TWI655570B - Conductive substrate, laminated conductive substrate, method for producing conductive substrate, and method for producing laminated conductive substrate - Google Patents

Abstract

A conductive substrate having a transparent substrate, a metal layer formed on at least one surface of the transparent substrate, and a blackened layer containing nickel and zinc formed on the metal layer by a wet method is provided.

Description

Conductive substrate, laminated conductive substrate, method for producing conductive substrate, and method for producing laminated conductive substrate

The present invention relates to a conductive substrate, a laminated conductive substrate, a method of producing a conductive substrate, and a method of producing a laminated conductive substrate.

The electrostatic capacitance type touch panel converts position information of an approaching object on a panel surface into an electrical signal by detecting a change in electrostatic capacitance caused by an object approaching the surface of the panel. Since the conductive substrate for the electrostatic capacitance type touch panel is provided on the surface of the display, the wiring material of the conductive substrate is required to have a low reflectance and is difficult to be recognized.

As a result, as a wiring material for a capacitance type touch panel, a wiring having a low reflectance and being difficult to be recognized 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.

In recent years, a display having a touch panel has been developed in a large screen, and accordingly, a conductive substrate such as a transparent conductive film for a touch panel has been required to have a large area. However, since the ITO resistance value is high and signal deterioration occurs, there is a problem that it is not suitable for a large panel.

For this reason, for example, Patent Documents 2 and 3 disclose a technical discussion in which a metal foil such as copper is used instead of the ITO film. However, for example, in the case where copper is used for the metal layer, since copper has a metallic luster, there is a problem that the visibility of the display is lowered due to reflection.

On the other hand, a conductive substrate in which a metal layer is formed of a metal foil such as copper and a blackened layer made of a black material is formed on the upper surface of the metal layer has been studied.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2003-151358

Patent Document 2: JP-A-2011-018194

Patent Document 3: Japanese Laid-Open Patent Publication No. 2013-069261

However, the conventional blackening layer is formed by a dry method, and in order to form a blackened layer which can sufficiently suppress the metallic luster of the metal layer composed of the metal foil, it is time-consuming to cause a problem of low productivity.

In view of the above-described conventional technical problems, an object of the present invention is to provide a conductive substrate which has a small electric resistance value, can suppress light reflection, and can be manufactured with good productivity.

In order to solve the above problems, an aspect of the invention provides a conductive substrate comprising a transparent substrate, a metal layer formed on at least one surface of the transparent substrate, and a nickel-containing layer formed on the metal layer by a wet method. The blackening layer of zinc.

According to an aspect of the present invention, it is possible to provide a conductive substrate which has a small electric resistance value and can suppress light reflection and can be manufactured with good productivity.

10A, 10B, 20, 201, 202, 40‧‧‧ conductive substrates

11, 111, 112‧‧‧ transparent substrate

12, 12A, 12B, 22, 221, 222, 42A, 42B‧‧‧ metal layers

13, 13A, 13B, 23, 231, 232, 43A, 43B‧‧‧ blackening layer

30‧‧‧Laminated conductive substrate

Fig. 1A is a cross-sectional view showing a conductive substrate according to an embodiment of the present invention.

Fig. 1B is a cross-sectional view showing a conductive substrate according to an embodiment of the present invention.

2A is a configuration explanatory view of a patterned conductive substrate according to an embodiment of the present invention.

2B is a configuration explanatory view of a patterned conductive substrate according to an embodiment of the present invention.

3A is a configuration explanatory view of a laminated conductive substrate including a mesh wiring according to an embodiment of the present invention.

3B is a configuration explanatory view of a laminated conductive substrate including a mesh wiring according to an embodiment of the present invention.

4 is a cross-sectional view showing a conductive substrate including a mesh wiring according to an embodiment of the present invention.

Fig. 5 is an explanatory view of a roll-to-roll sputtering apparatus according to an embodiment of the present invention.

Fig. 6 is a graph showing the surface resistance of the surface of the blackened layer of the conductive substrate produced in the examples and the comparative examples.

7 is a graph showing the regular reflectance of the surface of the blackened layer of the conductive substrate produced in the examples and the comparative examples.

8 is a graph showing the luminance of the surface of the blackened layer of the conductive substrate produced in the examples and the comparative examples.

Hereinafter, an embodiment of the conductive substrate, the laminated conductive substrate, the method for producing the conductive substrate, and the method for producing the laminated conductive substrate of the present invention will be described.

(conductive substrate)

The conductive substrate of the present embodiment may have a transparent substrate, a metal layer formed on at least one surface of the transparent substrate, and a blackened layer containing nickel and zinc formed on the metal layer by a wet method.

Further, the conductive substrate according to the present embodiment includes a substrate having a metal layer and a blackened layer on the surface of the transparent substrate before patterning the metal layer or the like, and a substrate on which the metal layer or the like is patterned. , wiring board. Further, since the conductive substrate after patterning the metal layer and the blackened layer includes a region in which the transparent substrate is not covered with a metal layer or the like, the light-transmitting can be performed. The transparent conductive substrate is formed.

Here, each member included in the conductive substrate will be described first.

The transparent substrate is not particularly limited, and a visible light-permeable resin substrate (resin film) or a glass substrate can be preferably used.

As a material of the visible light permeable resin substrate, for example, a polyamidamide resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, a cycloolefin resin, or a polyimine can be preferably used. A resin such as a resin or a polycarbonate resin. In particular, as a material of the visible light permeable resin substrate, PET (polyethylene terephthalate), COP (cycloolefin polymer), PEN (polyethylene naphthalate), and polyphthalamide can be preferably used. Amine, polycarbonate, etc.

The thickness of the transparent substrate is not particularly limited, and can be arbitrarily selected depending on the required strength, electrostatic capacity, light transmittance, and the like of the conductive substrate. The thickness of the transparent substrate may be, for example, 10 μm or more and 200 μm or less. In particular, in the case of use in a touch panel, 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 a touch panel, for example, in applications where the overall thickness of the display is particularly thin, the thickness of the transparent substrate is preferably 20 μm or more and 50 μm or less.

It is preferable that the transparent substrate has a high total light transmittance. 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 within the above range, for example, in the case of use for a touch panel, it is possible to ensure sufficient visibility of the display.

Here, the total light transmittance of the transparent substrate can be evaluated according to the method specified in JIS K 7361-1.

The transparent substrate has a first principal plane and a second principal plane, and the principal plane herein refers to a plane portion having the largest area among the planes included in the transparent substrate. And, the first main plane and the second main plane mean 1 The oppositely disposed faces of the transparent substrate.

Next, the metal layer will be described.

The material constituting the metal layer is not particularly limited, and a material having conductivity in accordance with the use can be selected. For example, Cu is preferably selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Mn, Co, and W. A copper alloy or a copper-containing material composed of at least one metal or more. Further, the metal layer may be a copper layer made of copper.

The method of forming the metal layer on the transparent substrate is not particularly limited, and in order not to lower the light transmittance, it is preferred that no adhesion agent is disposed between the transparent substrate and the metal layer. That is, it is preferred to form the metal layer directly on the upper surface of the transparent substrate. Further, in the case where the adhesion layer is disposed between the transparent substrate and the metal layer as described below, it is preferably formed directly on the upper surface of the adhesion layer.

In order to form a metal layer directly on the upper surface of the transparent substrate, it is preferred that the metal layer has a metal thin film layer. In addition, the metal layer may have a metal thin film layer and a metal plating layer.

For example, on a transparent substrate, a metal thin film layer can be formed by dry plating, and the metal thin film layer can be used as a metal layer. Thereby, the metal layer can be directly formed on the transparent substrate without using an adhesive. As described later in detail of the dry plating method, for example, a sputtering method, a vapor deposition method, or the like can be preferably used.

Further, in order to increase the thickness of the metal layer, the metal thin film layer can be used as the power supply layer, and the metal plating layer can be formed by a plating method which is one of wet plating methods to form a metal layer having a metal thin film layer and a metal plating layer. . Since the metal layer has a metal thin film layer and a metal plating layer, in this case, the metal layer can also be formed directly 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 depending on the magnitude of the current supplied to the wiring, the wiring width, and the like. In order to supply a sufficient current, the thickness of the metal layer is preferably 50 nm or more, more preferably 60 nm or more, and still more preferably 150 nm. the above. The upper limit of the thickness of the metal layer is not particularly limited. However, when the metal layer is thickened, etching time for etching to form a wiring pattern is prolonged, and side etching occurs, so that a resist is easily formed in the etching. Problems such as divestiture in the middle. Therefore, the thickness of the metal layer is preferably 8 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less.

Further, in the case where the metal layer has the metal thin film layer and the metal plating layer as described above, it is preferable that the sum of the thickness of the metal thin film layer and the thickness of the metal plating layer is within the above range.

In the case where the metal layer is composed of a metal thin film layer or the metal thin film layer and the metal plating layer, the thickness of the metal thin film layer is not particularly limited, but is preferably, for example, 50 nm or more and 500 nm or less.

As described below, for example, by patterning a metal layer to form a desired wiring pattern, it can be used as wiring. Further, since the metal layer is more resistant to the resistance than the ITO which has been conventionally used for the transparent conductive film, the resistance value of the conductive substrate can be reduced by providing the metal layer.

Hereinafter, the blackening layer will be described.

A blackening layer may be formed on the upper surface of the metal layer.

The blackening layer can be formed by a wet process and can contain nickel and zinc.

In the above conventional conductive substrate, the blackened layer is formed by a dry plating method. On the other hand, in the conductive substrate of the present embodiment, the blackening layer is formed by the wet method, and the film formation of the blackened layer can be performed in a shorter time than the dry plating method, and productivity can be improved. Further, by providing the blackening layer, it is possible to suppress light reflection on the upper surface of the metal layer.

The method of forming the blackening layer is a wet method, and is not particularly limited. For example, a method of newly forming a blackened layer by wet plating on a metal layer and laminating the layer may be mentioned. In this case, as the wet plating method, for example, an electroplating method can be suitably used.

The ratio of nickel to zinc contained in the blackening layer is not particularly limited, but the ratio of nickel contained in the blackening layer and nickel in the zinc is preferably 40% by weight or more and 99% by weight or less by weight.

In addition, the ratio of nickel in nickel and zinc contained in the blackening layer is the ratio of nickel in the total amount of nickel and zinc contained in the blackening layer as 100% by weight, and the rest. Part of the ratio of zinc. Therefore, when the above range is expressed by the weight ratio of nickel:zinc in the blackened layer, it means that it is preferably 40:60 or more and 99:1 or less.

By setting the ratio of nickel contained in the blackening layer and nickel in the zinc to 40% by weight or more, the color unevenness on the surface of the blackened layer can be suppressed. By suppressing the color unevenness on the surface of the blackening layer, for example, when forming a conductive substrate in which the metal layer and the blackened layer are patterned, the wiring portion in which the metal layer and the blackened layer are patterned can be made more It is not conspicuous, so that it can improve the appearance, so it is preferable.

Further, since the blackening layer contains nickel and zinc, the color of the nickel layer and the zinc contained in the blackening layer is 99% by weight regardless of the ratio. In the following, it is preferable to suppress light reflection by the metal layer in particular.

In particular, the ratio of nickel in the blackening layer and nickel in the zinc is more preferably 70% by weight or more and 99% by weight or less, and still more preferably 75% by weight or more and 99% by weight or less.

The blackening layer may contain any components other than nickel and zinc, and the composition thereof is not particularly limited, but it is preferably nickel and zinc as a main component, more preferably nickel or zinc. Here, the main component of nickel and zinc means that nickel and zinc contained in the blackened layer are more than 50% by weight. When the blackening layer is composed of nickel and zinc, it does not exclude impurities or inevitable components. In the case of blackening layer formation by wet plating, in addition to nickel and zinc, the blackening layer is also It may contain ingredients derived from the bath.

The thickness of the blackening layer is not particularly limited, and can be arbitrarily selected depending on the degree of reflectance required for the conductive substrate. In order to sufficiently suppress light reflection on the surface of the metal layer, the thickness of the blackening layer is The degree is preferably 5 nm or more, more preferably 15 nm or more.

The upper limit of the thickness of the blackened layer is not particularly limited, but the thickness of the blackened layer is preferably 1 μm or less in consideration of productivity in forming a wiring pattern. In particular, from the viewpoint of improving productivity, it is more preferably 500 nm or less.

Further, in addition to the transparent substrate, the metal layer, and the blackened layer described above, the conductive substrate may be provided with any layer. For example, an adhesive layer can be provided.

Hereinafter, a configuration example of the adhesion layer will be described.

As described above, the metal layer can be formed on the transparent substrate. However, when the metal layer is directly formed on the transparent substrate, the adhesion between the transparent substrate and the metal layer may be insufficient. Therefore, in the case where a metal layer is directly formed on the upper surface of the transparent substrate, the metal layer sometimes peels off from the transparent substrate during the manufacturing process or use.

On the other hand, in the conductive substrate of the present embodiment, in order to improve the adhesion between the transparent substrate and the metal layer, an adhesion layer may be disposed on the transparent substrate.

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 peeling of the metal layer from the transparent substrate can be suppressed.

Further, the adhesion layer can also function as a blackening layer. Therefore, it is also possible to suppress light reflection from the metal layer due to light on the lower surface side of the metal layer, that is, on the transparent substrate side.

The material constituting the adhesion layer is not particularly limited, and may be based on the adhesion to the transparent substrate and the metal layer, the degree of suppression of light reflection on the surface of the desired metal layer, and the environment in which the conductive substrate is used (for example, humidity and temperature). The degree of stability, etc., can be arbitrarily chosen.

The material constituting the adhesion layer preferably contains at least one metal selected from the group consisting of Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. In addition, close The layer may contain one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen.

Further, the adhesion layer may further contain a metal alloy containing at least two or more metals selected from the group consisting of Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. In this case, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen may be contained. Here, as the metal alloy containing at least two or more metals selected from the group consisting of Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn, Cu-Ti can be preferably used. -Fe alloy, Cu-Ni-Fe alloy, Ni-Cu alloy, Ni-Zn alloy, Ni-Ti alloy, Ni-W alloy, Ni-Cr alloy, Ni-Cu-Cr alloy.

The film formation method of the adhesion layer is not particularly limited, but it is preferably 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 preferable to use a sputtering method in view of easy control of the film thickness. Further, as described above, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen may be added to the adhesion layer. In this case, a reactive sputtering method is more preferably used.

In addition, when the adhesion layer contains one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen, it is possible to preliminarily add carbon, oxygen, and hydrogen from the atmosphere during film formation on the adhesion layer. A gas of one or more elements selected from nitrogen can be added to the adhesion layer. For example, in the case of adding carbon to the adhesion layer, carbon monoxide gas and/or carbon dioxide gas may be selected, oxygen may be selected when oxygen is added, hydrogen and/or water may be selected when hydrogen is added, and nitrogen may be selected when nitrogen is added. Nitrogen was added in advance to the atmosphere at the time of dry plating.

It is preferable to add a gas containing one or more elements selected from carbon, oxygen, hydrogen, and nitrogen to an inert gas as an atmosphere gas during dry plating. The inert gas is not particularly limited, and for example, argon can be preferably used.

By performing the mold formation of the adhesion layer by the dry plating method as described above, the adhesion between the transparent substrate and the adhesion layer can be improved. Further, since the adhesion layer can contain, for example, a metal as a main component, the adhesion to the metal layer is high. Thereby, by disposing an adhesion layer between a transparent substrate and a metal layer, peeling of a metal layer can be suppressed.

The thickness of the adhesion layer is not particularly limited, and is, for example, preferably 3 nm or more and 50 nm or less, more preferably 3 nm or more and 35 nm or less, and still more preferably 3 nm or more and 33 nm or less.

When the adhesion layer is also used as a blackening layer, that is, when the light reflection of the metal layer is suppressed, the thickness of the adhesion layer is preferably 3 nm or more as described above.

The upper limit of the thickness of the adhesion layer is not particularly limited, but the unnecessary thickening increases the time required for film formation or the time required for etching when wiring is formed, and the cost is increased. Therefore, the thickness of the adhesion layer is preferably 50 nm or less, more preferably 35 nm or less, still more preferably 33 nm or less as described above.

Next, a configuration example of the conductive substrate will be described.

As described above, the conductive substrate of the present embodiment includes a transparent substrate, a metal layer, and a blackened layer, and may have a structure in which a metal layer and a blackened layer are sequentially laminated on a transparent substrate.

A specific configuration example will be described below with reference to FIGS. 1A and 1B. 1A and 1B are views showing an example of a cross-sectional view of the conductive substrate of the embodiment along a plane parallel to the lamination direction of the transparent substrate, the metal layer, and the blackened layer.

For example, the conductive substrate 10A shown in FIG. 1A can be formed by laminating one layer of the metal layer 12 and the blackening layer 13 in this order on the first principal plane 11a side of the transparent substrate 11. Further, as shown in FIG. 1B, the conductive substrate 10B may be formed by sequentially laminating the metal layers 12A and 12B and the blackening layer 13A on the first principal plane 11a side and the second principal plane 11b side of the transparent substrate 11, respectively. The composition of each layer of 13B.

The conductive substrate of the present embodiment can be used for various applications such as a touch panel. Further, when used in various applications, it is preferred to pattern the metal layer and the blackened layer contained in the conductive substrate of the present embodiment. For example, the metal layer and the blackened layer may be patterned according to a desired wiring pattern, and the metal layer and the blackened layer are preferably patterned into the same shape.

In the conductive substrate of the present embodiment, as described above, the blackening layer 13 (13A, 13B) is disposed on the upper surface of the metal layer 12 (12A, 12B). Therefore, light reflection from the upper surface side of the metal layer 12 (12A, 12B) can be suppressed.

Further, as described above, for example, an adhesive layer (not shown) may be provided between the transparent substrate 11 and the metal layer 12. Here, in the case of the conductive substrate 10B shown in FIG. 1B, an adhesion layer may be provided between the transparent substrate 11 and the metal layer 12A and/or between the transparent substrate 11 and the metal layer 12B. By providing the adhesion layer, the adhesion between the transparent substrate 11 and the metal layers 12 (12A, 12B) can be improved, and the peeling of the metal layers 12 (12A, 12B) from the transparent substrate 11 can be suppressed. Further, by providing the adhesion layer, it is possible to suppress light reflection on the surface of the metal layer 12 (12A, 12B) where the blackening layer is not provided, which is preferable.

Further, when the metal layer and the blackened layer are patterned, the adhesion layer may be patterned, for example, according to a desired wiring pattern, and the adhesion layer, the metal layer, and the blackened layer are preferably patterned into the same shape.

The degree of light reflection of the conductive substrate of the present embodiment is not particularly limited. For example, the light reflectance (positive reflectance) of a wavelength of 400 nm or more and 700 nm or less is preferably 35% or less, and more preferably 30% or less. When the light reflectance of the wavelength of 400 nm or more and 700 nm or less is 35% or less, for example, when it is used as a conductive substrate for a touch panel, the visibility of the display is hardly reduced, which is preferable.

The measurement of the reflectance can be carried out by irradiating light to the blackening layer 13 (13A, 13B).

Specifically, for example, as shown in FIG. 1A, when the metal layer 12 and the blackening layer 13 are laminated in this order on the first principal plane 11a side of the transparent substrate 11, the blackening layer 13 is irradiated with light. The surface 13a side of the blackening layer 13 was irradiated with light and measured. At the time of measurement, light having a wavelength of 400 nm or more and 700 nm or less can be irradiated to the blackened layer 13 of the conductive substrate at intervals of, for example, a wavelength of 1 nm, and the average value of the measured values is used as the reflectance of the conductive substrate. .

Further, regarding the surface of the blackening layer 13 (13A, 13B) of the conductive substrate of the present embodiment, the value of the luminance (L*) of the L*a*b* color system is preferably small. The reason is that the smaller the value of the luminance (L*), the less conspicuous the blackening layer 13 (13A, 13B) and the metal layer 12 (12A, 12B), and the surface luminance of the blackening layer 13 (13A, 13B) (L) *) is preferably 60 or less.

Further, since the metal layer as described above is provided on the conductive substrate of the present embodiment, the surface resistance of the conductive substrate can be reduced. The surface resistance is preferably less than 0.2 Ω/□, more preferably less than 0.15 Ω/□, and still more preferably less than 0.06 Ω/□. The method for measuring the surface resistance is not particularly limited. For example, the measurement can be carried out by a 4-probe method, and it is preferred to measure the manner in which the probe is in contact with the blackened layer of the conductive substrate.

The conductive substrate of the present embodiment has been described so far, and a plurality of conductive substrates of the present embodiment may be laminated to form a laminated conductive substrate. When laminating a conductive substrate, it is preferable to pattern the metal layer and the blackened layer contained in the conductive substrate as described above. Further, in the case where the adhesion layer is provided, it is preferable to pattern the adhesion layer as well.

In particular, when it is used for a touch panel, the conductive substrate or the laminated conductive substrate preferably has mesh-like wiring as will be described later.

Here, a laminate guide having mesh-like wiring is formed by laminating two conductive substrates In the case of an electric substrate, an example of a configuration of a metal layer formed on a conductive substrate before lamination and a pattern shape of a metal layer will be described with reference to FIGS. 2A and 2B. Here, the patterned metal layer functions as a wiring, and the adhesion layer and/or the blackening layer may constitute a part of the wiring according to the resistance value thereof.

2A is a conductive substrate among two conductive substrates constituting a laminated conductive substrate including mesh wiring, from the upper surface side of the conductive substrate 20, that is, a direction perpendicular to the principal plane of the transparent substrate 11. A diagram when observing. In addition, Fig. 2B shows a cross-sectional view taken along line A-A' in Fig. 2A.

In the conductive substrate 20 shown in FIGS. 2A and 2B, the patterned metal layer 22 and the blackened layer 23 on the transparent substrate 11 have the same shape. For example, the patterned blackening layer 23 has a plurality of patterns (blackening layer patterns 23A to 23G) having a linear shape as shown in FIG. 2A, and the pattern of the plurality of linear shapes may be parallel to the Y axis in the drawing and in the figure X They are arranged apart from each other in the axial direction. Here, as shown in FIG. 2A, when the transparent substrate 11 has a square shape, it is preferable that the blackening layer patterns (blackening layer patterns 23A to 23G) are arranged in parallel with one side of the transparent substrate 11.

Further, as described above, the patterned metal layer 22 is patterned similarly to the patterned blackening layer 23, and also has a plurality of patterns (metal layer patterns) having a linear shape, and the plurality of patterns may be arranged in parallel and separated. Further, when an adhesion layer (not shown) is provided, the adhesion layer may be the same pattern. Therefore, the first main plane 11a of the transparent substrate 11 is exposed between the patterns.

The pattern forming method of the patterned metal layer 22 and the blackening layer 23 shown in FIGS. 2A and 2B is not particularly limited. For example, after the blackening layer 13 is formed on the conductive substrate shown in FIG. 1A, a mask having a shape corresponding to the pattern to be formed is disposed on the surface 13a of the blackening layer 13 and etched to form pattern. The etching liquid to be used is not particularly limited and may be configured according to the composition. The material of the etching layer is arbitrarily selected. For example, the etching liquid may be changed for each layer, or the metal layer and the blackening layer may be simultaneously etched using the same etching liquid, and the adhesion layer may be etched as the case may be.

Further, by laminating two conductive substrates on which the metal layer and the blackened layer are patterned, a laminated conductive substrate can be formed. The laminated conductive substrate will be described with reference to FIGS. 3A and 3B. 3A is a view showing the laminated conductive substrate 30 as viewed from the upper surface side in the stacking direction of the two conductive substrates, and FIG. 3B is a cross-sectional view taken along line BB' of FIG. 3A. .

As shown in FIG. 3B, the laminated conductive substrate 30 is formed by laminating a conductive substrate 201 and a conductive substrate 202. Here, the conductive substrates 201 and 202 are each formed with a patterned metal layer 221 (222) and a blackened layer 231 (232) on the first principal plane 111a (112a) of the transparent substrate 111 (112). Similarly to the above-described conductive substrate 20, the patterned metal layer 221 (222) and the blackened layer 231 (232) of the conductive substrates 201 and 202 are patterned into a plurality of patterns having a linear shape.

Further, the first main plane 111a of the transparent substrate 111 of the one conductive substrate 201 is opposed to the second principal plane 112b of the transparent substrate 112 of the other conductive substrate 202.

Here, the conductive substrate 201 may be laminated upside down so that the second principal plane 111b of the transparent substrate 111 of one conductive substrate 201 and the transparent substrate 112 of the other conductive substrate 202 may be laminated. 2 The main plane 112b is opposite. In this case, the configuration is the same as that of FIG. 4 described below.

When two conductive substrates are laminated, as shown in FIGS. 3A and 3B, the patterned metal layer 221 of one conductive substrate 201 and the patterned metal layer 222 of the other conductive substrate 202 may be laminated. Specifically, for example, in FIG. 3A and FIG. 3B, a conductive substrate 201 is used. The patterned metal layer 221 may be configured such that the length direction of the pattern is parallel to the X-axis direction in the drawing. The patterned metal layer 222 of the other conductive substrate 202 may be arranged such that the longitudinal direction of the pattern is parallel to the Y-axis direction in the drawing.

In addition, FIG. 3A is a view as seen from the direction in which the laminated conductive substrate 30 is laminated as described above, and thus the patterned blackened layers 231 and 232 disposed on the uppermost portions of the respective conductive substrates 201 and 202 are shown. Since the patterned metal layers 221 and 222 also have the same pattern as the patterned blackened layers 231 and 232, the patterned metal layers 221 and 222 also have the same mesh shape as the patterned blackened layers 231 and 232. Further, in the case where the adhesion layer is provided, the patterned adhesion layer may have the same mesh shape as the patterned blackening layers 231 and 232.

The method of attaching the two conductive substrates to be laminated is not particularly limited, and for example, it can be attached and fixed by using an adhesive or the like.

As described above, by laminating one conductive substrate 201 and the other conductive substrate 202, the laminated conductive substrate 30 having the mesh wiring as shown in FIG. 3A can be obtained.

In addition, although the example which combined the linear-shaped wiring and the mesh-shaped wiring (wiring pattern) was shown in FIG. 3A and FIG. 3B, it is not limited to this, and the wiring which comprises a wiring pattern can be arbitrary shapes. For example, in order to avoid generation of ripples (interference fringes) between the display images, the shapes of the wirings constituting the mesh-shaped wiring pattern may be various shapes such as a zigzag curved line (a zigzag straight line).

Here, an example in which two conductive substrates are laminated to form a laminated conductive substrate having a mesh wiring is described. However, the method of forming a conductive substrate including mesh wiring (layered) is not limited to this embodiment. For example, the conductive substrate 10B in which the metal layers 12A and 12B and the blackening layers 13A and 13B are laminated on the first main plane 11a and the second main plane 11b of the transparent substrate 11 as shown in FIG. 1B can be formed to have a mesh. A conductive substrate of a wiring.

In this case, the metal layer 12A and the blackening layer 13A laminated on the first principal plane 11a side of the transparent substrate 11 are patterned to form a Y-axis direction in FIG. 1B, that is, perpendicular to the paper surface. A pattern of a plurality of linear shapes parallel to the direction. In addition, the metal layer 12B and the blackening layer 13B which are laminated on the second principal plane 11b side of the transparent substrate 11 are patterned to form a plurality of linear patterns parallel to the X-axis direction in FIG. 1B. Patterning can be performed, for example, by etching as described above. As a result, as shown in FIG. 4, the patterned metal layer 42A formed on the first principal plane 11a side of the transparent substrate sandwiching the transparent substrate 11 and the patterned metal layer formed on the second principal plane 11b side are formed. 42B constitutes a conductive substrate 40 having mesh wiring. Further, in this case, the blackened layers 43A and 43B which are similarly patterned are disposed on the upper surfaces of the patterned metal layers 42A and 42B.

According to the (layered) conductive substrate described above, a patterned blackened layer is disposed on the upper surface of the patterned metal layer. Thereby, light reflection on the surface of the patterned metal layer can be suppressed. In addition, since the metal layer is disposed, the resistance value can be reduced. Further, since the blackened layer is formed by the wet method as described above, the productivity at the time of production is good.

(Method for Producing Conductive Substrate, Method for Manufacturing Multilayer Conductive Substrate)

Hereinafter, a configuration example of a method for producing a conductive substrate and a method for producing a laminated conductive substrate according to the present embodiment will be described.

The method for producing a conductive substrate of the present embodiment may have the following steps. A metal layer forming step of forming a metal layer on at least one side of the transparent substrate.

A blackening layer forming step of forming a blackened layer of nickel and zinc on the metal layer by a wet method.

In the following, a method for producing a conductive substrate and a method for producing a laminated conductive substrate according to the present embodiment will be described. In addition to the contents described below, the same configuration as in the case of the conductive substrate or the laminated conductive substrate can be employed. The description is omitted.

A transparent substrate for the metal layer forming step can be prepared in advance. The type of the transparent substrate to be used is not particularly limited, and a visible light-permeable resin substrate (resin film) or a glass substrate as described above can be preferably used. The transparent substrate can be previously cut into an arbitrary size or the like as needed.

Further, as described above, the metal layer preferably has a metal thin film layer. In addition, the metal layer may have a metal thin film layer and a metal plating layer. Therefore, the metal layer forming step may have a step of forming a metal thin film layer by, for example, dry plating. Further, the metal layer forming step may have a step of forming a metal thin film layer by dry plating, and a step of forming a metal plating layer by electroplating as one of wet plating methods using the metal thin film layer as a power supply layer.

The dry plating method used in the step of forming the metal thin film layer is not particularly limited, and for example, a vapor deposition method, a sputtering method, an ion plating method, or the like can be used. Here, a vacuum vapor deposition method can be preferably used as the vapor deposition method. As the dry plating method employed in the step of forming the metal thin film layer, in particular, it is preferable to use a sputtering method in view of easy control of the film thickness.

When the metal thin film layer is formed by a sputtering method, for example, a roll-to-roll sputtering apparatus can be suitably used for film formation.

A method of forming a metal thin film layer will be described by taking a case where the roll-to-roll sputtering apparatus 50 is used as an example.

Fig. 5 shows a configuration example of the roll-to-roll sputtering apparatus 50.

The roll-to-roll sputtering apparatus 50 has a casing 51 that houses almost all of its constituent parts.

The shape of the casing 51 in FIG. 5 is a rectangular parallelepiped shape. However, the shape of the casing 51 is not particularly limited, and any shape may be adopted depending on the apparatus, the installation position, the pressure resistance, and the like contained therein. For example, the shape of the housing 51 may be a cylindrical shape.

Here, in order to remove residual gas irrespective of film formation at the start of film formation, it is preferable to reduce the pressure inside the casing 51 to 10 ^-3 Pa or less, and more preferably to 10 ^-4 Pa or less. In addition, it is not necessary to reduce the pressure inside the casing 51 to the above-described pressure, and it is also possible to reduce only the region on the lower side in the drawing in which the can roll 53 described later is disposed, to the above-described sputtering. pressure.

The winding roller 52, the can roller 53, the sputtering cathodes 54a to 54d, the front supply roller 55a, the rear supply roller 55b, the tension roller 56a, and the deposition roller 52 for supplying the film formation substrate of the metal thin film layer may be disposed in the casing 51. 56b, take-up roll 57. Further, in addition to the above-described rollers, any of the guide rollers 58a to 58h, the heater 61, and the like may be provided on the transport path of the film formation substrate of the metal thin film layer.

The take-up roller 52, the can roller 53, the front feed roller 55a, and the take-up roller 57 may be provided with power supplied from a servo motor. The take-up roll 52 and the take-up roll 57 can be configured such that the tension balance of the film formation substrate of the metal thin film layer can be maintained by the torque control of the particle clutch or the like.

The configuration of the can roller 53 is not particularly limited. For example, it is preferably configured such that the surface thereof is processed by hard chrome plating, and the inside of the casing 51 has a refrigerant or a heat medium circulating from the outside of the casing 51, and can be adjusted to a substantially stable temperature.

For example, the tension rolls 56a, 56b are preferably machined with a hard chrome plating and have a tension sensor.

Further, the surfaces of the front supply roller 55a, the rear supply roller 55b, and the guide rollers 58a to 58h are also preferably processed by hard chrome plating.

Preferably, the sputtering cathodes 54a to 54d are arranged such that the magnetron cathode type faces the can roller 53. The size of the sputtering cathodes 54a to 54d is not particularly limited, and it is preferable that the thickness of the film-forming substrate of the metal thin film layer of the sputtering cathodes 54a to 54d in the width direction is larger than the width of the film-forming substrate of the metal thin film layer.

The film-forming substrate of the metal thin film layer is conveyed in a roll-to-roll sputtering apparatus 50 as a roll-to-roll vacuum film forming apparatus, and a metal thin film is formed by sputtering cathodes 54a to 54d opposed to the can roller 53. Floor.

When a film formation of a metal thin film layer is performed using the roll-to-roll sputtering apparatus 50, a prescribed target is mounted. The cathodes 54a to 54d are sputtered, and the film forming substrate of the metal thin film layer is placed in the winding roller 52, and evacuated by vacuum pumps 60a and 60b. Then, the sputtering gas is introduced into the casing 51 by the gas supply means 59. In this case, it is preferable to adjust the flow rate of the sputtering gas and the opening degree of the pressure regulating valve provided between the vacuum pump 60b and the casing 51, and to maintain the inside of the apparatus at, for example, 0.13 Pa or more and 13 Pa or less. membrane.

Further, the gas supply means 59 may include, for example, a cylinder (not shown) for each gas type of the sputtering gas supplied thereto. Further, a mass flow controller (MFC) or a valve as shown in the figure may be provided between the cylinder and the casing 51, for example, for each gas type, to constitute a configuration capable of adjusting the flow rate of the supplied sputtering gas.

Further, for example, vacuum gauges 62a and 62b may be provided in the casing 51 in advance to adjust the degree of vacuum in the casing 51 when the sputtering gas is supplied into the casing 51 when vacuum suction is applied to the casing 51. Composition.

In this state, for example, the substrate is conveyed from the take-up roll 52 at a speed of 1 m or more and 20 m or less per minute, and electric power is supplied from a DC power source for sputtering connected to the sputter cathodes 54a to 54d to perform sputtering discharge. Thereby, continuous film formation of a desired metal thin film layer can be performed on a base material.

Hereinafter, the step of forming a metal plating layer will be described. The conditions of the step of forming the metal plating layer by the wet plating method, that is, the conditions of the plating treatment are not particularly limited, and the conditions of the usual methods may be employed. For example, a substrate on which a metal thin film layer is formed is supplied to a plating tank containing a metal plating solution, and a metal plating layer can be formed by controlling the current density and the substrate transfer speed.

Hereinafter, the step of forming a blackening layer will be described.

In the step of forming a blackening layer, a blackening layer can be formed by a wet method. The blackening layer is formed by the wet method, and can be manufactured with good productivity as compared with the case where the blackening layer is conventionally formed only by the dry method. Conductive substrate.

Further, when the film formation of the blackened layer is carried out by a conventional dry method, for example, after the film formation of the metal plating layer is performed by a wet method, the film formation body is taken out from the film forming apparatus of the wet method, and it is necessary to form a film formation film. After the body is dried, it is placed on a dry process apparatus, resulting in a decrease in productivity. On the other hand, in the method for producing a conductive substrate of the present embodiment, since the blackened layer is formed by the wet method, the metal plating layer and the blackened layer can be continuously formed by the wet method, and the productivity can be remarkably improved.

The method of forming the blackening layer is a wet method, and is not particularly limited. For example, a method of newly forming a blackening layer by wet plating on a metal layer and laminating it may be mentioned. In this case, as the wet plating method, for example, an electroplating method can be preferably used.

Moreover, as a specific method of forming a blackening layer by a wet method, the method of forming a blackening layer by electroplating using the plating liquid containing nickel and zinc is mentioned. The type of the plating solution to be used in this case is not particularly limited, and for example, a black nickel plating solution containing nickel and zinc can be preferably used. Here, it is preferable to perform a preliminary test on the relationship between the composition of the plating solution and the composition of the blackening layer to be formed, and to select the composition of the plating solution to obtain a blackened layer having a desired composition.

In addition, any step can be implemented. For example, in the case where an adhesion layer is formed between the transparent substrate and the 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. In the case where the adhesion layer forming step is performed, the metal layer forming step may be performed after the adhesion layer forming step, and the film forming substrate of the metal thin film layer described in the metal layer forming step is formed on the transparent substrate in this step. The substrate of the adhesion layer.

For example, as shown in FIG. 1A, an adhesion layer can be formed on the first principal plane 11a which is a principal plane of the transparent substrate 11. Further, in the case of the conductive substrate 10B shown in FIG. 1B, an adhesion layer may be formed on both the first main plane 11a and the second main plane 11b of the transparent substrate 11. In transparent When both the first main plane 11a and the second main plane 11b of the substrate 11 form an adhesion layer, an adhesion layer may be simultaneously formed on the two principal planes. Alternatively, the adhesive layer may be formed on the other principal plane after the adhesive layer is formed on either of the main planes.

The material constituting the adhesion layer is not particularly limited, and may be based on the adhesion of the transparent substrate and the metal layer, the degree of suppression of light reflection on the surface of the metal layer, or the stability of the environment (for example, humidity or temperature) using the conductive substrate. Degree, etc., arbitrarily chosen. The materials which can be suitably used as the constituent adhesion layer have been described above, and a detailed description is omitted here.

The film formation method of the adhesion layer is not particularly limited, and for example, it can be formed by a dry plating method as described above. 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. As described above, one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen can be added to the adhesion layer. In this case, the reactive sputtering method is more preferably used.

Here, in order to make the adhesion layer contain one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen, it is possible to add one selected from carbon, oxygen, hydrogen, and nitrogen to the atmosphere in the film formation of the adhesion layer. The gas of the above elements can be added to the adhesion layer. For example, when carbon is added to the adhesion layer, carbon monoxide gas and/or carbon dioxide gas may be added in advance to an atmosphere during dry plating, and when oxygen is added, oxygen may be added in advance to an atmosphere during dry plating, and added. In the case of hydrogen, hydrogen gas and/or water may be added in advance to an atmosphere during dry plating, and when nitrogen is added, nitrogen gas may be added in advance to an atmosphere during dry plating.

It is preferable to add a gas containing one or more elements selected from carbon, oxygen, hydrogen, and nitrogen to an inert gas, thereby using it as an atmosphere gas in the dry plating. The inert gas is not particularly limited, and for example, argon is preferably used.

When the film formation of the adhesion layer is performed by a sputtering method, it can be used as a target to form a close contact. The target of the metal species of the layer. When the alloy layer is contained in the adhesion layer, the target may be used depending on the type of each metal contained in the adhesion layer, and an alloy may be formed on the surface of the film formation body such as a transparent substrate, or the metal contained in the adhesion layer may be alloyed in advance. The target.

For example, the roll-to-roll sputtering apparatus 50 shown in Fig. 5 can be used, and film formation of the adhesion layer is suitably performed.

The configuration of the roll-to-roll sputtering apparatus has been described, and a detailed description is omitted here.

When the adhesion layer is formed by the roll-to-roll sputtering apparatus 50, the metal target constituting the adhesion layer is attached to the sputtering cathodes 54a to 54d, and the substrate on which the adhesion layer is formed, for example, the transparent substrate is provided on the winding roller 52. . Then, vacuum evacuation is performed in the inside of the apparatus, for example, in the casing 51 by the vacuum pumps 60a and 60b. Then, a gas such as argon gas is introduced into the casing 51 by the gas supply means 59. In this case, it is preferable to adjust the opening degree of the pressure regulating valve provided between the vacuum pump 60b and the casing 51 by the flow rate of the sputtering gas, and to maintain the inside of the apparatus at, for example, 0.13 Pa or more and 13 Pa or less, and to perform film formation. .

In this state, the unwinding roller 52 transports the substrate at a speed of, for example, 0.5 m or more and 10 m or less, and electric power is supplied from a sputtering DC power source connected to the sputtering cathodes 54a to 54d to perform sputtering discharge. Thereby, a desired adhesive layer can be continuously formed on the substrate.

By forming the adhesion layer by the above dry plating method, the adhesion between the transparent substrate and the adhesion layer can be improved. Further, since the adhesion layer can contain, for example, a metal as a main component, the adhesion to the metal layer is high. Therefore, by disposing the adhesion layer between the transparent substrate and the metal layer, peeling of the metal layer can be suppressed.

The thickness of the adhesion layer is not particularly limited, and is, for example, preferably 3 nm or more and 50 nm or less, more preferably 3 nm or more and 35 nm or less, and still more preferably 3 nm or more and 33 nm or less.

The conductive substrate obtained by the method for producing a conductive substrate of the present embodiment can be used for various applications such as a touch panel. Moreover, when used in various applications, it is preferred to the present embodiment. The metal layer and the blackened layer contained in the conductive substrate are patterned. Further, in the case where the adhesion layer is provided, it is preferable to pattern the adhesion layer as well. For the metal layer and the blackened layer, the adhesion layer may be patterned according to a desired wiring pattern, for example, and the metal layer and the blackened layer are preferably patterned in the same shape as the case.

Thus, the method for producing a conductive substrate of the present embodiment may have a patterning step of patterning the metal layer and the blackened layer. Further, in the case where the adhesion layer is formed, the patterning step may be a step of patterning the adhesion layer, the metal layer, and the blackening layer.

The specific order of the patterning steps is not particularly limited and may be carried out in any order. For example, in the case where the conductive substrate 10A in which the metal layer 12 and the blackened layer 13 are laminated on the transparent substrate 11 shown in FIG. 1A, first, a mask having a desired pattern on the blackened layer 13 can be disposed. Membrane configuration steps. Next, an etching step of supplying an etching liquid to the upper surface of the blackening layer 13, that is, the surface side on which the mask is disposed is performed.

The etching liquid used in the etching step is not particularly limited, and may be arbitrarily selected depending on the material constituting the layer to be etched. For example, the etching liquid may be changed for each layer, or the metal layer and the blackening layer may be simultaneously etched by the same etching liquid, and the adhesion layer may be etched depending on the case.

The pattern formed in the etching step is not particularly limited. For example, the metal layer and the blackened layer may be patterned to form a plurality of patterns of a linear shape. When patterning is performed to form a plurality of patterns having a linear shape, as shown in FIGS. 2A and 2B, the patterned metal layer 22 and the blackened layer 23 may be parallel and separated from each other.

Further, the conductive substrate 10B in which the metal layers 12A and 12B and the blackening layers 13A and 13B are laminated on the first main plane 11a and the second main plane 11b of the transparent substrate 11 as shown in FIG. 1B can be carried out. Patterned patterning step. In this case, for example, it can be implemented in the blackening layers 13A, 13B. A mask configuration step of arranging a mask having a desired pattern thereon. Next, an etching step of supplying an etching liquid to the upper surface of the blackening layers 13A and 13B, that is, the surface side on which the mask is disposed may be performed.

In the etching step, for example, the metal layer 12A and the blackening layer 13A laminated on the first principal plane 11a side of the transparent substrate 11 can be patterned to form a Y-axis direction in FIG. 1B, that is, perpendicular to A pattern of a plurality of linear shapes in which the direction of the paper surface is parallel. In addition, the metal layer 12B and the blackening layer 13B which are laminated on the second principal plane 11b side of the transparent substrate 11 can be patterned to form a plurality of linear patterns parallel to the X-axis direction in FIG. 1B. As a result, as shown in FIG. 4, the patterned metal layer 42A formed on the first principal plane 11a side of the transparent substrate sandwiching the transparent substrate 11 and the patterned metal on the second principal plane 11b side are formed. The layer 42B constitutes a conductive substrate having mesh wiring.

Further, it is also possible to manufacture a laminated conductive substrate in which a plurality of conductive substrates described above are laminated. The method for producing a laminated conductive substrate may have a laminating step of laminating a plurality of conductive substrates obtained by the above-described method for producing a conductive substrate.

In the lamination step, for example, a plurality of patterned conductive substrates shown in FIGS. 2A and 2B can be laminated. Specifically, as shown in FIGS. 3A and 3B, the first principal plane 111a of the transparent substrate 111 of one conductive substrate 201 and the second principal plane 112b of the transparent substrate 112 of the other conductive substrate 202 may be employed. The implementation of the opposite layer.

After lamination, for example, two conductive substrates 201 and 202 may be fixed by an adhesive or the like.

Further, the conductive substrate 201 may be turned upside down, and the second principal plane 111b of the transparent substrate 111 of one conductive substrate 201 and the second principal plane 112b of the transparent substrate 112 of the other conductive substrate 202 may be paired. Gradient to the layer.

In the case of a laminated conductive substrate having mesh wiring, in the lamination step, As shown in FIGS. 3A and 3B, the patterned metal layer 221 formed in advance on one conductive substrate 201 and the patterned metal layer 222 formed on the other conductive substrate 202 may be laminated to each other.

3A and 3B show an example in which a mesh layer (wiring pattern) is formed by combining a metal layer patterned into a linear shape, but the embodiment is not limited thereto. The wiring constituting the wiring pattern, that is, the shape of the patterned metal layer may be any shape. For example, in order to avoid generation of ripples (interference fringes) between the display images, the shapes of the wirings constituting the mesh-shaped wiring pattern may be various shapes such as a zigzag curved line (a zigzag straight line). Further, as described above, the patterned metal layer functions as a wiring, but the adhesion layer and/or the blackening layer may constitute a part of the wiring depending on the resistance value.

In the conductive substrate and the laminated conductive substrate obtained by the method for producing a conductive substrate of the present embodiment and the method for producing a laminated conductive substrate, since the metal layer is provided, the resistance value can be reduced. Further, since the blackening layer is disposed on the metal layer, light reflection can be suppressed. Further, since the blackening layer can be formed by a wet method, it can be produced with good productivity.

[Examples]

Specific examples and comparative examples will be described below, but the present invention is not limited to these examples.

(evaluation method)

First, an evaluation method of the obtained conductive substrate will be described.

(composition of blackening layer)

The composition of the blackened layer formed on the surface of the obtained conductive substrate was analyzed using EPMA (Electron Probe MicroAnalyser, Japan Electronics Co., Ltd. model: JXA-8900R). Based on the measurement results, the sum of the weights of Ni and Zn contained in the blackened layer was calculated. It is the weight % of Ni and Zn at 100 hours.

(surface resistance)

The surface resistance of the conductive substrate produced in the following examples and comparative examples was measured using a low resistivity meter (manufactured by Dia Instruments Co., Ltd.: Loresta-EP MCP-T360). The measurement was carried out by means of a 4-probe method in such a manner that the probe was in contact with the blackening layer.

(Appearance evaluation)

The surface of the blackened layer was observed and evaluated for appearance. In the evaluation, the surface color of the blackened layer was uniform and the colorless spot was rated as “○”, the small spot was judged as “△”, and the surface of the blackened layer was marked as “×”.

(positive reflectance)

The reflectance measuring unit was set in an ultraviolet-visible spectrophotometer (model: UV-2600 manufactured by Shimadzu Corporation) and measured.

The surface of the blackened layer of the conductive substrate produced in the following examples and the comparative examples was irradiated with light having a wavelength of 400 nm or more and 700 nm or less at an incident angle of 5° and a light receiving angle of 5° at an interval of 1 nm, and the positive reflectance was measured. And the average value is used as the regular reflectance of the conductive substrate.

Further, in the conductive substrate produced in the following examples and comparative examples, an adhesive layer was formed between the transparent substrate 11 and the metal layer 12 in a cross section of a surface parallel to the lamination direction of each layer of the conductive substrate. Other than that, it has the same configuration as that of FIG. 1A. Therefore, the regular reflectance was measured by irradiating light to the surface 13a of the blackening layer 13. In the same manner as in the case of the following brightness, the surface 13a was irradiated with light and measured.

(brightness)

The surface of the blackened layer of the conductive substrate produced in the following examples and comparative examples was UV-coated. The spectrophotometer (Model: UV-2600, manufactured by Shimadzu Corporation) was irradiated with light having a wavelength of 400 nm or more and 700 nm or less at intervals of 1 nm, and the luminance was measured.

(production conditions of the sample)

As an example and a comparative example, a conductive substrate was produced under the conditions described below, and was evaluated by the above-described evaluation method.

[Example 1] (adhesion layer forming step)

A transparent substrate made of polyethylene terephthalate resin (PET) having a width of 500 mm and a thickness of 100 μm was placed in the roll-to-roll sputtering apparatus 50 shown in Fig. 5 .

In addition, the total light transmittance was evaluated by a method specified in JIS K 7361-1 on a transparent substrate made of a polyethylene terephthalate resin used as a transparent substrate, and it was 97%.

Further, by the roll-to-roll sputtering apparatus 50, the adhesion layer is formed on one principal plane of the transparent substrate. An oxygen-containing Ni-Cr alloy layer is formed as an adhesion layer.

The film formation conditions of the adhesion layer will be described.

As shown in Fig. 5, a target of Ni-17 wt% Cr alloy is connected to the sputtering cathodes 54a to 54d of the roll-to-roll sputtering apparatus 50.

The heater 61 of the roll-to-roll sputtering apparatus 50 was heated to 60 ° C to heat the transparent substrate to remove moisture contained in the transparent substrate.

Next, the inside of the casing 51 was evacuated to 1 × 10 ^-3 Pa, and then argon gas and oxygen gas were introduced to adjust the pressure in the casing 51 to 1.3 Pa. At this time, by adjusting the supply amount of argon gas and oxygen gas, the atmosphere in the casing 51 was made 30% by volume as oxygen, and the rest was argon.

Further, the transparent substrate is conveyed by the take-up roll 52, and is connected to the sputtering cathode 54a. The sputtering of 54d was supplied with electric power by a DC power source, and sputtering discharge was performed to form a desired adhesion layer continuously on the transparent substrate. By this operation, an adhesive layer having a thickness of 20 nm was formed on one principal plane of the transparent substrate.

(metal layer forming step)

In the metal layer forming step, a metal thin film layer forming step and a metal plating layer forming step are performed.

First, the metal thin film layer forming step will be described.

Film formation of the metal thin film layer is performed on the adhesion layer by the roll-to-roll sputtering apparatus 50. A copper thin film layer is formed as a metal thin film layer.

In the metal thin film layer forming step, the copper target is bonded to the sputtering cathodes 54A to 54d of the roll-to-roll sputtering apparatus 50 shown in Fig. 5, and the substrate is formed to be transparent in the adhesion layer forming step. An adhesive layer is formed on the substrate.

The conditions at the time of film formation of the metal thin film layer were carried out under the same conditions as those of the adhesion layer formation step except for the following two points and the above-described change of the target.

One of the points was that after the inside of the casing 51 was evacuated to 1 × 10 ^-3 Pa, argon gas was introduced, and the pressure inside the casing 51 was adjusted to 1.3 Pa.

On the other hand, the copper thin film layer as the metal thin film layer was molded to have a film thickness of 150 nm.

Then, in the metal plating layer forming step, a copper plating layer is formed as a metal plating layer. Film formation was performed by an electroplating method to make the thickness of the copper plating layer 2.0 μm.

(blackening layer forming step)

Black nickel bath black nickel GT solution (manufactured by Jessie Co., Ltd.), which is used in the plating solution The weight ratio of Ni to Zn was prepared to be a black nickel plating solution of 94:6, and a film was formed by electroplating to form a blackened layer having a thickness of 0.4 μm on the surface of the metal layer.

As described above, the blackening layer is formed on the upper surface of the metal layer, that is, on the opposite side of the surface of the metal layer opposite to the adhesion layer, and the adhesion layer and the metal layer are sequentially laminated on the transparent substrate. A conductive substrate of a blackened layer.

The composition, surface resistance, appearance, positive reflectance, and brightness of the above-described blackened layer were evaluated for the obtained conductive substrate. The results are shown in Table 1.

Here, the item described as "blackening layer composition (Ni:Zn)" in Table 1 indicates that Ni and Zn in the blackening layer are calculated based on the value of the EPMA analysis described above for the blackened layer produced. Weight ratio. In addition, the item of the "plating solution composition (Ni: Zn) at the time of formation of a blackening layer" shows the weight ratio of Ni and Zn in the plating liquid in the case of a blackening layer.

In the present embodiment and the following examples and comparative examples, the results of graphing the measured values of the surface resistance are shown in FIG. 6 , and the results of graphing the measured values of the regular reflectance are shown in FIG. 7 . The results of graphing the measured values of the brightness are shown in Fig. 8.

Regarding the conductive substrate obtained in the present experimental example, an etching step was performed after performing a mask disposing step of forming a mask corresponding to the pattern formed on the surface of the blackening layer. In the etching step, the adhesion layer, the metal layer and the blackening layer are etched by using an etching solution (aqueous copper dichloride solution), thereby obtaining an adhesion layer, a metal layer and a blackening layer are patterned into FIGS. 2A and 2B. A conductive substrate having a plurality of patterns in a straight line shape. Here, FIG. 2A and FIG. 2B show an example in which the adhesion layer is not disposed. In the present embodiment, an adhesion layer is disposed between the transparent substrate 11 and the metal layer 22, and the adhesion layer is patterned into a metal layer. And the same shape of the blackening layer.

In addition, in the same order as the method described above, an adhesion layer and a metal layer were fabricated. And the blackened layer is patterned into another conductive substrate having the same shape as the above case.

Then, the two conductive substrates produced were laminated as shown in FIGS. 3A and 3B, and two conductive substrates were fixed with an adhesive to form a laminated conductive substrate. Here, FIGS. 3A and 3B also show an example in which the adhesion layer is not provided. In the present embodiment, the adhesion between the transparent substrate 111 and the metal layer 221 and between the transparent substrate 112 and the metal layer 222 is disposed. The layer is patterned into the same shape as the metal layer 221 and the metal layer 222.

[Example 2]

In the blackening layer forming step, the black nickel bath black nickel GT solution (manufactured by Jessie Co., Ltd.) used as a weight ratio of Ni to Zn in the plating solution was prepared as a black nickel plating solution of 88:12. A conductive substrate was produced in the same manner as in Example 1 except the above.

The composition, surface resistance, appearance, positive reflectance, and brightness of the above-described blackened layer were evaluated for the obtained conductive substrate. The results are shown in Table 1.

Further, in the obtained conductive substrate, the adhesion layer, the metal layer, and the blackened layer were patterned in the same manner as in the first embodiment. Further, another conductive substrate in which the adhesion layer, the metal layer, and the blackening layer were patterned in the same manner was produced. Then, in the same manner as in the first embodiment, two conductive substrates were laminated and fixed to form a laminated conductive substrate.

[Example 3]

In the blackening layer forming step, the black nickel bath black nickel GT solution (manufactured by Jessie Co., Ltd.) was used as a black nickel plating solution having a weight ratio of Ni to Zn in the plating solution of 44:56. A conductive substrate was produced in the same manner as in Example 1 except the above.

The composition, surface resistance, appearance, positive reflectance, and brightness of the above-described blackened layer were evaluated for the obtained conductive substrate. The results are shown in Table 1.

Further, in the obtained conductive substrate, the adhesion layer, the metal layer, and the blackened layer were patterned in the same manner as in the first embodiment. Further, another conductive substrate in which the adhesion layer, the metal layer, and the blackening layer were patterned was also produced. Then, in the same manner as in the first embodiment, two conductive substrates were laminated and fixed, and a laminated conductive substrate was produced.

[Comparative Example 1]

In the blackening layer forming step, a nickel plating solution (manufactured by Jessie Co., Ltd.) in which the weight ratio of Ni to Zn in the plating solution was prepared to be 100:0 was used, except that it was the same as in Example 1. The conductive substrate was fabricated in the same manner.

The composition, surface resistance, appearance, positive reflectance, and brightness of the above-described blackened layer were evaluated for the obtained conductive substrate. The results are shown in Table 1.

Further, in the obtained conductive substrate, patterning of the adhesion layer, the metal layer, and the blackening layer was carried out in the same manner as in the case of Example 1. Further, another conductive substrate in which the adhesion layer, the metal layer, and the blackening layer were patterned in the same manner was produced. Then, in the same manner as in the case of Example 1, two conductive substrates were laminated and fixed to form a laminated conductive substrate.

[Comparative Example 2]

In the blackening layer forming step, a zinc plating solution (manufactured by Jessie Co., Ltd.) in which the weight ratio of Ni to Zn in the plating solution was prepared to 0:100 was used, except that it was the same as in Example 1. The conductive substrate was fabricated in the same manner.

The composition, surface resistance, appearance, positive reflectance, brightness, and the like of the above-described blackened layer were evaluated for the obtained conductive substrate. The results are shown in Table 1.

Further, in the obtained conductive substrate, patterning of the adhesion layer, the metal layer, and the blackening layer was carried out in the same manner as in the case of Example 1. Moreover, the same pair of adhesion layers, metal layers and The other layer of the conductive substrate on which the blackened layer is patterned. Then, in the same manner as in the case of Example 1, two conductive substrates were laminated and fixed to form a laminated conductive substrate.

From the results shown in Table 1 and FIG. 6 to FIG. 8 , the reflectance (positive reflectance) of the surface of the blackened layer of the conductive substrates of Examples 1 to 3 having a blackened layer containing nickel and zinc was confirmed. ) is 35% or less, the surface resistance is less than 0.06 Ω/□, and the luminance (L*) is 60 or less. From the results, it was confirmed that the conductive substrates obtained in Examples 1 to 3 can suppress reflection on the surface of the metal layer and have a small resistance value. Further, when the brightness was also 60 or less, it was confirmed that when the adhesion layer, the metal layer, and the blackened layer were patterned, the patterned adhesion layer, the metal layer, and the blackened layer were inconspicuous. Further, it was confirmed that the appearance of the conductive substrates of Examples 1 to 3 was evaluated as "○" or "Δ", and the color unevenness on the surface of the blackened layer was sufficiently suppressed.

On the other hand, in the comparative example 1 in which the blackening layer does not contain zinc, and the conductive substrate of the comparative example 2 in which the blackening layer does not contain nickel, it is confirmed that the reflectance is as high as 35.20% and 66.50%, respectively, and the surface of the metal layer cannot be sufficiently suppressed. Reflection. Further, in particular, the appearance of Comparative Example 2 was evaluated as "X", and it was confirmed that the stain on the surface of the blackened layer was severe.

Further, in the case of producing the laminated conductive substrates of Examples 1 to 3, it was confirmed that light reflection on the surface of the metal layer can be suppressed, and the laminate of the adhesion layer, the metal layer, and the blackened layer is inconspicuous.

From the above results, it was confirmed that the conductive substrate having the metal layer and the blackened layer containing nickel and zinc formed by the wet method has a small resistance value and can sufficiently suppress light reflection. Further, it has been confirmed that since the blackening layer can be formed by the wet method, it can be produced with good productivity.

The conductive substrate, the laminated conductive substrate, the method for producing the conductive substrate, and the method for producing the laminated conductive substrate have been described above by way of the embodiments and the examples, but the present invention is not limited to the above-described embodiments and examples. . Various modifications and changes can be made without departing from the spirit and scope of the invention.

The present application claims priority from Japanese Patent Application No. 2014-135123, the entire disclosure of which is incorporated herein by reference.

Claims (7)

A conductive substrate having: a transparent substrate; and comprising at least one side of the transparent substrate, containing Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, Mn An adhesion layer of at least one of the metals; a metal layer formed on the adhesion layer; and a blackening layer containing nickel and zinc formed on the metal layer by a wet method. The conductive substrate of the first aspect of the invention, wherein the proportion of nickel in the nickel and zinc contained in the blackened layer is 40% by weight or more and 99% by weight or less by weight. The conductive substrate of claim 1 or 2, wherein the adhesion layer, the metal layer, and the blackening layer are patterned. A laminated conductive substrate comprising a plurality of conductive substrates according to any one of claims 1 to 3. A method for producing a conductive substrate, comprising: forming at least one surface of a transparent substrate containing Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, Mn An adhesive layer forming step of an adhesive layer of at least one metal; a metal layer forming step of forming a metal layer on the adhesive layer; and a black layer containing a blackening layer of nickel and zinc on the metal layer by a wet method Layer formation step. The method for producing a conductive substrate according to claim 5, further comprising a patterning step of patterning the adhesion layer, the metal layer, and the blackening layer. A method for producing a laminated conductive substrate, comprising the step of laminating a plurality of conductive substrates obtained by a method for producing a conductive substrate according to claim 5 or 6.