coat composition as needed.

[0181] To form the hard coat layer 7, a diluent of the hard coat composition is applied to one surface in the thickness direction of the transparent substrate 2 and dried, and then the hard coat composition is cured by ultraviolet irradiation.

[0182] Thereby, the hard coat layer 7 is formed.

[0183] Regarding the thickness of the hard coat layer 7, from the viewpoint of scratch resistance, it is, for example, 0.1 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more. In addition, for example, it is 10 μm or less, preferably 2 μm or less. The thickness of the hard coat layer 7 can be measured, for example, by cross-sectional observation using a transmission electron microscope.

[0184] Then, a conductive layer 3 is formed on the upper surface (one surface in the thickness direction) of the hard coat layer 7 in the same manner as above.

[0185] In addition, the hard coat layer 7 can be disposed on both sides of the transparent substrate 2 (one side in the thickness direction and the other side in the thickness direction).

[0186] Examples

[0187] Examples and comparative examples are shown below to more specifically explain the present invention. It should be noted that the present invention is not limited by any of the examples and comparative examples. In addition, the specific numerical values such as the compounding ratio (content ratio), physical property values, parameters, etc. used in the following descriptions can be replaced with the upper limit values (numerical values defined as "below", "less than") or lower limit values (numerical values defined as "above", "more than") of the corresponding compounding ratio (content ratio), physical property values, parameters, etc. described in the above "Detailed Description".

[0188] 1. Manufacture of Test Transparent Conductive Film

[0189] In the following examples and comparative examples, a test transparent conductive film is manufactured as the transparent conductive film for evaluation described later.

[0190] The test transparent conductive film is formed by disposing a transparent conductive layer on the entire surface of one surface in the thickness direction of the conductive adhesion layer without forming a pattern (without forming a visually recognizable area and a border area) for the conductor layer and the conductive adhesion layer in the above second step.

[0191] The results of the evaluation (described later) of such a test transparent conductive film can be replaced with the results of the evaluation (described later) of the transparent conductive film of the present invention.

[0192] Example 1

[0193] As the transparent substrate, a cycloolefin-based film (thickness 40 μm, "ZEONOR FILM" manufactured by Zeon Corporation) is prepared.

[0194] A hard coat liquid containing an ultraviolet curable acrylic resin is coated on both sides of a transparent substrate and dried. Then, the curable resin composition is cured by ultraviolet irradiation. Thus, a hard coat with a thickness of 1.0 μm is formed.

[0195] Next, in the hard coats provided on both sides of the transparent substrate, a conductor layer is formed over the entire surface on one side in the thickness direction of the hard coat on one side in the thickness direction.

[0196] Specifically, by DC sputtering, the set thickness of the sputtering output is adjusted to 200 nm, and sputtering is performed using a copper target. For the vacuum conditions, argon gas is introduced, and the gas pressure is set to 0.3 Pa. Thus, a conductor layer (copper layer) with a thickness of 200 nm is formed.

[0197] Furthermore, a conductive adhesion layer is formed over the entire surface on one side in the thickness direction of the conductor layer.

[0198] Specifically, by DC sputtering, the set thickness of the sputtering output is adjusted to 5.0 nm, and sputtering is performed using a chromium target. For the vacuum conditions, argon gas is introduced, and the gas pressure is set to 0.3 Pa. Thus, a conductive adhesion layer (chromium layer) with a thickness of 5.0 nm is formed.

[0199] Then, a transparent conductive layer is formed over the entire surface on one side in the thickness direction of the conductive adhesion layer.

[0200] Specifically, a diluted solution of a transparent conductive composition containing 0.15 mass% of silver nanowires (average fiber length: 10 μm, average fiber diameter: 10 nm), 0.45 mass% of a binder resin (cellulose derivative), and 99.4 mass% of an aqueous solvent is coated and dried, thereby forming a transparent conductive layer with a thickness of 10 to 80 nm.

[0201] Thus, a test transparent conductive film is obtained, which sequentially includes a hard coat, a transparent substrate, a hard coat, and a conductive layer (conductor layer, conductive adhesion layer, and transparent conductive layer) toward one side in the thickness direction.

[0202] Example 2

[0203] The thickness of the conductive adhesion layer (chromium layer) is set to 2.5 nm, and otherwise, the same operations as in Example 1 are performed to obtain a test transparent conductive film.

[0204] Example 3

[0205] An SiO x (0 < x < 2) layer is provided as the conductive adhesion layer, the thickness of the SiO x layer is set to 5 nm, and otherwise, the same operations as in Example 1 are performed to obtain a test transparent conductive film.

[0206] Specifically, the set thickness of the sputtering output is adjusted to 5.0 nm, and a Si target is used as the target for sputtering to form a conductive adhesion layer accordingly.

[0207] It should be noted that for the vacuum condition, argon and oxygen are introduced at a weight ratio of 1:1.3, and the air pressure is set to 0.2 Pa.

[0208] Example 4

[0209] The thickness of the conductive adhesion layer (SiO x layer) is set to 2.5 nm. Except for this, the operation is the same as that in Example 3 to obtain a test transparent conductive film.

[0210] Example 5

[0211] A Cu-Ti-Ni layer is set as the conductive adhesion layer, and the thickness of the Cu-Ti-Ni layer is set to 5 nm. Except for this, the operation is the same as that in Example 1 to obtain a test transparent conductive film.

[0212] Specifically, the set thickness of the sputtering output is adjusted to 5.0 nm, and CuTiNi (Cu: 35% by mass, Ti: 3% by mass, Ni: 62% by mass) is used as the target for sputtering to form a conductive adhesion layer accordingly.

[0213] It should be noted that for the vacuum condition, argon is introduced and the air pressure is set to 0.3 Pa.

[0214] Example 6

[0215] The thickness of the conductive adhesion layer (Cu-Ni-Ti layer) is set to 2.5 nm. Except for this, the operation is the same as that in Example 5 to obtain a test transparent conductive film.

[0216] Example 7

[0217] A Ni layer is set as the conductive adhesion layer, and the thickness of the Ni layer is set to 5 nm. Except for this, the operation is the same as that in Example 1 to obtain a test transparent conductive film.

[0218] Specifically, the set thickness of the sputtering output is adjusted to 5.0 nm, and Ni is used as the target for sputtering to form a conductive adhesion layer accordingly.

[0219] It should be noted that for the vacuum condition, argon is introduced and the air pressure is set to 0.3 Pa.

[0220] Example 8

[0221] The thickness of the conductive adhesion layer (Ni layer) is set to 2.5 nm. Except for this, the operation is the same as that in Example 7 to obtain a test transparent conductive film.

[0222] Example 9

[0223] An aluminum-doped zinc oxide layer (AZO layer) is provided as a conductive adhesion layer, and the thickness of the AZO layer is set to 5 nm. Except for this, the operation is the same as in Example 1, and a test transparent conductive film is obtained.

[0224] Specifically, the set thickness of the sputtering output is adjusted to 5.0 nm, and sputtering is performed using AZO as a target to form a conductive adhesion layer.

[0225] It should be noted that for the vacuum condition, argon and oxygen are introduced at a weight ratio of 40:1, and the air pressure is set to 0.3 Pa.

[0226] Example 10

[0227] The thickness of the conductive adhesion layer (AZO layer) is set to 2.5 nm. Except for this, the operation is the same as in Example 9, and a test transparent conductive film is obtained.

[0228] Comparative Example 1

[0229] No conductive adhesion layer is provided. Except for this, the operation is the same as in Example 1, and a test transparent conductive film is obtained.

[0230] 2. Evaluation

[0231] (Adhesion)

[0232] For the test transparent conductive films of each example and each comparative example, based on the cross-cut method, slits are made in 10 grids × 10 grids (a total of 100 grids).

[0233] Then, the test transparent conductive film is immersed in a 1% by mass KOH aqueous solution at 40 °C for 5 minutes, then washed with pure water and dried.

[0234] Then, for the 100 grids, the grids where the transparent conductive layer has defects (defects), the grids where the transparent conductive layer has peeled off (peeling), and the grids where the transparent conductive layer has not peeled off and has no defects (no defects · peeling) are counted respectively.

[0235] The results are shown in Table 1.

[0236] [Table 1]

[0237]

[0238] It should be noted that the above invention is provided as an exemplary embodiment of the present invention, but this 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.

Claims

1. A transparent conductive film, characterized in that, On one side in the thickness direction, there are successively provided a transparent substrate and a conductive layer. The conductive layer has a visual recognition area and a border area disposed on the outer peripheral edge of the visual recognition area. The visual recognition area has a transparent conductive layer. The border area has: a conductor layer, the transparent conductive layer, and a conductive bonding layer disposed between them and used to achieve the bonding of the conductor layer and the transparent conductive layer. The transparent conductive layer contains metal nanowires. The conductive bonding layer contains one or more selected from the group consisting of chromium, silicon oxide, and copper-nickel-titanium alloy.

2. The transparent conductive film according to claim 1, wherein On one side in the thickness direction, the border area successively has the conductor layer, the conductive bonding layer, and the transparent conductive layer.

3. The transparent conductive film according to claim 1 or 2, wherein The conductive layer is disposed on both sides of the transparent substrate.

4. The transparent conductive thin film according to claim 1 or 2, characterized in that, The metal nanowires are silver nanowires.

5. The transparent conductive film according to claim 1 or 2, characterized in that, The conductor layer is a copper layer.

6. The transparent conductive thin film according to claim 1 or 2, characterized in that, It is used for photolithography or wet etching.

7. A method for manufacturing a transparent conductive thin film, characterized in that, It has: a first step of preparing a transparent substrate, and a second step of disposing a conductive layer having a visual recognition area and a border area disposed on the outer peripheral edge of the visual recognition area on the transparent substrate. In the second step, a transparent conductive layer is disposed in the visual recognition area, and a conductor layer, a transparent conductive layer, and a conductive bonding layer disposed between them and used to achieve the bonding of the conductor layer and the transparent conductive layer are disposed in the border area. The transparent conductive layer contains metal nanowires. The conductive bonding layer contains one or more selected from the group consisting of chromium, silicon oxide, and copper-nickel-titanium alloy.

8. An intermediate, characterized in that, It is used in the method for manufacturing the transparent conductive film according to claim 7. This intermediate successively has the transparent substrate, the conductor layer, and the conductive bonding layer on one side in the thickness direction, or successively has the transparent substrate, the transparent conductive layer, and the conductive bonding layer on one side in the thickness direction.

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