WO2017130867A1 - 導電性基板 - Google Patents

導電性基板 Download PDF

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Publication number
WO2017130867A1
WO2017130867A1 PCT/JP2017/002009 JP2017002009W WO2017130867A1 WO 2017130867 A1 WO2017130867 A1 WO 2017130867A1 JP 2017002009 W JP2017002009 W JP 2017002009W WO 2017130867 A1 WO2017130867 A1 WO 2017130867A1
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Prior art keywords
layer
metal layer
blackening
conductive substrate
metal
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PCT/JP2017/002009
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English (en)
French (fr)
Japanese (ja)
Inventor
下地　匠
志賀　大樹
Original Assignee
住友金属鉱山株式会社
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Application filed by 住友金属鉱山株式会社 filed Critical 住友金属鉱山株式会社
Priority to CN201780008071.8A priority Critical patent/CN108495749B/zh
Priority to JP2017564217A priority patent/JP6791172B2/ja
Priority to KR1020187020498A priority patent/KR102695185B1/ko
Publication of WO2017130867A1 publication Critical patent/WO2017130867A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present invention relates to a conductive substrate.
  • the capacitive touch panel converts information on the position of an adjacent object on the panel surface into an electrical signal by detecting a change in capacitance caused by the object adjacent to the panel surface. Since the conductive substrate used for the capacitive touch panel is installed on the surface of the display, the material of the conductive layer of the conductive substrate is required to have low reflectance and be difficult to be visually recognized.
  • the material of the conductive layer used for the conductive substrate for the touch panel a material having low reflectivity and difficult to be visually recognized is used and formed on the transparent substrate or the transparent film.
  • Patent Document 1 a transparent conductive film for a touch panel in which an ITO (indium-tin oxide) film is formed as a transparent conductive film on a polymer film has been conventionally used.
  • ITO indium-tin oxide
  • a display with a touch panel has been increased in screen size, and in response to this, a conductive substrate such as a transparent conductive film for a touch panel is required to have a large area.
  • ITO has a high electric resistance value, there is a problem that it cannot cope with an increase in the area of the conductive substrate.
  • Patent Document 2 discloses a step of forming a resist layer on a copper thin film supported by a film, a step of processing at least the resist layer into a striped wiring pattern and a drawing wiring pattern by photolithography, and exposure.
  • a method of manufacturing a film-like touch panel sensor is disclosed which includes a step of removing the copper thin film by etching to form a striped copper wiring and a drawing copper wiring, and a step of blackening the copper wiring.
  • Patent Document 2 employs a method of blackening the copper wiring after forming the striped copper wiring by etching, and there is a problem in productivity because the manufacturing process increases.
  • the manufacturing process of the conductive substrate that can reduce the manufacturing process and obtain high productivity was examined.
  • an object of one aspect of the present invention is to provide a conductive substrate including a metal layer and a blackening layer that can be etched simultaneously.
  • a transparent substrate A metal layer formed on at least one surface of the transparent substrate; A blackening layer formed on the metal layer, The blackening layer provides a conductive substrate containing nickel alone, nickel oxide, nickel hydroxide, and copper.
  • a conductive substrate provided with a metal layer and a blackened layer that can be etched simultaneously can be provided.
  • substrate which concerns on embodiment of this invention Sectional drawing of the electroconductive board
  • the conductive substrate of this embodiment can have a transparent base material, a metal layer formed on at least one surface of the transparent base material, and a blackening layer formed on the metal layer.
  • the blackening layer can contain nickel alone, nickel oxide, nickel hydroxide, and copper.
  • the conductive substrate in the present embodiment is a substrate having a metal layer and a blackened layer on the surface of a transparent base before patterning the metal layer, etc., and a substrate obtained by patterning the metal layer, that is, wiring A substrate. Since the conductive substrate after patterning the metal layer and the blackening layer includes a region where the transparent base material is not covered with the metal layer or the like, the conductive substrate can transmit light and is a transparent conductive substrate.
  • the transparent substrate is not particularly limited, and an insulating film that transmits visible light, a glass substrate, or the like can be preferably used.
  • a polyamide film, a polyethylene terephthalate film, a polyethylene naphthalate film, a cycloolefin film, a polyimide film, a polycarbonate film, or a resin film can be preferably used.
  • PET polyethylene terephthalate
  • COP cycloolefin polymer
  • PEN polyethylene naphthalate
  • polyamide, polyimide, polycarbonate, and the like can be more preferably used as a material for an insulating film that transmits visible light.
  • the thickness of the transparent base material is not particularly limited, and can be arbitrarily selected according to the strength required when a conductive substrate is used, the capacitance, the light transmittance, and the like.
  • the thickness of the transparent substrate can be, for example, 10 ⁇ m or more and 200 ⁇ m or less.
  • the thickness of the transparent substrate is preferably 20 ⁇ m or more and 120 ⁇ m or less, and more preferably 20 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the transparent substrate is preferably 20 ⁇ m or more and 50 ⁇ m or less.
  • the total light transmittance of the transparent substrate is preferably higher.
  • the total light transmittance is preferably 30% or more, and more preferably 60% or more.
  • the visibility of the display can be sufficiently secured.
  • the total light transmittance of the transparent substrate can be evaluated by the method defined in JIS K 7361-1.
  • the material constituting the metal layer is not particularly limited, and a material having electrical conductivity suitable for the application can be selected.
  • copper is used as the material constituting the metal layer because it has excellent electrical characteristics and is easily etched. It is preferable. That is, the metal layer preferably contains copper.
  • the material constituting the metal layer is, for example, Cu and at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Mn, Co, and W.
  • a copper alloy, or a material containing copper and one or more metals selected from the above metals is preferable.
  • the metal layer can be a copper layer made of copper.
  • the method for forming the metal layer is not particularly limited. However, in order to prevent the light transmittance from being reduced in the exposed portion of the transparent conductive substrate of the patterned conductive substrate, an adhesive is provided between the other member and the metal layer. It is preferable not to arrange them. That is, the metal layer is preferably disposed directly on the upper surface of another member. In addition, a metal layer can be formed and arrange
  • the metal layer preferably has a metal thin film layer formed by using a dry plating method.
  • a dry-type plating method For example, a vapor deposition method, sputtering method, an ion plating method etc. can be used.
  • the sputtering method is preferably used because the film thickness can be easily controlled.
  • the metal plating layer can be laminated using a wet plating method after the metal thin film layer is formed by dry plating.
  • a metal thin film layer is formed on a transparent substrate or an adhesion layer by a dry plating method, the metal thin film layer is used as a power feeding layer, and the metal plating layer is formed by electrolytic plating which is a kind of wet plating method. Can be formed.
  • the metal layer When the metal layer is formed only by the dry plating method as described above, the metal layer can be constituted by a metal thin film layer. Moreover, when a metal layer is formed by combining a dry plating method and a wet plating method, the metal layer can be composed of a metal thin film layer and a metal plating layer.
  • the metal layer is formed directly on the transparent substrate or the adhesion layer by using only the dry plating method or a combination of the dry plating method and the wet plating method to form a metal layer without using an adhesive. be able to.
  • the thickness of the metal layer is not particularly limited, and when the metal layer is used as a wiring, it can be arbitrarily selected according to the magnitude of the current supplied to the wiring, the wiring width, and the like.
  • the thickness of the metal layer is preferably 5 ⁇ m or less, and more preferably 3 ⁇ m or less.
  • the metal layer preferably has a thickness of 50 nm or more, more preferably 60 nm or more, and 150 nm. More preferably, it is the above.
  • a metal layer has a metal thin film layer and a metal plating layer as mentioned above, it is preferable that the sum total of the thickness of a metal thin film layer and the thickness of a metal plating layer is the said range.
  • the thickness of the metal thin film layer is not particularly limited. The thickness is preferably 700 nm or less.
  • the wiring reflects light only by forming the wiring by etching the metal layer on a transparent substrate.
  • the visibility of the display is reduced.
  • methods for providing a blackened layer have been studied.
  • the reactivity of the metal layer and the blackened layer may be greatly different from each other with respect to the etching solution. If the metal layer and the blackened layer are simultaneously etched, the metal layer and the blackened layer can be etched into a desired shape. There was a problem of dimensional variation. For this reason, it is necessary to etch the metal layer and the blackened layer in separate processes in the conductive substrate that has been studied conventionally, and it is difficult to etch the metal layer and the blackened layer simultaneously, that is, in one process. Met.
  • the inventors of the present invention have a blackened layer that can be etched at the same time as the metal layer, that is, excellent reactivity to the etching solution, and can be patterned into a desired shape even when etched at the same time as the metal layer.
  • the blackening layer that can suppress the occurrence was examined.
  • the blackening layer contains nickel alone, nickel oxide, nickel hydroxide, and copper, so that the reactivity of the blackening layer with respect to the etching solution can be made substantially equal to that of the metal layer.
  • the present invention was completed.
  • the blackening layer of the conductive substrate of the present embodiment can contain nickel alone, nickel oxide, nickel hydroxide, and copper as described above.
  • the state of copper contained in the blackened layer is not particularly limited, but copper can be contained, for example, as a simple substance of copper and / or a compound of copper.
  • the copper compound include copper oxide and copper hydroxide.
  • the blackening layer contains, for example, a simple substance of nickel, nickel oxide, and nickel hydroxide, and was further selected from a simple substance of copper, that is, metallic copper, copper oxide, and copper hydroxide.
  • a simple substance of nickel, nickel oxide, and nickel hydroxide contains, for example, a simple substance of nickel, nickel oxide, and nickel hydroxide, and was further selected from a simple substance of copper, that is, metallic copper, copper oxide, and copper hydroxide.
  • copper metallic copper, copper oxide, and copper hydroxide.
  • One or more types can be contained.
  • the blackened layer contains nickel oxide and nickel hydroxide, so that the blackened layer has a color that can suppress reflection of light on the surface of the metal layer, and functions as a blackened layer. be able to.
  • the blackened layer also contains copper, for example, a simple substance of copper and / or a copper compound
  • the reactivity of the blackened layer with respect to the etching solution can be made equivalent to that of the metal layer. Therefore, even when the metal layer and the blackened layer are etched at the same time, both layers can be etched into the desired shape, and it is possible to etch uniformly in a plane and suppress the occurrence of dimensional variations. Become. That is, the metal layer and the blackened layer can be etched simultaneously.
  • the ratio of each component contained in the blackening layer is not particularly limited, and can be arbitrarily selected depending on the degree of suppression of light reflection required for the conductive substrate, the degree of reactivity with the etching solution, and the like. You can choose. However, from the viewpoint of sufficiently increasing the reactivity to the etching solution, for example, the blackened layer is measured by X-ray photoelectron spectroscopy (XPS), and the number of nickel atoms determined from the Ni 2P spectrum and Cu LMM spectrum is 100. In this case, the ratio of the number of copper atoms is preferably 5 or more and 90 or less.
  • nickel and copper contained in the blackened layer are in a ratio of the number of atoms, and when nickel is 100, copper is preferably 5 or more and 90 or less.
  • the ratio of the number of copper atoms when the number of nickel atoms is 100 is more preferably 7 or more and 90 or less, and further preferably 7 or more and 65 or less.
  • the number of nickel atoms means the number of all nickel atoms contained in the blackened layer, and forms not only nickel but also compounds such as nickel oxide. Including nickel.
  • the nickel 2P spectrum peak separation analysis measured by XPS for the blackened layer was performed, and the calculated nickel simple substance contained in the blackened layer, that is, nickel oxide when the number of atoms of metallic nickel was 100
  • the number of nickel atoms is preferably 25 or more and 280 or less, and the number of nickel atoms in the nickel hydroxide is preferably 10 or more and 220 or less. This is because the blackened layer contains nickel oxide and nickel hydroxide in a predetermined ratio with respect to metallic nickel, thereby suppressing the reflection of light on the surface of the metal layer. This is because the color can be particularly suitable for.
  • the blackened layer is measured by XPS, for example, 10 nm from the outermost surface of the blackened layer is removed by Ar ion etching or the like so that the internal state can be analyzed. preferable.
  • the formation method of the blackened layer is not particularly limited, and any method can be selected as long as it can be formed so as to contain the above-described components. However, it is preferable to use a wet method since the composition of the blackened layer can be controlled relatively easily so as to contain the above-described components.
  • the wet method it is particularly preferable to use an electrolytic plating method.
  • the blackening plating solution used when forming the blackening layer by the electrolytic plating method may be prepared so that the blackening layer having the above composition can be formed, and the composition is not particularly limited. Absent.
  • a blackening plating solution containing nickel ions, copper ions, and a pH adjusting agent can be preferably used.
  • the concentration of each component in the blackening plating solution is not particularly limited, and may be arbitrarily selected depending on the degree of suppression of light reflection on the surface of the metal layer required for the formed blackening layer. Can do.
  • the nickel ion concentration in the blackening plating solution is preferably 2.0 g / l or more, and more preferably 3.0 g / l or more. This is because the nickel ion concentration in the blackening plating solution is set to 2.0 g / l or more so that the blackened layer has a color particularly suitable for suppressing reflection of light on the surface of the metal layer. This is because it is possible to suppress the reflectance.
  • the upper limit of the nickel ion concentration in the blackening plating solution is not particularly limited, but is preferably 20.0 g / l or less, for example, and more preferably 15.0 g / l or less. This is because when the nickel ion concentration in the blackening plating solution is 20.0 g / l or less, the nickel component in the formed blackening layer is prevented from becoming excessive, and the surface of the blackening layer is bright nickel. This is because it prevents plating-like surfaces and suppresses the reflectance of the conductive substrate.
  • the copper ion concentration in the blackening plating solution is preferably 0.005 g / l or more, and more preferably 0.008 g / l or more. This is because, when the copper ion concentration in the blackening plating solution is 0.005 g / l or more, the blackening layer has a color particularly suitable for suppressing reflection of light on the surface of the metal layer, and etching of the blackening layer is performed. This is because the reactivity to the liquid is increased, and even when the blackened layer is etched together with the metal layer, it can be patterned into a desired shape.
  • the upper limit value of the copper ion concentration in the blackening plating solution is not particularly limited, but is preferably 4.0 g / l or less, for example, and more preferably 1.02 g / l or less. This is because when the copper ion concentration in the blackening plating solution is 4.0 g / l or less, it is possible to suppress the reactivity of the formed blackening layer to the etching solution from becoming too high. This is because the color is particularly suitable for suppressing the reflection of light on the surface of the layer, and the reflectance of the conductive substrate can be suppressed.
  • the supply method of nickel ions and copper ions is not particularly limited, and can be supplied in a salt state, for example.
  • a salt state for example.
  • sulfamate and sulfate can be preferably used.
  • the same kind of salt may be used for each metal element, and different kinds of salts may be used at the same time.
  • a blackening plating solution can be prepared using the same type of salt as nickel sulfate and copper sulfate.
  • a blackening plating solution can also be prepared by simultaneously using different types of salts such as nickel sulfate and copper sulfamate.
  • an alkali metal hydroxide can be preferably used as the pH adjuster. This is because the reflectance of a conductive substrate having a blackened layer formed using the blackened plating solution can be particularly lowered by using an alkali metal hydroxide as a pH adjuster.
  • an alkali metal hydroxide is used as the pH adjuster, the reason why the reflectance of the conductive substrate having a blackened layer formed using the blackened plating solution can be suppressed is not clear. This is probably because the hydroxide ions supplied into the plating solution can promote the precipitation of nickel oxide. By promoting the precipitation of nickel oxide, the blackened layer can have a color particularly suitable for suppressing light reflection on the surface of the metal layer. For this reason, it is presumed that the reflectance of the conductive substrate having the blackened layer can be particularly suppressed.
  • the alkali metal hydroxide that is a pH adjuster for example, one or more selected from sodium hydroxide, potassium hydroxide, and lithium hydroxide can be used.
  • the alkali metal hydroxide that is a pH adjuster is more preferably one or more selected from sodium hydroxide and potassium hydroxide. This is because sodium hydroxide and potassium hydroxide are particularly easily available and are excellent in cost.
  • the pH of the blackening plating solution of the present embodiment is not particularly limited, but is preferably 4.0 or more and 5.2 or less, and more preferably 4.5 or more and 5.0 or less.
  • the blackening plating solution may further contain a complexing agent.
  • a complexing agent for example, amidosulfuric acid can be preferably used.
  • amidosulfuric acid a blackening layer having a color particularly suitable for suppressing light reflection on the surface of the metal layer can be formed.
  • the content of the complexing agent in the blackening plating solution is not particularly limited, and can be arbitrarily selected according to the degree of suppression of reflectance required for the blackening layer to be formed.
  • the concentration of amidosulfuric acid in the blackening plating solution is not particularly limited. For example, it is preferably 1 g / l or more and 50 g / l or less, and preferably 5 g / l or more and 20 g / l. The following is preferable. This is because when the concentration of amidosulfuric acid is 1 g / l or more, the blackened layer has a color particularly suitable for suppressing light reflection on the surface of the metal layer, and the reflectance of the conductive substrate can be suppressed. It is. Moreover, since the effect which suppresses the reflectance of an electroconductive board
  • the thickness of the blackening layer is not particularly limited, and can be arbitrarily selected according to the degree of suppression of light reflection required for the conductive substrate.
  • the thickness of the blackened layer is preferably 30 nm or more, for example, and more preferably 50 nm or more.
  • the blackening layer has a function of suppressing light reflection by the metal layer, but when the thickness of the blackening layer is thin, reflection of light by the metal layer may not be sufficiently suppressed. On the other hand, it is preferable to set the thickness of the blackened layer to 30 nm or more because reflection on the surface of the metal layer can be more reliably suppressed.
  • the upper limit value of the thickness of the blackened layer is not particularly limited. However, if the thickness is increased more than necessary, the time required for etching when forming the wiring is increased, resulting in an increase in cost. For this reason, the thickness of the blackened layer is preferably 120 nm or less, and more preferably 90 nm or less.
  • the conductive substrate can be provided with any layer other than the above-mentioned transparent base material, metal layer, and blackening layer.
  • an adhesion layer can be provided.
  • the metal layer can be formed on the transparent substrate, but when the metal layer is directly formed on the transparent substrate, the adhesion between the transparent substrate and the metal layer may not be sufficient. . For this reason, when a metal layer is directly formed on the upper surface of the transparent substrate, the metal layer may be peeled off from the transparent substrate during the production process or use.
  • an adhesion layer can be disposed on the transparent substrate in order to improve the adhesion between the transparent substrate and the metal layer. That is, it can also be set as the electroconductive board
  • the adhesion layer between the transparent substrate and the metal layer By disposing the adhesion layer between the transparent substrate and the metal layer, the adhesion between the transparent substrate and the metal layer can be improved, and the metal layer can be prevented from peeling from the transparent substrate.
  • the adhesion layer can function as a blackening layer. For this reason, it becomes possible to suppress the reflection of the light of the metal layer by the light from the lower surface side of the metal layer, that is, the transparent substrate side.
  • the material constituting the adhesion layer is not particularly limited, the adhesion strength with the transparent base material and the metal layer, the degree of suppression of light reflection on the surface of the required metal layer, and the use of a conductive substrate It can be arbitrarily selected according to the degree of stability to the environment (for example, humidity and temperature).
  • the adhesion layer preferably contains at least one metal selected from, for example, Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn.
  • the adhesion layer may further contain one or more elements selected from carbon, oxygen, hydrogen, and nitrogen.
  • the adhesion layer can also include a metal alloy containing at least two kinds of metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. Also in this case, the adhesion layer can further include one or more elements selected from carbon, oxygen, hydrogen, and nitrogen.
  • a metal alloy containing at least two kinds of metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn a Cu—Ti—Fe alloy is used as a metal alloy containing at least two kinds of metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn.
  • a Cu—Ti—Fe alloy is used as a metal alloy containing at least two kinds of metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn.
  • the method for forming the adhesion layer is not particularly limited, but it is preferable to form the film by a dry plating method.
  • a dry plating method for example, a sputtering method, an ion plating method, a vapor deposition method, or the like can be preferably used.
  • the adhesion layer is formed by a dry method, it is more preferable to use a sputtering method because the film thickness can be easily controlled.
  • one or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the adhesion layer, and in this case, the reactive sputtering method can be more preferably used.
  • the adhesion layer includes one or more elements selected from carbon, oxygen, hydrogen, and nitrogen
  • one or more elements selected from carbon, oxygen, hydrogen, and nitrogen in the atmosphere when forming the adhesion layer Can be added to the adhesion layer.
  • carbon monoxide gas and / or carbon dioxide gas when adding oxygen, oxygen gas, when adding hydrogen, hydrogen gas and / or water
  • nitrogen gas can be added to the atmosphere when dry plating is performed.
  • a gas containing one or more elements selected from carbon, oxygen, hydrogen, and nitrogen is preferably added to an inert gas and used as an atmosphere gas during dry plating.
  • an inert gas For example, argon can be used preferably.
  • the adhesion layer By forming the adhesion layer by the dry plating method as described above, the adhesion between the transparent substrate and the adhesion layer can be enhanced. And since an adhesion layer can contain a metal as a main component, for example, its adhesiveness with a metal layer is also high. For this reason, peeling of a metal layer can be suppressed by arrange
  • the thickness of the adhesion layer is not particularly limited, but is preferably 3 nm to 50 nm, for example, more preferably 3 nm to 35 nm, and still more preferably 3 nm to 33 nm.
  • the thickness of the adhesion layer is preferably 3 nm or more as described above.
  • the upper limit value of the thickness of the adhesion layer is not particularly limited, but even if it is thicker than necessary, the time required for film formation and the time required for etching when forming the wiring are increased, resulting in an increase in cost. Will be invited.
  • the thickness of the adhesion layer is preferably 50 nm or less as described above, more preferably 35 nm or less, and further preferably 33 nm or less.
  • the conductive substrate of the present embodiment can have a transparent base material, a metal layer, and a blackening layer. Further, a layer such as an adhesion layer can be optionally provided.
  • FIGS. 1A, 1B, 2A, and 2B show examples of cross-sectional views of the conductive substrate of the present embodiment on a plane parallel to the lamination direction of the transparent base material, the metal layer, and the blackening layer.
  • the conductive substrate of the present embodiment can have a structure in which, for example, a metal layer and a blackening layer are laminated in that order from the transparent substrate side on at least one surface of the transparent substrate.
  • the metal layer 12 and the blackening layer 13 may be stacked one by one on the one surface 11a side of the transparent base material 11 one by one. it can.
  • the layers 13A and 13B can be stacked one by one in that order.
  • an adhesion layer may be provided.
  • the adhesion layer 14, the metal layer 12, and the blackening layer 13 are laminated in that order on the one surface 11a side of the transparent base material 11. be able to.
  • an adhesion layer, a metal layer, and a blackening layer are laminated on both surfaces of the transparent substrate 11
  • the adhesion layers 14A and 14B and the metal layers 12A and 12B are respectively formed on the one surface 11a side and the other surface 11b side of the transparent base material 11.
  • the blackening layers 13A and 13B can be stacked in that order.
  • stacked on the upper and lower sides of the transparent base material 11 by making the transparent base material 11 into a symmetrical surface.
  • positioned so that becomes symmetrical was shown, it is not limited to the form which concerns.
  • the configuration on the one surface 11a side of the transparent substrate 11 is the same as the configuration in FIG. 1B, in which the metal layer 12A and the blackening layer 13A are laminated in that order without providing the adhesion layer 14A.
  • the layers laminated on the top and bottom of the transparent substrate 11 may be asymmetrical.
  • substrate of this embodiment by providing a metal layer and a blackening layer on a transparent base material, reflection of the light by a metal layer is suppressed and the reflectance of an electroconductive board
  • the degree of reflectivity of the conductive substrate of the present embodiment is not particularly limited.
  • the reflectivity is lower. Is good.
  • the average reflectance of light having a wavelength of 400 nm to 700 nm is preferably 15% or less, and more preferably 10% or less.
  • the reflectance can be measured by irradiating the blackened layer of the conductive substrate with light. Specifically, for example, when the metal layer 12 and the blackened layer 13 are laminated in this order on one surface 11a side of the transparent substrate 11 as shown in FIG. 1A, the blackened layer 13 is irradiated so that the blackened layer 13 is irradiated with light.
  • the surface A can be irradiated with light and measured.
  • light having a wavelength of 400 nm or more and 700 nm or less is irradiated to the blackened layer 13 of the conductive substrate, for example, at a wavelength of 1 nm as described above, and the average value of the measured values is used as the reflectance of the conductive substrate. be able to.
  • the conductive substrate of this embodiment can be preferably used as a conductive substrate for a touch panel.
  • the conductive substrate can be configured to have mesh-like wiring.
  • the conductive substrate provided with the mesh-like wiring can be obtained by etching the metal layer and the blackening layer of the conductive substrate of the present embodiment described so far.
  • a mesh-like wiring can be formed by two-layer wiring.
  • FIG. 3 shows a view of the conductive substrate 30 provided with mesh-like wiring as viewed from the upper surface side in the stacking direction of the metal layer or the like.
  • the transparent substrate and the metal layer are patterned so that the wiring pattern can be easily understood. Description of layers other than the wirings 31A and 31B formed in the same manner is omitted.
  • the wiring 31B seen through the transparent base material 11 is also shown.
  • the conductive substrate 30 shown in FIG. 3 has a transparent base material 11, a plurality of wirings 31A parallel to the Y-axis direction in the drawing, and wirings 31B parallel to the X-axis direction.
  • the wirings 31A and 31B are formed by etching a metal layer, and a blackening layer (not shown) is formed on the upper surface or the lower surface of the wirings 31A and 31B.
  • the blackened layer is etched in the same shape as the wirings 31A and 31B.
  • the arrangement of the transparent substrate 11 and the wirings 31A and 31B is not particularly limited.
  • positioning with the transparent base material 11 and wiring is shown to FIG. 4A and FIG. 4B.
  • 4A and 4B are cross-sectional views taken along line AA ′ of FIG.
  • wirings 31A and 31B may be arranged on the upper and lower surfaces of the transparent base material 11, respectively.
  • blackening layers 32A and 32B etched in the same shape as the wiring are arranged on the upper surface of the wiring 31A and the lower surface of 31B.
  • a pair of transparent base materials 11 is used, wirings 31A and 31B are arranged on the upper and lower surfaces across one transparent base material 11, and one wiring 31B is a transparent base material. 11 may be arranged. Also in this case, blackened layers 32A and 32B etched in the same shape as the wiring are disposed on the upper surfaces of the wirings 31A and 31B.
  • an adhesion layer can be provided in addition to the metal layer and the blackening layer. Therefore, in either case of FIG. 4A or FIG. 4B, for example, an adhesion layer can be provided between the wiring 31 ⁇ / b> A and / or the wiring 31 ⁇ / b> B and the transparent substrate 11. When the adhesion layer is provided, it is preferable that the adhesion layer is also etched in the same shape as the wirings 31A and 31B.
  • the conductive substrate having the mesh-like wiring shown in FIGS. 3 and 4A is, for example, a conductive substrate having metal layers 12A and 12B and blackening layers 13A and 13B on both surfaces of the transparent base material 11 as shown in FIG. 1B. It can be formed from a conductive substrate.
  • the metal layer 12A and the blackened layer 13A on the one surface 11a side of the transparent base material 11 are parallel to the Y-axis direction in FIG. 1B.
  • Etching is performed so that a plurality of linear patterns are arranged at predetermined intervals along the X-axis direction.
  • the X-axis direction in FIG. 1B means a direction parallel to the width direction of each layer.
  • the Y-axis direction in FIG. 1B means a direction perpendicular to the paper surface in FIG. 1B.
  • a plurality of linear patterns parallel to the X-axis direction in FIG. 1B are arranged along the Y-axis direction at predetermined intervals on the metal layer 12B and the blackening layer 13B on the other surface 11b side of the transparent substrate 11. Etching is performed so as to be disposed.
  • the conductive substrate having the mesh-like wiring shown in FIGS. 3 and 4A can be formed.
  • the etching of both surfaces of the transparent substrate 11 can be performed simultaneously. That is, the etching of the metal layers 12A and 12B and the blackening layers 13A and 13B may be performed simultaneously.
  • the conductive substrate having an adhesion layer patterned in the same shape as the wirings 31A and 31B between the wirings 31A and 31B and the transparent base material 11 is the conductive substrate shown in FIG. 2B. It can be produced by etching in the same manner.
  • FIG. 3 can also be formed by using two conductive substrates shown in FIG. 1A or FIG. 2A.
  • a case where the two conductive substrates shown in FIG. 1A are used will be described as an example.
  • a plurality of metal layers 12 and blackening layers 13 are provided in parallel to the X-axis direction. Etching is performed so that the linear patterns are arranged along the Y-axis direction at a predetermined interval. Then, the conductive substrate having mesh-like wiring is obtained by bonding the two conductive substrates so that the linear patterns formed on the respective conductive substrates intersect with each other by the etching process. be able to.
  • the surface to be bonded when the two conductive substrates are bonded is not particularly limited.
  • the surface A in FIG. 1A in which the metal layer 12 or the like is laminated and the other surface 11b in FIG. 1A in which the metal layer 12 or the like is not laminated are bonded together so that the structure shown in FIG. 4B is obtained. You can also.
  • the other surfaces 11b in FIG. 1A where the metal layer 12 or the like of the transparent base material 11 is not laminated can be bonded together so that the cross section has the structure shown in FIG. 4A.
  • FIG. 1A a conductive substrate having an adhesion layer patterned in the same shape as the wirings 31A and 31B between the wirings 31A and 31B and the transparent base material 11 is shown in FIG. 1A. It can be manufactured by using the conductive substrate shown in FIG. 2A instead of the conductive substrate.
  • the width of the wiring and the distance between the wirings in the conductive substrate having the mesh-like wiring shown in FIG. 3, FIG. 4A and FIG. 4B are not particularly limited. You can choose.
  • the conductive substrate of this embodiment has a blackened layer containing nickel alone, nickel oxide, nickel hydroxide, and copper, and the blackened layer and the copper layer Even when simultaneously etching and patterning, the blackened layer and the copper layer can be patterned into a desired shape. Specifically, for example, a wiring having a wiring width of 10 ⁇ m or less can be formed. For this reason, it is preferable that the conductive substrate of this embodiment includes a wiring having a wiring width of 10 ⁇ m or less.
  • the lower limit value of the wiring width is not particularly limited, but can be 3 ⁇ m or more, for example.
  • 4 ⁇ / b> A, and 4 ⁇ / b> B show examples in which a mesh-like wiring (wiring pattern) is formed by combining linear wirings, but the present invention is not limited to such a form.
  • the wiring that constitutes can be of any shape.
  • the shape of the wiring constituting the mesh-like wiring pattern can be changed to various shapes such as jagged lines (zigzag straight lines) so that moire (interference fringes) does not occur between the images on the display.
  • a conductive substrate having a mesh-like wiring composed of two layers of wiring can be preferably used as a conductive substrate for a projected capacitive touch panel, for example.
  • the conductive substrate of the present embodiment described above has a structure in which a blackening layer is laminated on a metal layer formed on at least one surface of a transparent base material. And since the blackening layer contains the simple substance of nickel, nickel oxide, nickel hydroxide, and copper, when patterning a metal layer and a blackening layer by an etching, a blackening layer Can be easily patterned into a desired shape.
  • the blackening layer included in the conductive substrate of the present embodiment can be a conductive substrate that sufficiently suppresses reflection of light on the surface of the metal layer and suppresses reflectance. Moreover, the visibility of a display can be improved when used for applications such as a touch panel. (Method for producing conductive substrate) Next, a configuration example of the method for manufacturing the conductive substrate according to the present embodiment will be described.
  • the manufacturing method of the conductive substrate of this embodiment can have the following processes.
  • a blackening layer containing nickel alone, nickel oxide, nickel hydroxide, and copper can be formed.
  • the conductive substrate described above can be suitably manufactured by the method for manufacturing a conductive substrate of the present embodiment. For this reason, since it can be set as the structure similar to the case of the above-mentioned electroconductive board
  • the transparent base material used for the metal layer forming step can be prepared in advance.
  • a transparent base material such as an insulating film (resin film) that transmits visible light or a glass substrate can be preferably used as described above.
  • the transparent base material can be cut into an arbitrary size in advance if necessary.
  • the metal layer preferably has a metal thin film layer as described above.
  • the metal layer can also have a metal thin film layer and a metal plating layer.
  • a metal layer formation process can have a process of forming a metal thin film layer, for example by a dry-type plating method.
  • the metal layer forming step includes a step of forming a metal thin film layer by a dry plating method, a step of forming a metal plating layer by an electroplating method which is a kind of wet plating method, using the metal thin film layer as a power feeding layer, You may have.
  • the dry plating method used in the step of forming the metal thin film layer is not particularly limited, and for example, an evaporation method, a sputtering method, an ion plating method, or the like can be used.
  • a vapor deposition method a vacuum vapor deposition method can be used preferably.
  • the dry plating method used in the step of forming the metal thin film layer it is more preferable to use the sputtering method because the film thickness is particularly easy to control.
  • the conditions in the step of forming the metal plating layer by the wet plating method that is, the conditions for the electroplating treatment are not particularly limited, and various conditions according to ordinary methods may be adopted.
  • a metal plating layer can be formed by supplying a base material on which a metal thin film layer is formed in a plating tank containing a metal plating solution and controlling the current density and the conveyance speed of the base material.
  • a blackening layer containing nickel alone, nickel oxide, nickel hydroxide, and copper can be formed.
  • the blackened layer can be formed by a wet method. Specifically, for example, a blackened layer can be formed on the metal layer by an electrolytic plating method in a plating tank containing the blackened plating solution described above, using the metal layer as a power feeding layer. Thus, by forming a blackened layer by an electrolytic plating method using the metal layer as a power feeding layer, the blackened layer can be formed on the entire surface of the metal layer opposite to the surface facing the transparent substrate.
  • an optional step can be further performed in addition to the above-described steps.
  • an adhesion layer forming step of forming an adhesion layer on the surface of the transparent substrate on which the metal layer is formed can be performed.
  • the metal layer forming step can be carried out after the adhesion layer forming step.
  • the metal is formed on the substrate on which the adhesion layer is formed on the transparent substrate in this step.
  • a thin film layer can be formed.
  • the method for forming the adhesion layer is not particularly limited, but it is preferable to form the film by a dry plating method.
  • a dry plating method for example, a sputtering method, an ion plating method, a vapor deposition method, or the like can be preferably used.
  • the adhesion layer is formed by a dry method, it is more preferable to use a sputtering method because the film thickness can be easily controlled.
  • one or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the adhesion layer, and in this case, the reactive sputtering method can be more preferably used.
  • the conductive substrate obtained by the conductive substrate manufacturing method of the present embodiment can be used for various applications such as a touch panel. And when using for various uses, it is preferable that the metal layer and blackening layer which are contained in the electroconductive board
  • the manufacturing method of the conductive substrate of the present embodiment can include a patterning step of patterning the metal layer and the blackened layer.
  • the patterning step can be a step of patterning the adhesion layer, the metal layer, and the blackening layer.
  • the specific procedure of the patterning step is not particularly limited, and can be performed by an arbitrary procedure.
  • a resist having a desired pattern is arranged on the surface A on the blackening layer 13.
  • a resist placement step can be performed.
  • an etching step of supplying an etching solution to the surface A on the blackened layer 13, that is, the surface side where the resist is disposed can be performed.
  • the etching solution used in the etching step is not particularly limited.
  • the blackened layer formed by the method for manufacturing a conductive substrate according to the present embodiment exhibits almost the same reactivity to the etching solution as the metal layer.
  • the etching liquid used in an etching step is not specifically limited,
  • the etching liquid generally used for the etching of a metal layer can be used preferably.
  • etching solution for example, a mixed aqueous solution containing one or more selected from sulfuric acid, hydrogen peroxide (hydrogen peroxide solution), hydrochloric acid, cupric chloride, and ferric chloride can be preferably used.
  • the content of each component in the etching solution is not particularly limited.
  • the etching solution can be used at room temperature, but it can also be used by heating in order to increase the reactivity. For example, it can be used by heating to 40 ° C. or more and 50 ° C. or less.
  • a patterning process is performed to pattern the conductive substrate 10B in which the metal layers 12A and 12B and the blackening layers 13A and 13B are stacked on the one surface 11a and the other surface 11b of the transparent substrate 11. it can.
  • a resist placement step of placing a resist having a desired pattern on the surface A and the surface B on the blackening layers 13A and 13B can be performed.
  • an etching step of supplying an etching solution to the surface A and the surface B on the blackening layers 13A and 13B, that is, the surface on which the resist is disposed can be performed.
  • the pattern formed in the etching step is not particularly limited, and can be an arbitrary shape.
  • the pattern is formed so that the metal layer 12 and the blackened layer 13 include a plurality of straight lines or jagged lines (zigzag straight lines) as described above. Can do.
  • a pattern can be formed by the metal layer 12A and the metal layer 12B so as to form a mesh-like wiring.
  • a lamination step of laminating two or more patterned conductive substrates may be performed.
  • laminating for example, by laminating so that the pattern of the metal layer of each conductive substrate intersects, a laminated conductive substrate provided with mesh-like wiring can be obtained.
  • the method of fixing two or more laminated conductive substrates is not particularly limited, but can be fixed by, for example, an adhesive.
  • the conductive substrate obtained by the above-described method for manufacturing a conductive substrate according to this embodiment has a structure in which a blackening layer is stacked on a metal layer formed on at least one surface of a transparent base material. . Since the blackened layer contains nickel alone, nickel oxide, nickel hydroxide, and copper, as described above, the metal layer and the blackened layer are patterned by etching. In this case, the blackened layer can be easily patterned into a desired shape.
  • the blackening layer included in the conductive substrate obtained by the method for manufacturing the conductive substrate of the present embodiment is a conductive substrate that sufficiently suppresses reflection of light on the surface of the metal layer and suppresses reflectance. Can do. For this reason, when it uses for uses, such as a touch panel, for example, the visibility of a display can be improved.
  • a conductive substrate having the structure of FIG. 1A was produced. Therefore, the surface A exposed to the outside of the blackening layer 13 in FIG. 1A was subjected to Ar ion etching, and the Ni 2P spectrum and Cu LMM spectrum inside 10 nm from the outermost surface were measured. From the obtained spectrum, the ratio of the number of copper atoms when the number of nickel atoms contained in the blackened layer was defined as 100 was calculated. In Table 1, the results are shown as the ratio of metal components.
  • the number of nickel atoms and nickel hydroxide contained in the blackened layer which is nickel oxide when the number of metal nickel atoms is defined as 100, is obtained.
  • the number of nickel atoms was calculated. In Table 1, the results are shown as nickel component ratios.
  • (2) Reflectance measurement The measurement was carried out by installing a reflectance measurement unit in an ultraviolet-visible spectrophotometer (model: UV-2600, manufactured by Shimadzu Corporation).
  • a conductive substrate having the structure shown in FIG. 1A was produced.
  • the reflectance measurement is performed with an incident angle of 5 ° and a light receiving angle of 5 ° with respect to the surface A of the blackened layer 13 of the conductive substrate 10A shown in FIG.
  • the regular reflectance was measured by irradiation, and the average value was defined as the reflectance (average reflectance) of the conductive substrate.
  • a dry film resist (Hitachi Kasei RY3310) was attached to the surface of the blackened layer of the conductive substrate obtained in the following experimental examples by a laminating method.
  • the sample was immersed in an etching solution of 10% by weight sulfuric acid and 3% by weight of hydrogen peroxide at 30 ° C. for 40 seconds, and the dry film resist was peeled off and removed with an aqueous sodium hydroxide solution.
  • the obtained sample was observed with a 200-fold microscope, and the minimum value of the wiring width of the metal wiring remaining on the conductive substrate was determined.
  • the minimum value of the wiring width of the remaining metal wiring is 3 ⁇ m or more and 10 ⁇ m or less, and there is no undissolved residue around the formed metal wiring, it was evaluated as “good”. Moreover, although the minimum value of the remaining metal wiring is 3 ⁇ m or more and 10 ⁇ m or less, it is evaluated as ⁇ when a part of the metal wiring is not melted, although there is no practical problem.
  • Example preparation conditions Conductive substrates were produced under the conditions described below and evaluated by the above-described evaluation method. Any of Experimental Examples 1 to 10 is an example.
  • a conductive substrate having the structure shown in FIG. 1A was produced.
  • a copper layer was formed as a metal layer on one surface of a long polyethylene terephthalate resin (PET) transparent substrate having a length of 300 m, a width of 250 mm, and a thickness of 100 ⁇ m.
  • PET polyethylene terephthalate resin
  • the transparent base material made of polyethylene terephthalate resin used as the transparent base material was evaluated to have a total light transmittance of 97% when evaluated by the method defined in JIS K 7361-1.
  • a metal thin film layer forming step and a metal plating layer forming step were performed.
  • the above-mentioned transparent base material was used as a base material, and a copper thin film layer was formed as a metal thin film layer on one surface of the transparent base material.
  • the above-mentioned transparent base material which was previously heated to 60 ° C. to remove moisture, was placed in the chamber of the sputtering apparatus.
  • Electric power was supplied to a copper target set in advance on the cathode of the sputtering apparatus, and a copper thin film layer was formed on one surface of the transparent substrate so as to have a thickness of 0.7 ⁇ m.
  • a copper plating layer was formed as a metal plating layer.
  • the copper plating layer was formed by electroplating so that the thickness of the copper plating layer was 0.3 ⁇ m.
  • a copper layer having a thickness of 1.0 ⁇ m was formed as a metal layer.
  • the following blackened layer forming step was carried out after immersing the substrate having a copper layer having a thickness of 1.0 ⁇ m formed on the transparent base material formed in the metal layer forming step in 20 g / L sulfuric acid for 30 seconds and washing it. .
  • Blackening layer forming process In the blackened layer forming step, a blackened layer was formed on one surface of the copper layer by electrolytic plating using a blackened plating solution.
  • a plating solution containing nickel ions, copper ions, amidosulfuric acid and sodium hydroxide was prepared as a blackening plating solution.
  • Nickel ions and copper ions were supplied to the blackening plating solution by adding nickel sulfate hexahydrate and copper sulfate pentahydrate.
  • each component was added and prepared so that the concentration of nickel ions in the blackening plating solution was 5 g / l, the concentration of copper ions was 0.03 g / l, and the concentration of amidosulfuric acid was 11 g / l.
  • an aqueous sodium hydroxide solution was added to the blackening plating solution to adjust the pH of the blackening plating solution to 4.9.
  • the blackening layer forming step electrolytic plating was performed under the conditions that the temperature of the blackening plating solution was 40 ° C., the current density was 0.10 A / dm 2 , and the plating time was 400 seconds to form a blackening layer.
  • the film thickness of the formed blackened layer was 70 nm.
  • the blackened layer contains nickel alone, nickel oxide, nickel hydroxide, and copper. It was.
  • the evaluation results for the etching characteristics were either “ ⁇ ” or “ ⁇ ”, and it was confirmed that the conductive substrate was provided with a metal layer and a blackened layer that could be etched simultaneously.
  • the experimental characteristics 1 to 8 in which the copper is 7 or more and 90 or less have the etching characteristics. It was confirmed that the reflectance was 10% or less.
  • the conductive substrates of Experimental Examples 1 to 8 are particularly close to the reactivity of the metal layer and the blackening layer with respect to the etching solution, and particularly capable of suppressing light reflection on the surface of the metal layer. It was confirmed that it had a layer.

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