JP2017133063A - Laminate substrate, conductive substrate, production method of laminate substrate, and production method of conductive substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate substrate having a suppressed reflectance.SOLUTION: In a laminate substrate including a transparent substrate, and a laminate formed on at least one surface side of the transparent substrate, the laminate includes a copper layer, a blackened layer containing at least one or more metals selected from Ni, Mo,Ta, Ti, V, Cr, Fe, Co, W and Cu, and a white metallic layer containing a Ni-Cu-based alloy.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminate substrate, a conductive substrate, a method for manufacturing a laminate substrate, and a method for manufacturing a conductive substrate.

  As disclosed in Patent Document 1, a transparent conductive film for a touch panel in which an ITO (indium tin-tin) film is formed as a transparent conductive film on the surface of a transparent base material such as a transparent polymer film has been conventionally used. It has been.

  By the way, in recent years, the display screen including a touch panel has been increased in screen size. 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, there is a problem that it cannot cope with an increase in the area of the conductive substrate.

  For this reason, for example, as disclosed in Patent Documents 2 and 3, the use of a metal wiring obtained by processing a metal foil such as copper instead of the ITO film wiring has been studied. However, for example, when copper is used for the metal wiring, since copper has a metallic luster, there is a problem that the visibility of the display decreases due to reflection.

  Therefore, a conductive substrate in which a blackened layer made of a black material is formed on a plane parallel to the surface of the transparent base material of the metal wiring together with a metal wiring such as copper has been studied.

JP 2003-151358 A JP 2011-018194 A JP 2013-0669261 A

  However, the reflectance of the conductive substrate provided with the metal wiring and the blackening layer on the transparent base material is simply provided on the surface of the copper metal wiring parallel to the surface of the transparent base material. May not be sufficiently suppressed.

  In view of the above problems of the prior art, an object of the present invention is to provide a laminate substrate with suppressed reflectance.

In order to solve the above problems, the present invention
A transparent substrate;
A laminate formed on at least one surface side of the transparent substrate,
The laminate is
A copper layer,
A blackening layer containing at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu;
There is provided a laminate substrate including a white metal layer containing a Ni-Cu alloy.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body board | substrate which suppressed the reflectance can be provided.

Sectional drawing of the laminated body board | substrate which concerns on embodiment of this invention. Sectional drawing of the laminated body board | substrate which concerns on embodiment of this invention. The top view of the electroconductive board | substrate provided with the mesh-shaped wiring which concerns on embodiment of this invention. Sectional drawing in the AA 'line of FIG. Explanatory drawing of a roll-to-roll sputtering apparatus.

Hereinafter, an embodiment of a laminate substrate, a conductive substrate, a laminate substrate manufacturing method, and a conductive substrate manufacturing method of the present invention will be described.
(Laminated substrate, conductive substrate)
The laminate substrate of this embodiment can have a configuration including a transparent base material and a laminate formed on at least one surface side of the transparent base material.
The laminate includes a copper layer, a blackening layer containing at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu, and a Ni—Cu alloy. And a white metal layer containing.

  In addition, the laminated body board | substrate in this embodiment is a board | substrate which has the copper layer before patterning, the blackening layer, and the white metal layer on the surface of a transparent base material. The conductive substrate is a wiring substrate having a copper wiring layer, a blackened wiring layer, and a white metal wiring layer that are patterned into a wiring shape on the surface of a transparent base material.

  As described above, the reflectance of the conductive substrate can be obtained simply by providing a copper metal wiring on a transparent base material and a blackened layer on the surface of the copper metal wiring parallel to the surface of the transparent base material. May not be sufficiently suppressed.

  Therefore, the inventors of the present invention have intensively studied the reason why the reflectance of the conductive substrate cannot be sufficiently suppressed only by providing the blackening layer.

  As a result, the provision of the blackened layer does not sufficiently suppress the color of the copper metal wiring when the copper layer is viewed from the blackened layer side, and therefore the reflectance of the conductive substrate is reduced. We found that it was not able to suppress enough.

  And by providing a white metal layer further on the blackened layer, when the copper layer is viewed from the blackened layer side, the tint of the copper layer can be suppressed, and the laminate substrate and the laminate substrate are used. The present inventors have found that the reflectivity of the conductive substrate thus obtained can be sufficiently suppressed.

  Below, the structure of the laminated body board | substrate of this embodiment is demonstrated concretely.

  Here, first, each member included in the multilayer substrate of the present embodiment will be described below.

  The transparent substrate is not particularly limited, and a polymer film that transmits visible light, a glass substrate, or the like can be preferably used.

  As the polymer film that transmits visible light, for example, a resin film such as a polyamide film, a polyethylene terephthalate film, a polyethylene naphthalate film, a cycloolefin film, a polyimide film, or a polycarbonate film can be preferably used.

  It does not specifically limit about the thickness of a transparent base material, It can select arbitrarily according to the intensity | strength required when it is set as an electroconductive board | substrate, the transmittance | permeability of light, etc. The thickness of the transparent substrate can be, for example, 10 μm or more and 250 μm or less. In particular, when used for touch panel applications, it is preferably 20 μm or more and 200 μm or less, more preferably 20 μm or more and 120 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 100 μm or less.

  Next, a laminated body is demonstrated. A laminated body is formed in the at least one surface side of a transparent base material, and can have a blackening layer, a white metal layer, and a copper layer.

  Here, the copper layer will be described first.

  The copper layer is not particularly limited, but it does not reduce the light transmittance, so it adheres between the copper layer and the transparent substrate, between the copper layer and the blackened layer, or between the copper layer and the white metal layer. It is preferable not to arrange the agent. That is, the copper layer is preferably formed directly on the upper surface of another member.

  In order to directly form a copper layer on the upper surface of another member, a copper thin film layer may be formed using a dry plating method such as a sputtering method, an ion plating method, or a vapor deposition method, and the copper thin film layer may be used as a copper layer. it can.

  Moreover, when making a copper layer thicker, it is preferable to use a wet plating method, after forming a copper thin film layer with a dry-type plating method. That is, for example, a copper thin film layer is formed by a dry plating method on a transparent substrate, a blackened layer, or a white metal layer, and the copper thin film layer is used as a power feeding layer to form a copper plating layer by a wet plating method. it can. In this case, the copper layer has a copper thin film layer and a copper plating layer.

  As described above, copper is formed directly on the transparent substrate, blackened layer, or white metal layer without using an adhesive by forming a copper layer only by the dry plating method or by combining the dry plating method and the wet plating method. This is preferable because a layer can be formed.

  The thickness of the copper layer is not particularly limited, and when the copper layer is used as a wiring, it can be arbitrarily selected according to the electrical resistance value, the wiring width, etc. of the wiring. In particular, the copper layer preferably has a thickness of 50 nm or more, more preferably 60 nm or more, and even more preferably 150 nm or more so that electricity flows sufficiently. The upper limit value of the thickness of the copper layer is not particularly limited. However, when the copper layer is thick, side etching occurs because etching takes time when performing etching to form a wiring, and the resist peels off during the etching. Etc. are likely to occur. For this reason, it is preferable that the thickness of a copper layer is 5000 nm or less, and it is more preferable that it is 3000 nm or less. In addition, when a copper layer has a copper thin film layer and a copper plating layer as mentioned above, it is preferable that the sum total of the thickness of a copper thin film layer and the thickness of a copper plating layer is the said range.

  Next, the blackened layer will be described.

  Since the copper layer has a metallic luster, the copper reflects light only by forming a copper wiring layer that is a wiring obtained by etching the copper layer on a transparent base material. For example, when used as a wiring board for a touch panel, There was a problem that visibility was lowered. For this reason, the laminated substrate of this embodiment can have a blackened layer.

  The composition of the blackening layer contained in the laminate substrate of the present embodiment is not particularly limited, but for example, at least selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu. It preferably contains one or more metals. The blackened layer can further contain one or more elements selected from carbon, oxygen, hydrogen, and nitrogen.

  The blackening layer can also contain a metal alloy containing at least two kinds of metals selected from Ni, 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. In this case, as a metal alloy containing at least two kinds of metals selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn, for example, Cu-Ti-Fe alloy or Cu-Ni-Fe alloy, Ni-Cu alloy, Ni-Ti alloy, Ni-W alloy, Ni-Cr alloy, Ni-Cu-Cr alloy can be preferably used.

  The formation method of a blackening layer is not specifically limited, It can form by arbitrary methods, For example, it can form into a film by a dry method or a wet method.

  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.

  When the blackened layer is formed by reactive sputtering, 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.

  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 is added. 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.

  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 10 nm or more, for example, and more preferably 15 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 10 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. For this reason, the thickness of the blackened layer is preferably 70 nm or less, and more preferably 50 nm or less.

  In the laminate substrate of this embodiment, the reflection of light on the surface of the copper layer can be suppressed by disposing a blackened layer. For this reason, when the electroconductive board | substrate produced using this laminated body board | substrate is used for uses, such as a touch panel, it becomes possible to suppress the fall of the visibility of a display.

  Next, the white metal layer will be described.

  Only by disposing the blackening layer on the surface of the copper layer, the tint of the copper layer could not be suppressed, and when the conductive substrate was used, the reflectance could not be sufficiently suppressed. For this reason, in the laminated body board | substrate of this embodiment, in addition to the blackening layer, it can have a white metal layer.

  The material of the white metal layer is not particularly limited, and a metal layer having a color suitable for suppressing the tint of the copper layer can be suitably used. However, according to the study of the inventors of the present invention, a layer containing a Ni—Cu alloy is particularly preferable from the viewpoint of suppressing the tint of the copper layer.

  As described above, the white metal layer can contain a Ni—Cu alloy, that is, an alloy containing nickel and copper. The white metal layer can also be composed of a Ni—Cu alloy.

  And it is preferable that the ratio of nickel is 10 mass% or more and 25 mass% or less among the metal components contained in a Ni-Cu type alloy. In addition, the ratio of nickel in the metal component contained in the Ni—Cu based alloy means that when the Ni—Cu based alloy contains only nickel and copper as the metal component, the nickel and copper in the Ni—Cu based alloy The ratio of nickel when the total content is 100 mass% is shown.

  Further, the Ni—Cu based alloy contained in the white metal layer can contain zinc in addition to nickel and copper.

  When the Ni-Cu alloy further contains zinc, among the metal components contained in the Ni-Cu alloy, the proportion of nickel is 10% by mass to 25% by mass, and the proportion of zinc is 10% by mass to 30% by mass. % Or less is preferable. That is, when the total content of the metal components in the Ni-Cu alloy is 100% by mass, the proportion of nickel is 10% by mass to 25% by mass and the proportion of zinc is 10% by mass to 30% by mass. It is preferable that

  In addition, when a Ni-Cu type alloy contains nickel, copper, and zinc as metal components, the total content of metal components in the alloy is, for example, nickel content, copper content, zinc It means the total with the content of.

  The Ni-Cu-based alloy contains copper, nickel, and zinc as described above, and the proportion of nickel when the content of the metal component in the alloy is 100% by mass is 10% by mass to 25% by mass. In this case, as the alloy, for example, white copper, white or the like can be suitably used.

  Note that the Ni—Cu alloy can contain nickel and copper as metal species as described above, and can further contain zinc and the like as described above. Moreover, although the metal component which a Ni-Cu type alloy contains can also be comprised only from nickel and copper, or only nickel, copper, and zinc, even in these cases, it is limited only to nickel and copper Instead, for example, 1% by mass or less of inevitable impurities may be contained.

  The Ni—Cu based alloy only needs to contain nickel and copper, and what kind of alloy each component specifically forms is not particularly limited.

  The method for forming the white metal layer disposed on the laminate substrate of the present embodiment is not particularly limited. The white metal layer is preferably formed by, for example, a dry film forming method such as a sputtering method.

  When forming the white metal layer by a sputtering method, for example, it is possible to form a film while supplying an inert gas used as a sputtering gas into the chamber using a target of a Ni—Cu alloy.

  In the case where a Ni—Cu based alloy target is used during sputtering, the nickel content in the Ni—Cu based alloy is preferably 10% by mass or more and 25% by mass or less. In addition, the ratio of nickel in the metal component contained in the Ni-Cu-based alloy means that when the Ni-Cu-based alloy contains only nickel and copper as metal components, the copper in the Ni-Cu-based alloy, The ratio of nickel is shown when the total content of nickel is 100% by mass.

  This is because the ratio of nickel in the metal component contained in the white metal layer to be deposited and the Ni-Cu alloy target of the Ni-Cu alloy target used for depositing the white metal layer in the Ni-Cu alloy. This is because the proportion of nickel in the contained metal components is the same.

  The inert gas for forming the white metal layer is not particularly limited. For example, argon gas or xenon gas can be used, and argon gas can be preferably used.

  The thickness of the white metal layer formed in the laminate substrate of the present embodiment is not particularly limited, and is arbitrarily selected according to, for example, the degree of suppression of the tint of the copper layer required for the laminate substrate can do.

  The lower limit value of the thickness of the white metal layer is, for example, preferably 5 nm or more, and more preferably 10 nm or more. The upper limit value of the thickness of the white metal layer is preferably, for example, 70 nm or less, and more preferably 50 nm or less.

  As described above, the white metal layer can function as a layer having a function of suppressing the color of the copper layer and suppressing the reflectance of the multilayer substrate, but when the thickness of the white metal layer is thin, The color of the copper layer may not be sufficiently suppressed. On the other hand, the color of a copper layer can be suppressed more reliably by making the thickness of a white metal layer into 5 nm or more.

  The upper limit of the thickness of the white metal 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 become longer, resulting in an increase in cost. Will be invited. Therefore, the thickness of the white metal layer is preferably 70 nm or less as described above, and more preferably 50 nm or less.

  In the laminate substrate of the present embodiment, a copper layer, a blackened layer, and a white metal layer can be laminated on a transparent substrate as described later, and the copper layer, the blackened layer, and the white metal layer are stacked. By patterning, a conductive substrate can be obtained.

  For this reason, the copper wiring layer, blackened wiring layer, and white metal wiring layer of the conductive substrate obtained from the laminated substrate of this embodiment are respectively the copper layer, blackened layer, and white metal of the laminated substrate of this embodiment. Layer characteristics are maintained.

  Next, a configuration example of the multilayer substrate of this embodiment will be described.

  As described above, the laminate substrate of the present embodiment can have a transparent substrate and a laminate having a copper layer, a blackening layer, and a white metal layer. At this time, the order in which the copper layer, the blackening layer, and the white metal layer are arranged on the transparent substrate in the laminate and the number of the layers are not particularly limited. That is, for example, two layers of a copper layer, a blackening layer, and a white metal layer can be laminated on at least one surface side of the transparent substrate. In addition, a plurality of one or more types of layers selected from a copper layer, a blackened layer, and a white metal layer can be formed in the laminate.

  However, when placing the copper layer and the blackened layer in the stack, the blackened layer is placed on the surface of the copper layer where the light reflection is particularly desired to be suppressed in order to suppress the reflection of light on the copper layer surface. It is preferable that they are arranged. Moreover, it is more preferable to provide a white metal layer in addition to the blackened layer on the surface of the copper layer on which the blackened layer is disposed, particularly on the surface in which light reflection is suppressed.

  In particular, it is more preferable to have a laminated structure in which the blackened layer is formed on the surface of the copper layer. Specifically, for example, the laminate has a plurality of blackened layers, and the copper layer is a blackened layer. Further, it can be configured to be disposed between other blackening layers.

  More specifically, for example, the first blackened layer, the copper layer, and the second blackened layer can be laminated in this order from the transparent substrate side.

  In this case, a white metal layer can be provided in combination with the first blackening layer and / or the second blackening layer. In the case of providing a white metal layer together with the first blackened layer, for example, the first white metal layer can be provided between the first blackened layer and the copper layer. When a white metal layer is provided together with the second blackened layer, for example, a second white metal layer can be provided between the copper layer and the second blackened layer. Note that only one of the first white metal layer and the second white metal layer can be provided, or both of them can be provided.

  Thus, by providing a white metal layer in addition to the blackened layer, it is possible to suppress light reflection particularly on the surface on which the blackened layer and the white metal layer are provided.

  A specific configuration example of the multilayer substrate of the present embodiment will be described below with reference to FIGS. FIG. 1 and FIG. 2 show examples of cross-sectional views in a plane parallel to the lamination direction of the transparent base material, the copper layer, the blackening layer, and the white metal layer of the laminate substrate of the present embodiment.

  For example, as in the laminate substrate 10A shown in FIG. 1A, the blackened layer 12, the white metal layer 13, and the copper layer 14 are arranged one by one on the one surface 11a side of the transparent base material 11 one by one. Can be stacked. The order of lamination of the blackened layer 12 and the white metal layer 13 is not particularly limited, but the white metal layer 13 is disposed between the blackened layer 12 and the copper layer 14. Is preferred.

  Further, as in the laminate substrate 10B shown in FIG. 1B, the blackened layer 12A on the one surface 11a side and the other surface (the other surface) 11b side of the transparent base material 11, respectively. 12B, white metal layers 13A and 13B, and copper layers 14A and 14B can be laminated one by one in that order.

  Furthermore, as described above, the laminate substrate of the present embodiment can be provided with a plurality of blackening layers and white metal layers on at least one surface side of the transparent base material 11. For example, as in the laminate substrate 20A shown in FIG. 2A, the first blackened layer 121, the first white metal layer 131, the copper layer 14, and the one surface 11a side of the transparent base material 11, The second white metal layer 132 and the second blackening layer 122 can be stacked in that order.

  As described above, the blackening layer and the white metal layer include the first blackening layer 121, the second blackening layer 122, the first white metal layer 131, and the second white metal layer 132, and the copper layer 14 is the first black metal layer. By disposing between the first blackened layer 121 and the second blackened layer 122, reflection of light incident from the upper surface side and the lower surface side of the copper layer 14 can be more reliably suppressed. Further, by providing a white metal layer in addition to the blackened layer, it is possible to suppress the color of the copper layer when viewed from the blackened layer side and to particularly suppress the reflectance.

  In this case as well, a configuration in which a copper layer, a first blackened layer, a second blackened layer, a first white metal layer, and a second white metal layer are laminated on both surfaces of the transparent substrate 11 can be adopted. Specifically, as in the laminate substrate 20B shown in FIG. 2B, the first black is formed on the one surface 11a side of the transparent base material 11 and the other surface (the other surface) 11b side. The first white metal layers 131A and 131B, the copper layers 14A and 14B, the second white metal layers 132A and 132B, and the second blackened layers 122A and 122B can be stacked in this order.

  In the configuration example of FIGS. 1B and 2B in which a copper layer, a blackened layer, and a white metal layer are laminated on both surfaces of the transparent substrate 11, the transparent substrate 11 is transparent as a symmetrical surface. Although the example arrange | positioned so that the layer laminated | stacked on the upper and lower sides of the base material 11 became symmetrical was shown, it is not limited to the form which concerns.

  For example, in FIG. 2B, the configuration on the one surface 11a side of the transparent base material 11 is similar to the configuration of FIG. 1B with the blackened layer 12A, the white metal layer 13A, and the copper layer 14A. It can be set as the form laminated | stacked in the order. The configuration on the other surface (the other surface) 11b side is made up of the first blackening layer 121B, the first white metal layer 131B, the copper layer 14B, the second white metal layer 132B, and the second blackening. As a form in which the layers 122B are laminated in that order, the layers laminated above and below the transparent base material 11 may be asymmetrical.

  The degree of light reflection of the laminate substrate of the present embodiment is not particularly limited. For example, the average regular reflectance of light having a wavelength of 400 nm to 700 nm is preferably 55% or less, and 40% or less. It is more preferable that it is 30% or less. This is because when the average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 55% or less, for example, when the laminate substrate of this embodiment is used as a conductive substrate for a touch panel, the visibility of the display is reduced. It is because it can suppress especially.

  The regular reflectance of the laminate substrate can be measured by irradiating the blackened layer with light. That is, measurement can be performed by irradiating light from the blackened layer side of the blackened layer and the copper layer included in the laminate substrate. Specifically, for example, when the blackened layer 12, the white metal layer 13, and the copper layer 14 are laminated in this order on one surface 11a of the transparent substrate 11 as shown in FIG. It can be measured by irradiating the surface of the blackened layer 12 with light from the surface 11b side of the transparent substrate 11 so that it can be performed.

  The average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less means an average value of measurement results when the wavelength is changed within a range of 400 nm or more and 700 nm or less. In the measurement, the width for changing the wavelength is not particularly limited. For example, it is preferable to measure the light in the wavelength range by changing the wavelength every 10 nm, and changing the wavelength every 1 nm to change the wavelength in the wavelength range. More preferably, the measurement is performed on light.

  As will be described later, the laminated substrate can be formed into a conductive substrate by forming a thin metal wire by wiring a blackened layer, a white metal layer, and a copper layer by etching. The regular reflectance of light on the conductive substrate means the regular reflectance on the light incident surface of the blackened layer disposed on the outermost surface when the transparent substrate is removed.

  For this reason, if it is an electroconductive board | substrate after performing an etching process, it is preferable that the measured value in the part in which a copper layer, a blackening layer, and a white metal layer remain satisfy | fills the said range.

  Next, the conductive substrate of this embodiment will be described.

  The electroconductive board | substrate of this embodiment can be equipped with a transparent base material and the metal fine wire formed in the at least one surface side of the transparent base material. The fine metal wire includes a copper wiring layer, a blackened wiring layer containing at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu, and Ni-Cu. And a white metal wiring layer containing a base alloy.

  The conductive substrate of this embodiment can be obtained, for example, by wiring the above-described laminated substrate. And in the conductive substrate of this embodiment, since the copper wiring layer, the blackened wiring layer, and the white metal wiring layer are provided on the transparent substrate, the reflection of light by the copper wiring layer is suppressed. Can do. Therefore, by providing the blackened wiring layer and the white metal wiring layer, it is possible to have good display visibility when used for a touch panel or the like, for example.

  The conductive substrate of this embodiment can be preferably used as a conductive substrate for a touch panel, for example. In this case, the conductive substrate can be configured to have a wiring pattern formed by providing openings in the copper layer, the blackened layer, and the white metal layer in the above-described laminate substrate. More preferably, it can be set as the structure provided with the mesh-shaped wiring pattern.

  A conductive substrate on which a wiring pattern having openings is formed can be obtained by etching the copper layer, the blackened layer, and the white metal layer of the multilayer substrate described so far. And it can be set as the electroconductive board | substrate which has a mesh-shaped wiring pattern, for example by a two-layer metal fine wire. A specific configuration example is shown in FIG.

  FIG. 3 shows a view of the conductive substrate 30 having a mesh-like wiring pattern as viewed from the upper surface side in the stacking direction of the copper wiring layer, the blackened wiring layer, and the white metal wiring layer. The conductive substrate 30 shown in FIG. 3 includes a transparent substrate 11, a plurality of copper wiring layers 31B parallel to the X-axis direction in the drawing, and a copper wiring layer 31A parallel to the Y-axis direction. The copper wiring layers 31A and 31B can be formed by etching the above-described laminated substrate, and a blackened wiring layer and a white metal wiring layer (not shown) are formed on the upper and / or lower surfaces of the copper wiring layers 31A and 31B. Is formed. Further, the blackened wiring layer and the white metal wiring layer have a cross-sectional shape in a plane parallel to the main surface of the transparent substrate 11, that is, the surface on which the copper wiring layers 31A and 31B of the transparent substrate 11 are laminated. Etching is performed so as to have substantially the same shape as the copper wiring layers 31A and 31B.

  The arrangement of the transparent substrate 11 and the copper wiring layers 31A and 31B is not particularly limited. An example of the arrangement of the transparent substrate 11 and the copper wiring layer is shown in FIG. 4 corresponds to a cross-sectional view taken along line AA ′ of FIG.

  For example, as shown in FIG. 4, copper wiring layers 31 </ b> A and 31 </ b> B may be disposed on the upper and lower surfaces of the transparent substrate 11, respectively. In the case of the conductive substrate shown in FIG. 4, the first blackened wiring layers 321A and 321B and the first white metal wiring layers 331A and 331B are arranged on the transparent substrate 11 side of the copper wiring layers 31A and 31B. Has been. The first blackened wiring layers 321A and 321B and the first white metal wiring layers 331A and 331B have substantially the same cross-sectional shape as the copper wiring layers 31A and 31B in a plane parallel to the main surface of the transparent substrate 11. can do.

  Further, as shown in FIG. 4, the second white metal wiring layers 332A and 332B and the second blackened wiring layers 322A and 322B are formed on the surface of the copper wiring layers 31A and 31B opposite to the transparent substrate 11. It can also be arranged. In this case, the second white metal wiring layers 332A and 332B and the second blackened wiring layers 322A and 322B also have a cross-sectional shape in a plane parallel to the main surface of the transparent substrate 11 and the copper wiring layers 31A and 31B. The shape can be almost the same.

  As in the conductive substrate shown in FIG. 4, the conductive substrate of this embodiment has a plurality of blackened wiring layers, and the copper wiring layer is a blackened wiring layer. The structure may be arranged between other blackened wiring layers.

  However, the conductive substrate of the present embodiment is not limited to the configuration example of the conductive substrate shown in FIG. 4. For example, the first blackened wiring layers 321A and 321B, the second blackened wiring layer 322A, Only one of 322B can be provided. Further, only one of the first white metal wiring layers 331A and 331B and the second white metal wiring layers 332A and 332B can be provided.

  However, when a white metal wiring layer is provided, it is also preferable to provide a blackened wiring layer that is laminated continuously with the white metal wiring layer. For this reason, the conductive substrate shown in FIG. 4 will be described as an example. When the first white metal wiring layers 331A and 331B are provided, it is preferable to provide the first blackened wiring layers 321A and 321B together. And when providing 2nd white metal wiring layer 332A, 332B, it is preferable to provide 2nd blackening wiring layer 322A, 322B together.

  The white metal wiring layer is preferably arranged between the blackened wiring layer and the copper wiring layer. Therefore, as shown in FIG. 4, it is preferable to dispose the first white metal wiring layers 331A and 331B between the first blackening wiring layers 321A and 321B and the copper wiring layers 31A and 31B. In addition, the second white metal wiring layers 332A and 332B are preferably disposed between the second blackened wiring layers 322A and 322B and the copper wiring layers 31A and 31B.

  In the conductive substrate shown in FIG. 4, the transparent base material 11 is used as a symmetry plane, and the type of layers stacked vertically is shown as an example, but the embodiment is limited to such a form. It is not a thing. For example, only one of the first white metal wiring layer 331A and the first white metal wiring layer 331B may be provided. Alternatively, only one of the second white metal wiring layer 332A and the second white metal wiring layer 332B may be provided. Similarly to the above-described white metal wiring layer, the first black wiring layer and the second black wiring layer can be arbitrarily provided according to the performance required for the conductive substrate.

  The conductive substrate having the mesh-like wiring shown in FIG. 3 includes, for example, copper layers 14A and 14B and a blackened layer 12A on both sides of the transparent base material 11 as shown in FIGS. 1B and 2B. 12B (121A, 121B, 122A, 122B) and a laminated substrate provided with white metal layers 13A, 13B (131A, 131B, 132A, 132B).

  For example, the conductive substrate including the first black wiring layer, the second black wiring layer, the first white metal wiring layer, and the second white metal wiring layer shown in FIG. 4 is shown in FIG. It can be formed from the laminated substrate shown.

  Therefore, a case where the multilayer substrate of FIG. 2B is used will be described as an example.

  First, the first blackened layer 121A, the first white metal layer 131A, the copper layer 14A, the second white metal layer 132A, and the second blackened layer 122B on the one surface 11a side of the transparent substrate 11 are formed as shown in FIG. ) Etching is performed so that a plurality of linear patterns parallel to the middle Y-axis direction are arranged at predetermined intervals along the X-axis direction. Note that the Y-axis direction in FIG. 2B indicates a direction perpendicular to the paper surface. In addition, the X-axis direction in FIG. 2B means a direction parallel to the width direction of each layer.

  Then, the first blackened layer 121B, the first white metal layer 131B, the copper layer 14B, the second white metal layer 132B, and the second blackened layer 122B on the other surface 11b side of the transparent substrate 11 are formed as shown in FIG. b) Etching is performed so that a plurality of linear patterns parallel to the middle X-axis direction are arranged at predetermined intervals along the Y-axis direction.

  Through the above operation, the conductive substrate having the mesh-like wiring shown in FIGS. 3 and 4 can be formed. Note that the etching of both surfaces of the transparent substrate 11 can be performed simultaneously. That is, the copper layers 14A and 14B, the first blackened layers 121A and 121B, the second blackened layers 122A and 122B, the first white metal layers 131A and 131B, and the second white metal layers 132A and 132B are simultaneously etched. Also good.

  In addition, except that the second blackened wiring layers 322A and 322B and the second white metal wiring layers 332A and 332B are not provided by performing etching in the same manner using the laminate substrate shown in FIG. Can form a conductive substrate having the same structure as the conductive substrate shown in FIGS.

  The conductive substrate having the mesh wiring shown in FIG. 3 can be formed by using two stacked substrates shown in FIG. 1A or FIG. The case where the conductive substrate of FIG. 2A is used will be described as an example. For the two laminated substrates shown in FIG. 2A, the first blackened layer 121, the first white metal layer 131, and the copper are respectively used. The layer 14, the second white metal layer 132, and the second blackening layer 122 are etched so that a plurality of linear patterns parallel to the X-axis direction are arranged at predetermined intervals along the Y-axis direction. Do. Then, the conductive substrate having mesh-like wiring is obtained by bonding the two conductive substrates so that the linear patterns formed on the respective conductive substrates intersect with each other by the etching process. be able to. The surface to be bonded when the two conductive substrates are bonded is not particularly limited.

  For example, the two conductive substrates can be configured as shown in FIG. 4 by bonding the surfaces 11b of the transparent base material 11 in FIG. .

  Note that the width of the fine metal wires and the distance between the fine metal wires in the conductive substrate having the mesh-like wiring shown in FIG. 3 are not particularly limited. For example, depending on the electrical resistance value required for the fine metal wires, etc. Can be selected.

  3 and 4 so far, an example in which a mesh-like wiring pattern is formed by combining linear thin metal wires is shown, but the present invention is not limited to such a form, and the fine metal wires constituting the wiring pattern are It can be of any shape. For example, the shape of the fine metal wires constituting the mesh-like wiring pattern can be changed to various shapes such as jagged lines (zigzag straight lines) so that moire (interference fringes) does not occur between the images on the display. .

The conductive substrate having a mesh-like wiring composed of the two-layer wiring of the present embodiment described so far can be preferably used as a conductive substrate for a projected capacitive touch panel, for example.
(Manufacturing method of laminated substrate, manufacturing method of conductive substrate)
Next, the structural example of the manufacturing method of the laminated body board | substrate of this embodiment is demonstrated.

The manufacturing method of the laminated body board | substrate of this embodiment can have the following processes.
A transparent base material preparation step for preparing a transparent base material.
The laminated body formation process which forms a laminated body in the at least one surface side of a transparent base material.
The laminated body forming process can further include the following steps.
A copper layer forming step of forming a copper layer by a copper layer forming means for depositing copper.
A blackened layer is formed by a blackened layer film forming means for depositing a blackened layer containing at least one kind of metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu. Blackening layer forming step.
A white metal layer forming step of forming a white metal layer by a white metal layer film forming means for depositing a white metal layer containing a Ni-Cu alloy.
The blackening layer forming step and the white metal layer forming step are preferably performed under a reduced pressure atmosphere.

  Although the manufacturing method of the laminated substrate of this embodiment is demonstrated below, since it can be set as the structure similar to the case of the above-mentioned laminated substrate except the point demonstrated below, description is abbreviate | omitted.

  As described above, the laminate substrate of the present embodiment can include a transparent substrate and a laminate having a copper layer, a blackening layer, and a white metal layer. At this time, the order in which the copper layer, the blackened layer, and the white metal layer are arranged on the transparent substrate in the laminated body and the number of the layers are not particularly limited. For example, a plurality of one or more layers selected from a copper layer, a blackening layer, and a white metal layer can be laminated on at least one surface side of the transparent substrate.

  For this reason, the order in which the copper layer forming step, the blackened layer forming step, and the white metal layer forming step are performed, and the number of times to be performed are not particularly limited. Therefore, each step can be performed at an arbitrary number of times according to the structure of the laminated substrate to be formed.

  The step of preparing the transparent substrate is a step of preparing a transparent substrate made of, for example, a polymer film that transmits visible light, a glass substrate, or the like, and the specific operation is not particularly limited. For example, it can be cut into an arbitrary size as necessary for use in the subsequent steps and steps. In addition, since what can be used suitably as a polymer film which permeate | transmits visible light is already stated, description is abbreviate | omitted here.

  Next, a laminated body formation process is demonstrated. A laminated body formation process is a process of forming a laminated body on the at least one surface side of a transparent base material, and can have a copper layer formation step, a blackening layer formation step, and a white metal layer formation step. Each step will be described below.

  First, the copper layer forming step will be described.

  In the copper layer forming step, the copper layer can be formed by a copper layer forming means for depositing copper on at least one surface side of the transparent substrate.

  In the copper layer forming step, it is preferable to form a copper thin film layer using a dry plating method. Moreover, when making a copper layer thicker, it is preferable to form a copper plating layer further using a wet plating method after forming a copper thin film layer by a dry plating method.

  For this reason, a copper layer formation step can have a copper thin film layer formation step which forms a copper thin film layer, for example with a dry-type plating method. The copper layer forming step includes a copper thin film layer forming step for forming a copper thin film layer by a dry plating method, and a copper plating layer forming step for forming a copper plating layer by a wet plating method using the copper thin film layer as a power feeding layer. , May be included.

  Therefore, the copper layer film forming means is not limited to one film forming means, and a plurality of film forming means can be used in combination.

  As described above, copper is formed directly on the transparent substrate, blackened layer, or white metal layer without using an adhesive by forming a copper layer only by the dry plating method or by combining the dry plating method and the wet plating method. This is preferable because a layer can be formed.

  Although it does not specifically limit as a dry-type plating method, Sputtering method, an ion plating method, a vapor deposition method etc. can be used preferably in a pressure-reduced atmosphere.

  In particular, as the dry plating method used for forming the copper thin film layer, it is more preferable to use the sputtering method because the thickness can be easily controlled. That is, in this case, sputtering film forming means (sputtering film forming method) can be preferably used as the copper layer film forming means for depositing copper in the copper layer forming step.

  The copper thin film layer can be suitably formed using, for example, the roll-to-roll sputtering apparatus 50 shown in FIG. The process of forming a copper thin film layer will be described below using a roll-to-roll sputtering apparatus as an example.

FIG. 5 shows a configuration example of the roll-to-roll sputtering apparatus 50. The roll-to-roll sputtering apparatus 50 includes a housing 51 that houses most of the components. In FIG. 5, the shape of the housing 51 is shown as a rectangular parallelepiped shape, but the shape of the housing 51 is not particularly limited, and may be any shape depending on the device accommodated therein, the installation location, the pressure resistance performance, and the like. It can be. For example, the shape of the housing 51 can be a cylindrical shape. However, in order to remove residual gas not related to film formation at the start of film formation, it is preferable that the inside of the casing 51 can be depressurized to 1 Pa or less, more preferably 10 ⁻³ Pa or less, more preferably 10 ⁻⁴ Pa or less. More preferably, it can be done. Note that it is not necessary that the entire interior of the casing 51 can be reduced to the above pressure, and it can be configured such that only the lower region in the figure in which a can roll 53 (to be described later) where sputtering is performed can be reduced to the above pressure. .

  In the housing 51, an unwinding roll 52, a can roll 53, sputtering cathodes 54a to 54d, a front feed roll 55a, a rear feed roll 55b, tension rolls 56a and 56b, which supply a base material for forming a copper thin film layer, A winding roll 57 can be arranged. In addition to the above rolls, guide rolls 58a to 58h, a heater 59, and the like can be arbitrarily provided on the transport path of the base material on which the copper thin film layer is formed.

  The unwinding roll 52, the can roll 53, the front feed roll 55a, and the winding roll 57 can be provided with power by a servo motor. The unwinding roll 52 and the winding roll 57 are configured to maintain the tension balance of the base material on which the copper thin film layer is formed by torque control using a powder clutch or the like.

  Although the structure of the can roll 53 is not particularly limited, for example, the surface thereof is finished with hard chrome plating, and a coolant or a heating medium supplied from the outside of the housing 51 circulates inside the can roll 53 so that the temperature can be adjusted to a constant temperature. It is preferable that it is comprised.

  For example, the tension rolls 56a and 56b are preferably finished with hard chrome plating and provided with a tension sensor. The front feed roll 55a, the rear feed roll 55b, and the guide rolls 58a to 58h are preferably finished with hard chrome plating.

  The sputtering cathodes 54 a to 54 d are preferably magnetron cathode types and arranged to face the can roll 53. The size of the sputtering cathodes 54a to 54d is not particularly limited, but the width dimension of the substrate on which the copper thin film layer of the sputtering cathodes 54a to 54d is formed is wider than the width of the substrate on which the opposing copper thin film layer is formed. It is preferable.

  The substrate on which the copper thin film layer is formed is transported through a roll-to-roll sputtering apparatus 50 that is a roll-to-roll vacuum film forming apparatus, and is positioned at a position facing the sputtering cathodes 54 a to 54 d of the can roll 53. As it passes, a copper thin film layer is deposited.

  A procedure for forming a copper thin film layer using the roll-to-roll sputtering apparatus 50 will be described.

  First, the copper target is mounted on the sputtering cathodes 54a to 54d, and the inside of the casing 51 in which the base material for forming the copper thin film layer is set on the unwinding roll 52 is evacuated by the vacuum pumps 60a and 60b.

  Thereafter, an inert gas, for example, a sputtering gas such as argon is introduced into the casing 51 by the gas supply means 61. The configuration of the gas supply means 61 is not particularly limited, but can have a gas storage tank (not shown). Then, mass flow controllers (MFC) 611a and 611b and valves 612a and 612b are provided for each gas type between the gas storage tank and the casing 51 so that the supply amount of each gas into the casing 51 can be controlled. Can be configured. Although FIG. 5 shows an example in which two sets of mass flow controllers and valves are provided, the number to be installed is not particularly limited, and the number to be installed can be selected according to the number of gas types to be used.

  When the sputtering gas is supplied into the casing 51 by the gas supply means 61, the flow rate of the sputtering gas and the opening of the pressure adjustment valve 62 provided between the vacuum pump 60b and the casing 51 are adjusted. Then, it is preferable to carry out film formation while maintaining the inside of the apparatus at, for example, 0.13 Pa or more and 1.3 Pa or less.

  In this state, while discharging the base material from the unwinding roll 52 at a speed of, for example, 1 m or more and 20 m or less per minute, power is supplied from a sputtering DC power source connected to the sputtering cathodes 54a to 54d to perform sputtering discharge. Thereby, a desired copper thin film layer can be continuously formed on a base material.

  In addition to the above, various members can be arranged in the roll-to-roll sputtering apparatus 50 as necessary. For example, pressure gauges 63a and 63b for measuring the pressure in the casing 51 and vent valves 64a and 64b may be provided.

  Further, as described above, a copper layer (copper plating layer) can be further formed using a wet plating method after dry plating.

  When a copper plating layer is formed by a wet plating method, the copper thin film layer formed by the dry plating described above can be used as a power feeding layer. In this case, electroplating film forming means can be preferably used as the copper layer forming means for depositing copper in the copper layer forming step.

  The conditions in the step of forming the copper plating layer by the wet plating method using the copper thin film layer as the power feeding layer, that is, the conditions of the electroplating treatment are not particularly limited, and various conditions according to ordinary methods may be adopted. For example, a copper plating layer can be formed by supplying a base material on which a copper thin film layer is formed in a plating tank containing a copper plating solution and controlling the current density and the conveyance speed of the base material.

  Next, the blackening layer forming step will be described.

  The blackening layer forming step includes blackening including at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu on at least one surface side of the transparent substrate. In this step, a blackened layer is formed by a blackened layer forming means for depositing the layer. The blackening layer film forming means in the blackening layer forming step is not particularly limited, and can be formed by, for example, a dry method or a wet method.

  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. In this case, the reactive sputtering method can be used more preferably.

  In particular, the blackening layer forming means is preferably, for example, a sputtering film forming means in a reduced pressure atmosphere, that is, a sputtering film forming method.

  The blackening layer can be suitably formed using, for example, the roll-to-roll sputtering apparatus 50 shown in FIG. Since the configuration of the roll-to-roll sputtering apparatus has already been described, the description thereof is omitted here.

  A configuration example of the procedure in the case of forming a blackened layer using the roll-to-roll sputtering apparatus 50 will be described.

  First, a target including a metal constituting the blackening layer is attached to the sputtering cathodes 54a to 54d. When the blackening layer contains an alloy, an alloy target can be used by previously synthesizing the alloy. However, a metal target contained in the alloy is placed on the sputtering cathodes 54a to 54d, and a substrate or the like is formed. An alloy can also be formed on the surface of the film body.

  And the inside of the housing | casing 51 which set the base material which forms a blackening layer to the unwinding roll 52 is evacuated by the vacuum pumps 60a and 60b. After that, a sputtering gas containing an inert gas, for example, argon and, optionally, a gas corresponding to any one selected from carbon, oxygen, hydrogen, and nitrogen added to the blackening layer is enclosed by the gas supply means 61. Introduce into the body 51. At this time, by adjusting the flow rate of the sputtering gas and the opening of the pressure adjustment valve 62 provided between the vacuum pump 60b and the housing 51, the inside of the apparatus is maintained at, for example, 0.13 Pa or more and 13 Pa or less, It is preferable to perform film formation.

  As a gas corresponding to any one selected from carbon, oxygen, hydrogen, and nitrogen added to the blackening layer, for example, when adding carbon to the blackening layer, carbon monoxide gas and / or carbon dioxide gas, When adding oxygen, oxygen gas can be added to the atmosphere during dry plating, hydrogen gas and / or water when adding hydrogen, and nitrogen gas when adding nitrogen.

  In addition, as the inert gas or the like, premixed gas can be supplied into the casing 51, but each gas is supplied individually to the casing 51 so that each gas has a desired partial pressure in the casing 51. The supply amount and pressure can be adjusted.

  In this state, while discharging the substrate from the unwinding roll 52 at a speed of, for example, about 0.5 m to 10 m per minute, power is supplied from the sputtering DC power source connected to the sputtering cathodes 54a to 54d to perform sputtering discharge. I do. Thereby, a desired blackening layer can be continuously formed on the substrate.

  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.

  Next, the white metal layer forming step will be described.

  As described above, in the white metal layer forming step, the white metal layer is formed by the white metal layer forming means for depositing the white metal layer containing the Ni—Cu alloy on at least one surface side of the transparent substrate. It is a step to do. The white metal layer film forming means for depositing the white metal layer containing the Ni—Cu alloy in the white metal layer forming step is not particularly limited, but is preferably a dry film forming method, for example, under a reduced pressure atmosphere. It is more preferable to use the sputtering film forming means, that is, the sputtering film forming method.

  The white metal layer can be suitably formed using, for example, the roll-to-roll sputtering apparatus 50 shown in FIG. Since the configuration of the roll-to-roll sputtering apparatus has already been described, the description thereof is omitted here.

  A configuration example of a procedure when forming a white metal layer using the roll-to-roll sputtering apparatus 50 will be described.

  First, a Ni—Cu-based alloy target is mounted on the sputtering cathodes 54a to 54d, and the inside of the casing 51 in which the base material on which the alloy layer is formed is set on the unwinding roll 52 is evacuated by the vacuum pumps 60a and 60b. Then, an inert gas, for example, a sputtering gas made of argon is introduced into the casing 51 by the gas supply means 61. At this time, the flow rate of the sputtering gas and the opening of the pressure adjustment valve 62 provided between the vacuum pump 60b and the housing 51 are adjusted to maintain the inside of the housing 51 at, for example, 0.13 Pa or more and 13 Pa or less. It is preferable to perform film formation.

  In this state, while discharging the substrate from the unwinding roll 52 at a speed of, for example, about 0.5 m to 10 m per minute, power is supplied from the sputtering DC power source connected to the sputtering cathodes 54a to 54d to perform sputtering discharge. I do. Thereby, a desired white metal layer can be continuously formed on the substrate.

  When forming the white metal layer, when the Ni-Cu alloy target is used as described above, the proportion of nickel in the metal component contained in the Ni-Cu alloy is 10 mass% or more and 25 mass%. % Or less is preferable. In addition, the ratio of nickel in the metal component contained in the Ni-Cu-based alloy means that when the Ni-Cu-based alloy contains only nickel and copper as metal components, the copper in the Ni-Cu-based alloy, The ratio of nickel is shown when the total content of nickel is 100% by mass.

  This is because the ratio of nickel in the metal component contained in the white metal layer to be deposited and the Ni-Cu alloy target of the Ni-Cu alloy target used for depositing the white metal layer in the Ni-Cu alloy. This is because the proportion of nickel in the contained metal components is the same.

  The inert gas used when forming the white metal layer is not particularly limited, and for example, argon gas or xenon gas can be used. As described above, argon gas can be preferably used. .

  So far, each process and step included in the method for manufacturing a laminated substrate according to the present embodiment have been described.

  In the laminate substrate obtained by the method for producing a laminate substrate according to this embodiment, the copper layer preferably has a thickness of 50 nm or more, more preferably 60 nm or more, as in the above-described laminate substrate. More preferably, it is 150 nm or more. The upper limit value of the thickness of the copper layer is not particularly limited, but the thickness of the copper layer is preferably 5000 nm or less, and more preferably 3000 nm or less. In addition, when a copper layer has a copper thin film layer and a copper plating layer as mentioned above, it is preferable that the sum total of the thickness of a copper thin film layer and the thickness of a copper plating layer is the said range.

  Further, the thickness of the blackening layer is not particularly limited, but is preferably 10 nm or more, for example, and more preferably 15 nm or more. The upper limit of the thickness of the blackening layer is not particularly limited, but is preferably 70 nm or less, and more preferably 50 nm or less.

  The thickness of the white metal layer is not particularly limited, but the lower limit is, for example, preferably 5 nm or more, and more preferably 10 nm or more. The upper limit value of the thickness of the white metal layer is preferably, for example, 70 nm or less, and more preferably 50 nm or less.

  Furthermore, in the laminate substrate obtained by the laminate substrate manufacturing method of the present embodiment, the average regular reflectance of light having a wavelength of 400 nm to 700 nm is preferably 55% or less, and preferably 40% or less. More preferably, it is more preferably 30% or less.

  Using a laminate substrate obtained by the laminate substrate manufacturing method of the present embodiment, a conductive substrate in which a wiring pattern having openings in copper layers, blackening layers, and white metal layers is formed is used. it can. More preferably, the conductive substrate can be configured to include mesh-like wiring.

  The conductive substrate manufacturing method according to this embodiment includes etching the copper layer, the blackening layer, and the white metal layer of the multilayer substrate obtained by the above-described multilayer substrate manufacturing method, And an etching step of forming a wiring pattern having a fine metal wire that is a laminate including a blackened wiring layer and a white metal wiring layer. And an opening part can be formed in a copper layer, a blackening layer, and a white metal layer by the etching process.

  In the etching step, for example, first, a resist having an opening corresponding to a portion to be removed by etching is formed on the outermost surface of the multilayer substrate. For example, in the case of the multilayer substrate shown in FIG. 1A, a resist can be formed on the exposed surface A of the copper layer 14 disposed on the multilayer substrate. Note that a method for forming a resist having an opening corresponding to a portion to be removed by etching is not particularly limited. For example, the resist can be formed by a photolithography method.

  Next, the blackening layer 12, the white metal layer 13, and the copper layer 14 can be etched by supplying an etching solution from the upper surface of the resist.

  In addition, when the blackening layer etc. are arrange | positioned on both surfaces of the transparent base material 11 like FIG.1 (b), the resist which has a predetermined-shaped opening part in the surface A and the surface B of a laminated substrate is formed, respectively. Then, the blackened layer, white metal layer, and copper layer formed on both surfaces of the transparent substrate 11 may be etched simultaneously. In addition, the blackening layer, the white metal layer, and the copper layer formed on both sides of the transparent substrate 11 can be etched on one side. That is, for example, after the blackening layer 12A, the white metal layer 13A, and the copper layer 14A are etched, the blackening layer 12B, the white metal layer 13B, and the copper layer 14B can be etched.

  The etching solution used in the etching step is not particularly limited, and an etching solution generally used for etching the copper layer can be preferably used.

  As an etching solution used in the etching process, for example, an aqueous solution containing one type selected from sulfuric acid, hydrogen peroxide solution, hydrochloric acid, cupric chloride, and ferric chloride, or two or more types selected from the above sulfuric acid, etc. A mixed aqueous solution containing can be more preferably used. The content of each component in the etching solution is not particularly limited.

  Although the etching solution can be used at room temperature, it can also be used by heating in order to increase the reactivity.

  The specific form of the mesh-like wiring obtained by the above-described etching process is as described above, and the description thereof is omitted here.

  Also, two laminated substrates having a blackened layer, a white metal layer, and a copper layer on one surface side of the transparent substrate 11 shown in FIGS. 1A and 2A are subjected to an etching process. In the case where two conductive substrates are bonded to each other to form a conductive substrate having mesh-like wiring, a step of bonding the conductive substrates can be further provided. In this case, a method for bonding the two conductive substrates is not particularly limited, and the bonding can be performed using, for example, an optical adhesive (OCA) or the like.

  In the conductive substrate obtained by the method for manufacturing a conductive substrate according to the present embodiment, the average regular reflectance of light having a wavelength of 400 nm to 700 nm is preferably 55% or less, and preferably 40% or less. More preferably, it is more preferably 30% or less.

  This is because, when the average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 55% or less, for example, when it is used as a conductive substrate for a touch panel, a reduction in display visibility can be particularly suppressed.

  In the above, the laminated body substrate of this embodiment, the electroconductive board | substrate, the manufacturing method of a laminated body board | substrate, and the manufacturing method of an electroconductive board | substrate were demonstrated. According to such a laminate substrate or a laminate substrate obtained by the method for producing a laminate substrate, by providing a white metal layer, the tint of the copper layer is suppressed and the reflectance of the laminate substrate is particularly lowered. be able to. For this reason, when the laminate substrate is, for example, a conductive substrate for a touch panel, the reflectance can be particularly lowered even in the conductive substrate, and a reduction in visibility can be suppressed. A conductive substrate having visibility can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited to these Examples.
(Evaluation method)
The regular reflectance was measured for the laminate substrates produced in the following examples and comparative examples.

  The measurement was performed by installing a reflectance measurement unit in an ultraviolet-visible spectrophotometer (Shimadzu Corporation model: UV-2550).

In each example, a laminate substrate having the structure of FIG. 2A was produced, and the reflectance was measured with respect to the surface C exposed to the outside of the second blackening layer 122 in FIG. 2A. The measurement was carried out by irradiating light having a wavelength of 400 nm or more and 700 nm or less at 5 ° and a light receiving angle of 5 °. In addition, the light irradiated to the laminate substrate is measured for regular reflectance with respect to light of each wavelength by changing the wavelength every 1 nm within a wavelength range of 400 nm or more and 700 nm or less, and the average of the measurement results is obtained. The average of the regular reflectance of the substrate was used. In Table 1, the reflectance is shown.
(Sample preparation conditions)
As examples and comparative examples, laminate substrates were produced under the conditions described below and evaluated by the above-described evaluation methods.
[Example 1]
A laminate substrate having the structure shown in FIG.
(Transparent substrate preparation process)
First, the transparent base material preparation process was implemented.

Specifically, a transparent substrate made of optical polyethylene terephthalate resin (PET) having a width of 500 mm and a thickness of 100 μm was prepared.
(Laminate formation process)
Next, the laminated body formation process was implemented.

As the laminated body forming process, a first blackened layer forming step, a first white metal layer forming step, a copper layer forming step, a second white metal layer forming step, and a second blackened layer forming step were performed. This will be specifically described below.
(1) First Blackening Layer Formation Step First, a first blackening layer formation step was performed.

  The prepared transparent substrate was set in the roll-to-roll sputtering apparatus 50 shown in FIG. Further, Ni—Cu alloy targets were mounted on the sputtering cathodes 54a to 54d. As shown in Table 1, the Ni—Cu alloy target contains 11% by mass of Ni, and the balance, that is, 89% by mass is Cu.

  And the heater 59 of the roll-to-roll sputtering apparatus 50 was heated to 100 degreeC, the transparent base material was heated, and the water | moisture content contained in a base material was removed.

Subsequently, after the inside of the casing 51 is evacuated to 1 × 10 ⁻⁴ Pa by the vacuum pumps 60a and 60b, the gas supply means 61 causes the argon gas flow rate to be 240 sccm and the oxygen gas flow rate to be 40 sccm. Oxygen gas was introduced into the housing 51. Then, while transporting the transparent base material from the unwinding roll 52 at a speed of 2 m / min, power is supplied from the DC power source for sputtering connected to the sputtering cathodes 54a to 54d, and sputtering discharge is performed on the transparent base material. A desired first blackening layer was continuously formed. With this operation, the first blackened layer 121 was formed on the transparent substrate so as to have a thickness of 10 nm.
(2) First White Metal Layer Formation Step Next, a first white metal layer formation step was performed.

  In the first white metal layer forming step, the target attached to the sputtering cathodes 54a to 54d is a Ni-Cu alloy target, and a nickel-copper alloy target (Sumitomo Metal) having a different composition from the first blackened layer forming step. Mine Co., Ltd.). As shown in Table 1, the nickel-copper alloy target contains 10% by mass of Ni, and the balance, that is, 90% by mass is Cu.

Further, after the inside of the casing 51 was evacuated to 1 × 10 ⁻⁴ Pa by the vacuum pumps 60 a and 60 b, argon gas was introduced into the casing 51 by the gas supply means 61 so that the flow rate became 240 sccm.

  Except for the above points, the first white metal layer was formed to a thickness of 10 nm in the same manner as in the first blackening layer forming step.

In addition, as a base material, in the 1st blackening layer formation step, the base material which formed the 1st blackening layer on the transparent base material was used, and the white metal layer was formed into a film on the 1st blackening layer. .
(3) Copper layer formation step Then, the copper layer formation step was implemented.

  In the copper layer forming step, the target to be attached to the sputtering cathode is changed to a copper target (manufactured by Sumitomo Metal Mining Co., Ltd.), the inside of the casing 51 is evacuated, and then argon is put into the casing 51 of the roll-to-roll sputtering apparatus 50. A copper layer was formed to a thickness of 1000 nm on the top surface of the first white metal layer in the same manner as the first blackened layer except that only gas was introduced.

In addition, as a base material which forms a copper layer, a 1st blackening layer and a 1st white metal layer are formed on a transparent base material by a 1st blackening layer formation step and a 1st white metal layer formation step. The base material formed in that order was used.
(4) Second White Metal Layer Formation Step In the second white metal layer formation step, the second white metal layer was formed on the upper surface of the copper layer under the same conditions and procedures as in the first white metal layer formation step.
(5) Second Blackening Layer Formation Step In the second blackening layer formation step, a second blackening layer was formed on the upper surface of the second white metal layer under the same conditions and procedures as in the first blackening layer formation step.

The average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less of the produced laminate substrate was measured by the above-described procedure, and the average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less was 50%.
[Example 2 to Example 9]
When forming the supply amount of oxygen supplied into the casing 51 when forming the first black layer and the second black layer, the composition of the sputtering target, the first white metal layer, and the second white metal layer A laminated substrate was produced and evaluated in the same manner as in Example 1 except that the composition of the sputtering target was changed as shown in Table 1.

The evaluation results are shown in Table 1.
[Example 10]
About the point which used the copper target as a sputtering target at the time of forming a 1st blackening layer and a 2nd blackening layer, and composition of a sputtering target at the time of forming a 1st white metal layer and a 2nd white metal layer A laminated substrate was prepared and evaluated in the same manner as in Example 1 except for the points changed as shown in Table 1.

The evaluation results are shown in Table 1.
[Example 11, Example 12]
The composition of the sputtering target at the time of forming the first black layer and the second black layer was changed as shown in Table 1. Moreover, the sputtering target used when forming the first white metal layer and the second white metal layer was a nickel-copper-zinc alloy target (manufactured by Sumitomo Metal Mining Co., Ltd.), which is a Ni-Cu alloy target. ). In addition, the used nickel-copper-zinc alloy target has the composition shown in Table 1. For example, in Example 11, Ni contains 25% by mass, Zn contains 10% by mass, and the rest, The composition is 65% by mass of Cu.

  Except for the above, a laminate substrate was prepared and evaluated in the same manner as in Example 1.

The evaluation results are shown in Table 1.
[Example 13]
Table 1 shows the composition of the sputtering target when forming the first black layer and the second black layer, and the composition of the sputtering target when forming the first white metal layer and the second white metal layer. A laminated substrate was produced and evaluated in the same manner as in Example 1 except for the points changed as described above.

The evaluation results are shown in Table 1.
[Example 14]
The composition of the sputtering target when forming the first black layer and the second black layer, the composition of the sputtering target when forming the first white metal layer and the second white metal layer, the first white metal layer, With respect to the film thickness of the second white metal layer, a laminate substrate was prepared and evaluated in the same manner as in Example 1 except that it was changed as shown in Table 1.

The evaluation results are shown in Table 1.
[Comparative Example 1]
Lamination was performed in the same manner as in Example 1 except that the film thickness of the first black layer and the second black layer was 20 nm, and the first white metal layer and the second white metal layer were not manufactured. A body substrate was prepared and evaluated.

  The evaluation results are shown in Table 1.

表１に示した結果によると、実施例１〜実施例１４については、得られた積層体基板の反射率が５５％以下となっているのに対して、比較例１では積層体基板の反射率が５６％と、実施例１〜実施例１４と比較して高くなることが確認できた。

According to the results shown in Table 1, in Examples 1 to 14, the obtained laminate substrate has a reflectance of 55% or less, whereas in Comparative Example 1, the reflection of the laminate substrate is shown. It was confirmed that the rate was 56%, which was higher than those in Examples 1 to 14.

  This is considered to be because in Example 1 to Example 14, by providing the white metal layer, the tint of the copper layer was suppressed and the reflectance of the laminate substrate could be reduced.

10A, 10B, 20A, 20B Laminate substrate 11 Transparent base material 14, 14A, 14B Copper layer 12, 12A, 12B, 121, 121A, 121B, 122, 122A, 122B Blackening layer 13, 13A, 13B, 131, 131A 131B, 132, 132A, 132B White metal layer 30 Conductive substrates 31A, 31B Copper wiring layers 321A, 321B, 322A, 322B Blackened wiring layers 331A, 331B, 332A, 332B White metal wiring layers

Claims (10)

A transparent substrate;
A laminate formed on at least one surface side of the transparent substrate,
The laminate is
A copper layer,
A blackening layer containing at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu;
And a white metal layer containing a Ni-Cu alloy. The laminate has a plurality of the blackening layers,
The laminate substrate according to claim 1, wherein the copper layer is disposed between one blackened layer and another blackened layer.   The laminate substrate according to claim 1 or 2, wherein the average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 55% or less. A transparent substrate;
A thin metal wire formed on at least one surface side of the transparent substrate,
The thin metal wire is
A copper wiring layer;
A blackened wiring layer containing at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu;
A conductive substrate which is a laminate including a white metal wiring layer containing a Ni-Cu alloy. The thin metal wire has a plurality of the blackened wiring layers,
The conductive substrate according to claim 4, wherein the copper wiring layer is disposed between one blackened wiring layer and another blackened wiring layer. A transparent substrate preparation step of preparing a transparent substrate;
A laminate forming step of forming a laminate on at least one surface side of the transparent substrate,
The laminate forming step includes
A copper layer forming step of forming a copper layer by a copper layer forming means for depositing copper;
A blackened layer is formed by a blackened layer film forming means for depositing a blackened layer containing at least one kind of metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu. A blackening layer forming step;
A white metal layer forming step of forming a white metal layer by a white metal layer film forming means for depositing a white metal layer containing a Ni-Cu based alloy,
The blackened layer forming step and the white metal layer forming step are a method for manufacturing a laminate substrate, which is performed under a reduced pressure atmosphere.   The method for manufacturing a laminate substrate according to claim 6, wherein the blackening layer forming unit and the white metal layer forming unit are sputtering film forming methods. The blackening layer has a thickness of 10 nm or more;
The method for manufacturing a laminate substrate according to claim 6 or 7, wherein the thickness of the white metal layer is 5 nm or more. A copper wiring layer obtained by etching the copper layer, the blackening layer, and the white metal layer of the multilayer substrate obtained by the method for manufacturing a multilayer substrate according to any one of claims 6 to 8. And an etching step of forming a wiring pattern having a fine metal wire that is a laminate including a blackened wiring layer and a white metal wiring layer,
The manufacturing method of the electroconductive board | substrate which forms an opening part in the said copper layer, the said blackening layer, and the said white metal layer according to the said etching process. The method for producing a conductive substrate according to claim 9, wherein an average of regular reflectance of light having a wavelength of 400 nm to 700 nm is 55% or less.

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