JP2016197554A - Transparent wiring member manufacturing method and transparent wiring member - Google Patents

Abstract

Provided is a method for manufacturing a transparent wiring member capable of manufacturing a transparent wiring member having a stable electrical connection between a metal film and a transparent conductive film and having a small thickness.
The following steps are included. A step of preparing a transparent conductor provided with a transparent conductive film and having metal nanowires exposed on the surface of the transparent conductive film, a step of forming a metal film on the transparent conductive film, and a step of forming a first resist layer on the metal film Removing a part of the first resist layer; removing the metal film; removing the first resist layer; removing the metal nanowire; forming a second resist layer on the metal film and the transparent conductive film A step of removing a part of the second resist layer, a step of removing the metal film, and a step of removing the second resist layer.
[Selection] Figure 1

Description

  The present invention generally relates to a method for manufacturing a transparent wiring member and a transparent wiring member, and more particularly to a method for manufacturing a transparent wiring member and a transparent wiring member used for a transparent electrode and the like.

  The transparent wiring member 1 is widely used as a transparent electrode in fields such as a liquid crystal display, a plasma display panel, a touch panel, an organic EL display, and a solar cell. Such a transparent wiring member 1 is conventionally manufactured as follows (see, for example, Patent Documents 1 and 2).

  First, a transparent conductor 5 as shown in FIG. 11A is prepared. The transparent conductor 5 includes a transparent substrate 2 and a transparent conductive film 3. The transparent substrate 2 is, for example, a polyethylene terephthalate film. The transparent conductive film 3 is, for example, an acrylic resin film, and is formed on the surface of the transparent substrate 2. The transparent conductive film 3 contains the metal nanowire 4 and thereby has conductivity. The metal nanowire 4 is, for example, a silver nanowire.

  Next, the transparent conductor 5 is patterned by photolithography. Specifically, first, as shown in FIG. 11B, a resist layer 70 is formed on the surface of the transparent conductive film 3. The resist layer 70 is formed, for example, by bringing a dry film into close contact with the surface of the transparent conductive film 3 or applying a liquid resist to the surface of the transparent conductive film 3 and drying it.

  Next, using a mask film, the resist layer 70 is exposed to a predetermined wiring pattern, and then developed to remove a portion of the resist layer 70 as shown in FIG. 11C. The transparent conductive film 3 is exposed at the location where the resist layer 70 is removed.

  Next, as shown in FIG. 12A, the metal nanowires 4 in the transparent conductive film 3 at the locations where the resist layer 70 has been removed are removed by etching using an etching solution. As a result, this portion becomes an electrically insulated insulating portion 32 (non-conductive portion). In the insulating portion 32, the pore 9 is formed at the position where the metal nanowire 4 was present. On the other hand, the metal nanowire 4 in the transparent conductive film 3 where the resist layer 70 has not been removed remains without being removed because the photocured resist layer 70 prevents entry of the etching solution. Thereby, this location becomes a conductive portion 31 having conductivity.

  Next, the remaining resist layer 70 is removed using an alkaline aqueous solution or solvent as shown in FIG. 12B. The transparent conductive film 3 is divided into a transparent region 301 and a peripheral region 302. The transparent region 301 includes a conductive portion 31 and an insulating portion 32 that are formed in a predetermined wiring pattern. A video or image is displayed in the transparent area 301. The peripheral region 302 is a region located around the transparent region 301 and includes the conductive portion 31.

  Then, by forming the peripheral wiring 60 by the printing method using the conductive paste in the peripheral region 302 of the transparent conductive film 3, the transparent wiring member 1 as shown in FIG. 12C is obtained. Then, as shown in FIG. 13C, the cover glass 11 is bonded to the transparent conductive film 3 side of the transparent wiring member 1 with the adhesive layer 10 to obtain a touch panel as shown in FIG. In this case, the transparent area 301 becomes an input operation area. An electrical signal generated at a location in the transparent region 301 by the input operation is output to the outside through the peripheral wiring 60. In addition, the anti-blocking layer 12 may be formed in the transparent wiring member 1 at the transparent base material 2 side.

Japan Patent Application Publication No. 2012-209030 Japan Patent Application Publication No. 2013-206050

  Conventionally, the transparent wiring member 1 shown in FIG. 12C has a problem that the electrical connection between the peripheral wiring 60 and the transparent conductive film 3 is unstable. Although the cause of this is unknown, the following reasons are presumed by the inventors' diligent research. That is, in the process shown in FIGS. 12A and 12B, when the photocured resist layer 70 is removed, the metal nanowires 4 existing on the surface layer portion of the transparent conductive film 3 are pulled by the resist layer 70 and cut. This is probably because the sheet resistance (surface resistivity) of the transparent conductive film 3 is increased. In this case, an increase in sheet resistance in the transparent region 301 of the transparent conductive film 3 is not particularly a problem, but an increase in sheet resistance in the peripheral region 302 of the transparent conductive film 3 is an electrical connection with the peripheral wiring 60. Can have adverse effects.

Further, the touch panel shown in FIG. 13C has a problem that the entire thickness is increased. Conventionally, the peripheral wiring 60 is formed of a cured product of a conductive paste containing metal particles, a binder resin, and a solvent. However, in order to develop the curability of the conductive paste, the content of the metal particles is limited. There is. As a result, the content of the binder resin is relatively increased, but the peripheral wiring 60 must be thickened to ensure conductivity. Specifically, the thickness T ₃ of the peripheral wiring 60 is about 5 to 10 μm, and even if it is thin, the limit is about 5 μm. If it is thinner than this, there is a possibility that the conductivity cannot be secured. Thus since the thickness T ₃ of the peripheral wiring 60 becomes thick, the transparent wiring member 1 becomes thicker including peripheral wire 60, it becomes thicker panel.

  The present invention has been made in view of the above points, and it is possible to manufacture a transparent wiring member having a thin electrical connection with a stable electrical connection between a metal film that can be a peripheral wiring and a transparent conductive film. It is an object of the present invention to provide a transparent wiring member having a thin thickness and a stable method for manufacturing a transparent wiring member and a stable electrical connection between a metal film that can be a peripheral wiring and a transparent conductive film.

  The method for producing a transparent wiring member according to the present invention includes the following steps A1 to K1.

Step A1: A transparent base material and a transparent conductive film formed on the surface of the transparent base material, the transparent conductive film contains metal nanowires, and a part of the metal nanowires are made of the transparent conductive film. Preparing a transparent conductor exposed on the surface;
Step B1: forming a metal film on the surface of the transparent conductive film,
Step C1: a step of forming a first resist layer on the surface of the metal film,
Step D1: Step of removing a part of the first resist layer;
Step E1: a step of removing the metal film at the place where the first resist layer has been removed,
Step F1: Step of removing the remaining first resist layer;
Step G1: A step of removing the metal nanowires in the transparent conductive film at the place where the metal film is removed,
Step H1: forming a second resist layer on the surface of the remaining metal film and the surface of the transparent conductive film where the metal film has been removed,
Step I1: a step of removing a part of the second resist layer;
Step J1: a step of removing the metal film at a portion where the second resist layer has been removed, and a step K1: a step of removing the remaining second resist layer.

  It is preferable to further include the following step A1-2 between the step A1 and the step B1.

  Step A1-2: Step of hydrophilizing the surface of the transparent conductive film.

  The method for producing a transparent wiring member according to the present invention includes the following steps A2 to L2.

Step A2: comprising a transparent base material and a transparent conductive film formed on the surface of the transparent base material, wherein the transparent conductive film contains metal nanowires, and a part of the metal nanowires is made of the transparent conductive film. Preparing a transparent conductor exposed on the surface;
Step B2: forming a metal film on the surface of the transparent conductive film,
Step C2: forming a rust preventive film on the surface of the metal film,
Step D2: Step of forming a first resist layer on the surface of the rust preventive film,
Step E2: a step of removing a part of the first resist layer;
Step F2: a step of removing the metal film and the rust preventive film at the place where the first resist layer is removed,
Step G2: Step of removing the remaining first resist layer,
Step H2: a step of removing the metal nanowires in the transparent conductive film where the metal film and the rust preventive film have been removed,
Step I2: forming a second resist layer on the surface of the transparent conductive film where the metal film and the anticorrosive film that remain and the metal film are removed,
Step J2: a step of removing a part of the second resist layer,
Step K2: a step of removing the metal film and the rust preventive film at the place where the second resist layer has been removed, and a step L2: a step of removing the remaining second resist layer.

  It is preferable to further include the following step A2-2 between the step A2 and the step B2.

  Step A2-2: Step of hydrophilizing the surface of the transparent conductive film.

  The method for manufacturing a transparent wiring member according to the present invention includes the following steps A3 to J3.

Step A3: comprising a transparent base material and a transparent conductive film formed on the surface of the transparent base material, wherein the transparent conductive film contains metal nanowires, and a part of the metal nanowires is made of the transparent conductive film. Preparing a transparent conductor exposed on the surface;
Step B3: forming a first resist layer on the surface of the transparent conductive film,
Step C3: a step of removing a part of the first resist layer;
Step D3: a step of forming a metal film on the surface of the transparent conductive film at a location where the first resist layer is not formed,
Step E3: Step of removing the remaining first resist layer,
Step F3: a step of removing the metal nanowires in the transparent conductive film at the place where the first resist layer is removed,
Step G3: forming a second resist layer on the surface of the metal film and the surface of the transparent conductive film where the first resist layer has been removed,
Step H3: a step of removing a part of the second resist layer,
Step I3: a step of removing the metal film where the second resist layer has been removed, and a step J3: a step of removing the remaining second resist layer.

  It is preferable that the metal nanowire includes a silver nanowire.

  The metal film preferably includes a copper film.

The transparent wiring member according to the present invention is
A transparent substrate;
A transparent conductive film formed on the surface of the transparent substrate;
A metal film formed on a part of the surface of the transparent conductive film,
The transparent conductive film contains metal nanowires,
A part of the metal nanowire is in contact with the metal film.

  A rust preventive film is preferably formed on the surface of the metal film.

  It is preferable that the metal nanowire includes a silver nanowire.

  The metal film preferably includes a copper film.

  According to the present invention, since the metal film is formed on the surface of the transparent conductive film before forming the first resist layer, the electrical connection between the metal film that can be a peripheral wiring and the transparent conductive film is stable. Can be made. Furthermore, since the metal film is thinly formed and can be a peripheral wiring, the thickness of the transparent wiring member can be reduced as compared with the case where the peripheral wiring is formed with a conductive paste.

1A and 1B are schematic cross-sectional views illustrating a part of the steps of the transparent wiring member manufacturing method according to the first and second embodiments. 2A to 2C are schematic cross-sectional views illustrating a part of the process of the manufacturing method of the transparent wiring member according to the first embodiment. 3A to 3C are schematic cross-sectional views illustrating a part of the process of the transparent wiring member manufacturing method according to the first embodiment. 4A to 4C are schematic cross-sectional views illustrating a part of the steps of the method for manufacturing the transparent wiring member according to the first embodiment. 5A to 5D are schematic cross-sectional views illustrating a part of the process of the method for manufacturing the transparent wiring member according to the second embodiment. 6A to 6C are schematic cross-sectional views illustrating a part of the process of the method for manufacturing the transparent wiring member according to the second embodiment. 7A to 7C are schematic cross-sectional views illustrating a part of the process of the method for manufacturing the transparent wiring member according to the second embodiment. 8A to 8D are schematic cross-sectional views illustrating a part of the process of the transparent wiring member manufacturing method according to the third embodiment. 9A to 9C are schematic cross-sectional views illustrating a part of the steps of the method for manufacturing the transparent wiring member according to the third embodiment. 10A to 10C are schematic cross-sectional views illustrating a part of the process of the manufacturing method of the transparent wiring member according to the third embodiment. FIG. 11A to FIG. 11C are schematic cross-sectional views illustrating a part of the process of the conventional method for manufacturing a transparent wiring member. 12A to 12C are schematic cross-sectional views illustrating a part of the process of the conventional method for manufacturing a transparent wiring member. 13A is a schematic cross-sectional view showing a part of the touch panel of Embodiments 1 and 3, FIG. 13B is a schematic cross-sectional view showing a part of the touch panel of Embodiment 2, and FIG. 13C shows a conventional touch panel. It is a schematic sectional drawing which shows a part. It is a schematic plan view which shows an example of a touch panel.

  Embodiments of the present invention will be described below.

(Embodiment 1)
First, the manufacturing method of the transparent wiring member 1 of this embodiment is demonstrated. The manufacturing method of the transparent wiring member 1 of the present embodiment uses a photoetching method (photolithography) and includes the following steps A1 to K1. Through these steps, a transparent wiring member 1 as shown in FIG. 4C is obtained, and can be used for a touch panel as shown in FIGS. 13A and 14. Each step will be described in order.

  First, step A1 will be described. In step A1, the transparent conductor 5 is prepared as shown in FIG. 1A. The transparent conductor 5 includes a transparent substrate 2 and a transparent conductive film 3.

  First, the transparent substrate 2 will be described.

  The transparent substrate 2 preferably has light transmittance. The total light transmittance of the transparent substrate 2 is preferably 50% or more, more preferably 70% or more, and particularly preferably 80% or more.

  The shape of the transparent substrate 2 is not particularly limited, but is preferably a plate shape, a sheet shape, or a film shape. In particular, from the viewpoint of improving the productivity and transportability of the transparent wiring member 1, the shape of the transparent substrate 2 is preferably a film.

  When the transparent base material 2 is a film form, it is preferable that the thickness of the transparent base material 2 exists in the range of 10-500 micrometers. In this case, the transparency of the transparent substrate 2 is particularly good, and the workability during production and handling of the transparent wiring member 1 is also good. The thickness of the transparent substrate 2 is more preferably in the range of 25 to 200 μm, and still more preferably in the range of 25 to 150 μm. In this case, the transparent wiring member 1 can be made thinner and lighter, light interference between the front and back surfaces of the transparent wiring member 1 is suppressed, and thermal contraction when the transparent substrate 2 is heated is suppressed. Thus, problems such as deterioration of workability due to heat shrinkage of the transparent substrate 2 are suppressed.

  The material of the transparent substrate 2 is not particularly limited. Examples of the material of the transparent substrate 2 include glass and transparent resin. Examples of transparent resins include polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polymethyl methacrylate copolymer, triacetyl cellulose, polyolefin, polyamide, polyvinyl chloride, amorphous polyolefin, cycloolefin polymer, cycloolefin copolymer, acrylate Resin and urethane acrylate resin are mentioned.

  The transparent substrate 2 is preferably a polyester film. Among the polyester films, biaxially stretched films made of polyethylene terephthalate (PET) or polyethylene naphthalate have excellent mechanical properties, heat resistance, and chemical resistance, so magnetic tape, ferromagnetic thin film tape, packaging film It is suitable as a material for a film for electronic parts, an electrical insulating film, a film for laminating, a film to be attached to the surface of a display, and a protective film for various members. Especially for display applications, prism lens sheets that are members of liquid crystal display devices, base films such as touch panels and backlights, base films for television optical films, optical films used for front optical filters for plasma televisions, and near-infrared cut films It is suitable as a base film for an electromagnetic wave shielding film.

  Examples of the polyester constituting the polyester film include aromatic dicarboxylic acid components such as terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, and 4,4′-diphenyldicarboxylic acid, ethylene glycol, and 1,4-butanediol. An aromatic polyester produced by a reaction with a glycol component such as 1,4-cyclohexanedimethanol or 1,6-hexanediol is preferred. In particular, polyethylene terephthalate and polyethylene-2,6-naphthalene dicarboxylate are preferable. The polyester may be produced by copolymerization of the above-described plurality of components.

  The transparent substrate 2 may contain at least one of organic particles and inorganic particles. In this case, the winding property and transportability of the transparent substrate 2 are improved. Examples of the organic particles include crosslinked acrylic resin particles, crosslinked polystyrene resin particles, urea resin particles, melamine resin particles, and crosslinked silicone resin particles. Examples of inorganic particles include calcium carbonate particles, calcium oxide particles, aluminum oxide particles, kaolin, silicon oxide particles, and zinc oxide particles.

  The transparent substrate 2 may further contain a colorant, an antistatic agent, an ultraviolet absorber, an antioxidant, a lubricant, a catalyst, and other resins as long as the transparency is not impaired.

  The haze of the transparent substrate 2 is preferably 3% or less. In this case, the visibility of the image or image through the transparent wiring member 1 is improved, and it is particularly suitable as a member for optical use. The haze of the transparent substrate 2 is more preferably 1.5% or less.

  Next, the transparent conductive film 3 will be described.

  The transparent conductive film 3 is formed on the surface of the transparent substrate 2. The transparent conductive film 3 contains metal nanowires 4 and a transparent binder 7, and a plurality of metal nanowires 4 come into contact with each other to form a conductive path. In this state, the plurality of metal nanowires 4 are transparent binders 7. It is fixed. Thus, the transparent conductive film 3 has conductivity by the metal nanowires 4. Formation of the transparent conductive film 3 is performed by, for example, applying a composition (a composition for forming a transparent conductive film) containing at least the metal nanowires 4 and the transparent binder 7 on the surface of the transparent substrate 2 and then drying and curing. This can be done by solidifying. A part of the metal nanowire 4 is exposed on the surface of the transparent conductive film 3. When considering only the transparent region 301 of the transparent conductive film 3, the metal nanowire 4 does not necessarily have to protrude from the surface of the transparent conductive film 3, but the electrical connection between the transparent conductive film 3 and the peripheral wiring 60. Since it is necessary to ensure a secure connection, it is preferable that a part of the metal nanowire 4 protrudes from the surface of the transparent conductive film 3 as shown in FIG. 1A.

  The metal nanowire 4 is a metal fiber having a nano-sized (1 to 1000 nm) diameter. The type of metal constituting the metal nanowire 4 is not particularly limited, and examples thereof include silver (Ag), gold (Au), copper (Cu), cobalt (Co), aluminum (Al), and platinum (Pt). It is done. In particular, in order to improve the conductivity of the transparent conductive film 3, the metal constituting the metal nanowire 4 includes at least one selected from gold (Au), silver (Ag), copper (Cu), and platinum (Pt). In particular, it is more preferable that at least one selected from silver (Ag) and copper (Cu) is included.

  It is preferable that the metal nanowire 4 contains a silver nanowire. The metal nanowire 4 itself is not transparent, but the conductivity of the silver nanowire is high. Therefore, if the metal nanowire 4 includes silver nanowires, the transparency of the transparent conductive film 3 can be secured high by reducing the content of the entire metal nanowire 4 in the transparent conductive film 3. Furthermore, high conductivity can be imparted to the transparent conductive film 3.

  The method for producing the metal nanowire 4 is not particularly limited, and examples thereof include known methods such as a liquid phase method and a gas phase method. For example, as a method for producing silver nanowires, Adv. Mater. 2002, 14, P833-837, Chem. Mater. Examples include methods disclosed in documents such as 2002, 14, P4736-4745, and Japanese translations of PCT publication No. 2009-505358. Moreover, as a manufacturing method of gold nanowire, the method currently disclosed by Unexamined-Japanese-Patent No. 2006-233252 is mentioned. Moreover, as a manufacturing method of copper nanowire, the method currently disclosed by Unexamined-Japanese-Patent No. 2002-266007 is mentioned. Moreover, as a manufacturing method of cobalt nanowire, the method currently disclosed by Unexamined-Japanese-Patent No. 2004-148771 is mentioned. In particular, Adv. Mater. 2002, 14, P 833-837 and Chem. Mater. If it is the method currently disclosed by 2002, 14, P4736-4745, silver nanowire can be manufactured simply and in large quantities by an aqueous system.

  The average diameter of the metal nanowire 4 is preferably in the range of 10 to 100 nm. When the average diameter is 10 nm or more, the conductivity of the transparent conductive film 3 is particularly high. When the average diameter is 100 nm or less, the transparency of the transparent conductive film 3 is particularly high. The average diameter of the metal nanowire 4 is more preferably in the range of 20 to 100 nm, and further preferably in the range of 40 to 100 nm.

  The average length of the metal nanowire 4 is preferably in the range of 1 to 100 μm. When the average length is 1 μm or more, the conductivity of the transparent conductive film 3 is particularly high. When the average length is 100 μm or less, the metal nanowires 4 are less likely to aggregate in the transparent conductive film 3, thereby improving the transparency of the transparent conductive film 3. The average length of the metal nanowire 4 is more preferably in the range of 1 to 50 μm, and further preferably in the range of 3 to 50 μm.

  The average diameter of the metal nanowire 4 is a value obtained by measuring the diameter of a sufficient number of metal nanowires 4 and arithmetically averaging the results. The average length of the metal nanowire 4 is a value obtained by measuring the length of a sufficient number of metal nanowires 4 and arithmetically averaging the results. The diameter and length of the metal nanowire 4 are derived by image analysis of an electron microscope image of the metal nanowire 4. For example, when the electron microscope image of the metal nanowire 4 is bent, the diameter (projection diameter (D)) and area (projection area (S)) of the metal nanowire 4 are calculated by image analysis. By dividing the projected area (S) by the projected diameter (D), the length (L = S / D) of the metal nanowire 4 is obtained. In order to derive the average diameter and average length of the metal nanowires 4, it is preferable to measure the diameter and length of at least 100 metal nanowires 4, and the diameter and length of 300 or more metal nanowires 4 It is more preferable to measure the thickness.

  Although content in particular of the metal nanowire 4 in the transparent conductive film 3 is not restrict | limited, It is preferable to exist in the range of 0.01-90 mass%, and it is more preferable to exist in the range of 0.1-30 mass%. Preferably, it is in the range of 0.5 to 10% by mass.

  Examples of the transparent binder 7 include cellulose resin, silicone resin, fluorine resin, acrylic resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polystyrene resin, polyethersulfone resin, polyarylate resin, polycarbonate resin, Polyurethane resin, polyacrylonitrile resin, polyvinyl acetal resin, polyamide resin, polyimide resin, diacryl phthalate resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, other thermoplastic resins, constituting these resins A copolymer formed by polymerizing two or more types of monomers can be mentioned. The metal nanowire 4 can be fixed to the surface of the transparent substrate 2 by the transparent binder 7.

  It is also preferable that the transparent binder 7 contains a reactive curable resin. The reactive curable resin preferably includes, for example, at least one of a thermosetting resin and an ionizing radiation curable resin.

  Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, silicon resin, and polysiloxane resin. When the composition for forming a transparent conductive film contains a thermosetting resin, it may contain a crosslinking agent, a polymerization initiator, a curing agent, a curing accelerator, and a solvent as necessary.

  As the ionizing radiation curable resin, a resin having an acrylate functional group is preferable. Examples of the resin having an acrylate-based functional group include oligomers and prepolymers such as (meth) acrylates of polyfunctional compounds having a relatively low molecular weight. Examples of the polyfunctional compound include polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and polyhydric alcohols. When the composition for forming a transparent conductive film contains an ionizing radiation curable resin, it is preferable to further contain a reactive diluent. Examples of the reactive diluent include monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone, trimethylolpropane tri (meth) acrylate, hexanediol (meta ) Acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl A polyfunctional monomer of glycol di (meth) acrylate is exemplified.

  When the composition for forming a transparent conductive film contains an ionizing radiation curable resin, and the ionizing radiation curable resin is a photocurable resin such as an ultraviolet curable resin, the composition for forming a transparent conductive film further includes It is preferable to contain a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, α-amyloxime esters, and thioxanthones. When the composition for transparent conductive film formation contains a photocurable resin and a photopolymerization initiator, it may contain a photosensitizer in addition to the photopolymerization initiator or instead of the photopolymerization initiator. Examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone.

  The composition for forming a transparent conductive film may contain a solvent as necessary. Examples of the solvent include an organic solvent and water. If the organic solvent and water are compatible, they may be mixed to form a solvent. Examples of the organic solvent include alcohols such as methanol, ethanol and isopropyl alcohol (IPA); ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; , Aromatic hydrocarbons such as xylene, and mixtures thereof.

  The amount of the solvent in the composition for forming a transparent conductive film is appropriately adjusted so that the solid content is uniformly dissolved or dispersed. The solid content concentration in the composition for forming a transparent conductive film is preferably in the range of 0.1 to 50% by mass, and more preferably in the range of 0.5 to 30% by mass.

  Examples of the method for applying the transparent conductive film forming composition to the surface of the transparent substrate 2 include a roll coating method, a spin coating method, and a dip coating method. When the composition for forming a transparent conductive film contains a thermosetting resin, the transparent conductive film 3 is formed by heating and thermosetting the composition for forming a transparent conductive film after being applied to the transparent substrate 2. can do. When the composition for forming a transparent conductive film contains an ionizing radiation curable resin, the composition for forming a transparent conductive film after being applied to the transparent substrate 2 is irradiated with ionizing radiation such as ultraviolet rays to be photocured. A transparent conductive film 3 can be formed.

  In forming the transparent conductive film 3, the application of the composition for forming the transparent conductive film is performed in one stage, but it may be performed in two stages. When divided into two stages, the transparent conductive film 3 is formed using a first composition containing at least the metal nanowires 4 and the transparent binder 7 and a second composition containing at least the transparent binder 7. In this case, in the first stage, after the first composition is applied to the surface of the transparent substrate 2, the metal nanowire layer is formed by drying and curing or solidifying. Next, in the second stage, after the second composition is applied to the surface of the metal nanowire layer, the transparent conductive film 3 can be formed by drying and curing or solidifying.

  As shown in FIG. 1A, the transparent conductive film 3 is formed on one surface of the transparent substrate 2, but the anti-blocking layer 12 may be formed on the other surface. The anti-blocking layer 12 is a layer having irregularities on the surface and having light transmittance. When the transparent wiring member 1 is wound in a roll shape and stacked, the anti-blocking layer 12 can prevent scratches or suppress adhesion. The irregularities on the surface of the anti-blocking layer 12 may be applied by mechanical processing, or may be formed by the anti-blocking layer 12 containing fine particles such as silica particles. In the latter case, the anti-blocking layer 12 contains, for example, acrylate resin or urethane acrylate resin in the range of 80 to 95% by mass, and further contains silica particles having an average particle diameter of 250 nm in the range of 5 to 20% by mass. It is preferable.

  The anti-blocking layer 12 preferably contains a silicone leveling agent. Thereby, the lubricity of the transparent wiring member 1 can be improved.

  When forming the antiblocking layer 12, it is preferable to surface-treat to the transparent base material 2 previously. In this case, the wettability and adhesion between the surface of the transparent substrate 2 that has been surface-treated and the anti-blocking layer 12 are improved. Examples of the surface treatment method include physical surface treatment such as plasma treatment, corona discharge treatment and flame treatment, and chemical surface treatment with a coupling agent, an acidic component, an alkaline component, and the like.

  Next, process B1 is demonstrated. In step B1, a metal film 6 is formed on the surface of the transparent conductive film 3 as shown in FIG. 1B. Examples of the method for forming the metal film 6 include physical vapor deposition (PVD) and chemical vapor deposition (CVD). Examples of physical vapor deposition include sputtering and vacuum vapor deposition. The material of the metal film 6 is not particularly limited, but is preferably a metal different from the metal constituting the metal nanowire 4 from the viewpoint of selective etching described later. Since the copper film has high conductivity, the metal film 6 preferably includes a copper film. In particular, when the metal nanowire 4 includes silver nanowire, the metal film 6 preferably includes a copper film. In this case, both the metal nanowire 4 and the metal film 6 have high conductivity and are suitable for selective etching. The thickness of the metal film 6 is preferably in the range of 50 to 1000 nm, more preferably in the range of 100 to 500 nm. However, the thinner the transparent wiring member 1 is, the better.

  It is preferable that the following step A1-2 is further included between step A1 and step B1. In step A1-2, the surface of the transparent conductive film 3 is subjected to a hydrophilic treatment. Thereby, the adhesiveness of the transparent conductive film 3 and the metal film 6 can be improved. Examples of the hydrophilic treatment include plasma treatment and corona treatment. Specific treatment conditions are not particularly limited as long as the metal nanowires 4 present in the surface layer portion of the transparent conductive film 3 are not lost.

  Next, the process C1 will be described. In step C1, a first resist layer 71 is formed on the surface of the metal film 6 as shown in FIG. 2A. The first resist layer 71 may be formed of either a negative resist or a positive resist. The first resist layer 71 may be formed of either a dry film or liquid. The first resist layer 71 is formed, for example, by bringing a dry film into close contact with the surface of the metal film 6 or applying a liquid resist onto the surface of the metal film 6 and drying it.

  Next, the process D1 will be described. In step D1, as shown in FIG. 2B, a part of the first resist layer 71 is removed. Specifically, the first resist layer 71 shown in FIG. 2A is exposed in a predetermined wiring pattern using a mask film, and then developed with a developing solution, whereby the first resist layer 71 is shown in FIG. 2B. A part of can be removed. Examples of the light source for exposure include a metal halide lamp, a semiconductor laser, a high-pressure mercury lamp, and an excimer laser. Examples of the developer include an alkaline solution. As shown in FIG. 2B, the metal film 6 is exposed at the place where the first resist layer 71 is removed.

  Next, the process E1 will be described. In step E1, as shown in FIG. 2C, the metal film 6 where the first resist layer 71 has been removed is removed. Specifically, as shown in FIG. 2B and FIG. 2C, the metal film 6 at a portion not covered with the first resist layer 71 is removed by etching using an etching solution. The etching solution to be used is appropriately selected according to the type of metal constituting the metal film 6. For example, when the metal film 6 is a copper film, examples of the etchant include a ferric chloride etchant, a sulfuric acid / hydrogen peroxide-based copper etchant, and a hydrochloric acid / cupric chloride-based copper etchant. As shown in FIG. 2C, the transparent conductive film 3 is exposed at the place where the metal film 6 is removed. The portion of the metal film 6 covered with the first resist layer 71 remains substantially unremoved because the first resist layer 71 prevents the etching solution from entering. In this case, it is preferable that the side etching of the metal film 6 covered with the first resist layer 71 is small.

  Next, the process F1 will be described. In step F1, as shown in FIG. 3A, the remaining first resist layer 71 is removed. The removal of the first resist layer 71 can be performed using an alkaline aqueous solution or a solvent. The removal of the first resist layer 71 may be performed after the next step G1.

  Next, the process G1 will be described. In step G1, as shown in FIG. 3B, the metal nanowires 4 in the transparent conductive film 3 where the metal film 6 has been removed are removed. Specifically, as shown in FIGS. 3A and 3B, the metal nanowire 4 in the transparent conductive film 3 in a portion not covered with the metal film 6 is removed by etching using an etching solution. This etching is preferably selective etching. Since the etching solution contacts the metal nanowire 4 and the metal film 6, it is preferable that the metals constituting the metal nanowire 4 and the metal film 6 are different. Basically, the etching solution to be used is appropriately selected according to the type of metal constituting the metal nanowire 4. For example, when the metal nanowire 4 is a silver nanowire, a ferric nitrate etchant may be used as the etchant. Preferably, the etching solution is preferably one that selectively removes the metal nanowires 4 and does not substantially remove the metal film 6. For example, when the metal nanowire 4 is a silver nanowire and the metal film 6 is a copper film, a ferric nitrate etchant may be used as the etchant. As shown in FIG. 3B, the portion of the transparent conductive film 3 from which the metal nanowires 4 are removed becomes an electrically insulated insulating portion 32 (non-conductive portion). In the insulating portion 32, the pore 9 can be formed at the position where the metal nanowire 4 was present. On the other hand, the metal nanowire 4 in the transparent conductive film 3 at the location covered with the metal film 6 remains without being removed because the metal film 6 prevents the etching solution from entering. Thereby, this location becomes a conductive portion 31 having conductivity. The transparent conductive film 3 is divided into a transparent region 301 and a peripheral region 302. The transparent region 301 includes a conductive portion 31 and an insulating portion 32 that are formed in a predetermined wiring pattern. The peripheral region 302 is a region located around the transparent region 301 and includes the conductive portion 31.

  Next, the process H1 will be described. In step H1, as shown in FIG. 3C, a second resist layer 72 is formed on the surface of the remaining metal film 6 and the surface of the transparent conductive film 3 where the metal film 6 has been removed. The material of the second resist layer 72 may be the same as or different from the material of the first resist layer 71. That is, the second resist layer 72 may be formed of either a negative resist or a positive resist. The second resist layer 72 may be formed of either a dry film or liquid. The second resist layer 72 may be, for example, a dry film adhered to the surface of the remaining metal film 6 and the surface of the transparent conductive film 3 where the metal film 6 is removed, or a liquid resist is applied and dried. Or formed.

  Next, step I1 will be described. In Step I1, as shown in FIG. 4A, a part of the second resist layer 72 is removed. This part is a part that overlaps the transparent region 301, and a part that overlaps the peripheral region 302 is not removed. Specifically, when the second resist layer 72 is formed of a negative resist, exposure is performed using a mask film so that the peripheral region 302 of the second resist layer 72 shown in FIG. 3C is irradiated with light. Do. When the second resist layer 72 is formed of a positive resist, exposure is performed using a mask film so that light is applied to the transparent region 301 of the second resist layer 72 shown in FIG. 3C. After the exposure, by developing with a developer, the transparent region 301 of the second resist layer 72 can be removed as shown in FIG. 4A. Examples of the light source and the developer for exposure include the same as those described above. As shown in FIG. 4A, the insulating portion 32 of the transparent conductive film 3 and the metal film 6 are exposed at the location where the second resist layer 72 is removed.

  Next, the process J1 will be described. In step J1, as shown in FIG. 4B, the metal film 6 where the second resist layer 72 has been removed is removed. Specifically, as shown in FIG. 4A and FIG. 4B, the metal film 6 at a portion not covered with the second resist layer 72 (that is, the metal film 6 in the transparent region 301) is etched by using an etching solution. Remove. The etching solution to be used is appropriately selected according to the type of metal constituting the metal film 6. For example, when the metal film 6 is a copper film, examples of the etchant include a ferric chloride etchant, a sulfuric acid / hydrogen peroxide-based copper etchant, and a hydrochloric acid / cupric chloride-based copper etchant. As shown in FIG. 4B, the transparent region 301 of the transparent conductive film 3 is exposed at the place where the metal film 6 is removed. The portion of the metal film 6 covered with the second resist layer 72 remains substantially unremoved because the second resist layer 72 prevents the etchant from entering. In this case, it is preferable that the side etching of the metal film 6 covered with the second resist layer 72 is small.

  Next, the process K1 will be described. In step K1, as shown in FIG. 4C, the remaining second resist layer 72 is removed. The removal of the second resist layer 72 can be performed using an alkaline aqueous solution or a solvent. Since the metal layer 6 exposed after the removal of the second resist layer 72 is formed in the peripheral region 302 of the transparent conductive film 3, it can be the peripheral wiring 60.

  Through the steps A1 to K1, the transparent wiring member 1 as shown in FIG. 4C can be manufactured. Thereafter, as shown in FIG. 13A, the cover glass 11 is bonded to the transparent conductive member 3 side of the transparent wiring member 1 with the adhesive layer 10 to obtain a touch panel as shown in FIG. In this case, the transparent area 301 becomes an input operation area. An electrical signal generated at a location in the transparent region 301 by the input operation is output to the outside through the peripheral wiring 60. The pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer 10 and the cover glass 11 are not particularly limited.

  Next, the transparent distribution member 1 of this embodiment will be described. The transparent wiring member 1 of the present embodiment includes a transparent substrate 2, a transparent conductive film 3, and a metal film 6. The transparent wiring member 1 may or may not include the anti-blocking layer 12.

  As shown in FIG. 4C, in the transparent wiring member 1, the transparent conductive film 3 is formed on the surface of the transparent substrate 2. When the transparent wiring member 1 includes the anti-blocking layer 12, the transparent conductive film 3 is disposed on one surface of the transparent substrate 2, and the anti-blocking layer 12 is disposed on the other surface.

  As shown in FIG. 4C, the transparent conductive film 3 in the transparent wiring member 1 contains metal nanowires 4. Specifically, the conductive portion 31 of the transparent conductive film 3 contains the metal nanowire 4. It is preferable that the metal nanowire 4 contains a silver nanowire. Since silver nanowire has high electrical conductivity, it can give high electroconductivity especially to the electroconductive part 31 of the transparent conductive film 3. FIG. The metal nanowire 4 of the conductive portion 31 is exposed on the surface of the transparent conductive film 3. Thereby, the sheet resistance (surface resistivity) of the transparent conductive film 3 can be reduced. Preferably, the metal nanowire 4 of the conductive portion 31 protrudes from the surface of the transparent conductive film 3. Thereby, the sheet resistance (surface resistivity) of the transparent conductive film 3 can be further reduced. On the other hand, the insulating portion 32 of the transparent conductive film 3 does not substantially contain the metal nanowire 4. The insulating portion 32 of the transparent conductive film 3 may have pores 9 formed by removing the metal nanowires 4 by etching.

  As shown in FIG. 4C, in the transparent wiring member 1, the metal film 6 is formed on a part of the surface of the transparent conductive film 3. Specifically, the metal film 6 is formed in the peripheral region 302 of the transparent conductive film 3, and the metal film 6 can be used as the peripheral wiring 60. The metal film 6 preferably includes a copper film. Since the copper film has high conductivity, it is suitable as the peripheral wiring 60. From the viewpoint of selective etching at the time of manufacturing the transparent wiring member 1, the metal nanowire 4 preferably includes silver nanowires, and the metal film 6 preferably includes a copper film.

  As shown in FIG. 4C, a part of the metal nanowire 4 is in contact with the metal film 6 in the transparent wiring member 1. Specifically, the metal nanowires 4 in the peripheral region 302 of the transparent conductive film 3 are in contact with the metal film 6 that can be the peripheral wiring 60.

  In the conventional transparent wiring member 1 shown in FIG. 12C, the electrical connection between the peripheral wiring 60 and the transparent conductive film 3 is unstable. As described above, this is caused by the process shown in FIGS. 12A and 12B. This is considered to be because when the photocured resist layer 70 is removed, the metal nanowires 4 existing in the surface layer portion of the transparent conductive film 3 are pulled by the resist layer 70 and cut.

  On the other hand, in the present embodiment, the conductive portion 31 (including the peripheral region 302) of the transparent conductive film 3 includes the first resist layer 71 and the second resist layer 72 from the step A1 to the step K1. There is no contact. That is, as shown in FIG. 2A, since the metal film 6 is formed on the surface of the transparent conductive film 3 before the first resist layer 71 is formed, the first resist layer 71 and the second resist layer 72 are formed. When removing, the metal nanowire 4 which exists in the surface layer part of the electroconductive part 31 of the transparent conductive film 3 is not cut | disconnected. Therefore, the electrical connection between the metal film 6 that can be the peripheral wiring 302 and the transparent conductive film 3 can be stabilized. And since the metal nanowire 4 exists in the surface layer part of the electroconductive part 31 in the transparent area | region 301 of the transparent conductive film 3, the sheet resistance (surface resistivity) of the transparent conductive film 3 can also be reduced.

Further, in this embodiment, the metal film 6 is formed thin and can be the peripheral wiring 60. For example, in the touch panel of this embodiment shown in FIG. 13A, the thickness T ₁ of the peripheral wiring 60 formed of the metal film 6 is preferably in the range of 50 to 1000 nm, more preferably in the range of 100 to 500 nm. is there. On the other hand, in the conventional touch panel shown in FIG. 13C, the thickness T3 of the peripheral wiring 60 formed of a conductive paste is about ₅ to 10 μm. In this way, the thickness of the transparent wiring member 1 including the peripheral wiring 60 is made thinner in the case where the peripheral wiring 60 is formed with the metal film 6 than in the case where the peripheral wiring 60 is formed with a conductive paste. And the thickness of the touch panel can be reduced.

(Embodiment 2)
First, the manufacturing method of the transparent wiring member 1 of this embodiment is demonstrated. The manufacturing method of the transparent wiring member 1 of this embodiment utilizes the photo-etching method (photolithography), and includes the following processes A2 to L2. Through these steps, the transparent wiring member 1 as shown in FIG. 7C is obtained and can be used for the touch panel as shown in FIGS. 13B and 14. Each step will be described in order.

  First, step A2 and step B2 will be described. Process A2 and process B2 are the same as process A1 and process B1 of Embodiment 1, respectively.

  It is preferable that the following step A2-2 is further included between step A2 and step B2. In step A2-2, the surface of the transparent conductive film 3 is subjected to a hydrophilic treatment. Thereby, the adhesiveness of the transparent conductive film 3 and the metal film 6 can be improved. Examples of the hydrophilic treatment include plasma treatment and corona treatment. Specific treatment conditions are not particularly limited as long as the metal nanowires 4 present in the surface layer portion of the transparent conductive film 3 are not lost.

  Next, step C2 will be described. In step C2, as shown in FIG. 5A, a rust preventive treatment is performed on the surface of the metal film 6 to form a rust preventive film 8. Examples of the rust prevention treatment include anodization and chromate treatment. Examples of the rust preventive film 8 include a metal oxide film such as a black copper oxide film. The formation of the rust preventive film 8 is more effective as the metal film 6 is more easily oxidized. By forming the rust preventive film 8 on the metal film 6, it is difficult to oxidize the metal film 6, and a decrease in the conductivity of the metal film 6 can be suppressed.

  Next, the process D2 will be described. In step D2, a first resist layer 71 is formed on the surface of the rust preventive film 8 as shown in FIG. 5B. The first resist layer 71 may be formed of either a negative resist or a positive resist. The first resist layer 71 may be formed of either a dry film or liquid. The first resist layer 71 is formed by, for example, bringing a dry film into close contact with the surface of the rust preventive film 8 or applying a liquid resist to the surface of the rust preventive film 8 and drying it.

  Next, step E2 will be described. In step E2, as shown in FIG. 5C, a part of the first resist layer 71 is removed. More specifically, the first resist layer 71 shown in FIG. 5B is exposed in a predetermined wiring pattern using a mask film, and then developed with a developer, thereby forming the first resist layer 71 as shown in FIG. 5C. A part of can be removed. Examples of the light source and the developer for exposure include the same light source and developer as in the first embodiment. As shown in FIG. 5C, the rust preventive film 8 is exposed at the place where the first resist layer 71 is removed.

  Next, the process F2 will be described. In step F2, as shown in FIG. 5D, the metal film 6 and the rust preventive film 8 at the place where the first resist layer 71 has been removed are removed. Specifically, as shown in FIGS. 5C and 5D, the metal film 6 and the rust preventive film 8 that are not covered with the first resist layer 71 are removed by etching using an etching solution. The etching solution to be used is appropriately selected according to the type of metal constituting the metal film 6 and the material of the rust preventive film 8. Examples of the etching solution include ferric chloride etching solution. As shown in FIG. 5D, the transparent conductive film 3 is exposed at the place where the metal film 6 and the rust preventive film 8 are removed. The metal film 6 and the rust preventive film 8 that are covered with the first resist layer 71 remain substantially unremoved because the first resist layer 71 prevents the etching solution from entering. In this case, it is preferable that the side etching of the metal film 6 that is indirectly covered with the first resist layer 71 through the rust prevention film 8 is small.

  Next, the process G2 will be described. In step G2, as shown in FIG. 6A, the remaining first resist layer 71 is removed. The removal of the first resist layer 71 can be performed using an alkaline aqueous solution or a solvent. The first resist layer 71 may be removed after the next step H2.

  Next, the process H2 will be described. In step H2, as shown in FIG. 6B, the metal nanowires 4 in the transparent conductive film 3 where the metal film 6 and the rust preventive film 8 have been removed are removed. Specifically, as shown in FIG. 6A and FIG. 6B, the metal nanowire 4 in the transparent conductive film 3 in a portion not covered with the metal film 6 is removed by etching using an etching solution. This etching is preferably selective etching. Since the etching solution contacts the metal nanowire 4, the rust preventive film 8, and the metal film 6, the metals constituting the metal nanowire 4 and the metal film 6 are preferably different. Basically, the etching solution to be used is appropriately selected according to the type of metal constituting the metal nanowire 4. For example, when the metal nanowire 4 is a silver nanowire, a ferric nitrate etchant may be used as the etchant. Preferably, the etching solution is preferably one that selectively removes the metal nanowires 4 and does not substantially remove the metal film 6. For example, when the metal nanowire 4 is a silver nanowire and the metal film 6 is a copper film, a ferric nitrate etchant may be used as the etchant. As shown in FIG. 6B, the portion of the transparent conductive film 3 from which the metal nanowires 4 are removed becomes an electrically insulated insulating portion 32 (non-conductive portion). In the insulating portion 32, the pore 9 can be formed at the position where the metal nanowire 4 was present. On the other hand, the metal nanowire 4 in the transparent conductive film 3 at the location covered with the metal film 6 remains without being removed because the metal film 6 prevents the etching solution from entering. Thereby, this location becomes a conductive portion 31 having conductivity. The transparent conductive film 3 is divided into a transparent region 301 and a peripheral region 302. The transparent region 301 includes a conductive portion 31 and an insulating portion 32 that are formed in a predetermined wiring pattern. The peripheral region 302 is a region located around the transparent region 301 and includes the conductive portion 31.

  Next, step I2 will be described. In step I2, as shown in FIG. 6C, a second resist layer 72 is formed on the surfaces of the remaining metal film 6 and the rust preventive film 8 and on the surface of the transparent conductive film 3 where the metal film 6 has been removed. The material of the second resist layer 72 may be the same as or different from the material of the first resist layer 71. That is, the second resist layer 72 may be formed of either a negative resist or a positive resist. The second resist layer 72 may be formed of either a dry film or liquid. The second resist layer 72 is formed by, for example, bringing a dry film into close contact with the surface of the remaining metal film 6 and the rust preventive film 8 and the surface of the transparent conductive film 3 where the metal film 6 is removed, or by applying a liquid resist. It is formed by applying and drying.

  Next, the process J2 will be described. In step J2, as shown in FIG. 7A, part of the second resist layer 72 is removed. This part is a part that overlaps the transparent region 301, and a part that overlaps the peripheral region 302 is not removed. Specifically, when the second resist layer 72 is formed of a negative resist, exposure is performed using a mask film so that light is applied to the peripheral region 302 of the second resist layer 72 shown in FIG. 6C. Do. When the second resist layer 72 is formed of a positive resist, exposure is performed using a mask film so that light is applied to the transparent region 301 of the second resist layer 72 shown in FIG. 6C. After the exposure, by developing with a developer, the transparent region 301 of the second resist layer 72 can be removed as shown in FIG. 7A. Examples of the light source and the developer for exposure include the same as those described above. As shown in FIG. 7A, the insulating portion 32 of the transparent conductive film 3 and the metal film 6 on which the rust preventive film 8 is formed are exposed at the place where the second resist layer 72 is removed.

  Next, the process K2 will be described. In step K2, as shown in FIG. 7B, the metal film 6 and the rust preventive film 8 at the place where the second resist layer 72 is removed are removed. Specifically, using an etching solution, as shown in FIGS. 7A and 7B, the metal film 6 and the rust preventive film 8 (that is, the metal film in the transparent region 301) not covered with the second resist layer 72 are used. 6 and the antirust film 8) are removed by etching. The etching solution to be used is appropriately selected according to the type of metal constituting the metal film 6. For example, when the metal film 6 is a copper film, examples of the etchant include a ferric chloride etchant, a sulfuric acid / hydrogen peroxide-based copper etchant, and a hydrochloric acid / cupric chloride-based copper etchant. Since the rust preventive film 8 is not directly formed on the transparent conductive film 3 but is formed on the metal film 6, the rust preventive film 8 is also removed if only the metal film 6 is removed. As shown in FIG. 7B, the transparent region 301 of the transparent conductive film 3 is exposed at the location where the metal film 6 and the rust preventive film 8 are removed. The metal film 6 and the rust preventive film 8 that are covered with the second resist layer 72 remain substantially unremoved because the second resist layer 72 prevents the etching solution from entering. In this case, it is preferable that the side etching of the metal film 6 that is indirectly covered with the second resist layer 72 through the rust prevention film 8 is small.

  Next, the process L2 will be described. In step L2, as shown in FIG. 7C, the remaining second resist layer 72 is removed. The removal of the second resist layer 72 can be performed using an alkaline aqueous solution or a solvent. Since the metal layer 6 covered with the rust preventive film 8 exposed after the removal of the second resist layer 72 is formed in the peripheral region 302 of the transparent conductive film 3, it can be the peripheral wiring 60.

  Through the steps A2 to L2, the transparent wiring member 1 as shown in FIG. 7C can be manufactured. Thereafter, as shown in FIG. 13B, the cover glass 11 is bonded to the transparent conductive film 3 side of the transparent wiring member 1 with the adhesive layer 10 to obtain a touch panel as shown in FIG. In this case, the transparent area 301 becomes an input operation area. An electrical signal generated at a location in the transparent region 301 by the input operation is output to the outside through the peripheral wiring 60. The pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer 10 and the cover glass 11 are not particularly limited.

Next, the transparent wiring member 1 of this embodiment is demonstrated. The transparent wiring member 1 of the present embodiment shown in FIG. 7C is different from the transparent wiring member 1 of the first embodiment shown in FIG. 4C in that the rust preventive film 8 is formed on the surface of the metal film 6, but the other The point is the same. Therefore, the transparent wiring member 1 of the present embodiment also has the same effect as the transparent wiring member 1 of the first embodiment. Furthermore, in the transparent wiring member 1 of the present embodiment, since the rust preventive film 8 is formed on the surface of the metal film 6 that can become the peripheral wiring 60, the metal film 6 becomes difficult to be oxidized, and the conductivity of the metal film 6 is reduced. Is suppressed. Incidentally, in the touch panel of the present embodiment shown in FIG. 13B, the total thickness _{T 2} of the peripheral wiring 60 and anti-corrosion film 8 formed of a metal film 6 is preferably in the range of 50-1000 nm, more preferably 100 Within the range of ~ 500 nm. The thickness of the rust preventive film 8 is preferably in the range of 10 to 100 nm, and more preferably in the range of 20 to 50 nm.

(Embodiment 3)
First, the manufacturing method of the transparent wiring member 1 of this embodiment is demonstrated. The manufacturing method of the transparent wiring member 1 of this embodiment uses the lift-off method and the photoetching method (photolithography), and includes the following processes A3 to J3. Through these steps, a transparent wiring member 1 as shown in FIG. 10C is obtained, and can be used for a touch panel as shown in FIGS. 13A and 14. Each step will be described in order.

  First, step A3 will be described. Step A3 is the same as step A1 in the first embodiment. Step A3 is shown in FIG. 8A.

  Next, step B3 will be described. In step B3, as shown in FIG. 8B, a first resist layer 71 is formed on the surface of the transparent conductive film 3. The first resist layer 71 may be formed of either a negative resist or a positive resist, but the negative resist is formed in that the first resist layer 71 having a reverse tapered shape (reverse trapezoidal shape) is easily formed after development. preferable. Hereinafter, a case where the first resist layer 71 is formed of a negative resist will be described, but the present embodiment is not limited to this case. The first resist layer 71 preferably contains a light absorber. As a result, the cross-sectional shape of the first resist layer 71 after development is more likely to be a reverse tapered shape (reverse trapezoidal shape). A light absorber is an additive that absorbs light irradiated during exposure. For example, when irradiating ultraviolet rays at the time of exposure, the light absorber is an ultraviolet absorber. The first resist layer 71 may be formed of either a dry film or liquid. The first resist layer 71 is formed by, for example, bringing a dry film into close contact with the surface of the transparent conductive film 3 or applying a liquid resist to the surface of the transparent conductive film 3 and drying it.

  Next, step C3 will be described. In step C3, as shown in FIG. 8C, a part of the first resist layer 71 is removed. Specifically, the first resist layer 71 shown in FIG. 8B is exposed in a predetermined wiring pattern using a mask film, and then developed with a developing solution, whereby the first resist layer 71 is shown in FIG. 8C. A part of can be removed. Light during exposure passes through the first resist layer 71 in the thickness direction and reaches the transparent conductive film 3. In this case, the exposure intensity is high on the outer surface of the first resist layer 71, but the exposure intensity decreases as it approaches the transparent conductive film 3. Therefore, as shown in FIG. 8C, the first resist layer 71 having a reverse taper cross section (reverse trapezoidal cross section) remains after development. The first resist layer 71 is photocured and remains in the portion that becomes the insulating portion 32. If the first resist layer 71 contains a light absorber, the cross-sectional shape of the first resist layer 71 after development is more likely to be an inversely tapered shape (inverse trapezoidal shape). Examples of the light source and the developer for exposure include the same light source and developer as in the first embodiment. As shown in FIG. 8C, the transparent conductive film 3 is exposed at the place where the first resist layer 71 is removed. Since the first resist layer 71 removed at this time is not photocured, there is substantially no possibility that the metal nanowires 4 existing on the surface layer portion of the transparent conductive film 3 are cut by the first resist layer 71. be equivalent to.

  Next, the process D3 will be described. In step D3, as shown in FIG. 8D, the metal film 6 is formed on the surface of the transparent conductive film 3 where the first resist layer 71 is not formed. At this time, the metal film 6 may be formed on the first resist layer 71. Examples of the method for forming the metal film 6 include physical vapor deposition (PVD) and chemical vapor deposition (CVD). Examples of physical vapor deposition include sputtering and vacuum vapor deposition. For convenience of explanation, in FIG. 8C, when the vertical relationship is defined with the resist layer 71 on the upper side and the anti-blocking layer 12 on the lower side, when the metal film 6 is formed by the above-described method, the metal film 6 becomes the first resist layer 71. Is not substantially formed on the side surfaces of the first resist layer 71 and is not substantially formed near the boundary between the first resist layer 71 and the transparent conductive film 3. The metal film 6 is formed on the exposed transparent conductive film 3 other than the vicinity of the boundary between the first resist layer 71 and the transparent conductive film 3 and the upper surface of the first resist layer 71. The material of the metal film 6 is not particularly limited, but is preferably a metal different from the metal constituting the metal nanowire 4 from the viewpoint of selective etching described later. Since the copper film has high conductivity, the metal film 6 preferably includes a copper film. In particular, when the metal nanowire 4 includes silver nanowire, the metal film 6 preferably includes a copper film. In this case, both the metal nanowire 4 and the metal film 6 have high conductivity and are suitable for selective etching. The thickness of the metal film 6 is preferably in the range of 50 to 1000 nm, more preferably in the range of 100 to 500 nm. However, the thinner the transparent wiring member 1 is, the better.

  Next, step E3 will be described. In step E3, as shown in FIG. 9A, the remaining first resist layer 71 is removed. Thereby, the metal film 6 formed on the upper surface of the first resist layer 71 is also removed at the same time. The removal of the first resist layer 71 can be performed using an alkaline aqueous solution or a solvent. The first resist layer 71 removed at this time is photocured, but remains in the portion to be the insulating portion 32, so that the metal nanowires 4 present in the surface layer portion of this portion are the first resist layer. Even if cut by 71, there is no particular problem.

  Next, the process F3 will be described. In step F3, as shown in FIG. 9B, the metal nanowires 4 in the transparent conductive film 3 where the first resist layer 71 has been removed are removed. Specifically, as shown in FIGS. 9A and 9B, the metal nanowire 4 in the transparent conductive film 3 in a portion not covered with the metal film 6 is removed by etching using an etching solution. This etching is preferably selective etching. Since the etching solution contacts the metal nanowire 4 and the metal film 6, it is preferable that the metals constituting the metal nanowire 4 and the metal film 6 are different. Basically, the etching solution to be used is appropriately selected according to the type of metal constituting the metal nanowire 4. For example, when the metal nanowire 4 is a silver nanowire, a ferric nitrate etchant may be used as the etchant. Preferably, the etching solution is preferably one that selectively removes the metal nanowires 4 and does not substantially remove the metal film 6. For example, when the metal nanowire 4 is a silver nanowire and the metal film 6 is a copper film, a ferric nitrate etchant may be used as the etchant. As shown in FIG. 9B, the portion of the transparent conductive film 3 from which the metal nanowires 4 are removed becomes an electrically insulated insulating portion 32 (non-conductive portion). In the insulating portion 32, the pore 9 can be formed at the position where the metal nanowire 4 was present. On the other hand, the metal nanowire 4 in the transparent conductive film 3 at the location covered with the metal film 6 remains without being removed because the metal film 6 prevents the etching solution from entering. Thereby, this location becomes a conductive portion 31 having conductivity. The transparent conductive film 3 is divided into a transparent region 301 and a peripheral region 302. The transparent region 301 includes a conductive portion 31 and an insulating portion 32 that are formed in a predetermined wiring pattern. The peripheral region 302 is a region located around the transparent region 301 and includes the conductive portion 31.

  Next, the process G3 will be described. In step G3, as shown in FIG. 9C, a second resist layer 72 is formed on the surface of the remaining metal film 6 and the surface of the transparent conductive film 3 where the first resist layer 71 has been removed. The material of the second resist layer 72 may be the same as or different from the material of the first resist layer 71. That is, the second resist layer 72 may be formed of either a negative resist or a positive resist. The second resist layer 72 may be formed of either a dry film or liquid. The second resist layer 72 is formed by, for example, attaching a dry film or applying a liquid resist to the surface of the remaining metal film 6 and the surface of the transparent conductive film 3 where the first resist layer 71 is removed. It is formed by drying.

  Next, step H3 to step J3 will be described. Step H3 to Step J3 are the same as Step I1 to Step K1 in Embodiment 1, respectively. Process H3 to process J3 are shown in FIGS. 10A to 10C.

  The transparent wiring member 1 as shown in FIG. 10C can be manufactured through the steps A3 to J3. Thereafter, in the same manner as in the first embodiment, the cover glass 11 is bonded to the transparent conductive film 3 side of the transparent wiring member 1 with the adhesive layer 10 as shown in FIG. can get. In the first and second embodiments, a total of two etchings are performed when removing the metal film 6 and the metal nanowire 4. On the other hand, in this embodiment, it is only necessary to perform one etching when removing the metal nanowires 4. Therefore, this embodiment has an advantage that the number of etchings can be reduced as compared with the first and second embodiments.

  Next, the transparent wiring member 1 of this embodiment is demonstrated. The transparent wiring member 1 of this embodiment shown in FIG. 10C is substantially the same as the transparent wiring member 1 of Embodiment 1 shown in FIG. 4C. Therefore, the transparent wiring member 1 of this embodiment also has substantially the same effect as the transparent wiring member 1 of Embodiment 1.

  In particular, in step C3 shown in FIG. 8C, since the first resist layer 71 to be removed is not photocured, the metal nanowires 4 present in the surface layer portion of the transparent conductive film 3 where the conductive portions 31 are formed are There is substantially no risk of being cut by one resist layer 71. Therefore, the electrical connection between the metal film 6 that can be the peripheral wiring 302 and the transparent conductive film 3 can be stabilized. In step E3 shown in FIG. 9A, the first resist layer 71 to be removed is photocured, but remains in the portion that becomes the insulating portion 32, so that the metal nanowires present in the surface layer portion of this portion Even if 4 is cut by the first resist layer 71, there is no particular problem.

DESCRIPTION OF SYMBOLS 1 Transparent wiring member 2 Transparent base material 3 Transparent electrically conductive film 4 Metal nanowire 5 Transparent conductor 6 Metal film 71 1st resist layer 72 2nd resist layer 8 Rust prevention film

Claims (11)

The manufacturing method of the transparent wiring member containing the following process A1-process K1.
Step A1: A transparent base material and a transparent conductive film formed on the surface of the transparent base material, the transparent conductive film contains metal nanowires, and a part of the metal nanowires are made of the transparent conductive film. Preparing a transparent conductor exposed on the surface;
Step B1: forming a metal film on the surface of the transparent conductive film,
Step C1: a step of forming a first resist layer on the surface of the metal film,
Step D1: Step of removing a part of the first resist layer;
Step E1: a step of removing the metal film at the place where the first resist layer has been removed,
Step F1: Step of removing the remaining first resist layer;
Step G1: A step of removing the metal nanowires in the transparent conductive film at the place where the metal film is removed,
Step H1: forming a second resist layer on the surface of the remaining metal film and the surface of the transparent conductive film where the metal film has been removed,
Step I1: a step of removing a part of the second resist layer;
Step J1: a step of removing the metal film at a portion where the second resist layer has been removed, and a step K1: a step of removing the remaining second resist layer. The method for producing a transparent wiring member according to claim 1, further comprising the following step A1-2 between the step A1 and the step B1.
Step A1-2: Step of hydrophilizing the surface of the transparent conductive film. The manufacturing method of the transparent wiring member containing the following process A2-process L2.
Step A2: comprising a transparent base material and a transparent conductive film formed on the surface of the transparent base material, wherein the transparent conductive film contains metal nanowires, and a part of the metal nanowires is made of the transparent conductive film. Preparing a transparent conductor exposed on the surface;
Step B2: forming a metal film on the surface of the transparent conductive film,
Step C2: forming a rust preventive film on the surface of the metal film,
Step D2: Step of forming a first resist layer on the surface of the rust preventive film,
Step E2: a step of removing a part of the first resist layer;
Step F2: a step of removing the metal film and the rust preventive film at the place where the first resist layer is removed,
Step G2: Step of removing the remaining first resist layer,
Step H2: a step of removing the metal nanowires in the transparent conductive film where the metal film and the rust preventive film have been removed,
Step I2: forming a second resist layer on the surface of the transparent conductive film where the metal film and the anticorrosive film that remain and the metal film are removed,
Step J2: a step of removing a part of the second resist layer,
Step K2: a step of removing the metal film and the rust preventive film at the place where the second resist layer has been removed, and a step L2: a step of removing the remaining second resist layer. The method for manufacturing a transparent wiring member according to claim 3, further comprising the following step A2-2 between the step A2 and the step B2.
Step A2-2: Step of hydrophilizing the surface of the transparent conductive film. The manufacturing method of the transparent wiring member containing the following process A3-process J3.
Step A3: comprising a transparent base material and a transparent conductive film formed on the surface of the transparent base material, wherein the transparent conductive film contains metal nanowires, and a part of the metal nanowires is made of the transparent conductive film. Preparing a transparent conductor exposed on the surface;
Step B3: forming a first resist layer on the surface of the transparent conductive film,
Step C3: a step of removing a part of the first resist layer;
Step D3: a step of forming a metal film on the surface of the transparent conductive film at a location where the first resist layer is not formed,
Step E3: Step of removing the remaining first resist layer,
Step F3: a step of removing the metal nanowires in the transparent conductive film at the place where the first resist layer is removed,
Step G3: forming a second resist layer on the surface of the metal film and the surface of the transparent conductive film where the first resist layer has been removed,
Step H3: a step of removing a part of the second resist layer,
Step I3: a step of removing the metal film where the second resist layer has been removed, and a step J3: a step of removing the remaining second resist layer. The manufacturing method of the transparent wiring member as described in any one of Claims 1 thru | or 5 in which the said metal nanowire contains silver nanowire. The method for manufacturing a transparent wiring member according to claim 1, wherein the metal film includes a copper film. A transparent substrate;
A transparent conductive film formed on the surface of the transparent substrate;
A metal film formed on a part of the surface of the transparent conductive film,
The transparent conductive film contains metal nanowires,
A transparent wiring member in which a part of the metal nanowire is in contact with the metal film. The transparent wiring member according to claim 8, wherein a rust prevention film is formed on a surface of the metal film. The transparent wiring member according to claim 8 or 9, wherein the metal nanowire includes a silver nanowire. The transparent wiring member according to claim 8, wherein the metal film includes a copper film.

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