WO2017022596A1 - Conductive substrate, and method for manufacturing conductive substrate - Google Patents

Conductive substrate, and method for manufacturing conductive substrate Download PDF

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Publication number
WO2017022596A1
WO2017022596A1 PCT/JP2016/072055 JP2016072055W WO2017022596A1 WO 2017022596 A1 WO2017022596 A1 WO 2017022596A1 JP 2016072055 W JP2016072055 W JP 2016072055W WO 2017022596 A1 WO2017022596 A1 WO 2017022596A1
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WIPO (PCT)
Prior art keywords
layer
metal layer
metal
conductive substrate
adhesion
Prior art date
Application number
PCT/JP2016/072055
Other languages
French (fr)
Japanese (ja)
Inventor
志賀　大樹
宏樹 秦
芳英 西山
貴広 須田
裕洲 葉
宗和 葉
志明 胡
弘信 有馬
Original Assignee
住友金属鉱山株式会社
介面光電股▲ふん▼有限公司
ジェイタッチ・ジャパン株式会社
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Application filed by 住友金属鉱山株式会社, 介面光電股▲ふん▼有限公司, ジェイタッチ・ジャパン株式会社 filed Critical 住友金属鉱山株式会社
Priority to JP2017532529A priority Critical patent/JP6705455B2/en
Publication of WO2017022596A1 publication Critical patent/WO2017022596A1/en

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    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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
    • 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
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means

Definitions

  • the present invention relates to a conductive substrate and a method for manufacturing 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.
  • Patent Document 1 discloses 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.
  • a conductive substrate in which a black layer formed of a material capable of suppressing light reflection on the surface of the metal layer is formed on the upper surface of the metal layer together with a metal layer formed of a metal foil such as copper has been studied. .
  • the blackened layer is formed on the upper surface of the metal layer, the adhesion between the metal layer and the blackened layer is not sufficient, and the blackened layer may peel off when patterning the metal layer or the blackened layer. There was a problem.
  • an object of one aspect of the present invention is to provide a conductive substrate in which the blackened layer is prevented from peeling off.
  • a transparent substrate A metal layer formed on at least one surface of the transparent substrate; A protective layer formed on the metal layer and containing an organic compound containing a sulfur atom and / or a nitrogen atom; There is provided a conductive substrate having a blackening layer formed on the protective layer.
  • the explanatory schematic diagram of the mechanism in which the blackening layer peels in the conventional conductive substrate The explanatory schematic diagram of the mechanism in which the blackening layer peels in the conventional conductive substrate.
  • the structure explanatory view of the conductive substrate concerning the embodiment of the present invention The structure explanatory view of the conductive substrate concerning the embodiment of the present invention.
  • the conductive substrate of the present embodiment includes a transparent substrate, a metal layer formed on at least one surface of the transparent substrate, and an organic compound formed on the metal layer and containing sulfur atoms and / or nitrogen atoms. It can have a protective layer to be contained and a blackening layer formed on the protective layer.
  • the conductive substrate in the present embodiment is a substrate having a metal layer, a protective layer, and a blackened layer on the surface of the transparent base material before patterning the metal layer, and a substrate obtained by patterning the metal layer. That is, the wiring board is included. Since the conductive substrate after patterning the metal layer, the protective layer, and the blackening layer includes a region where the transparent base material is not covered with the metal layer or the like, it can transmit light and becomes a transparent conductive substrate. Yes.
  • the transparent substrate is not particularly limited, and a resin substrate (resin film) that transmits visible light, a glass substrate, or the like can be preferably used.
  • a resin such as a polyamide resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, a cycloolefin resin, a polyimide resin, or a polycarbonate resin can be preferably used.
  • PET polyethylene terephthalate
  • COP cycloolefin polymer
  • PEN polyethylene naphthalate
  • polyimide polycarbonate
  • the like can be more preferably used as the material for the resin substrate that transmits visible light.
  • the thickness of the transparent base material is not particularly limited, and can be arbitrarily selected according to the strength, capacitance, light transmittance, and the like required for a conductive substrate.
  • 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 ensured when used for, for example, a touch panel.
  • the total light transmittance of the transparent substrate can be evaluated by the method defined in JIS K 7361-1.
  • the transparent substrate can have a first main plane and a second main plane.
  • the main plane here refers to the plane part with the largest area among the surfaces contained in a transparent base material.
  • a 1st main plane and a 2nd main plane mean the surface arrange
  • the second main plane can also be referred to as a plane located on the opposite side of the first main plane in one transparent substrate.
  • the material which comprises a metal layer is not specifically limited, The material which has the electrical conductivity according to the application can be selected,
  • the material which comprises a metal layer is Cu, Ni, Mo, Ta, Ti, V, Cr , Fe, Mn, Co and W are preferably a copper alloy with at least one metal selected from the group consisting of copper, or a material containing copper.
  • the metal layer can be a copper layer made of copper.
  • the method for forming the metal layer on the transparent substrate is not particularly limited, it is preferable not to dispose an adhesive between the transparent substrate and the metal layer in order not to reduce the light transmittance. That is, the metal layer is preferably formed directly on at least one surface of the transparent substrate. In addition, when arrange
  • the metal layer In order to directly form the metal layer on the upper surface of the transparent substrate, the metal layer preferably has a metal thin film layer. Moreover, the metal layer may have a metal thin film layer and a metal plating layer.
  • a metal thin film layer can be formed on a transparent substrate by a dry plating method, and the metal thin film layer can be used as a metal layer. Thereby, a metal layer can be directly formed on the transparent substrate without using an adhesive.
  • the dry plating method will be described in detail later.
  • a sputtering method, a vapor deposition method, an ion plating method, or the like can be preferably used.
  • the metal thin film layer and the metal plating layer are formed by forming the metal plating layer by electroplating, which is a kind of wet plating method, using the metal thin film layer as a power feeding layer. It can also be a metal layer. Since the metal layer has the metal thin film layer and the metal plating layer, the metal layer can be directly formed on the transparent substrate without using an adhesive.
  • 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 500 nm or more.
  • the metal layer can be used as a wiring by patterning it into a desired wiring pattern, for example. And since a metal layer can make an electrical resistance value lower than ITO conventionally used as a transparent conductive film, the electrical resistance value of an electroconductive board
  • substrate can be made small by providing a metal layer.
  • the conductive substrate of this embodiment by disposing a protective layer to be described later, it is possible to suppress the blackening layer from peeling off from the metal layer during patterning.
  • the surface roughness of the surface of the metal layer facing the protective layer can be further improved through the protective layer so that the adhesion between the metal layer and the blackened layer can be further increased and the blackened layer can be further prevented from peeling.
  • the thickness Ra is preferably 0.03 ⁇ m or more and 0.08 ⁇ m or less.
  • the surface roughness Ra here is defined in JIS B 0601 and can be evaluated by, for example, a stylus method or an optical method.
  • the method of setting the surface roughness Ra of the surface of the metal layer facing the protective layer within the above range is not particularly limited, and any method can be selected.
  • a method of forming a rough metal layer according to film forming conditions, or after forming a smooth metal layer, the surface of the metal layer facing the protective layer is roughened by sandblasting, micro roughening etching, or the like.
  • a desired surface roughness Ra can be obtained by the method.
  • the protective layer can be formed on the metal layer and can contain an organic compound containing a sulfur atom and / or a nitrogen atom.
  • the inventors of the present invention have studied the cause of peeling of the blackened layer when patterning the metal layer or blackened layer on a conventional conductive substrate.
  • the blackened layer 2 includes the fine holes 3 first. It was.
  • the etching solution is supplied to the surface of the blackening layer 2 for patterning, the etching solution penetrates from the fine holes 3 included in the blackening layer 2 to the surface of the metal layer 1 as shown in FIG. 1B. In some cases, the surface melts and a gap 4 is formed between the metal layer 1 and the blackened layer 2.
  • the contact area between the metal layer 1 and the blackening layer 2 is reduced, the adhesion between the metal layer 1 and the blackening layer 2 is significantly reduced, and the blackening layer 2 may be peeled off from the metal layer 1. It is thought that there was.
  • the protective layer is disposed between the metal layer and the blackened layer, thereby improving the adhesion between the metal layer and the blackened layer via the protective layer. It is considered that the height is higher than that of the conventional conductive substrate shown in FIGS. 1A and 1B. For this reason, it becomes possible to suppress that a blackening layer peels from a metal layer.
  • the material for the protective layer is not particularly limited, and any material can be used without particular limitation as long as it can prevent the blackened layer from peeling off from the metal layer during etching.
  • an organic compound containing a sulfur atom and / or a nitrogen atom can be preferably used.
  • the protective layer preferably contains an organic compound containing a sulfur atom and / or a nitrogen atom, and more preferably is composed of the above-described organic compound containing a sulfur atom and / or a nitrogen atom.
  • a benzotriazole type compound a mercaptobenzothiazole type compound, an imidazole type compound, amines etc. can be used preferably.
  • benzotriazole compounds include 1,2,3-benzotriazole (Chemical Formula 1), 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole (Chemical Formula 2), carboxybenzotriazole (Chemical Formula) 3) 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole (Formula 4), 2,2 ′-[[(Methyl-1H-benzotriazol-1-yl) methyl] imino] Bisethanol (chemical formula 5), 1,2,3-benzotriazole sodium salt aqueous solution (chemical formula 6), tolyltriazole (5-methyl 1H-benzotriazole), tolyltriazole sodium salt and the like can be preferably used.
  • imidazole compound for example, alkylimidazole, benzimidazole, allylphenylimidazole, or the like can be preferably used.
  • a benzotriazole-based compound can be more preferably used as the organic compound containing a sulfur atom and / or a nitrogen atom. That is, it is more preferable that the protective layer contains a benzotriazole-based compound.
  • the blackened layer can be formed on the upper surface of the protective layer.
  • the material of the blackening layer is not particularly limited, and any material that can suppress the reflection of light on the surface of the metal layer can be suitably used.
  • the blackening 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. Further, the blackening layer can further contain one or more elements selected from carbon, oxygen, hydrogen, and nitrogen.
  • the blackening layer can 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 blackening layer may further contain 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.
  • a Cu—Ni—Fe alloy, Ni—Cu alloy, Ni—Zn alloy, Ni—Ti alloy, Ni—W alloy, Ni—Cr alloy, and Ni—Cu—Cr alloy can be preferably used.
  • the method for forming the blackened layer is not particularly limited, and can be formed by any method, for example, by a dry method or a wet method.
  • the specific method is not particularly limited, but for example, a dry plating method such as a sputtering method, an ion plating method or a vapor deposition method can be preferably used.
  • a dry plating method such as a sputtering method, an ion plating method or a vapor deposition method
  • the blackening 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 blackened layer, and in this case, the reactive sputtering method can be more preferably used.
  • a target containing a metal species constituting the blackened layer can be used as the target.
  • the blackened layer contains an alloy
  • a target may be used for each metal species contained in the blackened layer, and the alloy may be formed on the surface of the film-deposited body such as a substrate, and is included in the blackened layer in advance. It is also possible to use a target obtained by alloying a metal.
  • the blackened layer contains one or more elements selected from carbon, oxygen, hydrogen, and nitrogen
  • these are added to the atmosphere when the blackened layer is formed, so that the blackened layer Can be added inside.
  • carbon monoxide gas and / or carbon dioxide gas is used
  • oxygen, oxygen gas is used
  • hydrogen, hydrogen gas and / or water is used.
  • nitrogen gas can be added to the atmosphere during sputtering.
  • One or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the blackening layer by adding these gases to the inert gas when forming the blackening layer.
  • Argon can be preferably used as the inert gas.
  • the blackened layer When the blackened layer is formed by a wet method, it can be formed by, for example, an electroplating method using a plating solution corresponding to the material of the blackened layer.
  • the thickness of the blackening layer is not particularly limited, but is preferably 15 nm or more, for example, and more preferably 25 nm or more. This is because when the thickness of the blackened layer is thin, reflection of light on the surface of the metal layer may not be sufficiently suppressed. Therefore, the thickness of the blackened layer is set to 15 nm or more as described above. This is because it is preferable to configure so that reflection of light on the surface of the layer can be particularly suppressed.
  • the upper limit of the thickness of the blackening 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 blackened layer is preferably 70 nm or less, and more preferably 50 nm or less.
  • the reflection of light on the surface of the metal layer can be suppressed by arranging the blackened layer as described above. For this reason, when it uses for uses, such as a touch panel, for example, it becomes possible to suppress the fall of the visibility of a display.
  • the conductive substrate can be provided with any layer other than the above-mentioned transparent base material, metal layer, protective 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.
  • 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 base material 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 can further contain one or more elements selected from carbon, oxygen, hydrogen, and nitrogen.
  • the adhesion layer can include a metal alloy including 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.
  • a sputtering 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, a reactive sputtering method can be more preferably used.
  • the adhesion layer contains 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 includes a transparent base material, a metal layer, a protective layer, and a blackening layer, and the metal layer, the protective layer, and the blackening layer are provided on the transparent base material. It can be set as the structure laminated
  • FIGS. 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 metal layer 12, the protective layer 13, and the blackening layer 14 are laminated one by one on the first main plane 11a side of the transparent substrate 11. Can be configured. Further, like the conductive substrate 10B shown in FIG. 2B, the metal layers 12A and 12B and the protective layer 13A are respectively formed on the first main plane 11a side and the second main plane 11b side of the transparent base material 11. , 13B and the blackening layers 14A, 14B can be stacked one by one in that order.
  • the blackening layer 14 (14A, 14B) is disposed on the upper surface of the metal layer 12 (12A, 12B) via the protective layer 13 (13A, 13B). . For this reason, reflection of the light from the upper surface side of the metal layer 12 (12A, 12B) can be suppressed. Moreover, since the protective layer 13 (13A, 13B) is disposed, the blackening layer 14 (14A, 14B) can be prevented from peeling off.
  • an adhesion layer (not shown) can be provided between the transparent substrate 11 and the metal layer 12.
  • an adhesion layer can be provided between the transparent base material 11 and the metal layer 12A and / or between the transparent base material 11 and the metal layer 12B.
  • the adhesion layer By providing the adhesion layer, the adhesion between the transparent substrate 11 and the metal layer 12 (12A, 12B) can be improved, and the metal layer 12 (12A, 12B) is particularly prevented from peeling from the transparent substrate 11. can do.
  • it is preferable to provide an adhesion layer because the reflection of light can be suppressed even on the surface of the metal layer 12 (12A, 12B) where the blackening layer is not provided.
  • the conductive substrate of this 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, protective layer, and blackening layer which are contained in the electroconductive board
  • the metal layer, the protective layer, and the blackened layer can be patterned in accordance with, for example, a desired wiring pattern, and the metal layer, the protective layer, and the blackened layer are preferably patterned in the same shape.
  • the adhesion layer when the metal layer, the protective layer, and the blackening layer are patterned, the adhesion layer can be patterned in accordance with a desired wiring pattern. For this reason, when an adhesion layer is provided, it is preferable to pattern the adhesion layer, the metal layer, the protective layer, and the blackening layer in the same shape.
  • the metal layer or the like can be patterned into a desired shape, but the pattern to be formed at this time is not particularly limited, and can be an arbitrary shape.
  • the pattern is preferably formed so that the conductive substrate has mesh-like wiring.
  • the metal layer constituting the wiring can be patterned so as to constitute a desired mesh-like wiring, and the protective layer, the blackening layer, and the like can be patterned in the same shape.
  • the method for forming a conductive substrate having mesh-like wiring is not particularly limited.
  • a mesh-like wiring can be formed by stacking two conductive substrates to form a laminated conductive substrate.
  • a plurality of linear wiring patterns such as a linear shape or a zigzag shape can be formed so as to be separated from each other along one direction.
  • the wiring pattern formed on one conductive substrate and the wiring pattern formed on the other conductive substrate are stacked so as to intersect each other.
  • the laminated conductive substrate can be fixed with an adhesive or the like, for example.
  • the metal layer 12A formed on the first main plane 11a side and the metal layer 12B formed on the second main plane 11b side are respectively patterned into predetermined shapes, and mesh-like wiring is formed. It can also be formed. Also in this case, it is preferable to pattern the protective layers 13A and 13B, the blackening layers 14A and 14B, and in some cases, the adhesion layer in accordance with the shapes of the metal layers 12A and 12B.
  • the method for patterning the metal layer or the like is not particularly limited. For example, after a mask having a shape corresponding to the pattern to be formed is placed on the upper surface of the blackened layer 14 (14A, 14B), an etching process is performed. Can be patterned.
  • the etching solution to be used is not particularly limited, and can be arbitrarily selected according to the material constituting the layer to be etched.
  • the etching solution can be changed for each layer, and the metal layer and the blackening layer, and in some cases, the adhesion layer can be etched simultaneously with the same etching solution.
  • the degree of light reflection of the conductive substrate of the present embodiment is not particularly limited, for example, the regular reflectance (reflectance) of light having a wavelength of 400 nm to 700 nm is preferably 35% or less, More preferably, it is 30% or less.
  • the reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 35% or less, for example, even when used as a conductive substrate for a touch panel, the display visibility is hardly lowered, which is preferable.
  • the reflectance can be measured by irradiating the blackened layer 14 (14A, 14B) with light.
  • the blackened layer 14 is irradiated with light.
  • it can measure by irradiating light from the surface 14a side of the blackened layer 14.
  • light having a wavelength of 400 nm to 700 nm is irradiated on the surface 14a of the blackened layer 14 of the conductive substrate at a wavelength of 1 nm, for example, as described above, and the regular reflectance is measured.
  • the regular reflectance of the conductive substrate can be the regular reflectance of the conductive substrate.
  • the value of lightness (L * ) in the L * a * b * color system is small. This is because the blackening layer 14 (14A, 14B), the protective layer 13 (13A, 13B), and the metal layer 12 (12A, 12B) become less conspicuous as the value of the lightness (L * ) decreases.
  • the lightness (L * ) of the surface of the blackened layer 14 (14A, 14B) is preferably 70 or less.
  • substrate can be made small.
  • the surface resistance is preferably less than 0.2 ⁇ / ⁇ , and more preferably less than 0.10 ⁇ / ⁇ .
  • the method for measuring the surface resistance is not particularly limited. For example, it can be measured by a four-probe method, and it is preferable to perform the measurement so that the probe contacts the surface of the conductive substrate, for example, the blackened layer surface. . (Method for producing conductive substrate) Next, a configuration example of the method for manufacturing the conductive substrate according to this embodiment will be described.
  • the manufacturing method of the conductive substrate of this embodiment can have the following processes.
  • substrate can be suitably manufactured with the manufacturing method of the electroconductive board
  • the transparent base material used for the metal layer forming step can be prepared in advance.
  • the kind of transparent base material to be used is not particularly limited, a resin substrate (resin film) that transmits visible light, a glass substrate, or the like 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 protective layer can be formed on the metal layer.
  • the protective layer can suppress the peeling of the blackened layer from the metal layer when the metal layer, the blackened layer, or the like is patterned.
  • the method for forming the protective layer is not particularly limited.
  • the protective layer can be formed by applying a solution containing a material constituting the protective layer on the metal layer and drying it.
  • the method for applying the solution containing the material constituting the protective layer on the metal layer is not particularly limited, and can be applied by any method.
  • a solution containing a material constituting the protective layer can be applied on the metal layer by spraying or dipping.
  • the material for the protective layer is not particularly limited, and any material can be used without particular limitation as long as it can prevent the blackened layer from peeling off from the metal layer during etching.
  • an organic compound containing a sulfur atom and / or a nitrogen atom can be preferably used.
  • the protective layer preferably contains an organic compound containing a sulfur atom and / or a nitrogen atom, and more preferably is composed of the above-described organic compound containing a sulfur atom and / or a nitrogen atom.
  • a benzotriazole type compound, a mercaptobenzothiazole type compound, an imidazole type compound, amines etc. can be used preferably.
  • a benzotriazole-based compound can be more preferably used as the organic compound containing a sulfur atom and / or a nitrogen atom. That is, it is more preferable that the protective layer contains a benzotriazole-based compound. Description of benzotriazole compounds that can be suitably used in the protective layer is omitted because they have already been described.
  • the method for forming the blackened layer is not particularly limited, and can be formed by any method.
  • a dry plating method such as a sputtering method, an ion plating method or a vapor deposition method can be preferably used.
  • the sputtering method is more preferable because the film thickness can be easily controlled.
  • the blackened layer can be formed by a wet method such as an electroplating method.
  • 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, and is transparent in this step with the substrate on which the metal thin film layer described in the metal layer forming step is formed.
  • the base material has an adhesion layer formed on the base material.
  • the adhesion layer can be formed, for example, on the first main plane 11a which is one main plane of the transparent substrate 11 in FIG. 2A.
  • an adhesion layer can be formed on the first main plane 11a and / or the second main plane 11b of the transparent substrate 11.
  • the adhesion layer may be formed simultaneously on both main planes.
  • the adhesion layer may be formed on the other main plane.
  • the material constituting the adhesion layer is not particularly limited, the adhesion strength with the transparent substrate and the metal layer, the degree of suppression of light reflection on the surface of the metal layer, and the environment in which the conductive substrate is used ( For example, it can be arbitrarily selected according to the degree of stability with respect to humidity and temperature. Since materials that can be suitably used as the material constituting the adhesion layer have already been described, description thereof is omitted here.
  • the adhesion layer can be formed 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.
  • a sputtering 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, a reactive sputtering method can be more preferably used.
  • the adhesion layer contains one or more elements selected from carbon, oxygen, hydrogen, and nitrogen
  • one or more selected from carbon, oxygen, hydrogen, and nitrogen in the atmosphere when forming the adhesion layer By adding a gas containing these elements, it can be added to the adhesion layer.
  • a gas containing these elements it 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.
  • a target containing a metal species constituting the adhesion layer can be used as the target.
  • the adhesion layer contains an alloy
  • a target may be used for each metal species contained in the adhesion layer, and the alloy may be formed on the surface of the film-formed body such as a transparent substrate.
  • An alloyed target can also be used.
  • 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.
  • a metal layer surface processing step for processing the surface of the metal layer so that the surface of the metal layer on which the protective layer is formed (the surface facing the protective layer of the metal layer) has a predetermined surface roughness Ra may be performed. it can.
  • the surface of the metal layer on which the protective layer is formed has a surface roughness Ra of 0.03 ⁇ m or more and 0.08 ⁇ m or less. Processing steps can be performed.
  • the method of setting the surface roughness Ra of the surface on which the protective layer of the metal layer is formed is not particularly limited, and any method can be selected.
  • a method of forming a rough metal layer according to film forming conditions, or after forming a smooth metal layer, the surface of the metal layer facing the protective layer is roughened by sandblasting, micro roughening etching, or the like.
  • the method can be preferably used.
  • any of the metal layer 12A and the metal layer 12B Only the surface of the surface on which the protective layer is formed may be the above-described surface roughness Ra. Moreover, it is good also considering the surface of the surface which forms protective layer 13A, 13B as above-mentioned surface roughness Ra about both metal layer 12A, 12B.
  • 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, protective layer, and blackening layer which are contained in the electroconductive board
  • the metal layer, the protective layer, and the blackening layer, and in some cases, the adhesion layer can be patterned in accordance with, for example, a desired wiring pattern.
  • the layers are preferably patterned in the same shape.
  • the manufacturing method of the conductive substrate of the present embodiment can include a patterning step of patterning the metal layer, the protective layer, and the blackening layer.
  • the patterning step can be a step of patterning the adhesion layer, the metal layer, the protective 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 mask having a desired pattern is first placed on the blackened layer 14.
  • a mask placement step can be performed.
  • an etching step of supplying an etching solution to the upper surface of the blackening layer 14, that is, the surface side where the mask is disposed can be performed.
  • the etching solution used in the etching step is not particularly limited, and can be arbitrarily selected depending on the material constituting the layer to be etched.
  • the etching solution can be changed for each layer, and the metal layer, the protective layer, and the blackening layer, and in some cases, the adhesion layer can be etched simultaneously with the same etching solution.
  • a patterning process for patterning 10B can also be performed.
  • a mask placement step of placing a mask having a desired pattern on the blackening layers 14A and 14B can be performed.
  • an etching step of supplying an etching solution to the upper surfaces of the blackening layers 14A and 14B, that is, the surface side where the mask is disposed can be performed.
  • the pattern formed in the etching process is not particularly limited and can be an arbitrary shape.
  • the metal layer 12, the protective layer 13, and the blackening layer 14 include a plurality of straight lines or jagged lines (zigzag straight lines). A pattern can be formed.
  • a pattern can be formed so that the metal layer 12A and the metal layer 12B form a mesh-like wiring.
  • the protective layer 13A and the blackened layer 14A may be patterned to have the same shape as the metal layer 12A, and the protective layer 13B and the blackened layer 14B may be patterned to have the same shape as the metal layer 12B. preferable.
  • 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 protective layer is provided between the metal layer and the blackened layer, for example, when the metal layer and the blackened layer are patterned in the patterning step. It can suppress that a blackening layer peels.
  • the conductive substrate obtained by the method for manufacturing the conductive substrate of the present embodiment has a metal layer
  • the electrical resistance should be lower than that of a conventional conductive substrate using ITO for the wiring layer. Can do.
  • the blackening layer is disposed, it is possible to suppress the reflection of light on the surface of the metal layer, and to suppress the deterioration of the visibility of the display when used as a conductive substrate for a touch panel, for example. Become.
  • Regular reflection by irradiating light with a wavelength of 400 nm or more and 700 nm or less at an interval of 1 nm with an incident angle of 5 ° and a light receiving angle of 5 ° on the surface of the blackened layer of the conductive substrate prepared in the following examples and comparative examples The average value was measured as the regular reflectance of the conductive substrate. (brightness) With respect to the blackened layer surface of the conductive substrate prepared in the following examples and comparative examples, light with a wavelength of 400 nm or more and 700 nm or less was emitted at intervals of 1 nm with an ultraviolet-visible spectrophotometer (model: UV-2600 manufactured by Shimadzu Corporation). The brightness was measured by irradiation.
  • Surface roughness Ra was measured about the surface which forms a protective layer among metal layers after a metal layer formation process. In addition, when the metal layer surface processing step is performed, the surface roughness Ra is measured after the metal layer surface processing step is performed.
  • the surface roughness Ra was measured using a laser microscope (manufactured by Keyence Corporation: VK9500). (Peeling test for blackened layer) The manufactured conductive substrate was subjected to a test for confirming whether the blackened layer was peeled off when etching was performed. In the test, an etching solution was sprayed on the entire surface of the blackened layer surface of the produced conductive substrate, left standing for 10 seconds, and then washed to evaluate whether the blackened layer was peeled off.
  • a cupric chloride aqueous solution having a concentration of 0.5 mol / l was used as an etchant.
  • sample preparation conditions As examples and comparative examples, conductive substrates were produced under the conditions described below and evaluated by the above-described evaluation method.
  • Example 1 Adhesion layer forming process
  • An adhesion layer was formed on one main plane of a transparent substrate made of polyethylene terephthalate resin (PET) having a length of 500 mm ⁇ width of 500 mm and a thickness of 50 ⁇ 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 Ni—Cr alloy layer containing oxygen was formed as an adhesion layer using a sputtering apparatus equipped with a Ni-17 wt% Cr alloy target. The procedure for forming the adhesion layer will be described below.
  • 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.
  • Metal layer forming process In the metal layer forming step, a metal thin film layer forming step and a metal plating layer forming step were performed.
  • a substrate in which the adhesion layer was formed on the transparent substrate in the adhesion layer forming step was used, and a copper thin film layer was formed as the metal thin film layer on the adhesion layer.
  • the metal thin film layer is a sputtering apparatus as in the case of the adhesion layer except that a copper target is used and the inside of the chamber in which the substrate is set is evacuated and then an argon gas is supplied to form an argon atmosphere. Was formed.
  • the copper thin film layer which is a metal thin film layer, was formed to a thickness of 150 nm.
  • a copper plating layer was formed as the metal plating layer.
  • the copper plating layer was formed by electroplating so that the thickness of the copper plating layer was 2.0 ⁇ m.
  • the protective layer forming step After finishing the metal layer forming step, that is, after forming the copper plating layer, when the surface roughness Ra was measured for the surface on which the protective layer was formed, it was confirmed to be 0.04 ⁇ m.
  • the protective layer forming step the protective layer was formed on the metal layer of the laminate in which the adhesion layer and the metal layer were formed on the transparent substrate.
  • the protective layer forming step first, the above laminate was immersed in a 1,2,3-benzotriazole solution for 8 seconds. And after removing the solution adhering except the upper surface (surface on the opposite side to the surface opposite to the contact
  • Blackening layer forming process In the blackening layer forming step, a Ni—Cu layer containing oxygen was formed as a blackening layer by sputtering on the protective layer formed in the protective layer forming step.
  • a Ni—Cu alloy layer containing oxygen was formed as a blackening layer by a sputtering apparatus equipped with a Ni-35 wt% Cu alloy target. The procedure for forming the blackened layer will be described below.
  • adherence layer, the metal layer, and the protective layer on the transparent base material was set in the chamber of the sputtering device.
  • a blackening layer is formed on the upper surface of the metal layer, that is, the surface opposite to the surface facing the adhesion layer of the metal layer via the protective layer, and the adhesion layer and the metal layer are formed on the transparent substrate.
  • a conductive substrate in which a protective layer and a blackening layer were laminated in that order was obtained.
  • Example 2 A conductive substrate was produced in the same manner as in Example 1 except that after the metal layer forming step and before the protective layer forming step, the surface of the metal layer was roughened as a metal layer surface processing step.
  • the metal layer surface processing step was performed after the metal layer forming step, and the metal layer surface was processed by micro roughening etching.
  • Example 2 Thereafter, in the same manner as in Example 1, a protective layer forming step and a blackening layer forming step were performed to produce a conductive substrate.
  • the obtained conductive substrate has a structure in which an adhesion layer, a metal layer, and a blackening layer are laminated in this order on a transparent base material.

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Abstract

Provided is a conductive substrate having: a transparent base; a metal layer formed on at least one surface of the transparent base; a protective layer formed on the metal layer, the protective layer containing an organic compound that includes sulfur atoms and/or nitrogen atoms; and a blackening layer formed on the protective layer.

Description

導電性基板、導電性基板の製造方法Conductive substrate, method for manufacturing conductive substrate
　本発明は、導電性基板、導電性基板の製造方法に関する。 The present invention relates to a conductive substrate and a method for manufacturing a conductive substrate.
　静電容量式タッチパネルは、パネル表面に近接する物体により引き起こされる静電容量の変化を検出することにより、パネル表面上での近接する物体の位置の情報を電気信号に変換する。静電容量式タッチパネルに用いられる導電性基板は、ディスプレイの表面に設置されるため、導電性基板の導電層の材料には反射率が低く、視認されにくいことが要求されている。 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.
　そこで、静電容量式タッチパネルに用いられる導電層の材料としては、反射率が低く、視認されにくい材料が用いられ、透明基板または透明なフィルム上に配線が形成されている。例えば、特許文献１には、高分子フィルム上に透明導電膜としてＩＴＯ（酸化インジウム－スズ）膜を形成したタッチパネル用の透明導電性フィルムが開示されている。 Therefore, as a material for the conductive layer used for the capacitive touch panel, a material having low reflectivity and not easily visible is used, and wiring is formed on a transparent substrate or a transparent film. For example, Patent Document 1 discloses 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.
　近年タッチパネルを備えたディスプレイの大画面化が進んでおり、これに対応してタッチパネル用の透明導電性フィルム等の導電性基板についても大面積化が求められている。しかし、ＩＴＯは電気抵抗値が高く信号の劣化を生じるため、大型パネルには不向きという問題があった。 In recent years, display screens equipped with a touch panel have been enlarged, and correspondingly, a conductive substrate such as a transparent conductive film for a touch panel is required to have a large area. However, since ITO has a high electric resistance value and causes signal deterioration, there is a problem that ITO is not suitable for a large panel.
　このため、例えば特許文献２、３に開示されているように導電層としてＩＴＯ膜にかえて銅等の金属箔を用いることが検討されている。しかし、例えば導電層として銅等の金属箔により構成される金属層を用いた場合、銅は金属光沢を有しているため、反射によりディスプレイの視認性が低下するという問題がある。 For this reason, for example, as disclosed in Patent Documents 2 and 3, it is considered to use a metal foil such as copper instead of the ITO film as the conductive layer. However, for example, when a metal layer composed of a metal foil such as copper is used as the conductive layer, since copper has a metallic luster, there is a problem that the visibility of the display decreases due to reflection.
　そこで、銅等の金属箔により構成される金属層と共に、金属層の上面に金属層表面での光の反射を抑制できる材料により構成される黒化層を形成した導電性基板が検討されている。 Therefore, a conductive substrate in which a black layer formed of a material capable of suppressing light reflection on the surface of the metal layer is formed on the upper surface of the metal layer together with a metal layer formed of a metal foil such as copper has been studied. .
日本国特開２００３－１５１３５８号公報Japanese Unexamined Patent Publication No. 2003-151358 日本国特開２０１１－０１８１９４号公報Japanese Unexamined Patent Publication No. 2011-018194 日本国特開２０１３－０６９２６１号公報Japanese Unexamined Patent Publication No. 2013-0669261
　しかしながら金属層の上面に黒化層を形成した場合に金属層と黒化層との密着性が十分ではなく、金属層や黒化層をパターニングする際に黒化層が剥離する場合があるという問題があった。 However, when the blackened layer is formed on the upper surface of the metal layer, the adhesion between the metal layer and the blackened layer is not sufficient, and the blackened layer may peel off when patterning the metal layer or the blackened layer. There was a problem.
　上記従来技術の問題に鑑み、本発明の一側面では、黒化層が剥離することを抑制した導電性基板を提供することを目的とする。 In view of the above-described problems of the prior art, an object of one aspect of the present invention is to provide a conductive substrate in which the blackened layer is prevented from peeling off.
　上記課題を解決するため本発明の一側面では、
　透明基材と、
　前記透明基材の少なくとも一方の面上に形成された金属層と、
　金属層上に形成され、硫黄原子および／または窒素原子を含む有機化合物を含有する保護層と、
　前記保護層上に形成された黒化層と、を有する導電性基板を提供する。 In order to solve the above problems, in one aspect of the present invention,
A transparent substrate;
A metal layer formed on at least one surface of the transparent substrate;
A protective layer formed on the metal layer and containing an organic compound containing a sulfur atom and / or a nitrogen atom;
There is provided a conductive substrate having a blackening layer formed on the protective layer.
　本発明の一側面によれば、黒化層が剥離することを抑制した導電性基板を提供することができる。 According to one aspect of the present invention, it is possible to provide a conductive substrate in which the blackened layer is prevented from peeling off.
従来の導電性基板において黒化層が剥離するメカニズムの説明模式図。The explanatory schematic diagram of the mechanism in which the blackening layer peels in the conventional conductive substrate. 従来の導電性基板において黒化層が剥離するメカニズムの説明模式図。The explanatory schematic diagram of the mechanism in which the blackening layer peels in the conventional conductive substrate. 本発明の実施形態に係る導電性基板の構成説明図。The structure explanatory view of the conductive substrate concerning the embodiment of the present invention. 本発明の実施形態に係る導電性基板の構成説明図。The structure explanatory view of the conductive substrate concerning the embodiment of the present invention.
　以下、本発明の導電性基板、及び導電性基板の製造方法の一実施形態について説明する。
（導電性基板）
　本実施形態の導電性基板は、透明基材と、透明基材の少なくとも一方の面上に形成された金属層と、金属層上に形成され、硫黄原子および／または窒素原子を含む有機化合物を含有する保護層と、保護層上に形成された黒化層と、を有することができる。 Hereinafter, an embodiment of a conductive substrate and a method for manufacturing the conductive substrate of the present invention will be described.
(Conductive substrate)
The conductive substrate of the present embodiment includes a transparent substrate, a metal layer formed on at least one surface of the transparent substrate, and an organic compound formed on the metal layer and containing sulfur atoms and / or nitrogen atoms. It can have a protective layer to be contained and a blackening layer formed on the protective layer.
　なお、本実施形態における導電性基板とは、金属層等をパターニングする前の、透明基材の表面に金属層、保護層、及び黒化層を有する基板と、金属層等をパターン化した基板、すなわち、配線基板と、を含む。金属層、保護層、及び黒化層をパターニングした後の導電性基板は透明基材が金属層等により覆われていない領域を含むため光を透過することができ、透明導電性基板となっている。 The conductive substrate in the present embodiment is a substrate having a metal layer, a protective layer, and a blackened layer on the surface of the transparent base material before patterning the metal layer, and a substrate obtained by patterning the metal layer. That is, the wiring board is included. Since the conductive substrate after patterning the metal layer, the protective layer, and the blackening layer includes a region where the transparent base material is not covered with the metal layer or the like, it can transmit light and becomes a transparent conductive substrate. Yes.
　ここでまず、導電性基板に含まれる各部材について以下に説明する。 Here, first, each member included in the conductive substrate will be described below.
　透明基材としては特に限定されるものではなく、可視光を透過する樹脂基板（樹脂フィルム）や、ガラス基板等を好ましく用いることができる。 The transparent substrate is not particularly limited, and a resin substrate (resin film) that transmits visible light, a glass substrate, or the like can be preferably used.
　可視光を透過する樹脂基板の材料としては例えば、ポリアミド系樹脂、ポリエチレンテレフタレート系樹脂、ポリエチレンナフタレート系樹脂、シクロオレフィン系樹脂、ポリイミド系樹脂、ポリカーボネート系樹脂等の樹脂を好ましく用いることができる。特に、可視光を透過する樹脂基板の材料として、ＰＥＴ（ポリエチレンテレフタレート）、ＣＯＰ（シクロオレフィンポリマー）、ＰＥＮ（ポリエチレンナフタレート）、ポリイミド、ポリカーボネート等をより好ましく用いることができる。 As a material for the resin substrate that transmits visible light, for example, a resin such as a polyamide resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, a cycloolefin resin, a polyimide resin, or a polycarbonate resin can be preferably used. In particular, PET (polyethylene terephthalate), COP (cycloolefin polymer), PEN (polyethylene naphthalate), polyimide, polycarbonate, and the like can be more preferably used as the material for the resin substrate that transmits visible light.
　透明基材の厚さについては特に限定されず、導電性基板とした場合に要求される強度や静電容量、光の透過率等に応じて任意に選択することができる。透明基材の厚さとしては例えば１０μｍ以上２００μｍ以下とすることができる。特にタッチパネルの用途に用いる場合、透明基材の厚さは２０μｍ以上１２０μｍ以下とすることが好ましく、２０μｍ以上１００μｍ以下とすることがより好ましい。タッチパネルの用途に用いる場合で、例えば特にディスプレイ全体の厚さを薄くすることが求められる用途においては、透明基材の厚さは２０μｍ以上５０μｍ以下であることが好ましい。 The thickness of the transparent base material is not particularly limited, and can be arbitrarily selected according to the strength, capacitance, light transmittance, and the like required for a conductive substrate. The thickness of the transparent substrate can be, for example, 10 μm or more and 200 μm or less. In particular, when used for touch panel applications, the thickness of the transparent substrate is preferably 20 μm or more and 120 μm or less, and more preferably 20 μm or more and 100 μm or less. In the case of use for touch panel applications, for example, particularly in applications where it is required to reduce the thickness of the entire display, the thickness of the transparent substrate is preferably 20 μm or more and 50 μm or less.
　透明基材の全光線透過率は高い方が好ましく、例えば全光線透過率は３０％以上であることが好ましく、６０％以上であることがより好ましい。透明基材の全光線透過率が上記範囲であることにより、例えばタッチパネルの用途に用いた場合にディスプレイの視認性を十分に確保することができる。 The total light transmittance of the transparent substrate is preferably higher. For example, the total light transmittance is preferably 30% or more, and more preferably 60% or more. When the total light transmittance of the transparent substrate is in the above range, the visibility of the display can be sufficiently ensured when used for, for example, a touch panel.
　なお透明基材の全光線透過率はＪＩＳ　Ｋ　７３６１－１に規定される方法により評価することができる。 Note that the total light transmittance of the transparent substrate can be evaluated by the method defined in JIS K 7361-1.
　透明基材は第１の主平面と、第２の主平面とを有することができる。なお、ここでいう主平面とは透明基材に含まれる面のうち最も面積の大きい平面部を指している。そして、第１の主平面と、第２の主平面とは１つの透明基材の中で対向して配置された面を意味する。第２の主平面は、１つの透明基材の中で、第１の主平面の反対側に位置する面ということもできる。 The transparent substrate can have a first main plane and a second main plane. In addition, the main plane here refers to the plane part with the largest area among the surfaces contained in a transparent base material. And a 1st main plane and a 2nd main plane mean the surface arrange | positioned facing in one transparent base material. The second main plane can also be referred to as a plane located on the opposite side of the first main plane in one transparent substrate.
　次に、金属層について説明する。 Next, the metal layer will be described.
　金属層を構成する材料は特に限定されず用途にあった電気伝導率を有する材料を選択できるが、例えば、金属層を構成する材料は、Ｃｕと、Ｎｉ，Ｍｏ，Ｔａ，Ｔｉ，Ｖ，Ｃｒ，Ｆｅ，Ｍｎ，Ｃｏ，Ｗから選ばれる少なくとも１種の以上の金属との銅合金、または銅を含む材料であることが好ましい。また、金属層は銅から構成される銅層とすることもできる。 Although the material which comprises a metal layer is not specifically limited, The material which has the electrical conductivity according to the application can be selected, For example, the material which comprises a metal layer is Cu, Ni, Mo, Ta, Ti, V, Cr , Fe, Mn, Co and W are preferably a copper alloy with at least one metal selected from the group consisting of copper, or a material containing copper. The metal layer can be a copper layer made of copper.
　透明基材上に金属層を形成する方法は特に限定されないが、光の透過率を低減させないため、透明基材と金属層との間に接着剤を配置しないことが好ましい。すなわち金属層は、透明基材の少なくとも一方の面上に直接形成されていることが好ましい。なお、後述のように透明基材と金属層との間に密着層を配置する場合には、密着層の上面に直接形成されていることが好ましい。 Although the method for forming the metal layer on the transparent substrate is not particularly limited, it is preferable not to dispose an adhesive between the transparent substrate and the metal layer in order not to reduce the light transmittance. That is, the metal layer is preferably formed directly on at least one surface of the transparent substrate. In addition, when arrange | positioning an adhesion layer between a transparent base material and a metal layer like the after-mentioned, it is preferable to form directly on the upper surface of an adhesion layer.
　透明基材の上面に金属層を直接形成するため、金属層は金属薄膜層を有することが好ましい。また、金属層は金属薄膜層と金属めっき層とを有していてもよい。 In order to directly form the metal layer on the upper surface of the transparent substrate, the metal layer preferably has a metal thin film layer. Moreover, the metal layer may have a metal thin film layer and a metal plating layer.
　例えば透明基材上に、乾式めっき法により金属薄膜層を形成し該金属薄膜層を金属層とすることができる。これにより、透明基材上に接着剤を介さずに直接金属層を形成できる。なお、乾式めっき法としては後で詳述するが、例えばスパッタリング法や蒸着法、イオンプレーティング法等を好ましく用いることができる。 For example, a metal thin film layer can be formed on a transparent substrate by a dry plating method, and the metal thin film layer can be used as a metal layer. Thereby, a metal layer can be directly formed on the transparent substrate without using an adhesive. The dry plating method will be described in detail later. For example, a sputtering method, a vapor deposition method, an ion plating method, or the like can be preferably used.
　また、金属層の膜厚を厚くする場合には、金属薄膜層を給電層として湿式めっき法の一種である電気めっき法により金属めっき層を形成することにより、金属薄膜層と金属めっき層とを有する金属層とすることもできる。金属層が金属薄膜層と金属めっき層とを有することにより、この場合も透明基材上に接着剤を介さずに直接金属層を形成できる。 In addition, when increasing the thickness of the metal layer, the metal thin film layer and the metal plating layer are formed by forming the metal plating layer by electroplating, which is a kind of wet plating method, using the metal thin film layer as a power feeding layer. It can also be a metal layer. Since the metal layer has the metal thin film layer and the metal plating layer, the metal layer can be directly formed on the transparent substrate without using an adhesive.
　金属層の厚さは特に限定されるものではなく、金属層を配線として用いた場合に、該配線に供給する電流の大きさや配線幅等に応じて任意に選択することができる。 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.
　ただし、金属層が厚くなると、配線パターンを形成するためにエッチングを行う際にエッチングに時間を要するためサイドエッチが生じ易くなり、細線が形成しにくくなる等の問題を生じる場合がある。このため、金属層の厚さは５μｍ以下であることが好ましく、３μｍ以下であることがより好ましい。 However, if the metal layer is thick, it takes time to perform etching to form a wiring pattern, so that side etching is likely to occur, and it may be difficult to form fine lines. For this reason, the thickness of the metal layer is preferably 5 μm or less, and more preferably 3 μm or less.
　また、特に導電性基板の抵抗値を低くし、十分に電流を供給できるようにする観点から、例えば金属層は厚さが５０ｎｍ以上であることが好ましく、６０ｎｍ以上であることがより好ましく、１５０ｎｍ以上であることがさらに好ましい。 In particular, from the viewpoint of reducing the resistance value of the conductive substrate and supplying a sufficient current, for example, 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.
　なお、金属層が上述のように金属薄膜層と、金属めっき層を有する場合には、金属薄膜層の厚さと、金属めっき層の厚さとの合計が上記範囲であることが好ましい。 In addition, when 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.
　金属層が金属薄膜層により構成される場合、または金属薄膜層と金属めっき層とにより構成される場合のいずれの場合でも、金属薄膜層の厚さは特に限定されるものではないが、例えば５０ｎｍ以上５００ｎｍ以下とすることが好ましい。 In any case where the metal layer is composed of a metal thin film layer or a metal thin film layer and a metal plating layer, the thickness of the metal thin film layer is not particularly limited. The thickness is preferably 500 nm or more.
　金属層は後述するように例えば所望の配線パターンにパターニングすることにより配線として用いることができる。そして、金属層は従来透明導電膜として用いられていたＩＴＯよりも電気抵抗値を低くすることができるから、金属層を設けることにより導電性基板の電気抵抗値を小さくできる。 As described later, the metal layer can be used as a wiring by patterning it into a desired wiring pattern, for example. And since a metal layer can make an electrical resistance value lower than ITO conventionally used as a transparent conductive film, the electrical resistance value of an electroconductive board | substrate can be made small by providing a metal layer.
　また、本実施形態の導電性基板においては、後述する保護層を配置することにより、パターニングを行う際に黒化層が金属層から剥離することを抑制することができる。特に、保護層を介して金属層と黒化層との密着性をさらに高め、黒化層が剥離することをさらに抑制することができるように、金属層の保護層と対向する面の表面粗さＲａは０．０３μｍ以上０．０８μｍ以下であることが好ましい。 Moreover, in the conductive substrate of this embodiment, by disposing a protective layer to be described later, it is possible to suppress the blackening layer from peeling off from the metal layer during patterning. In particular, the surface roughness of the surface of the metal layer facing the protective layer can be further improved through the protective layer so that the adhesion between the metal layer and the blackened layer can be further increased and the blackened layer can be further prevented from peeling. The thickness Ra is preferably 0.03 μm or more and 0.08 μm or less.
　なお、ここでの表面粗さＲａは、ＪＩＳ　Ｂ　０６０１に規定されており、測定方法としては、例えば触針法もしくは光学的方法等により評価することができる。 The surface roughness Ra here is defined in JIS B 0601 and can be evaluated by, for example, a stylus method or an optical method.
　金属層の保護層と対向する面の表面粗さＲａを上述の範囲とする方法は特に限定されるものではなく、任意の方法を選択することができる。例えば成膜条件により粗面の金属層を形成する方法、または、平滑な金属層を成膜後、金属層の保護層と対向する面をサンドブラストや、マイクロ粗化エッチング等により粗化処理を施す方法により、所望の表面粗さＲａとすることができる。 The method of setting the surface roughness Ra of the surface of the metal layer facing the protective layer within the above range is not particularly limited, and any method can be selected. For example, a method of forming a rough metal layer according to film forming conditions, or after forming a smooth metal layer, the surface of the metal layer facing the protective layer is roughened by sandblasting, micro roughening etching, or the like. A desired surface roughness Ra can be obtained by the method.
　次に保護層について説明する。 Next, the protective layer will be described.
　保護層は金属層上に形成することができ、硫黄原子および／または窒素原子を含む有機化合物を含有することができる。 The protective layer can be formed on the metal layer and can contain an organic compound containing a sulfur atom and / or a nitrogen atom.
　本発明の発明者らは、従来の導電性基板において金属層や黒化層をパターニングする際に黒化層が剥離する原因について検討を行った。 The inventors of the present invention have studied the cause of peeling of the blackened layer when patterning the metal layer or blackened layer on a conventional conductive substrate.
　本発明の発明者らの検討によると、まず図１Ａに示すように、金属層１上に黒化層２を形成した従来の導電性基板においては、黒化層２に微細な孔３が含まれていた。そして、パターニングのため黒化層２の表面にエッチング液を供給した際、図１Ｂに示すように黒化層２に含まれる微細な孔３からエッチング液が金属層１表面まで浸透し金属層１表面が溶解して金属層１と黒化層２との間に隙間４が形成される場合があった。このため、金属層１と黒化層２とが接触する面積が小さくなり、金属層１と黒化層２との密着性が著しく低下し、金属層１から黒化層２が剥離する場合があったと考えられる。 According to the study of the inventors of the present invention, as shown in FIG. 1A, in the conventional conductive substrate in which the blackened layer 2 is formed on the metal layer 1, the blackened layer 2 includes the fine holes 3 first. It was. When the etching solution is supplied to the surface of the blackening layer 2 for patterning, the etching solution penetrates from the fine holes 3 included in the blackening layer 2 to the surface of the metal layer 1 as shown in FIG. 1B. In some cases, the surface melts and a gap 4 is formed between the metal layer 1 and the blackened layer 2. For this reason, the contact area between the metal layer 1 and the blackening layer 2 is reduced, the adhesion between the metal layer 1 and the blackening layer 2 is significantly reduced, and the blackening layer 2 may be peeled off from the metal layer 1. It is thought that there was.
　これに対して本実施形態の導電性基板においては、金属層と、黒化層との間に保護層を配置することにより、保護層を介して金属層と黒化層との密着性を図１Ａ、図１Ｂに示した従来の導電性基板の構成よりも高められていると考えられる。このため、金属層から黒化層が剥離することを抑制することが可能になる。 On the other hand, in the conductive substrate of the present embodiment, the protective layer is disposed between the metal layer and the blackened layer, thereby improving the adhesion between the metal layer and the blackened layer via the protective layer. It is considered that the height is higher than that of the conventional conductive substrate shown in FIGS. 1A and 1B. For this reason, it becomes possible to suppress that a blackening layer peels from a metal layer.
　保護層の材料としては特に限定されるものではなく、エッチングの際に、金属層から黒化層が剥離することを抑制できる材料であれば特に限定されることなく使用することができる。保護層の材料としては例えば、硫黄原子および／または窒素原子を含む有機化合物を好ましく用いることができる。保護層は硫黄原子および／または窒素原子を含む有機化合物を含むことが好ましく、上述の硫黄原子および／または窒素原子を含む有機化合物から構成されていることがより好ましい。 The material for the protective layer is not particularly limited, and any material can be used without particular limitation as long as it can prevent the blackened layer from peeling off from the metal layer during etching. As the material for the protective layer, for example, an organic compound containing a sulfur atom and / or a nitrogen atom can be preferably used. The protective layer preferably contains an organic compound containing a sulfur atom and / or a nitrogen atom, and more preferably is composed of the above-described organic compound containing a sulfur atom and / or a nitrogen atom.
　硫黄原子および／または窒素原子を含む有機化合物としては限定されるものではないが例えば、ベンゾトリアゾール系化合物、メルカプトベンゾチアゾール系化合物、イミダゾール系化合物、アミン類等を好ましく用いることができる。 Although it does not limit as an organic compound containing a sulfur atom and / or a nitrogen atom, For example, a benzotriazole type compound, a mercaptobenzothiazole type compound, an imidazole type compound, amines etc. can be used preferably.
　ベンゾトリアゾール系化合物としては例えば、１，２，３－ベンゾトリアゾール（化学式１）や、１－［Ｎ,Ｎ－ビス（２－エチルヘキシル）アミノメチル］ベンゾトリアゾール（化学式２）、カルボキシベンゾトリアゾール（化学式３）、１－［Ｎ,Ｎ－ビス（２－エチルヘキシル）アミノメチル］メチルベンゾトリアゾール（化学式４）、２，２'－［［（メチル－１Ｈ－ベンゾトリアゾール－１－イル）メチル］イミノ］ビスエタノール（化学式５）、１，２，３－ベンゾトリアゾールナトリウム塩水溶液（化学式６）、トリルトリアゾール（５－メチル１Ｈ－ベンゾトリアゾール）、トリルトリアゾールナトリウム塩等を好ましく用いることができる。 Examples of the benzotriazole compounds include 1,2,3-benzotriazole (Chemical Formula 1), 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole (Chemical Formula 2), carboxybenzotriazole (Chemical Formula) 3) 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole (Formula 4), 2,2 ′-[[(Methyl-1H-benzotriazol-1-yl) methyl] imino] Bisethanol (chemical formula 5), 1,2,3-benzotriazole sodium salt aqueous solution (chemical formula 6), tolyltriazole (5-methyl 1H-benzotriazole), tolyltriazole sodium salt and the like can be preferably used.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
 　また、イミダゾール系化合物としては例えば、アルキルイミダゾールや、ベンゾイミダゾール、アリルフェニルイミダゾール等を好ましく用いることができる。
Figure JPOXMLDOC01-appb-C000006
 Moreover, as an imidazole compound, for example, alkylimidazole, benzimidazole, allylphenylimidazole, or the like can be preferably used.
　特に、硫黄原子および／または窒素原子を含む有機化合物としてはベンゾトリアゾール系化合物をより好ましく用いることができる。すなわち、保護層はベンゾトリアゾール系化合物を含有することがより好ましい。 In particular, a benzotriazole-based compound can be more preferably used as the organic compound containing a sulfur atom and / or a nitrogen atom. That is, it is more preferable that the protective layer contains a benzotriazole-based compound.
　次に黒化層について説明する。 Next, the blackened layer will be described.
　黒化層は、保護層の上面に形成することができる。 The blackened layer can be formed on the upper surface of the protective layer.
　黒化層の材料は特に限定されるものではなく、金属層表面における光の反射を抑制できる材料であれば好適に用いることができる。 The material of the blackening layer is not particularly limited, and any material that can suppress the reflection of light on the surface of the metal layer can be suitably used.
　黒化層は例えば、Ｎｉ，Ｚｎ，Ｍｏ，Ｔａ，Ｔｉ，Ｖ，Ｃｒ，Ｆｅ，Ｃｏ，Ｗ，Ｃｕ，Ｓｎ，Ｍｎから選ばれる少なくとも１種以上の金属を含むことが好ましい。また、黒化層は、炭素、酸素、水素、窒素から選ばれる１種以上の元素をさらに含むことができる。 The blackening 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. Further, the blackening layer can further contain one or more elements selected from carbon, oxygen, hydrogen, and nitrogen.
　なお、黒化層は、Ｎｉ，Ｚｎ，Ｍｏ，Ｔａ，Ｔｉ，Ｖ，Ｃｒ，Ｆｅ，Ｃｏ，Ｗ，Ｃｕ，Ｓｎ，Ｍｎから選ばれる少なくとも２種以上の金属を含む金属合金を含むことができる。この場合についても、黒化層は炭素、酸素、水素、窒素から選ばれる１種以上の元素をさらに含むこともできる。この際、Ｎｉ，Ｚｎ，Ｍｏ，Ｔａ，Ｔｉ，Ｖ，Ｃｒ，Ｆｅ，Ｃｏ，Ｗ，Ｃｕ，Ｓｎ，Ｍｎから選ばれる少なくとも２種以上の金属を含む金属合金としては、Ｃｕ－Ｔｉ－Ｆｅ合金や、Ｃｕ－Ｎｉ－Ｆｅ合金、Ｎｉ－Ｃｕ合金、Ｎｉ－Ｚｎ合金、Ｎｉ－Ｔｉ合金、Ｎｉ－Ｗ合金、Ｎｉ－Ｃｒ合金、Ｎｉ－Ｃｕ－Ｃｒ合金を好ましく用いることができる。 The blackening layer can 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 blackening layer may further contain one or more elements selected from carbon, oxygen, hydrogen, and nitrogen. At this time, 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. In addition, a Cu—Ni—Fe alloy, Ni—Cu alloy, Ni—Zn alloy, Ni—Ti alloy, Ni—W alloy, Ni—Cr alloy, and Ni—Cu—Cr alloy can be preferably used.
　黒化層の形成方法は特に限定されるものではなく、任意の方法により形成することができ、例えば乾式法、または湿式法により成膜することができる。 The method for forming the blackened layer is not particularly limited, and can be formed by any method, for example, by a dry method or a wet method.
　黒化層を乾式法により成膜する場合、その具体的な方法は特に限定されるものではないが、例えばスパッタリング法、イオンプレーティング法や蒸着法等の乾式めっき法を好ましく用いることができる。黒化層を乾式法により成膜する場合、膜厚の制御が容易であることから、スパッタリング法を用いることがより好ましい。なお、黒化層には上述のように炭素、酸素、水素、窒素から選ばれる１種以上の元素を添加することができ、この場合は反応性スパッタリング法をさらに好ましく用いることができる。 When the blackening layer is formed by a dry method, the specific method is not particularly limited, but for example, a dry plating method such as a sputtering method, an ion plating method or a vapor deposition method can be preferably used. When the blackening layer is formed by a dry method, it is more preferable to use a sputtering method because the film thickness can be easily controlled. As described above, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the blackened layer, and in this case, the reactive sputtering method can be more preferably used.
　反応性スパッタリング法により黒化層を成膜する場合、ターゲットとしては、黒化層を構成する金属種を含むターゲットを用いることができる。黒化層が合金を含む場合には、黒化層に含まれる金属種毎にターゲットを用い、基材等の被成膜体の表面で合金を形成してもよく、予め黒化層に含まれる金属を合金化したターゲットを用いることもできる。 When forming the blackened layer by the reactive sputtering method, a target containing a metal species constituting the blackened layer can be used as the target. When the blackened layer contains an alloy, a target may be used for each metal species contained in the blackened layer, and the alloy may be formed on the surface of the film-deposited body such as a substrate, and is included in the blackened layer in advance. It is also possible to use a target obtained by alloying a metal.
　また、黒化層に炭素、酸素、水素、窒素から選ばれる１種以上の元素が含まれる場合、これらは黒化層を成膜する際の雰囲気中に添加しておくことにより、黒化層中に添加することができる。例えば、黒化層に炭素を添加する場合には一酸化炭素ガスおよび／または二酸化炭素ガスを、酸素を添加する場合には酸素ガスを、水素を添加する場合には水素ガスおよび／または水を、窒素を添加する場合には窒素ガスを、スパッタリングを行う際の雰囲気中に添加しておくことができる。黒化層を成膜する際の不活性ガス中にこれらのガスを添加することにより、炭素、酸素、水素、窒素から選ばれる１種以上の元素を黒化層中に添加することができる。なお、不活性ガスとしてはアルゴンを好ましく用いることができる。 Further, when the blackened layer contains one or more elements selected from carbon, oxygen, hydrogen, and nitrogen, these are added to the atmosphere when the blackened layer is formed, so that the blackened layer Can be added inside. For example, when adding carbon to the blackening layer, carbon monoxide gas and / or carbon dioxide gas is used, when adding oxygen, oxygen gas is used, and when adding hydrogen, hydrogen gas and / or water is used. In the case of adding nitrogen, nitrogen gas can be added to the atmosphere during sputtering. One or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the blackening layer by adding these gases to the inert gas when forming the blackening layer. Argon can be preferably used as the inert gas.
　黒化層を湿式法により成膜する場合には、黒化層の材料に応じためっき液を用い、例えば電気めっき法により成膜することができる。 When the blackened layer is formed by a wet method, it can be formed by, for example, an electroplating method using a plating solution corresponding to the material of the blackened layer.
　黒化層の厚さは特に限定されるものではないが、例えば１５ｎｍ以上であることが好ましく、２５ｎｍ以上であることがより好ましい。これは、黒化層の厚さが薄い場合には、金属層表面における光の反射を十分に抑制できない場合があるため、上述のように黒化層の厚さを１５ｎｍ以上とすることにより金属層表面における光の反射を特に抑制できるように構成することが好ましいためである。 The thickness of the blackening layer is not particularly limited, but is preferably 15 nm or more, for example, and more preferably 25 nm or more. This is because when the thickness of the blackened layer is thin, reflection of light on the surface of the metal layer may not be sufficiently suppressed. Therefore, the thickness of the blackened layer is set to 15 nm or more as described above. This is because it is preferable to configure so that reflection of light on the surface of the layer can be particularly suppressed.
　黒化層の厚さの上限値は特に限定されるものではないが、必要以上に厚くしても成膜に要する時間や、配線を形成する際のエッチングに要する時間が長くなり、コストの上昇を招くことになる。このため、黒化層の厚さは７０ｎｍ以下とすることが好ましく、５０ｎｍ以下とすることがより好ましい。 The upper limit of the thickness of the blackening 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. For this reason, the thickness of the blackened layer is preferably 70 nm or less, and more preferably 50 nm or less.
　本実施形態の導電性基板においては、黒化層を配置することにより、上述のように金属層表面における光の反射を抑制することができる。このため、例えばタッチパネル等の用途に用いた場合にディスプレイの視認性の低下を抑制することが可能になる。 In the conductive substrate of this embodiment, the reflection of light on the surface of the metal layer can be suppressed by arranging the blackened layer as described above. For this reason, when it uses for uses, such as a touch panel, for example, it becomes possible to suppress the fall of the visibility of a display.
　また、導電性基板は上述の透明基材、金属層、保護層、黒化層以外に任意の層を設けることもできる。例えば密着層を設けることができる。 Also, the conductive substrate can be provided with any layer other than the above-mentioned transparent base material, metal layer, protective layer, and blackening layer. For example, an adhesion layer can be provided.
　密着層の構成例について説明する。 A configuration example of the adhesion layer will be described.
　上述のように金属層は透明基材上に形成することができるが、透明基材上に金属層を直接形成した場合に、透明基材と金属層との密着性は十分ではない場合がある。このため、透明基材の上面に直接金属層を形成した場合、製造過程、または、使用時に透明基材から金属層が剥離する場合がある。 As described above, 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.
　そこで、本実施形態の導電性基板においては、透明基材と金属層との密着性を高めるため、透明基材上に密着層を配置することができる。 Therefore, in the conductive substrate of the present embodiment, an adhesion layer can be disposed on the transparent substrate in order to improve the adhesion between the transparent substrate and the metal layer.
　透明基材と金属層との間に密着層を配置することにより、透明基材と金属層との密着性を高め、透明基材から金属層が剥離することを抑制できる。 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.
　また、密着層は黒化層としても機能させることができる。このため、金属層の下面側、すなわち透明基材側からの光による金属層の光の反射も抑制することが可能になる。 Also, 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 base material side.
　密着層を構成する材料は特に限定されるものではなく、透明基材及び金属層との密着力や、要求される金属層表面での光の反射の抑制の程度、また、導電性基板を使用する環境（例えば湿度や、温度）に対する安定性の程度等に応じて任意に選択することができる。 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).
　密着層は例えば、Ｎｉ，Ｚｎ，Ｍｏ，Ｔａ，Ｔｉ，Ｖ，Ｃｒ，Ｆｅ，Ｃｏ，Ｗ，Ｃｕ，Ｓｎ，Ｍｎから選ばれる少なくとも１種以上の金属を含むことが好ましい。また、密着層は炭素、酸素、水素、窒素から選ばれる１種以上の元素をさらに含むことができる。 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 can further contain one or more elements selected from carbon, oxygen, hydrogen, and nitrogen.
　なお、密着層は、Ｎｉ，Ｚｎ，Ｍｏ，Ｔａ，Ｔｉ，Ｖ，Ｃｒ，Ｆｅ，Ｃｏ，Ｗ，Ｃｕ，Ｓｎ，Ｍｎから選ばれる少なくとも２種以上の金属を含む金属合金を含むことができる。この場合についても、密着層は炭素、酸素、水素、窒素から選ばれる１種以上の元素をさらに含むこともできる。この際、Ｎｉ，Ｚｎ，Ｍｏ，Ｔａ，Ｔｉ，Ｖ，Ｃｒ，Ｆｅ，Ｃｏ，Ｗ，Ｃｕ，Ｓｎ，Ｍｎから選ばれる少なくとも２種以上の金属を含む金属合金としては、Ｃｕ－Ｔｉ－Ｆｅ合金や、Ｃｕ－Ｎｉ－Ｆｅ合金、Ｎｉ－Ｃｕ合金、Ｎｉ－Ｚｎ合金、Ｎｉ－Ｔｉ合金、Ｎｉ－Ｗ合金、Ｎｉ－Ｃｒ合金、Ｎｉ－Ｃｕ－Ｃｒ合金を好ましく用いることができる。 Note that the adhesion layer can include a metal alloy including 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. At this time, 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. In addition, a Cu—Ni—Fe alloy, Ni—Cu alloy, Ni—Zn alloy, Ni—Ti alloy, Ni—W alloy, Ni—Cr alloy, and Ni—Cu—Cr alloy can be preferably used.
　密着層の成膜方法は特に限定されるものではないが、乾式めっき法により成膜することが好ましい。乾式めっき法としては例えばスパッタリング法、イオンプレーティング法や蒸着法等を好ましく用いることができる。密着層を乾式法により成膜する場合、膜厚の制御が容易であることから、スパッタリング法を用いることがより好ましい。なお、密着層には上述のように炭素、酸素、水素、窒素から選ばれる１種以上の元素を添加することもでき、この場合は反応性スパッタリング法をさらに好ましく用いることができる。 The method for forming the adhesion layer is not particularly limited, but it is preferable to form the film by a dry plating method. As the dry plating method, for example, a sputtering method, an ion plating method, a vapor deposition method, or the like can be preferably used. In the case where 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. Note that, as described above, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the adhesion layer, and in this case, a reactive sputtering method can be more preferably used.
　密着層が炭素、酸素、水素、窒素から選ばれる１種以上の元素を含む場合には、密着層を成膜する際の雰囲気中に炭素、酸素、水素、窒素から選ばれる１種以上の元素を含有するガスを添加しておくことにより、密着層中に添加することができる。例えば、密着層に炭素を添加する場合には一酸化炭素ガスおよび／または二酸化炭素ガスを、酸素を添加する場合には酸素ガスを、水素を添加する場合には水素ガスおよび／または水を、窒素を添加する場合には窒素ガスを、乾式めっきを行う際の雰囲気中に添加しておくことができる。 When the adhesion layer contains 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. For example, when adding carbon 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, In the case of adding nitrogen, nitrogen gas can be added to the atmosphere when dry plating is performed.
　炭素、酸素、水素、窒素から選ばれる１種以上の元素を含有するガスは、不活性ガスに添加し、乾式めっきの際の雰囲気ガスとすることが好ましい。不活性ガスとしては特に限定されないが、例えばアルゴンを好ましく用いることができる。 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. Although it does not specifically limit as an inert gas, For example, argon can be used preferably.
　密着層を上述のように乾式めっき法により成膜することにより、透明基材と密着層との密着性を高めることができる。そして、密着層は例えば金属を主成分として含むことができるため金属層との密着性も高い。このため、透明基材と金属層との間に密着層を配置することにより、金属層の剥離を抑制することができる。 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 | positioning an adhesion layer between a transparent base material and a metal layer.
　密着層の厚さは特に限定されるものではないが、例えば３ｎｍ以上５０ｎｍ以下とすることが好ましく、３ｎｍ以上３５ｎｍ以下とすることがより好ましく、３ｎｍ以上３３ｎｍ以下とすることがさらに好ましい。 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.
　密着層についても黒化層として機能させる場合、すなわち金属層における光の反射を抑制する場合、密着層の厚さを上述のように３ｎｍ以上とすることが好ましい。 When the adhesion layer also functions as a blackening layer, that is, when light reflection in the metal layer is suppressed, the thickness of the adhesion layer is preferably 3 nm or more as described above.
　密着層の厚さの上限値は特に限定されるものではないが、必要以上に厚くしても成膜に要する時間や、配線を形成する際のエッチングに要する時間が長くなり、コストの上昇を招くことになる。このため、密着層の厚さは上述のように５０ｎｍ以下とすることが好ましく、３５ｎｍ以下とすることがより好ましく、３３ｎｍ以下とすることがさらに好ましい。 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. For this reason, 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.
　次に、導電性基板の構成例について説明する。 Next, a configuration example of the conductive substrate will be described.
　上述のように、本実施形態の導電性基板は透明基材と、金属層と、保護層と、黒化層と、を備え、透明基材上に、金属層、保護層、黒化層をその順で積層した構成とすることができる。 As described above, the conductive substrate of the present embodiment includes a transparent base material, a metal layer, a protective layer, and a blackening layer, and the metal layer, the protective layer, and the blackening layer are provided on the transparent base material. It can be set as the structure laminated | stacked in the order.
　具体的な構成例について、図２Ａ、図２Ｂを用いて以下に説明する。図２Ａ、図２Ｂは、本実施形態の導電性基板の、透明基材、金属層、黒化層の積層方向と平行な面における断面図の例を示している。 Specific configuration examples will be described below with reference to FIGS. 2A and 2B. 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.
　例えば、図２Ａに示した導電性基板１０Ａのように、透明基材１１の第１の主平面１１ａ側に金属層１２と、保護層１３と、黒化層１４と、を一層ずつその順に積層した構成とすることができる。また、図２Ｂに示した導電性基板１０Ｂのように、透明基材１１の第１の主平面１１ａ側と、第２の主平面１１ｂ側と、にそれぞれ金属層１２Ａ、１２Ｂと、保護層１３Ａ、１３Ｂと、黒化層１４Ａ、１４Ｂを一層ずつその順に積層することもできる。 For example, like the conductive substrate 10A shown in FIG. 2A, the metal layer 12, the protective layer 13, and the blackening layer 14 are laminated one by one on the first main plane 11a side of the transparent substrate 11. Can be configured. Further, like the conductive substrate 10B shown in FIG. 2B, the metal layers 12A and 12B and the protective layer 13A are respectively formed on the first main plane 11a side and the second main plane 11b side of the transparent base material 11. , 13B and the blackening layers 14A, 14B can be stacked one by one in that order.
　本実施形態の導電性基板においては上述のように、金属層１２（１２Ａ、１２Ｂ）の上面に保護層１３（１３Ａ、１３Ｂ）を介して黒化層１４（１４Ａ、１４Ｂ）を配置している。このため、金属層１２（１２Ａ、１２Ｂ）の上面側からの光の反射を抑制することができる。また、保護層１３（１３Ａ、１３Ｂ）を配置したため、黒化層１４（１４Ａ、１４Ｂ）が剥離することを抑制することができる。 In the conductive substrate of this embodiment, as described above, the blackening layer 14 (14A, 14B) is disposed on the upper surface of the metal layer 12 (12A, 12B) via the protective layer 13 (13A, 13B). . For this reason, reflection of the light from the upper surface side of the metal layer 12 (12A, 12B) can be suppressed. Moreover, since the protective layer 13 (13A, 13B) is disposed, the blackening layer 14 (14A, 14B) can be prevented from peeling off.
　また、既述のように例えば透明基材１１と金属層１２との間には図示しない密着層を設けることもできる。なお、図２Ｂに示した導電性基板１０Ｂの場合、透明基材１１と金属層１２Ａとの間、および／または透明基材１１と金属層１２Ｂとの間に密着層を設けることができる。密着層を設けることにより、透明基材１１と金属層１２（１２Ａ、１２Ｂ）との密着性を高めることができ、透明基材１１から金属層１２（１２Ａ、１２Ｂ）が剥離することを特に抑制することができる。また、密着層を設けることにより、金属層１２（１２Ａ、１２Ｂ）の黒化層を設けていない面についても光の反射を抑制することが可能になり好ましい。 Further, as described above, for example, an adhesion layer (not shown) can be provided between the transparent substrate 11 and the metal layer 12. In the case of the conductive substrate 10B shown in FIG. 2B, an adhesion layer can be provided between the transparent base material 11 and the metal layer 12A and / or between the transparent base material 11 and the metal layer 12B. By providing the adhesion layer, the adhesion between the transparent substrate 11 and the metal layer 12 (12A, 12B) can be improved, and the metal layer 12 (12A, 12B) is particularly prevented from peeling from the transparent substrate 11. can do. In addition, it is preferable to provide an adhesion layer because the reflection of light can be suppressed even on the surface of the metal layer 12 (12A, 12B) where the blackening layer is not provided.
　本実施形態の導電性基板は例えばタッチパネル等の各種用途に用いることができる。そして、各種用途に用いる場合には、本実施形態の導電性基板に含まれる、金属層、保護層、及び黒化層がパターン化されていることが好ましい。金属層、保護層、及び黒化層は、例えば所望の配線パターンにあわせてパターン化することができ、金属層、保護層、及び黒化層は同じ形状にパターン化することが好ましい。 The conductive substrate of this 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, protective layer, and blackening layer which are contained in the electroconductive board | substrate of this embodiment are patterned. The metal layer, the protective layer, and the blackened layer can be patterned in accordance with, for example, a desired wiring pattern, and the metal layer, the protective layer, and the blackened layer are preferably patterned in the same shape.
　なお、密着層を設けた場合、金属層、保護層、及び黒化層をパターン化する際、密着層についても所望の配線パターンにあわせてパターン化することができる。このため、密着層を設けた場合、密着層、金属層、保護層、及び黒化層を同じ形状にパターン化することが好ましい。 When the adhesion layer is provided, when the metal layer, the protective layer, and the blackening layer are patterned, the adhesion layer can be patterned in accordance with a desired wiring pattern. For this reason, when an adhesion layer is provided, it is preferable to pattern the adhesion layer, the metal layer, the protective layer, and the blackening layer in the same shape.
　上述のように、金属層等を所望の形状にパターニングすることができるが、この際形成するパターンは特に限定されるものではなく、任意の形状とすることができる。例えば導電性基板がメッシュ状の配線を有するようにパターンを形成することが好ましい。この場合、配線を構成する金属層を、所望のメッシュ状の配線を構成するようにパターニングすることができ、保護層、黒化層等も同様の形状にパターニングすることができる。 As described above, the metal layer or the like can be patterned into a desired shape, but the pattern to be formed at this time is not particularly limited, and can be an arbitrary shape. For example, the pattern is preferably formed so that the conductive substrate has mesh-like wiring. In this case, the metal layer constituting the wiring can be patterned so as to constitute a desired mesh-like wiring, and the protective layer, the blackening layer, and the like can be patterned in the same shape.
　メッシュ状の配線を有する導電性基板とする方法は特に限定されるものではない。 The method for forming a conductive substrate having mesh-like wiring is not particularly limited.
　例えば、図２Ａに示した導電性基板を用いてメッシュ状の配線を形成する場合、２枚の導電性基板を積層し、積層導電性基板とすることによりメッシュ状の配線を形成することができる。この場合、例えばまず各導電性基板について、直線状や、ジグザグ状等の複数の線状の配線パターンを、一方向に沿って、互いに離隔するように形成することができる。そして、２枚の導電性基板の積層方向上面側から見た場合に、一方の導電性基板に形成した配線パターンと、他方の導電性基板に形成した配線パターンとが、交差するように積層することにより、メッシュ状の配線パターンを構成することができる。なお、積層した導電性基板は例えば接着剤等により固定することができる。 For example, when forming a mesh-like wiring using the conductive substrate shown in FIG. 2A, a mesh-like wiring can be formed by stacking two conductive substrates to form a laminated conductive substrate. . In this case, for example, for each conductive substrate, a plurality of linear wiring patterns such as a linear shape or a zigzag shape can be formed so as to be separated from each other along one direction. Then, when viewed from the upper surface side in the stacking direction of the two conductive substrates, the wiring pattern formed on one conductive substrate and the wiring pattern formed on the other conductive substrate are stacked so as to intersect each other. Thus, a mesh-like wiring pattern can be configured. The laminated conductive substrate can be fixed with an adhesive or the like, for example.
　また、例えば図２Ｂにおいて、第１の主平面１１ａ側に形成した金属層１２Ａと、第２の主平面１１ｂ側に形成した金属層１２Ｂとをそれぞれ所定の形状にパターニングし、メッシュ状の配線を形成することもできる。この場合も金属層１２Ａ、１２Ｂの形状にあわせて、保護層１３Ａ、１３Ｂ、黒化層１４Ａ，１４Ｂ、場合によっては密着層もパターニングしておくことが好ましい。 Further, for example, in FIG. 2B, the metal layer 12A formed on the first main plane 11a side and the metal layer 12B formed on the second main plane 11b side are respectively patterned into predetermined shapes, and mesh-like wiring is formed. It can also be formed. Also in this case, it is preferable to pattern the protective layers 13A and 13B, the blackening layers 14A and 14B, and in some cases, the adhesion layer in accordance with the shapes of the metal layers 12A and 12B.
　金属層等をパターニングする方法は特に限定されるものではなく、例えば、黒化層１４（１４Ａ、１４Ｂ）の上面に、形成するパターンに対応した形状を有するマスクを配置した後、エッチング処理を行うことによりパターニングできる。 The method for patterning the metal layer or the like is not particularly limited. For example, after a mask having a shape corresponding to the pattern to be formed is placed on the upper surface of the blackened layer 14 (14A, 14B), an etching process is performed. Can be patterned.
　用いるエッチング液は特に限定されるものではなく、エッチングする層を構成する材料に応じて任意に選択することができる。例えば、層毎にエッチング液を変えることもでき、また、同じエッチング液により同時に金属層、及び黒化層、場合によってはさらに密着層をエッチングすることもできる。 The etching solution to be used is not particularly limited, and can be arbitrarily selected according to the material constituting the layer to be etched. For example, the etching solution can be changed for each layer, and the metal layer and the blackening layer, and in some cases, the adhesion layer can be etched simultaneously with the same etching solution.
　本実施形態の導電性基板の光の反射の程度については特に限定されるものではないが、例えば波長４００ｎｍ以上７００ｎｍ以下の光の正反射率（反射率）は３５％以下であることが好ましく、３０％以下であることがより好ましい。波長４００ｎｍ以上７００ｎｍ以下の光の反射率が３５％以下の場合、例えばタッチパネル用の導電性基板として用いた場合でもディスプレイの視認性の低下をほとんど引き起こさないため好ましい。 Although the degree of light reflection of the conductive substrate of the present embodiment is not particularly limited, for example, the regular reflectance (reflectance) of light having a wavelength of 400 nm to 700 nm is preferably 35% or less, More preferably, it is 30% or less. When the reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 35% or less, for example, even when used as a conductive substrate for a touch panel, the display visibility is hardly lowered, which is preferable.
　反射率の測定は、黒化層１４（１４Ａ、１４Ｂ）に光を照射するようにして測定を行うことができる。 The reflectance can be measured by irradiating the blackened layer 14 (14A, 14B) with light.
　具体的には例えば図２Ａのように透明基材１１の第１の主平面１１ａ側に金属層１２、保護層１３、黒化層１４の順に積層した場合、黒化層１４に光を照射するように、黒化層１４の表面１４ａ側から光を照射し、測定できる。測定に当たっては波長４００ｎｍ以上７００ｎｍ以下の光を例えば波長１ｎｍ間隔で上述のように導電性基板の黒化層１４の表面１４ａに対して照射して正反射率を測定し、測定した値の平均値を該導電性基板の正反射率とすることができる。 Specifically, for example, when the metal layer 12, the protective layer 13, and the blackened layer 14 are laminated in this order on the first main plane 11a side of the transparent substrate 11 as shown in FIG. 2A, the blackened layer 14 is irradiated with light. Thus, it can measure by irradiating light from the surface 14a side of the blackened layer 14. In the measurement, light having a wavelength of 400 nm to 700 nm is irradiated on the surface 14a of the blackened layer 14 of the conductive substrate at a wavelength of 1 nm, for example, as described above, and the regular reflectance is measured. Can be the regular reflectance of the conductive substrate.
　また、本実施形態の導電性基板の黒化層１４（１４Ａ、１４Ｂ）の表面については、Ｌ＊ａ＊ｂ＊表色系のうちの明度（Ｌ＊）の数値が小さいことが好ましい。これは明度（Ｌ＊）の数値が小さくなるほど黒化層１４（１４Ａ、１４Ｂ）及び保護層１３（１３Ａ、１３Ｂ）、金属層１２（１２Ａ、１２Ｂ）が目立たなくなるためである。黒化層１４（１４Ａ、１４Ｂ）の表面の明度（Ｌ＊）は７０以下であることが好ましい。 In addition, regarding the surface of the blackening layer 14 (14A, 14B) of the conductive substrate of the present embodiment, it is preferable that the value of lightness (L * ) in the L * a * b * color system is small. This is because the blackening layer 14 (14A, 14B), the protective layer 13 (13A, 13B), and the metal layer 12 (12A, 12B) become less conspicuous as the value of the lightness (L * ) decreases. The lightness (L * ) of the surface of the blackened layer 14 (14A, 14B) is preferably 70 or less.
　そして、本実施形態の導電性基板においては上述のように金属層１２（１２Ａ、１２Ｂ）を設けていることから、導電性基板の表面抵抗を小さくすることができる。表面抵抗は、０．２Ω／□未満であることが好ましく、０．１０Ω／□未満であることがより好ましい。表面抵抗の測定方法は特に限定されないが、例えば、４探針法により測定することができ、導電性基板の表面、例えば黒化層表面に探針が接触するようにして測定を行うことが好ましい。
（導電性基板の製造方法）
　次に本実施形態の導電性基板の製造方法の一構成例について説明する。 And since the metal layer 12 (12A, 12B) is provided in the electroconductive board | substrate of this embodiment as mentioned above, the surface resistance of an electroconductive board | substrate can be made small. The surface resistance is preferably less than 0.2Ω / □, and more preferably less than 0.10Ω / □. The method for measuring the surface resistance is not particularly limited. For example, it can be measured by a four-probe method, and it is preferable to perform the measurement so that the probe contacts the surface of the conductive substrate, for example, the blackened layer surface. .
(Method for producing conductive substrate)
Next, a configuration example of the method for manufacturing the conductive substrate according to this embodiment will be described.
　本実施形態の導電性基板の製造方法は、以下の工程を有することができる。　
　透明基材の少なくとも一方の面上に金属層を形成する金属層形成工程。　
　金属層上に硫黄原子および／または窒素原子を含む有機化合物を含有する保護層を形成する保護層形成工程。　
　保護層上に黒化層を形成する黒化層形成工程。 The manufacturing method of the conductive substrate of this embodiment can have the following processes.
A metal layer forming step of forming a metal layer on at least one surface of the transparent substrate.
A protective layer forming step of forming a protective layer containing an organic compound containing a sulfur atom and / or a nitrogen atom on the metal layer.
A blackening layer forming step of forming a blackening layer on the protective layer.
　以下に本実施形態の導電性基板の製造方法について具体的に説明する。 Hereinafter, the manufacturing method of the conductive substrate of the present embodiment will be specifically described.
　なお、本実施形態の導電性基板の製造方法により上述の導電性基板を好適に製造することができる。このため、以下に説明する点以外については上述の導電性基板の場合と同様の構成とすることができるため説明を省略する。 In addition, the above-mentioned electroconductive board | substrate can be suitably manufactured with the manufacturing method of the electroconductive board | substrate of this embodiment. For this reason, since it can be set as the structure similar to the case of the above-mentioned electroconductive board | substrate except the point demonstrated below, description is abbreviate | omitted.
　金属層形成工程に供する透明基材は予め準備しておくことができる。用いる透明基材の種類は特に限定されるものではないが、既述のように可視光を透過する樹脂基板（樹脂フィルム）や、ガラス基板等を好ましく用いることができる。透明基材は必要に応じて予め任意のサイズに切断等行っておくこともできる。 The transparent base material used for the metal layer forming step can be prepared in advance. Although the kind of transparent base material to be used is not particularly limited, a resin substrate (resin film) that transmits visible light, a glass substrate, or the like can be preferably used as described above. The transparent base material can be cut into an arbitrary size in advance if necessary.
　そして、金属層は既述のように、金属薄膜層を有することが好ましい。また、金属層は金属薄膜層と金属めっき層とを有することもできる。このため、金属層形成工程は、例えば乾式めっき法により金属薄膜層を形成する工程を有することができる。また、金属層形成工程は、乾式めっき法により金属薄膜層を形成する工程と、該金属薄膜層を給電層として、湿式めっき法の一種である電気めっき法により金属めっき層を形成する工程と、を有していてもよい。 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. For this reason, 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.
　金属薄膜層を形成する工程で用いる乾式めっき法としては、特に限定されるものではなく、例えば、蒸着法、スパッタリング法、又はイオンプレーティング法等を用いることができる。なお、蒸着法としては真空蒸着法を好ましく用いることができる。金属薄膜層を形成する工程で用いる乾式めっき法としては、特に膜厚の制御が容易であることから、スパッタリング法を用いることがより好ましい。 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. In addition, as a vapor deposition method, a vacuum vapor deposition method can be used preferably. As 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.
　次に金属めっき層を形成する工程について説明する。湿式めっき法により金属めっき層を形成する工程における条件、すなわち、電気めっき処理の条件は、特に限定されるものではなく、常法による諸条件を採用すればよい。例えば、金属めっき液を入れためっき槽に金属薄膜層を形成した基材を供給し、電流密度や、基材の搬送速度を制御することによって、金属めっき層を形成できる。 Next, the process for forming the metal plating layer will be described. 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. For example, 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.
　次に、保護層形成工程について説明する。 Next, the protective layer forming step will be described.
　保護層形成工程においては、金属層上に保護層を形成することができる。 In the protective layer forming step, a protective layer can be formed on the metal layer.
　既述のように、保護層は金属層や黒化層等をパターニングする際に、黒化層が金属層から剥離することを抑制することができる。 As described above, the protective layer can suppress the peeling of the blackened layer from the metal layer when the metal layer, the blackened layer, or the like is patterned.
　保護層の形成方法は特に限定されるものではないが、例えば保護層を構成する材料を含む溶液を金属層上に塗布、乾燥することにより形成することができる。 The method for forming the protective layer is not particularly limited. For example, the protective layer can be formed by applying a solution containing a material constituting the protective layer on the metal layer and drying it.
　金属層上に保護層を構成する材料を含む溶液を塗布する方法としては特に限定されるものではなく、任意の方法により塗布することができる。例えば、スプレーや浸漬により金属層上に保護層を構成する材料を含む溶液を塗布することができる。 The method for applying the solution containing the material constituting the protective layer on the metal layer is not particularly limited, and can be applied by any method. For example, a solution containing a material constituting the protective layer can be applied on the metal layer by spraying or dipping.
　保護層の材料としては特に限定されるものではなく、エッチングの際に、金属層から黒化層が剥離することを抑制できる材料であれば特に限定されることなく使用することができる。保護層の材料としては例えば、硫黄原子および／または窒素原子を含む有機化合物を好ましく用いることができる。保護層は硫黄原子および／または窒素原子を含む有機化合物を含むことが好ましく、上述の硫黄原子および／または窒素原子を含む有機化合物から構成されていることがより好ましい。 The material for the protective layer is not particularly limited, and any material can be used without particular limitation as long as it can prevent the blackened layer from peeling off from the metal layer during etching. As the material for the protective layer, for example, an organic compound containing a sulfur atom and / or a nitrogen atom can be preferably used. The protective layer preferably contains an organic compound containing a sulfur atom and / or a nitrogen atom, and more preferably is composed of the above-described organic compound containing a sulfur atom and / or a nitrogen atom.
　硫黄原子および／または窒素原子を含む有機化合物としては限定されるものではないが例えば、ベンゾトリアゾール系化合物、メルカプトベンゾチアゾール系化合物、イミダゾール系化合物、アミン類等を好ましく用いることができる。特に、硫黄原子および／または窒素原子を含む有機化合物としてはベンゾトリアゾール系化合物をより好ましく用いることができる。すなわち、保護層はベンゾトリアゾール系化合物を含有することがより好ましい。保護層で好適に用いることができるベンゾトリアゾール系化合物等については既述のため、説明を省略する。 Although it does not limit as an organic compound containing a sulfur atom and / or a nitrogen atom, For example, a benzotriazole type compound, a mercaptobenzothiazole type compound, an imidazole type compound, amines etc. can be used preferably. In particular, a benzotriazole-based compound can be more preferably used as the organic compound containing a sulfur atom and / or a nitrogen atom. That is, it is more preferable that the protective layer contains a benzotriazole-based compound. Description of benzotriazole compounds that can be suitably used in the protective layer is omitted because they have already been described.
　次に、黒化層形成工程について説明する。 Next, the blackening layer forming process will be described.
　黒化層形成工程において、黒化層を形成する方法は特に限定されるものではなく、任意の方法により形成することができる。 In the blackened layer forming step, the method for forming the blackened layer is not particularly limited, and can be formed by any method.
　黒化層形成工程において黒化層を形成する際、例えばスパッタリング法、イオンプレーティング法や蒸着法等の乾式めっき法を好ましく用いることができる。特に、膜厚の制御が容易であることから、スパッタリング法を用いることがより好ましい。 When forming the blackened layer in the blackened layer forming step, for example, a dry plating method such as a sputtering method, an ion plating method or a vapor deposition method can be preferably used. In particular, the sputtering method is more preferable because the film thickness can be easily controlled.
　また、既述のように黒化層は電気めっき法等の湿式法により成膜することもできる。 Further, as described above, the blackened layer can be formed by a wet method such as an electroplating method.
　本実施形態の導電性基板の製造方法においては、上述の工程に加えてさらに任意の工程を実施することもできる。 In the method for manufacturing a conductive substrate according to the present embodiment, an optional step can be further performed in addition to the above-described steps.
　例えば透明基材と金属層との間に密着層を形成する場合、透明基材の金属層を形成する面上に密着層を形成する密着層形成工程を実施することができる。密着層形成工程を実施する場合、金属層形成工程は、密着層形成工程の後に実施することができ、金属層形成工程で説明した金属薄膜層を成膜する基材とは、本工程で透明基材上に密着層を形成した基材となる。 For example, when forming an adhesion layer between a transparent substrate and a metal layer, 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. When carrying out the adhesion layer forming step, the metal layer forming step can be carried out after the adhesion layer forming step, and is transparent in this step with the substrate on which the metal thin film layer described in the metal layer forming step is formed. The base material has an adhesion layer formed on the base material.
　密着層は例えば図２Ａにおいて、透明基材１１の一方の主平面である第１の主平面１１ａ上に形成することができる。また、図２Ｂに示した導電性基板１０Ｂの場合、透明基材１１の第１の主平面１１ａおよび／または第２の主平面１１ｂに密着層を形成することもできる。透明基材１１の第１の主平面１１ａ及び第２の主平面１１ｂの両方に密着層を形成する場合には、両主平面に同時に密着層を形成してもよい。また、いずれか一方の主平面に密着層を形成後に他方の主平面に密着層を形成してもよい。 The adhesion layer can be formed, for example, on the first main plane 11a which is one main plane of the transparent substrate 11 in FIG. 2A. In the case of the conductive substrate 10B shown in FIG. 2B, an adhesion layer can be formed on the first main plane 11a and / or the second main plane 11b of the transparent substrate 11. In the case where an adhesion layer is formed on both the first main plane 11a and the second main plane 11b of the transparent substrate 11, the adhesion layer may be formed simultaneously on both main planes. In addition, after the adhesion layer is formed on one of the main planes, the adhesion layer may be formed on the other main plane.
　密着層を構成する材料は特に限定されるものではなく、透明基材及び金属層との密着力や、金属層表面での光の反射の抑制の程度、また、導電性基板を使用する環境（例えば湿度や、温度）に対する安定性の程度等に応じて任意に選択することができる。密着層を構成する材料として好適に用いることができる材料については既述のため、ここでは説明を省略する。 The material constituting the adhesion layer is not particularly limited, the adhesion strength with the transparent substrate and the metal layer, the degree of suppression of light reflection on the surface of the metal layer, and the environment in which the conductive substrate is used ( For example, it can be arbitrarily selected according to the degree of stability with respect to humidity and temperature. Since materials that can be suitably used as the material constituting the adhesion layer have already been described, description thereof is omitted here.
　密着層の成膜方法は特に限定されないが、例えば上述のように、乾式めっき法により成膜することができる。乾式めっき法としては例えばスパッタリング法、イオンプレーティング法や蒸着法等を好ましく用いることができる。密着層を乾式法により成膜する場合、膜厚の制御が容易であることから、スパッタリング法を用いることがより好ましい。なお、密着層には上述のように炭素、酸素、水素、窒素から選ばれる１種以上の元素も添加することができ、この場合は反応性スパッタリング法をさらに好ましく用いることができる。 The method for forming the adhesion layer is not particularly limited. For example, as described above, the adhesion layer can be formed by a dry plating method. As the dry plating method, for example, a sputtering method, an ion plating method, a vapor deposition method, or the like can be preferably used. In the case where 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. Note that, as described above, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the adhesion layer, and in this case, a reactive sputtering method can be more preferably used.
　なお、密着層が炭素、酸素、水素、窒素から選ばれる１種以上の元素を含む場合には、密着層を成膜する際の雰囲気中に炭素、酸素、水素、窒素から選ばれる１種以上の元素を含有するガスを添加しておくことにより、密着層中に添加することができる。例えば、密着層に炭素を添加する場合には一酸化炭素ガスおよび／または二酸化炭素ガスを、酸素を添加する場合には酸素ガスを、水素を添加する場合には水素ガスおよび／または水を、窒素を添加する場合には窒素ガスを、乾式めっきを行う際の雰囲気中に添加しておくことができる。 In the case where the adhesion layer contains one or more elements selected from carbon, oxygen, hydrogen, and nitrogen, one or more selected from carbon, oxygen, hydrogen, and nitrogen in the atmosphere when forming the adhesion layer By adding a gas containing these elements, it can be added to the adhesion layer. For example, when adding carbon 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, In the case of adding nitrogen, nitrogen gas can be added to the atmosphere when dry plating is performed.
　炭素、酸素、水素、窒素から選ばれる１種以上の元素を含有するガスは、不活性ガスに添加し、乾式めっきの際の雰囲気ガスとすることが好ましい。不活性ガスとしては特に限定されないが、例えばアルゴンを好ましく用いることができる。 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. Although it does not specifically limit as an inert gas, For example, argon can be used preferably.
　反応性スパッタリング法により密着層を成膜する場合、ターゲットとしては、密着層を構成する金属種を含むターゲットを用いることができる。密着層が合金を含む場合には、密着層に含まれる金属種毎にターゲットを用い、透明基材等の被成膜体の表面で合金を形成してもよく、予め密着層に含まれる金属を合金化したターゲットを用いることもできる。 When the adhesion layer is formed by the reactive sputtering method, a target containing a metal species constituting the adhesion layer can be used as the target. When the adhesion layer contains an alloy, a target may be used for each metal species contained in the adhesion layer, and the alloy may be formed on the surface of the film-formed body such as a transparent substrate. An alloyed target can also be used.
　密着層を上述のように乾式めっき法により成膜することにより、透明基材と密着層との密着性を高めることができる。そして、密着層は例えば金属を主成分として含むことができるため金属層との密着性も高い。このため、透明基材と金属層との間に密着層を配置することにより、金属層の剥離を抑制することができる。 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 | positioning an adhesion layer between a transparent base material and a metal layer.
　密着層の厚さは特に限定されるものではないが、例えば３ｎｍ以上５０ｎｍ以下とすることが好ましく、３ｎｍ以上３５ｎｍ以下とすることがより好ましく、３ｎｍ以上３３ｎｍ以下とすることがさらに好ましい。 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.
　また、金属層の保護層を形成する面（金属層の保護層と対向する面）について所定の表面粗さＲａとなるように、金属層表面に加工する金属層表面加工工程を実施することもできる。 In addition, a metal layer surface processing step for processing the surface of the metal layer so that the surface of the metal layer on which the protective layer is formed (the surface facing the protective layer of the metal layer) has a predetermined surface roughness Ra may be performed. it can.
　具体的には例えば、金属層形成工程後、保護層形成工程を実施する前に、金属層の保護層を形成する面の表面粗さＲａを０．０３μｍ以上０．０８μｍ以下とする金属層表面加工工程を実施することができる。 Specifically, for example, after the metal layer forming step and before the protective layer forming step, the surface of the metal layer on which the protective layer is formed has a surface roughness Ra of 0.03 μm or more and 0.08 μm or less. Processing steps can be performed.
　金属層の保護層を形成する面の表面粗さＲａを上述の範囲とする方法は特に限定されるものではなく、任意の方法を選択することができる。例えば成膜条件により粗面の金属層を形成する方法、または、平滑な金属層を成膜後、金属層の保護層と対向する面をサンドブラストや、マイクロ粗化エッチング等により粗化処理を施す方法を好ましく用いることができる。 The method of setting the surface roughness Ra of the surface on which the protective layer of the metal layer is formed is not particularly limited, and any method can be selected. For example, a method of forming a rough metal layer according to film forming conditions, or after forming a smooth metal layer, the surface of the metal layer facing the protective layer is roughened by sandblasting, micro roughening etching, or the like. The method can be preferably used.
　なお、図２Ｂに示したように透明基材１１の第１の主平面１１ａ及び第２の主平面１１ｂに金属層１２Ａ、１２Ｂを形成した場合、金属層１２Ａ、及び金属層１２Ｂのうち、いずれか一方のみについて保護層を形成する面の表面を上述の表面粗さＲａとしてもよい。また、両方の金属層１２Ａ、１２Ｂについて、保護層１３Ａ、１３Ｂを形成する面の表面を上述の表面粗さＲａとしてもよい。 As shown in FIG. 2B, when the metal layers 12A and 12B are formed on the first main plane 11a and the second main plane 11b of the transparent substrate 11, any of the metal layer 12A and the metal layer 12B Only the surface of the surface on which the protective layer is formed may be the above-described surface roughness Ra. Moreover, it is good also considering the surface of the surface which forms protective layer 13A, 13B as above-mentioned surface roughness Ra about both metal layer 12A, 12B.
　本実施形態の導電性基板の製造方法で得られる導電性基板は例えばタッチパネル等の各種用途に用いることができる。そして、各種用途に用いる場合には、本実施形態の導電性基板に含まれる金属層、保護層、及び黒化層がパターン化されていることが好ましい。なお、密着層を設ける場合は、密着層についてもパターン化されていることが好ましい。金属層、保護層、及び黒化層、場合によってはさらに密着層は、例えば所望の配線パターンにあわせてパターン化することができ、金属層、保護層、及び黒化層、場合によってはさらに密着層は同じ形状にパターン化されていることが好ましい。 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, protective layer, and blackening layer which are contained in the electroconductive board | substrate of this embodiment are patterned. In addition, when providing an adhesion layer, it is preferable that the adhesion layer is also patterned. The metal layer, the protective layer, and the blackening layer, and in some cases, the adhesion layer can be patterned in accordance with, for example, a desired wiring pattern. The metal layer, the protection layer, and the blackening layer, and in some cases, further adhesion The layers are preferably patterned in the same shape.
　このため、本実施形態の導電性基板の製造方法は、金属層、保護層及び黒化層をパターニングするパターニング工程を有することができる。なお、密着層を形成した場合には、パターニング工程は、密着層、金属層、保護層、及び黒化層をパターニングする工程とすることができる。 For this reason, the manufacturing method of the conductive substrate of the present embodiment can include a patterning step of patterning the metal layer, the protective layer, and the blackening layer. When the adhesion layer is formed, the patterning step can be a step of patterning the adhesion layer, the metal layer, the protective layer, and the blackening layer.
　パターニング工程の具体的手順は特に限定されるものではなく、任意の手順により実施することができる。例えば図２Ａのように透明基材１１上に金属層１２、保護層１３、黒化層１４が積層された導電性基板１０Ａの場合、まず黒化層１４上に所望のパターンを有するマスクを配置するマスク配置工程を実施することができる。次いで、黒化層１４の上面、すなわち、マスクを配置した面側にエッチング液を供給するエッチング工程を実施できる。 The specific procedure of the patterning step is not particularly limited, and can be performed by an arbitrary procedure. For example, in the case of the conductive substrate 10A in which the metal layer 12, the protective layer 13, and the blackened layer 14 are laminated on the transparent substrate 11 as shown in FIG. 2A, a mask having a desired pattern is first placed on the blackened layer 14. A mask placement step can be performed. Next, an etching step of supplying an etching solution to the upper surface of the blackening layer 14, that is, the surface side where the mask is disposed can be performed.
　エッチング工程において用いるエッチング液は特に限定されるものではなく、エッチングを行う層を構成する材料に応じて任意に選択することができる。例えば、層毎にエッチング液を変えることもでき、また、同じエッチング液により同時に金属層、保護層、及び黒化層、場合によってはさらに密着層をエッチングすることもできる。 The etching solution used in the etching step is not particularly limited, and can be arbitrarily selected depending on the material constituting the layer to be etched. For example, the etching solution can be changed for each layer, and the metal layer, the protective layer, and the blackening layer, and in some cases, the adhesion layer can be etched simultaneously with the same etching solution.
　また、図２Ｂのように透明基材１１の第１の主平面１１ａ、第２の主平面１１ｂに金属層１２Ａ、１２Ｂ、保護層１３Ａ、１３Ｂ、黒化層１４Ａ、１４Ｂを積層した導電性基板１０Ｂについてもパターニングするパターニング工程を実施できる。この場合例えば黒化層１４Ａ、１４Ｂ上に所望のパターンを有するマスクを配置するマスク配置工程を実施できる。次いで、黒化層１４Ａ、１４Ｂの上面、すなわち、マスクを配置した面側にエッチング液を供給するエッチング工程を実施できる。 Further, as shown in FIG. 2B, the conductive substrate in which the metal layers 12A and 12B, the protective layers 13A and 13B, and the blackening layers 14A and 14B are stacked on the first main plane 11a and the second main plane 11b of the transparent substrate 11. A patterning process for patterning 10B can also be performed. In this case, for example, a mask placement step of placing a mask having a desired pattern on the blackening layers 14A and 14B can be performed. Next, an etching step of supplying an etching solution to the upper surfaces of the blackening layers 14A and 14B, that is, the surface side where the mask is disposed can be performed.
　エッチング工程で形成するパターンについては特に限定されるものではなく、任意の形状とすることができる。例えば図２Ａに示した導電性基板１０Ａの場合、既述のように金属層１２、保護層１３、及び黒化層１４を複数の直線や、ぎざぎざに屈曲した線（ジグザグ直線）を含むようにパターンを形成することができる。 The pattern formed in the etching process is not particularly limited and can be an arbitrary shape. For example, in the case of the conductive substrate 10A shown in FIG. 2A, as described above, the metal layer 12, the protective layer 13, and the blackening layer 14 include a plurality of straight lines or jagged lines (zigzag straight lines). A pattern can be formed.
　また、図２Ｂに示した導電性基板１０Ｂの場合、金属層１２Ａと、金属層１２Ｂとでメッシュ状の配線となるようにパターンを形成することができる。この場合、保護層１３Ａ、及び黒化層１４Ａは、金属層１２Ａと同様の形状に、保護層１３Ｂ、及び黒化層１４Ｂは金属層１２Ｂと同様の形状になるようにそれぞれパターニングを行うことが好ましい。 Further, in the case of the conductive substrate 10B shown in FIG. 2B, a pattern can be formed so that the metal layer 12A and the metal layer 12B form a mesh-like wiring. In this case, the protective layer 13A and the blackened layer 14A may be patterned to have the same shape as the metal layer 12A, and the protective layer 13B and the blackened layer 14B may be patterned to have the same shape as the metal layer 12B. preferable.
　また、例えばパターニング工程で上述の導電性基板１０Ａについて金属層１２等をパターン化した後、パターン化した２枚以上の導電性基板を積層する積層工程を実施することもできる。積層する際、例えば各導電性基板の金属層のパターンが交差するように積層することにより、メッシュ状の配線を備えた積層導電性基板を得ることもできる。 Further, for example, after the metal layer 12 and the like are patterned on the above-described conductive substrate 10A in the patterning step, a lamination step of laminating two or more patterned conductive substrates may be performed. When 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.
　積層した２枚以上の導電性基板を固定する方法は特に限定されるものではないが、例えば接着剤等により固定することができる。 The method of fixing two or more laminated conductive substrates is not particularly limited, but can be fixed by, for example, an adhesive.
　以上の本実施形態の導電性基板の製造方法によれば、金属層と黒化層との間に保護層を設けた為、例えばパターニング工程において、金属層、及び黒化層をパターニングする際に黒化層が剥離することを抑制できる。 According to the conductive substrate manufacturing method of the present embodiment described above, since the protective layer is provided between the metal layer and the blackened layer, for example, when the metal layer and the blackened layer are patterned in the patterning step. It can suppress that a blackening layer peels.
　さらに、本実施形態の導電性基板の製造方法により得られる導電性基板については、金属層を有しているため、配線層にＩＴＯを使用した従来の導電性基板よりも電気抵抗を低くすることができる。また、黒化層を配置しているため、金属層表面における光の反射を抑制し、例えばタッチパネル用の導電性基板として用いた場合にディスプレイの視認性が低下することを抑制することが可能になる。 Furthermore, since the conductive substrate obtained by the method for manufacturing the conductive substrate of the present embodiment has a metal layer, the electrical resistance should be lower than that of a conventional conductive substrate using ITO for the wiring layer. Can do. Moreover, since the blackening layer is disposed, it is possible to suppress the reflection of light on the surface of the metal layer, and to suppress the deterioration of the visibility of the display when used as a conductive substrate for a touch panel, for example. Become.
　以下に具体的な実施例、比較例を挙げて説明するが、本発明はこれらの実施例に限定されるものではない。
（評価方法）
　まず、得られた導電性基板の評価方法について説明する。 Specific examples and comparative examples will be described below, but the present invention is not limited to these examples.
(Evaluation methods)
First, a method for evaluating the obtained conductive substrate will be described.
　（表面抵抗）
　低抵抗率計（株式会社ダイアインスツルメンツ製　型番：ロレスターＥＰ　ＭＣＰ－Ｔ３６０）を用いて、以下の実施例、比較例で作製した導電性基板の表面抵抗を測定した。測定は４探針法により行い、導電性基板を作製後、黒化層に探針が接触するようにして測定を行った。 (Surface resistance)
Using a low resistivity meter (model number: Lorester EP MCP-T360, manufactured by Dia Instruments Co., Ltd.), the surface resistance of the conductive substrates produced in the following examples and comparative examples was measured. The measurement was performed by a four-probe method, and after making a conductive substrate, the measurement was performed so that the probe was in contact with the blackened layer.
　（正反射率）
　測定は、紫外可視分光光度計（株式会社　島津製作所製　型式：ＵＶ－２６００）に反射率測定ユニットを設置して行った。 (Regular reflectance)
The measurement was performed by installing a reflectance measurement unit in an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model number: UV-2600).
　以下の実施例、比較例で作製した導電性基板の黒化層表面に対して、入射角５°、受光角５°として、波長４００ｎｍ以上７００ｎｍ以下の光を波長１ｎｍ間隔で照射して正反射率を測定し、その平均値を該導電性基板の正反射率とした。
（明度）
　以下の実施例、比較例で作製した導電性基板の黒化層表面について、紫外可視分光光度計（株式会社　島津製作所製　型式：ＵＶ－２６００）により波長４００ｎｍ以上７００ｎｍ以下の光を波長１ｎｍ間隔で照射して明度を測定した。
（表面粗さＲａ）
　金属層形成工程後に、金属層のうち、保護層を形成する面について表面粗さＲａを測定した。なお、金属層表面加工工程を実施した場合には、金属層表面加工工程を実施した後に表面粗さＲａの測定を実施している。 Regular reflection by irradiating light with a wavelength of 400 nm or more and 700 nm or less at an interval of 1 nm with an incident angle of 5 ° and a light receiving angle of 5 ° on the surface of the blackened layer of the conductive substrate prepared in the following examples and comparative examples The average value was measured as the regular reflectance of the conductive substrate.
(brightness)
With respect to the blackened layer surface of the conductive substrate prepared in the following examples and comparative examples, light with a wavelength of 400 nm or more and 700 nm or less was emitted at intervals of 1 nm with an ultraviolet-visible spectrophotometer (model: UV-2600 manufactured by Shimadzu Corporation). The brightness was measured by irradiation.
(Surface roughness Ra)
Surface roughness Ra was measured about the surface which forms a protective layer among metal layers after a metal layer formation process. In addition, when the metal layer surface processing step is performed, the surface roughness Ra is measured after the metal layer surface processing step is performed.
　表面粗さＲａはレーザー顕微鏡（株式会社キーエンス製　型式：ＶＫ９５００）を用いて測定を行った。
（黒化層の剥離試験）
　作製した導電性基板について、エッチングを行う際に黒化層に剥離が生じるかを確認する試験を実施した。試験は、作製した導電性基板の黒化層表面の全面にエッチング液を噴射し、１０秒間放置した後洗浄し、黒化層の剥離の有無を評価した。 The surface roughness Ra was measured using a laser microscope (manufactured by Keyence Corporation: VK9500).
(Peeling test for blackened layer)
The manufactured conductive substrate was subjected to a test for confirming whether the blackened layer was peeled off when etching was performed. In the test, an etching solution was sprayed on the entire surface of the blackened layer surface of the produced conductive substrate, left standing for 10 seconds, and then washed to evaluate whether the blackened layer was peeled off.
　黒化層が金属層から全く剥離しなかった場合には◎、一部剥離が見られた場合には〇、黒化層が金属層から完全に剥離した場合には×と評価した。 When the blackened layer did not peel from the metal layer at all, it was evaluated as ◎, when partial peeling was observed, ◯, and when the blackened layer was completely peeled off from the metal layer, it was evaluated as ×.
　なお、エッチング液としては、濃度が０．５ｍｏｌ／ｌの塩化第二銅水溶液を用いた。
（試料の作製条件）
　実施例、比較例として、以下に説明する条件で導電性基板を作製し、上述の評価方法により評価を行った。
［実施例１］
（密着層形成工程）
　縦５００ｍｍ×横５００ｍｍ、厚さ５０μｍのポリエチレンテレフタレート樹脂（ＰＥＴ）製の透明基材の一方の主平面上に密着層を成膜した。なお、透明基材として用いたポリエチレンテレフタレート樹脂製の透明基材について、全光線透過率をＪＩＳ　Ｋ　７３６１－１に規定された方法により評価を行ったところ９７％であった。 As an etchant, a cupric chloride aqueous solution having a concentration of 0.5 mol / l was used.
(Sample preparation conditions)
As examples and comparative examples, conductive substrates were produced under the conditions described below and evaluated by the above-described evaluation method.
[Example 1]
(Adhesion layer forming process)
An adhesion layer was formed on one main plane of a transparent substrate made of polyethylene terephthalate resin (PET) having a length of 500 mm × width of 500 mm and a thickness of 50 μm. 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.
　密着層形成工程では、Ｎｉ－１７重量％Ｃｒ合金のターゲットを装着したスパッタリング装置により、密着層として酸素を含有するＮｉ－Ｃｒ合金層を成膜した。以下に密着層の成膜手順について説明する。 In the adhesion layer forming step, a Ni—Cr alloy layer containing oxygen was formed as an adhesion layer using a sputtering apparatus equipped with a Ni-17 wt% Cr alloy target. The procedure for forming the adhesion layer will be described below.
　予め６０℃まで加熱して水分を除去した上述の透明基材を、スパッタリング装置のチャンバー内に設置した。 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.
　次に、チャンバー内を１×１０－３Ｐａまで排気した後、アルゴンガスと酸素ガスとを導入し、チャンバー内の圧力を１．３Ｐａとした。なお、この際チャンバー内の雰囲気は体積比で３０％が酸素、残部がアルゴンとしている。 Next, after evacuating the chamber to 1 × 10 −3 Pa, argon gas and oxygen gas were introduced, and the pressure in the chamber was set to 1.3 Pa. At this time, the atmosphere in the chamber is 30% oxygen by volume, and the remainder is argon.
　そして係る雰囲気下でターゲットに電力を供給し、透明基材の一方の主平面上に密着層を厚さが２０ｎｍになるように成膜した。
（金属層形成工程）
　金属層形成工程では、金属薄膜層形成工程と、金属めっき層形成工程と、を実施した。 Then, power was supplied to the target in such an atmosphere, and an adhesion layer was formed on one main plane of the transparent substrate so as to have a thickness of 20 nm.
(Metal layer forming process)
In the metal layer forming step, a metal thin film layer forming step and a metal plating layer forming step were performed.
　まず、金属薄膜層形成工程について説明する。 First, the metal thin film layer forming process will be described.
　金属薄膜層形成工程では、基材として密着層形成工程で透明基材上に密着層を成膜したものを用い、密着層上に金属薄膜層として銅薄膜層を形成した。 In the metal thin film layer forming step, a substrate in which the adhesion layer was formed on the transparent substrate in the adhesion layer forming step was used, and a copper thin film layer was formed as the metal thin film layer on the adhesion layer.
　金属薄膜層は、銅のターゲットを用いた点と、基材をセットしたチャンバー内を排気した後、アルゴンガスを供給してアルゴン雰囲気とした点以外は、密着層の場合と同様にしてスパッタリング装置により成膜した。 The metal thin film layer is a sputtering apparatus as in the case of the adhesion layer except that a copper target is used and the inside of the chamber in which the substrate is set is evacuated and then an argon gas is supplied to form an argon atmosphere. Was formed.
　金属薄膜層である銅薄膜層は膜厚が１５０ｎｍとなるように成膜した。 The copper thin film layer, which is a metal thin film layer, was formed to a thickness of 150 nm.
　次に、金属めっき層形成工程においては、金属めっき層として銅めっき層を形成した。銅めっき層は、電気めっき法により銅めっき層の厚さが２．０μｍになるように成膜した。 Next, in the metal plating layer forming step, a copper plating layer was formed as the metal plating layer. The copper plating layer was formed by electroplating so that the thickness of the copper plating layer was 2.0 μm.
　金属層形成工程を終えた後、すなわち銅めっき層を形成後、保護層を形成する面について表面粗さＲａを測定したところ、０．０４μｍであることが確認できた。
（保護層形成工程）
　保護層形成工程では、透明基材上に、密着層と、金属層とが形成された積層体の金属層上に保護層を形成した。 After finishing the metal layer forming step, that is, after forming the copper plating layer, when the surface roughness Ra was measured for the surface on which the protective layer was formed, it was confirmed to be 0.04 μm.
(Protective layer forming step)
In the protective layer forming step, the protective layer was formed on the metal layer of the laminate in which the adhesion layer and the metal layer were formed on the transparent substrate.
　保護層形成工程ではまず、上述の積層体を１，２，３－ベンゾトリアゾール溶液に８秒間浸漬した。そして、金属層の上面（金属層の密着層と対向する面と反対側の面）以外に付着した溶液を除去した後、乾燥することで、金属層上に保護層を形成した。
（黒化層形成工程）
　黒化層形成工程では、保護層形成工程で形成した保護層上に、スパッタリング法により黒化層として酸素を含有するＮｉ－Ｃｕ層を形成した。 In the protective layer forming step, first, the above laminate was immersed in a 1,2,3-benzotriazole solution for 8 seconds. And after removing the solution adhering except the upper surface (surface on the opposite side to the surface opposite to the contact | adherence layer of a metal layer) of a metal layer, the protective layer was formed on the metal layer by drying.
(Blackening layer forming process)
In the blackening layer forming step, a Ni—Cu layer containing oxygen was formed as a blackening layer by sputtering on the protective layer formed in the protective layer forming step.
　黒化層形成工程では、Ｎｉ－３５重量％Ｃｕ合金のターゲットを装着したスパッタリング装置により、黒化層として酸素を含有するＮｉ－Ｃｕ合金層を成膜した。以下に黒化層の成膜手順について説明する。 In the blackening layer forming step, a Ni—Cu alloy layer containing oxygen was formed as a blackening layer by a sputtering apparatus equipped with a Ni-35 wt% Cu alloy target. The procedure for forming the blackened layer will be described below.
　まず、透明基材上に、密着層と、金属層と、保護層と、を積層した積層体をスパッタリング装置のチャンバー内にセットした。 First, the laminated body which laminated | stacked the contact | adherence layer, the metal layer, and the protective layer on the transparent base material was set in the chamber of the sputtering device.
　次にチャンバー内を１×１０－３Ｐａまで排気した後、アルゴンガスと酸素ガスとを導入し、チャンバー内の圧力を１．３Ｐａとした。なお、この際チャンバー内の雰囲気は体積比で３０％が酸素、残部がアルゴンとしている。 Next, after evacuating the chamber to 1 × 10 −3 Pa, argon gas and oxygen gas were introduced, and the pressure in the chamber was set to 1.3 Pa. At this time, the atmosphere in the chamber is 30% oxygen by volume, and the remainder is argon.
　そして係る雰囲気下でターゲットに電力を供給し、保護層上に厚さ３０ｎｍになるように黒化層を成膜した。 Then, power was supplied to the target in such an atmosphere, and a blackened layer was formed on the protective layer so as to have a thickness of 30 nm.
　以上の工程により、金属層の上面、すなわち、金属層の密着層と対向する面と反対側の面に保護層を介して黒化層を形成し、透明基材上に、密着層、金属層、保護層、黒化層がその順で積層された導電性基板が得られた。 Through the above steps, a blackening layer is formed on the upper surface of the metal layer, that is, the surface opposite to the surface facing the adhesion layer of the metal layer via the protective layer, and the adhesion layer and the metal layer are formed on the transparent substrate. A conductive substrate in which a protective layer and a blackening layer were laminated in that order was obtained.
　得られた導電性基板について、上述の表面抵抗、正反射率、明度、黒化層の剥離試験を評価した。 The above-described surface resistance, regular reflectance, brightness, and blackening layer peeling test were evaluated for the obtained conductive substrate.
　表面抵抗は、０．０５００Ω／□、正反射率は２０．８０％、明度（Ｌ＊）は５３．００であることが確認できた。 It was confirmed that the surface resistance was 0.0500Ω / □, the regular reflectance was 20.80%, and the lightness (L * ) was 53.00.
　また、黒化層の剥離試験を行ったところ、ごく一部に剥離が見られたが、黒化層はほとんど剥離しないことを確認できた。このため、評価は〇となった。
［実施例２］
　金属層形成工程後、保護層形成工程前に、金属層表面加工工程として金属層の表面の粗化処理を実施した点以外は実施例１と同様にして導電性基板を作製した。 Moreover, when the peeling test of the blackened layer was performed, peeling was observed in a very small part, but it was confirmed that the blackened layer hardly peeled off. For this reason, the evaluation was ◯.
[Example 2]
A conductive substrate was produced in the same manner as in Example 1 except that after the metal layer forming step and before the protective layer forming step, the surface of the metal layer was roughened as a metal layer surface processing step.
　金属層表面加工工程は、金属層形成工程後に実施し、マイクロ粗化エッチングにより金属層表面を処理した。 The metal layer surface processing step was performed after the metal layer forming step, and the metal layer surface was processed by micro roughening etching.
　金属層表面加工工程実施後に保護層を形成する面について表面粗さＲａを測定したところ、０．０６μｍであることが確認できた。 When the surface roughness Ra was measured on the surface on which the protective layer was formed after the metal layer surface processing step, it was confirmed to be 0.06 μm.
　その後、実施例１と同様にして、保護層形成工程、黒化層形成工程を実施し、導電性基板を作製した。 Thereafter, in the same manner as in Example 1, a protective layer forming step and a blackening layer forming step were performed to produce a conductive substrate.
　得られた導電性基板について実施例１と同様に評価を行ったところ、表面抵抗は、０．０５００Ω／□、正反射率は２０．８０％、明度（Ｌ＊）は５３．００であることが確認できた。 When the obtained conductive substrate was evaluated in the same manner as in Example 1, the surface resistance was 0.0500Ω / □, the regular reflectance was 20.80%, and the lightness (L * ) was 53.00. Was confirmed.
　また、黒化層の剥離試験を行ったところ、剥離が生じないことを確認できた。このため、評価は◎となった。
［比較例１］
　保護層形成工程を実施しなかった点以外は実施例１と同様にして導電性基板を作製した。 Moreover, when the peeling test of the blackened layer was conducted, it was confirmed that no peeling occurred. For this reason, evaluation was (double-circle).
[Comparative Example 1]
A conductive substrate was produced in the same manner as in Example 1 except that the protective layer forming step was not performed.
　すなわち得られた導電性基板は透明基材上に密着層、金属層、黒化層がその順で積層された構成を有している。 That is, the obtained conductive substrate has a structure in which an adhesion layer, a metal layer, and a blackening layer are laminated in this order on a transparent base material.
　なお、金属層形成工程を終えた後、すなわち銅めっき層を形成後、黒化層を形成する面について表面粗さＲａを測定したところ実施例１の場合と同様の値になっていることが確認できた。 In addition, after finishing a metal layer formation process, ie, after forming a copper plating layer, when surface roughness Ra was measured about the surface which forms a blackening layer, it was the same value as the case of Example 1. It could be confirmed.
　得られた導電性基板について実施例１と同様に評価を行ったところ、表面抵抗は、０．０５００Ω／□、正反射率は２０．８０％、明度（Ｌ＊）は５３．００であることが確認できた。 When the obtained conductive substrate was evaluated in the same manner as in Example 1, the surface resistance was 0.0500Ω / □, the regular reflectance was 20.80%, and the lightness (L * ) was 53.00. Was confirmed.
　しかしながら、黒化層の剥離試験を行ったところ、黒化層は金属層から完全に剥離することが確認できた。このため、評価は×となった。 However, when a blackening layer peeling test was performed, it was confirmed that the blackening layer completely peeled off from the metal layer. For this reason, evaluation was set to x.
　以上に導電性基板、導電性基板の製造方法を、実施形態および実施例等で説明したが、本発明は上記実施形態および実施例等に限定されない。特許請求の範囲に記載された本発明の要旨の範囲内において、種々の変形、変更が可能である。 Although the conductive substrate and the method for manufacturing the conductive substrate have been described in the embodiments and examples, the present invention is not limited to the above-described embodiments and examples. Various modifications and changes are possible within the scope of the gist of the present invention described in the claims.
　本出願は、２０１５年７月３１日に日本国特許庁に出願された特願２０１５－１５２８９１号に基づく優先権を主張するものであり、特願２０１５－１５２８９１号の全内容を本国際出願に援用する。 This application claims priority based on Japanese Patent Application No. 2015-152891 filed with the Japan Patent Office on July 31, 2015. The entire contents of Japanese Patent Application No. 2015-152891 are incorporated herein by reference. Incorporate.
１０Ａ、１０Ｂ　　　　　　　　　　　導電性基板
１１　　　　　　　　　　　　　　　　透明基材
１、１２、１２Ａ、１２Ｂ　　　　　　金属層
１３、１３Ａ、１３Ｂ　　　　　　　　保護層
２、１４、１４Ａ、１４Ｂ　　　　　　黒化層 10A, 10B Conductive substrate 11 Transparent base material 1, 12, 12A, 12B Metal layer 13, 13A, 13B Protective layer 2, 14, 14A, 14B Blackening layer

Claims (4)

  1. 　透明基材と、
    　前記透明基材の少なくとも一方の面上に形成された金属層と、
    　金属層上に形成され、硫黄原子および／または窒素原子を含む有機化合物を含有する保護層と、
    　前記保護層上に形成された黒化層と、を有する導電性基板。     A transparent substrate;
    A metal layer formed on at least one surface of the transparent substrate;
    A protective layer formed on the metal layer and containing an organic compound containing a sulfur atom and / or a nitrogen atom;
    And a blackening layer formed on the protective layer.
  2. 　前記保護層は、ベンゾトリアゾール系化合物を含有する請求項１に記載の導電性基板。 The conductive substrate according to claim 1, wherein the protective layer contains a benzotriazole-based compound.
  3. 　透明基材の少なくとも一方の面上に金属層を形成する金属層形成工程と、
    　前記金属層上に硫黄原子および／または窒素原子を含む有機化合物を含有する保護層を形成する保護層形成工程と、
    　前記保護層上に黒化層を形成する黒化層形成工程と、を有する導電性基板の製造方法。     A metal layer forming step of forming a metal layer on at least one surface of the transparent substrate;
    A protective layer forming step of forming a protective layer containing an organic compound containing a sulfur atom and / or a nitrogen atom on the metal layer;
    And a blackened layer forming step of forming a blackened layer on the protective layer.
  4. 　前記保護層は、ベンゾトリアゾール系化合物を含有する請求項３に記載の導電性基板の製造方法。 The method for producing a conductive substrate according to claim 3, wherein the protective layer contains a benzotriazole-based compound.
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