TW201739967A - Blackening plating solution and method for manufacturing conductive substrate - Google Patents

Abstract

Provided is a blackening plating solution containing nickel ions, copper ions, and a pH adjusting agent, wherein the pH adjusting agent is an alkali metal hydroxide.

Description

Blackening plating solution and method for producing conductive substrate

The present invention relates to a blackening plating solution and a method of producing a conductive substrate.

The electrostatic capacitance type touch screen can detect the positional information of the approaching object on the surface of the panel 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 used in the electrostatic capacity type touch panel is provided on the surface of the display, the material of the conductive layer of the conductive substrate is required to have a low reflectance and is difficult to be visually recognized.

Therefore, as a material of the conductive layer used in the electrostatic capacitance type touch panel, a material having a low reflectance and being difficult to be visually recognized is used, and wiring is formed on the transparent substrate or the transparent film.

For example, Patent Document 1 discloses a transparent conductive film including a transparent conductive film composed of a metal oxide provided on a polymer film and a vapor phase film forming method thereof, and disclosed as As the transparent conductive film composed of a metal oxide, an indium oxide-tin oxide (ITO) film can be used.

In addition, in recent years, a display having a touch panel is becoming larger in size, and accordingly, a conductive substrate such as a transparent conductive film for a touch panel is required to have a large area. However, since the resistance value of ITO is high, there is a problem that it is impossible to cope with a large area of the conductive substrate.

Therefore, as a material of the conductive layer, it has been studied to use a metal such as copper instead of ITO. However, since the metal has a metallic luster, there is a problem that reflection causes a decrease in visibility of the display. To this end, it has been studied to form a black material on the surface of the conductive layer by a dry method. A blackened conductive substrate is formed on the layer formed.

However, it takes a long time to sufficiently carry out the blackening treatment on the surface of the conductive layer by the dry method, so that the productivity is low.

Therefore, the inventors of the present invention conducted the following research, that is, since the wet method does not require a vacuum environment as required by the dry method, the apparatus can be simplified and the productivity is also high, so that the wet method can be used for black. Processing. Specifically, it has been studied to use a plating solution containing Ni and Zn as a main component, and to form a blackening layer by a wet method.

[Previous Technical Literature] [Patent Document]

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

However, in the case of using a blackening treatment using a plating solution containing Ni and Zn as a main component and forming a blackening layer by a wet method, that is, a wet plating method, the blackened layer formed and The copper layer formed by the conductive layer may have higher reactivity with respect to the etching liquid than the copper layer formed. Further, in the case of producing a conductive substrate having a desired wiring pattern, after forming a copper layer and a blackening layer as a conductive layer, patterning by etching is required, however, due to the relative relationship between the copper layer and the blackening layer Since the reactivity of the etching liquid is different, there is a case where it is difficult to pattern the blackened layer into a desired shape.

In view of the above problems of the prior art, in an aspect of the invention, it is an object of the invention to provide a blackening plating solution capable of forming a blackening layer which can be patterned into a desired shape in the case of being etched together with a copper layer.

In order to solve the above problems, in one aspect of the invention, a blackening plating solution comprising: nickel ions, copper ions, and a pH adjuster, wherein the pH adjuster is an alkali metal hydroxide, is provided.

According to an aspect of the present invention, it is possible to provide a blackening plating solution capable of forming a blackening layer which can be patterned into a desired shape in the case of being etched together with a copper layer.

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

[Fig. 1B] A cross-sectional view of a conductive substrate according to an embodiment of the present invention.

[Fig. 2A] A cross-sectional view of a conductive substrate according to an embodiment of the present invention.

[Fig. 2B] A cross-sectional view of a conductive substrate according to an embodiment of the present invention.

[Fig. 3] A plan view of a conductive substrate including a mesh wiring according to an embodiment of the present invention.

[Fig. 4A] A cross-sectional view taken along line A-A' of Fig. 3.

[Fig. 4B] A cross-sectional view taken along line A-A' of Fig. 3.

Hereinafter, an embodiment of the blackening plating solution and the conductive substrate of the present invention will be described.

(blackening bath)

The blackening plating solution of the present embodiment includes nickel ions, copper ions, and a pH adjuster as a pH. An alkali metal hydroxide can be used as the regulator.

As described above, for example, by using a blackening layer containing a plating solution containing Ni and Zn as a main component and using a wet method, since the reactivity with respect to the etching liquid is higher than that of the copper layer, In the case of being etched together with the copper layer, it is difficult to be patterned into a desired shape. Therefore, the inventors of the present invention have conducted intensive studies on a blackening plating solution capable of forming a blackening layer which can be patterned into a desired shape in the case of being etched together with a copper layer.

Further, in the course of examining the blackening plating solution, the inventors of the present invention have also found that the reactivity of the blackening layer with respect to the etching liquid can be performed by making the blackening layer a layer containing nickel and copper. Suppression, even in the case of being etched together with the copper layer, a desired shape can be obtained. Further, by including nickel and copper in the blackening layer, a color which can suppress light reflection on the surface of the copper layer can be obtained. In addition, the desired shape (expected shape) in the case where the copper layer and the blackened layer are simultaneously etched as described herein means, for example, a shape and a pattern including a wiring having a wiring width of 10 μm or less.

Therefore, in the blackening plating solution of the present embodiment, it is preferable to form a plating solution containing a layer of nickel and copper as a metal component, and the blackening plating solution of the present embodiment may contain nickel ions and copper ions.

The concentration of each component in the blackening plating solution is not particularly limited. However, the concentration of nickel ions in the blackening plating solution is preferably 2.0 g/l or more, and preferably 3.0 g/l or more. The reason for this is that the blackening layer can have a color which is particularly suitable for suppressing light reflection on the surface of the copper layer by making the nickel ion concentration in the blackening plating solution 2.0 g/l or more, and can be applied to the conductive substrate. The reflectance is suppressed.

The upper limit of the nickel ion concentration in the blackening plating solution is not particularly limited, however, For example, it is preferably 20.0 g/l or less, preferably 15.0 g/l or less. The reason for this is that the nickel ion concentration in the blackening plating solution is 20.0 g/l or less, thereby suppressing the excessive nickel component in the blackened layer formed, and preventing the surface of the blackened layer from having nickel plating gloss. Such a surface can suppress the reflectance of the conductive substrate.

Further, the concentration of copper ions in the blackening plating solution is preferably 0.005 g/l or more, and preferably 0.008 g/l or more. The reason for this is that, in the case where the concentration of copper ions in the blackening plating solution is 0.005 g/l or more, the blackening layer can have a color which is particularly suitable for suppressing light reflection on the surface of the copper layer, and the blackening layer can be formed. The reactivity with respect to the etching liquid becomes a particularly suitable reactivity, and even if the copper layer and the blackening layer are etched together, it can be more reliably patterned into a desired shape.

The upper limit of the concentration of the copper ions in the blackening plating solution is not particularly limited, and is, for example, preferably 1.02 g/l or less, preferably 0.5 g/l or less. This is because the copper ion concentration in the blackening plating solution is 1.02 g/l or less, whereby the reactivity of the blackened layer formed with respect to the etching liquid can be prevented from being excessively high, and the blackening layer can be made special. It is suitable for suppressing the color of light reflection on the surface of the copper layer, and can suppress the reflectance of the conductive substrate.

When the blackening plating solution is prepared, the method of supplying nickel ions and copper ions is not particularly limited, and for example, it can be supplied in a salt state. For example, a sulfamic acid salt or a sulfate salt can be preferably used. In addition, as for the kind of salt, each metal element may be the same kind of salt, and different types of salt may be used simultaneously. Specifically, for example, a blackening plating solution can be prepared using the same type of salt such as nickel sulfate or copper sulfate. Further, for example, a different type of salt such as nickel sulfate or copper thiolate may be simultaneously used to prepare a blackening plating solution.

Further, the blackening plating solution of the present embodiment may further contain a pH adjuster.

As the pH adjuster, an alkali metal hydroxide can be preferably used. This is because the alkali metal hydroxide is used as the pH adjuster, and in particular, the reflectance of the conductive substrate having the blackened layer formed using the blackened plating solution can be reduced. When an alkali metal hydroxide is used as the pH adjuster, the reason why the reflectance of the conductive substrate having the blackened layer formed using the blackened plating solution can be reduced is not clear. The reason for this is considered to be that the hydroxide ions supplied to the blackening plating solution can excessively promote the precipitation of nickel oxide. By promoting the precipitation of nickel oxide, the blackened layer can be made to have a color which is particularly suitable for suppressing light reflection on the surface of the copper layer. Therefore, it can be inferred that the reflectance of the conductive substrate having the blackened layer can be suppressed.

As the alkali metal hydroxide of the pH adjuster, for example, one or more selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide can be used. In particular, the alkali metal hydroxide as the pH adjuster is preferably one or more selected from the group consisting of sodium hydroxide and potassium hydroxide. The reason is that sodium hydroxide and potassium hydroxide are very easy to obtain and the cost is also low.

The pH of the blackening plating solution of the present embodiment is not particularly limited. However, for example, it is preferably 4.0 or more and 5.2 or less, and preferably 4.5 or more and 5.0 or less.

The reason for this is that when the blackening plating solution is used to form a blackening layer by using the blackening plating solution at a pH of 4.0 or more, color unevenness in the blackening layer can be more reliably prevented, and it is possible to form A blackened layer of color suitable for suppressing light reflection on the surface of the copper layer. Further, by setting the pH of the blackening plating solution to 5.2 or less, precipitation of a part of the components of the blackening plating solution can be suppressed.

In addition, it is preferable that the blackening plating solution of this embodiment contains a pH adjuster so that a pH may fall in the said range.

The blackening plating solution of the present embodiment may include, in addition to nickel ions and copper ions An amide sulfuric acid that functions as a correcting agent. By containing an amide sulfuric acid, a blackening layer having a color particularly suitable for suppressing light reflection on the surface of the copper layer can be obtained.

The content of the amide sulfuric acid in the blackening plating solution is not particularly limited, and may be arbitrarily selected depending on the degree of suppression of the reflectance required for the blackened layer to be formed.

For example, although the concentration of the amide sulfuric acid in the blackening plating solution is not particularly limited, it is preferably, for example, 1 g/L or more and 50 g/L or less, preferably 5 g/l or more and 20 g/l or less. This is because the blackening layer can have a color which is particularly suitable for suppressing light reflection on the surface of the copper layer by setting the concentration of the amide sulfuric acid to 1 g/l or more, and can suppress the reflectance of the conductive substrate. In addition, even if an excessive amount of amide sulfuric acid of more than 50 g/l is added, the effect of suppressing the reflectance of the conductive substrate does not largely change. Therefore, as described above, it is preferably 50 g/l or less.

The blackening plating solution of the present embodiment may further contain any components other than the components described above. As a component which can be contained arbitrarily, a pit prevention agent for nickel plating is mentioned, for example. Examples of the pit-preventing agent for nickel plating include Pitless S (trade name) manufactured by Nippon Chemical Industry Co., Ltd., and Nickel Gleam NAW4 (trade name) manufactured by Rohm & Hass Co., Ltd., and the like.

According to the blackening plating solution of the present embodiment described above, in the case of being etched together with the copper layer, a blackening layer which can be patterned into a desired shape can be formed.

Further, the blackening plating solution of the present embodiment is particularly suitable for forming a blackening layer capable of sufficiently suppressing light reflection on the surface of the copper layer of the conductive substrate. Further, by using the blackening plating solution of the present embodiment, since the blackening layer can be formed by a wet method such as electrolytic plating, it is comparable to the blackening layer which has been formed by the dry method. The blackening layer is formed productively.

(conductive substrate)

Next, a configuration example of a conductive substrate including a blackened layer formed using the blackening plating solution of the present embodiment will be described.

The conductive substrate of the present embodiment may have a transparent substrate, a copper layer disposed on at least one surface of the transparent substrate, and a blackened layer formed by using a blackening plating solution on the copper layer.

In addition, the conductive substrate of the present embodiment includes a substrate having a copper layer and a blackened layer on the surface of the transparent substrate before patterning the copper layer or the like; and the copper layer and the like are performed. The patterned substrate, that is, the wiring substrate.

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

The transparent substrate is particularly limited, and a transparent substrate such as a resin substrate (resin film) or a glass substrate that allows visible light to pass through is preferably used.

As a material of the resin substrate which can transmit visible light, for example, a polyamide resin, a polyethylene terephthalate resin (PET), or a polyethylene naphthalate (PEN) system can be preferably used. A resin such as a resin, a cycloolefin resin, a polyimide (PI) resin, or a polycarbonate (PC) resin. In particular, as a material of the resin substrate through which visible light can be transmitted, PET (polyethylene terephthalate), COP (cycloolefin polymer), and PEN (polyethylene naphthalate) can be preferably used. , polyamide, polyimide, polycarbonate, and the like.

The thickness of the transparent substrate is not particularly limited, and can be arbitrarily selected depending on the strength, electrostatic capacity, light transmittance, and the like required when used as a conductive substrate. The thickness of the transparent substrate is, for example, preferably 10 μm or more and 200 μm or less. In particular, in the case of use for a touch panel, the thickness of the transparent substrate is preferably 20 μm or more and 120 μm or less, and preferably 20 μm or more and 100 μm or less. In the case of use for touch screens, for example, especially where the overall thickness of the display requires a thinner use The thickness of the transparent substrate is preferably 20 μm or more and 50 μm or less.

The total light transmittance of the transparent substrate is preferably high. For example, the total light transmittance is preferably 30% or more, and preferably 60% or more. When the total light transmittance of the transparent substrate is in the above range, for example, in the case of use for a touch panel, the visibility of the display can be sufficiently ensured.

It should be noted that the total light transmittance of the transparent substrate can be evaluated by the method specified in JIS K 7361-1.

Next, the copper layer will be described.

The method of forming the copper layer on the transparent substrate is not particularly limited. However, in order not to lower the light transmittance, it is preferred not to arrange an adhesive between the transparent substrate and the copper layer. That is, the copper layer is preferably formed directly on at least one surface of the transparent substrate. In the case where an adhesion layer is disposed between the transparent substrate and the copper layer as will be described later, the copper layer is preferably formed directly on the upper surface of the adhesion layer.

In order to form the copper layer directly on the upper surface of the transparent substrate or the like, the copper layer preferably has a copper thin film layer. In addition, the copper layer may also have a copper thin film layer and a copper plating layer.

For example, a copper thin film layer can be formed by dry plating on a transparent substrate, and the copper thin film layer can be used as a copper layer. According to this, the copper layer can be directly formed on the transparent substrate without using an adhesive. In addition, as a dry plating method, a sputtering method, a vapor deposition method, an ion plating method, etc. are preferable, for example.

Further, when the thickness of the copper layer is made thick, a copper thin film layer can be obtained by forming a copper plating layer by using a copper thin film layer as a power supply layer and using a plating method which is one of wet plating methods. Copper layer of copper plating. In this case, the copper layer has a copper thin film layer and a copper plating layer. The copper layer can also be formed directly on the transparent substrate without an adhesive.

The thickness of the copper layer is not particularly limited. When the copper layer is used as a wiring, it can be arbitrarily selected depending on the magnitude of the current supplied to the wiring, the width of the wiring, and the like.

However, if the copper layer is thick, since the time required for etching to form a wiring pattern is long, side etching is likely to occur, and there is a problem that it is difficult to form a thin line or the like. For this reason, the thickness of the copper layer is preferably 5 μm or less, and preferably 3 μm or less.

In particular, the thickness of the copper layer is preferably 50 nm or more, more preferably 60 nm or more, and preferably 150 nm or more from the viewpoint of reducing the electric resistance value of the conductive substrate so that current can be sufficiently supplied.

In the case where the copper layer has a copper thin film layer and a copper plating layer as described above, the total thickness of the copper thin film layer and the thickness of the copper plating layer are preferably in the above range.

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

As will be described later, the copper layer can be used as a wiring, for example, by being patterned into a desired wiring pattern. Further, since the resistance value of the copper layer can be made lower than that of the ITO used as the transparent conductive film, the resistance value of the conductive substrate can be lowered by providing the copper layer.

Next, the blackening layer will be described.

The blackening layer can be formed into a film using the blackening plating solution described above. For this reason, for example, after the formation of the copper layer, the blackening layer can be formed on the upper surface of the copper layer by a wet method such as electrolytic plating.

Since the blackening plating solution has been described above, the description thereof is omitted here.

The thickness of the blackening layer is not particularly limited, and is, for example, preferably 30 nm or more, and preferably 50 nm or more. This is because the light reflection on the surface of the copper layer can be suppressed particularly by making the thickness of the blackening layer 30 nm or more.

The upper limit of the thickness of the blackening layer is not particularly limited. However, if it is too thick, the time required for film formation and the time required for etching when wiring is formed become long, which leads to an increase in cost. For this reason, the thickness of the blackening layer is preferably 120 nm or less, preferably 90 nm or less.

It should be noted that, in the case where the blackening layer is formed by the above blackening plating solution, the blackening layer may be a layer including nickel and copper. Further, a component derived from various additive components contained in the blackening plating solution may be contained.

Further, an optional layer may be provided on the conductive substrate in addition to the above-described transparent substrate, copper layer, and blackened layer. For example, an adhesive layer can be provided.

A configuration example of the adhesion layer will be described.

As described above, the copper layer can be formed on the transparent substrate. However, in the case where the copper layer is directly formed on the transparent substrate, there is a case where the adhesion between the transparent substrate and the copper layer is insufficient. For this reason, in the case where a copper layer is directly formed on the upper surface of the transparent substrate, there is a case where the copper layer is peeled off from the transparent substrate during use or during use.

Therefore, in the conductive substrate of the present embodiment, in order to improve the adhesion between the transparent substrate and the copper layer, an adhesive layer can be disposed on the transparent substrate. That is, it may be a conductive substrate having an adhesion layer between the transparent substrate and the copper layer.

By providing an adhesive layer between the transparent substrate and the copper layer, the adhesion between the transparent substrate and the copper layer can be improved, and peeling of the copper layer from the transparent substrate can be prevented.

Further, the adhesion layer can also function as a blackening layer. For this, you can also Light reflection from the underside of the copper layer, that is, the light on the transparent substrate side, on the copper layer is suppressed.

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

The adhesion layer preferably includes, for example, at least one selected from the group consisting of Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. Further, the adhesion layer may further include one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen.

It should be noted that the adhesion layer may further include a metal alloy including at least 2 selected from the group consisting of Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. More than one kind of metal. In this case, the adhesion layer may further include one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen. In this case, Cu is preferably used as the metal alloy including 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. -Ti-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, however, it is preferable to form a film by a dry plating method. As the dry plating method, for example, a sputtering method, an ion plating method, a vapor deposition method, or the like can be preferably used. In the case where the adhesion layer is formed by a dry method, the film thickness can be easily controlled by the sputtering method, and therefore, a sputtering method is preferably used. In addition, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen may be added to the adhesion layer as described above. In this case, a reactive sputtering method is preferably used.

When the adhesion layer includes one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen, the inclusion of carbon, oxygen, hydrogen, and nitrogen from the ambient gas formed in advance in the adhesion layer is contained. The gas of one or more elements selected in the above may 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 to the ambient gas during dry plating in advance, and in the case where oxygen is added, the ambient gas may be previously subjected to dry plating. Oxygen is added thereto, and when hydrogen is added, hydrogen gas and/or water may be added to the ambient gas during dry plating in advance, and when nitrogen is added, nitrogen gas may be added to the ambient gas during dry plating in advance.

A gas containing one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen is preferably added to the inert gas as an ambient gas gas during dry plating. The inert gas is not particularly limited, and, for example, argon gas is preferably used.

By forming the film 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 may include, for example, a metal as a main component, the adhesion to the copper layer is also high. For this reason, peeling of the copper layer can be suppressed by disposing an adhesive layer between the transparent substrate and the copper layer.

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

When the adhesion layer also functions as a blackening layer, that is, when the light reflection of the copper 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. However, if it is too thick, the time required for film formation and the time required for etching when wiring are formed become long, resulting in an increase in cost. for Therefore, the thickness of the adhesion layer is preferably 50 nm or less as described above, more preferably 35 nm or less, and is preferably 33 nm or less.

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

As described above, the conductive substrate of the present embodiment may have a transparent substrate, a copper layer, and a blackened layer. Further, a layer having an adhesion layer or the like may be arbitrarily provided.

The specific configuration example will be described below with reference to FIGS. 1A, 1B, 2A, and 2B. 1A, 1B, 2A, and 2B show an example of a cross-sectional view of a surface of a conductive substrate of the present embodiment which is parallel to a lamination direction of a transparent substrate, a copper layer, and a blackened layer.

The conductive substrate of the present embodiment may have, for example, a structure in which a copper layer and a blackening layer are laminated in order from the transparent substrate side on at least one surface of the transparent substrate.

Specifically, for example, as in the conductive substrate 10A shown in FIG. 1A, a layer of each of the layers of the copper substrate 12 and the blackening layer 13 can be formed on the one surface 11a side of the transparent substrate 11. Further, as in the conductive substrate 10B shown in FIG. 1B, the copper layers 12A, 12B and the blackening layer 13A may be respectively on the one surface 11a side and the other surface (the other surface) 11b side of the transparent substrate 11. The order of 13B is performed as a layer of each layer.

Further, as an arbitrary layer, for example, an adhesion layer may be provided. In this case, for example, the adhesion layer, the copper layer, and the blackening layer may be formed in order from the transparent substrate side on at least one surface of the transparent substrate.

Specifically, for example, as in the conductive substrate 20A shown in FIG. 2A, the adhesion layer 14, the copper layer 12, and the blackening layer 13 may be laminated on the one surface 11a side of the transparent substrate 11.

In this case, a structure in which an adhesion layer, a copper layer, and a blackening layer are laminated on both surfaces of the transparent substrate 11 may be employed. Specifically, as in the conductive substrate 20B shown in FIG. 2B, the adhesion layers 14A, 14B, the copper layers 12A, 12B, and the black may be respectively on the one surface 11a side and the other surface 11b side of the transparent substrate 11. The layers 13A and 13B are laminated in this order.

In addition, in FIGS. 1B and 2B, in the case where a laminate of a copper layer, a blackening layer, or the like is performed on both surfaces of the transparent substrate, the transparent substrate 11 is used as a plane of symmetry. The layer in which the layers of the transparent substrate 11 are laminated in the upper and lower layers is symmetrical, but the configuration is not limited thereto. For example, in FIG. 2B, the structure on the one surface 11a side of the transparent substrate 11 can be made the same as that of FIG. 1B, that is, the adhesion layer 14A is not provided and the copper layer 12A and the blackening layer 13A are laminated in this order. Thus, the layer laminated on the upper and lower sides of the transparent substrate 11 can have an asymmetrical structure.

In the conductive substrate of the present embodiment, by providing a copper layer and a blackening layer on the transparent substrate, light reflection of the copper layer can be suppressed, and the reflectance of the conductive substrate can be performed. inhibition.

The degree of reflectance of the conductive substrate of the present embodiment is not particularly limited. However, in order to improve the visibility of the display when used as a conductive substrate for a touch panel, for example, the reflectance is preferably low. For example, the average reflectance of light having a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, more preferably 18% or less, and is preferably 10% or less.

The measurement of the reflectance can be performed by irradiating light to the blackened layer of the conductive substrate. Specifically, for example, as shown in FIG. 1A, on one surface 11a of the transparent substrate 11. When the copper layer 12 and the blackening layer 13 are layered in this order, the surface A of the blackening layer 13 is irradiated with light to irradiate the blackening layer 13 with light, and thus the measurement can be performed. 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 can be used as the conductivity. The reflectivity of the substrate.

The conductive substrate of the present embodiment is preferably used as a conductive substrate for a touch panel. In this case, the conductive substrate may have a structure including a mesh wiring.

The conductive substrate having the mesh wiring can be obtained by etching the copper layer and the blackened layer of the conductive substrate of the present embodiment described above.

For example, two layers of wiring can be used to obtain the mesh wiring. A specific configuration is shown in Fig. 3. FIG. 3 is a view showing a state in which the conductive substrate 30 having the mesh wiring is viewed from the upper surface side in the stacking direction of the copper layer or the like, and the transparent substrate and the copper layer are patterned in order to easily understand the wiring pattern. The illustration of the layers other than the formed wirings 31A and 31B is omitted. In addition, the wiring 31B which can be observed by the transparent substrate 11 is also shown.

The conductive substrate 30 shown in FIG. 3 has a transparent substrate 11 , a plurality of wires 31A parallel to the Y-axis direction in the drawing, and a wire 31B parallel to the X-axis direction. In addition, the wirings 31A and 31B are formed by etching a copper layer, and a blackening layer (not shown) is formed on the upper surface or the lower surface of the wirings 31A and 31B. Further, the blackening layer is etched into the same shape as the wirings 31A, 31B.

The arrangement of the transparent substrate 11 and the wirings 31A and 31B is not particularly limited. The configuration of the arrangement of the transparent substrate 11 and the wiring is shown in FIGS. 4A and 4B. 4A and 4B are cross-sectional views taken along line A-A' of Fig. 3.

First, as shown in FIG. 4A, wirings 31A and 31B can be disposed on the upper and lower surfaces of the transparent substrate 11. In addition, in FIG. 4A, the blackening layers 32A and 32B which are etched in the same shape as the wiring are disposed on the upper surface of the wiring 31A and the lower surface of the 31B.

Further, as shown in FIG. 4B, one set of the transparent substrate 11 may be used, the wirings 31A, 31B may be disposed on the upper and lower surfaces of the one transparent substrate 11, and the wiring 31B may be disposed between the transparent substrates 11. . In this case, blackening layers 32A and 32B which are etched into the same shape as the wiring may be disposed on the upper surfaces of the wirings 31A and 31B. It should be noted that as described above, an adhesion layer may be provided in addition to the copper layer and the blackening layer. For this reason, in the case of FIG. 4A or FIG. 4B, for example, an adhesion layer may be provided between the wiring 31A and/or the wiring 31B and the transparent substrate 11. When the adhesion layer is provided, the adhesion layer is preferably etched into the same shape as the wirings 31A and 31B.

For example, the conductive substrate having the mesh wiring shown in FIGS. 3 and 4A can be based on having the copper layers 12A, 12B and the blackening layers 13A, 13B on both surfaces of the transparent substrate 11 as shown in FIG. 1B. A conductive substrate is formed.

The case where the conductive substrate of FIG. 1B is used will be described as an example. First, the copper layer 12A and the blackened layer 13A on one surface 11a side of the transparent substrate 11 are etched so as to be in the Y-axis direction in FIG. 1B. A plurality of parallel linear patterns are arranged at predetermined intervals in the X-axis direction. It should be noted that the X-axis direction in FIG. 1B means a direction parallel to the width direction of each layer. In addition, the Y-axis direction in FIG. 1B means a direction perpendicular to the paper surface in FIG. 1B.

Next, the copper layer 12B on the other surface 11b side of the transparent substrate 11 is The blackening layer 13B is etched so that a plurality of linear patterns parallel to the X-axis direction in FIG. 1B are arranged along the Y-axis direction at predetermined intervals.

By the above operation, the conductive substrate having the mesh wiring shown in FIGS. 3 and 4A can be formed. It should be noted that both surfaces of the transparent substrate 11 may be simultaneously etched. That is, the copper layers 12A and 12B and the blackening layers 13A and 13B may be simultaneously etched. Further, as for the conductive substrate having the adhesion layer patterned in the same shape as the wirings 31A and 31B between the wirings 31A and 31B and the transparent substrate 11 in FIG. 4A, the conductive substrate can be used as shown in FIG. 2B. The conductive substrate is made by the same etching.

The conductive substrate having the mesh wiring shown in FIG. 3 can also be formed by using the two conductive substrates shown in FIG. 1A or 2A. The case where two conductive substrates shown in FIG. 1A are used will be described as an example, and the copper layer 12 and the blackening layer 13 of the conductive substrate shown in FIG. 1A are respectively etched so as to be X-axis. A plurality of linear patterns parallel in the direction are arranged along the Y-axis direction at predetermined intervals. Then, the two conductive substrates are bonded to each other so that the directions of the linear patterns formed on the respective conductive substrates by the etching treatment are mutually different, whereby a conductive substrate including the mesh wiring can be obtained. When bonding two conductive substrates, the bonding surface is not particularly limited. For example, the surface A in FIG. 1A in which the copper layer 12 or the like is laminated and the other surface 11b in FIG. 1A in which the copper layer 12 or the like is not laminated may be bonded, thereby obtaining the structure as shown in FIG. 4B. .

Further, for example, the other surface 11b of FIG. 1A in which the laminate of the copper layer 12 or the like is not laminated on the transparent substrate 11 can be bonded to each other, whereby a structure having a cross section as shown in FIG. 4A can be obtained.

It should be noted that, in the wirings 31A, 31 in FIGS. 4A and 4B Further, between B and the transparent substrate 11, there is a conductive substrate patterned into an adhesive layer having the same shape as the wirings 31A and 31B, which can be replaced by using the conductive substrate shown in FIG. 2A instead of FIG. 1A. The conductive substrate is shown.

The width of the wiring or the distance between the wirings in the conductive substrate having the mesh wiring shown in FIG. 3, FIG. 4A and FIG. 4B is not particularly limited, and for example, it can be selected according to the amount of current flowing in the wiring or the like.

However, according to the conductive substrate of the present embodiment, it is known that the blackened layer formed using the blackening plating solution described above can be used even when the blackening layer and the copper layer are simultaneously etched for patterning. The blackening layer and the copper layer are patterned into a desired shape. Specifically, for example, a wiring having a wiring width of 10 μm or less can be formed. Therefore, the conductive substrate of the present embodiment preferably includes a wiring having a wiring width of 10 μm or less. The lower limit of the wiring width is not particularly limited, and may be, for example, 3 μm or more.

In addition, in FIGS. 3, 4A, and 4B, although an example in which a linear wiring is formed to form a mesh wiring (wiring pattern) is shown, the configuration is not limited to this, and the wiring constituting the wiring pattern may be Arbitrary shape. For example, in order not to generate a moiré (interference pattern) with the image of the display, the shapes of the wirings constituting the mesh wiring pattern may be designed into various shapes such as a zigzag line ("straight line").

For the conductive substrate having the mesh wiring formed of the two-layer wiring, for example, it is preferably used as a projection type electrostatic capacitance type conductive substrate for a touch panel.

According to the conductive substrate of the present embodiment described above, the copper layer formed on at least one surface of the transparent substrate has a structure in which the blackened layer is laminated. In addition, since the blackening layer is formed using the blackening plating solution described above, the copper layer and blackening are performed by using etching. When the layer is patterned, the blackened layer can be easily patterned into a desired shape.

Further, in the conductive substrate of the present embodiment, the blackened layer included in the conductive substrate can sufficiently suppress light reflection on the surface of the copper layer, and thus it can be a conductive substrate in which the reflectance is suppressed. Further, for example, when used for a touch panel or the like, the visibility of the display can be improved.

Further, since the blackening layer can be formed by the wet method using the blackening plating solution described above, conductivity can be produced with good productivity as compared with the case of forming a blackening layer by the conventional dry method. Substrate.

(Method of Manufacturing Conductive Substrate)

Next, a configuration example of a method of manufacturing a conductive substrate of the present embodiment will be described.

The method for producing a conductive substrate of the present embodiment may have the following steps.

A copper layer forming step of forming a copper layer on at least one surface of the transparent substrate.

A blackening layer forming step of forming a blackening layer on the copper layer using a blackening plating solution.

It should be noted that as the blackening plating solution, the blackening plating solution described above may be used, and specifically, blackening plating including nickel ions, copper ions, and a pH adjusting agent and a pH adjusting agent as an alkali metal hydroxide may be used. liquid.

Hereinafter, a method of manufacturing the conductive substrate of the present embodiment will be specifically described.

In addition, the above-described conductive substrate can be preferably produced by the method for producing a conductive substrate of the present embodiment. For this reason, the portions other than the portions described below may be the same as those of the above-described conductive substrate, and thus the description thereof will be omitted.

A transparent substrate for use in the copper layer forming step can be prepared in advance. The type of the transparent substrate to be used is not particularly limited. However, as described above, a transparent substrate such as a resin substrate (resin film) or a glass substrate through which visible light can be transmitted can be preferably used. In addition, as needed, Cutting or the like is performed in advance to cut the transparent substrate into an arbitrary size.

Further, the copper layer preferably has a copper thin film layer as described above. In addition, the copper layer may also have a copper thin film layer and a copper plating layer. To this end, the copper layer forming step may have a step of forming a copper thin film layer by, for example, dry plating. Further, the copper layer forming step may have a step of forming a copper thin film layer by dry plating, and a step of forming the copper plating layer by using the copper thin film layer as a power supply layer and using a plating method which is one of wet plating methods.

The dry plating method used in the step of forming the copper 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. In addition, as a vapor deposition method, a vacuum vapor deposition method is preferable. As the dry plating method used in the step of forming the copper thin film layer, a sputtering method is preferably used from the viewpoint of particularly easily controlling the film thickness.

Next, the step of forming a copper plating layer will be described. The conditions in the step of forming the copper plating layer by the wet plating method, that is, the conditions of the plating treatment are not particularly limited, and various conditions in the conventional method can be employed. For example, the substrate on which the copper thin film layer is formed can be placed in a plating bath having a copper plating solution, and the copper plating layer can be formed by controlling the current density or the transport speed of the substrate.

Next, the blackening layer forming step will be described.

In the blackening layer forming step, a blackening layer may be formed using a blackening plating solution including the above-described nickel ions, copper ions, and a pH adjuster, and the pH adjusting agent is an alkali metal hydroxide.

The blackening layer can be formed by a wet method. Specifically, for example, a copper layer may be used as a power supply layer, and a blackening layer may be formed on the copper layer by electrolytic plating in a plating tank including the above-described blackening plating solution. By forming the blackened layer by electrolytic plating using the copper layer as the power supply layer in this manner, a blackened layer can be formed on the entire surface of the surface of the copper layer opposite to the surface facing the transparent substrate.

As far as the blackening bath is concerned, since it has already been described above, it is omitted. Bright.

In the method for producing a conductive substrate of the present embodiment, in addition to the above steps, any step may be carried out.

For example, in the case where an adhesion layer is formed between the transparent substrate and the copper layer, an adhesion layer forming step of forming an adhesion layer on the surface of the transparent substrate on which the copper layer is to be formed may be performed. In the case where the adhesion layer forming step is performed, the copper layer forming step may be performed after the adhesion layer forming step, in which case, in the copper layer forming step, an adhesion layer may be formed on the transparent substrate in this step. A copper thin film layer is formed on the substrate.

In the adhesion layer forming step, the film formation method of the adhesion layer is not particularly limited. However, it is preferable to form a film by a dry plating method. As the dry plating method, for example, a sputtering method, an ion plating method, a vapor deposition method, or the like can be preferably used. In the case where the adhesion layer is formed by a dry method, since the film thickness control can be easily performed, a sputtering method is preferably used. In addition, 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 preferably used.

The conductive substrate obtained by the method for producing a conductive substrate of the present embodiment can be used for various purposes such as a touch panel. Further, when used in various applications, the copper layer and the blackened layer included in the conductive substrate of the present embodiment are preferably patterned. In addition, in the case where an adhesion layer is provided, it is preferable to pattern the adhesion layer. With regard to the copper layer and the blackening layer and, as the case may be, the adhesion layer, for example, it can be patterned to conform to the intended wiring pattern, in terms of the copper layer and the blackening layer and, if appropriate, the adhesion layer, preferably To be patterned into the same shape.

Therefore, the method of manufacturing the conductive substrate of the present embodiment may have a copper layer and The blackening layer performs a patterning step of patterning. It should be noted that, in the case where the adhesion layer is formed, the patterning step may be a step of patterning the adhesion layer, the copper layer, and the blackening layer.

The specific steps of the patterning step are not particularly limited and may be carried out in any step. For example, in the case of the conductive substrate 10A in which the copper layer 12 and the blackening layer 13 are laminated on the transparent substrate 11 as shown in FIG. 1A, first, it can be disposed on the surface A of the blackening layer 13. A photoresist arrangement step of a resist having a predetermined pattern. Next, an etching step of supplying an etching liquid to the surface A of the blackening layer 13, that is, the surface side on which the photoresist is disposed can be performed.

The etching liquid used in the etching step is not particularly limited. However, the blackened layer formed by the method for producing a conductive substrate of the present embodiment has substantially the same reactivity with respect to the etching liquid as the copper layer. For this reason, the etching liquid used in the etching step is not particularly limited, and an etching liquid used in usual copper layer etching can be preferably used.

As the etching liquid, for example, a mixed aqueous solution containing one or more selected from the group consisting of sulfuric acid, hydrogen peroxide (hydrogen peroxide water), hydrochloric acid, cupric chloride, and ferric chloride can be preferably used. . The content of each component in the etching solution is not particularly limited.

The etching solution can be used at room temperature. However, in order to improve the reactivity, it may be heated. For example, it may be heated to 40 ° C or more and 50 ° C or less before use.

Further, for the conductive substrate 10B in which the copper layers 12A, 12B and the blackening layers 13A, 13B are laminated on one surface 11a and the other surface 11b of the transparent substrate 11 as shown in Fig. 1B, A patterning step for patterning is performed. In this case, for example, a photoresist arrangement step of arranging a photoresist having a desired pattern on the surface A and the surface B of the blackening layers 13A, 13B may be first performed. Can then be applied to the blackening layer 1 The surface A and the surface B of 3A and 13B, that is, the etching step of supplying the etching liquid to the surface side on which the photoresist is disposed.

The pattern formed in the etching step is not particularly limited and may be any shape. For example, in the case of the conductive substrate 10A shown in FIG. 1A, as described above, the copper layer 12 and the blackening layer 13 can be formed into a line including a plurality of straight lines or curved in a zigzag shape ("straight line") pattern.

Further, in the case of the conductive substrate 10B shown in FIG. 1B, a pattern such as a mesh wiring can be formed on the copper layer 12A and the copper layer 12B. In this case, the blackening layer 13A is preferably patterned to have the same shape as the copper layer 12A, and the blackening layer 13B is preferably patterned into the same shape as the copper layer 12B.

Further, for example, after the copper layer 12 or the like of the above-described conductive substrate 10A is patterned in the patterning step, a lamination step of laminating two or more patterned conductive substrates may be performed. In the case of laminating, for example, the pattern of the copper layer of each of the conductive substrates can be laminated, whereby a laminated conductive substrate including mesh wiring can be obtained.

The method of fixing the two or more laminated conductive substrates is not particularly limited, and may be fixed by, for example, an adhesive.

In the conductive substrate obtained by the method for producing a conductive substrate of the present embodiment, the black layer formed on at least one surface of the transparent substrate has a structure in which a blackened layer is laminated. Further, since the blackening layer is formed using the blackening plating solution described above, when the copper layer and the blackening layer are patterned by etching, the blackening layer can be easily patterned into a desired shape.

Moreover, it is obtained by the method for producing a conductive substrate of the present embodiment. In the conductive substrate, since the blackening layer included in the conductive layer can sufficiently suppress light reflection on the surface of the copper layer, it can be a conductive substrate in which the reflectance is suppressed. For this reason, for example, when it is used for a touch panel or the like, the visibility of the display can be improved.

Further, since the blackening layer is formed by the wet method using the above-described blackening plating solution, it is possible to produce conductively with good productivity as compared with the case of forming a blackening layer by the conventional dry method. Substrate.

[Examples]

The specific examples and comparative examples are described below, but the present invention is not limited to the examples.

(evaluation method)

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

(1) Reflectance

The measurement was carried out by providing a reflectance measuring unit on a UV-visible spectrophotometer (Model: UV-2600, manufactured by Shimadzu Corporation).

As described later, a conductive substrate having the structure shown in Fig. 1A was produced in each experimental example. For this reason, in the measurement of the reflectance, the surface of the blackening layer 13 of the conductive substrate 10A shown in Fig. 1A was applied at an interval of a wavelength of 1 nm under the conditions of an incident angle of 5° and a light receiving angle of 5°. A is irradiated with light having a wavelength of 400 nm or more and 700 nm or less, and the regular reflectance is measured, and then the average value thereof is taken as the reflectance (average reflectance) of the conductive substrate.

(2) Etching characteristics

First, a laminate was used on the surface of the blackening layer of the conductive substrate obtained in the following experimental examples. Laminating paste dry film photoresist (Hitachi Chemical Co., Ltd. RY3310). Next, ultraviolet exposure was performed by a photomask, and the photoresist was dissolved using a 1% aqueous sodium carbonate solution for development. According to this, a sample having a pattern having a different photoresist width per 0.5 μm in the range of 3.0 μm or more and 10.0 μm or less was produced. That is, 15 types of linear patterns each having a photoresist width of 3.0 μm, 3.5 μm, 4.0 μm, ‧‧ ‧ 9.5 μm, and 10.0 μm per 0.5 μm were formed.

Next, the sample was immersed in an etching solution of 30 ° C composed of 10% by weight of sulfuric acid and 3% by weight of hydrogen peroxide for 40 seconds, after which the dry film resist was peeled off and removed using an aqueous sodium hydroxide solution.

The obtained sample was observed using a 200-fold microscope, and the minimum value of the wiring width of the metal wiring remaining on the conductive substrate was obtained. In addition, the metal wiring here is a wire-shaped blackening layer and copper layer which are patterned into the wiring width corresponding to the photoresist width, ie, wiring.

After the photoresist is peeled off, the smaller the minimum value of the wiring width of the metal wiring remaining on the conductive substrate, the closer the reactivity of the copper layer and the blackened layer to the etching liquid is. When the minimum value of the wiring width of the remaining metal wiring is 10 μm or less, it is evaluated as ○ in Table 2, that is, it is acceptable. In addition, in the case where the metal wiring having a wiring width of 10 μm was not formed, it was evaluated as × in Table 2, that is, it was unacceptable.

(production conditions of the sample)

In each of the following experimental examples, a conductive substrate was produced under the conditions described below, and was evaluated by the above evaluation method.

Experimental Example 1 to Experimental Example 21 are examples, and Experimental Example 22 to Experimental Example 25 For the comparative example.

[Experimental Example 1]

(1) Blackening bath

In Experimental Example 1, a blackening plating solution containing nickel ions, copper ions, amide sulfuric acid, and sodium hydroxide was prepared. It is to be noted that the supply of nickel ions and copper ions is carried out by adding nickel sulfate 6 water and copper sulfate and water to the blackening plating solution.

Further, each component was added and prepared so that the nickel ion concentration in the blackening plating solution was 2.0 g/liter, the copper ion concentration was 0.005 g/liter, and the amide sulfuric acid concentration was 11 g/l.

Further, an aqueous sodium hydroxide solution was added to the blackening plating solution to adjust the pH of the blackening plating solution to 5.0.

(2) Conductive substrate

(copper layer forming step)

A copper layer was formed on one surface of a long transparent polyethylene terephthalate resin (PET) substrate having a length of 100 m, a width of 500 mm, and a thickness of 100 μm. In addition, the total light transmittance of the polyethylene terephthalate resin transparent substrate used as a transparent substrate was evaluated by the method prescribed by JIS K 7361-1, which was 97%. .

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

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

In the copper thin film layer forming step, the above transparent substrate is used as a substrate, and A copper thin film layer is formed on one surface of the transparent substrate.

In the copper thin film layer forming step, the transparent substrate previously heated to 60 ° C to remove moisture is first placed in the cavity of the sputtering apparatus.

Next, after evacuating the inside of the chamber to 1 × 10 ^-3 Pa, argon gas was introduced to adjust the pressure inside the chamber to 1.3 Pa.

Electric power was supplied to the copper target previously placed on the cathode of the sputtering apparatus, whereby film formation of a copper thin film layer having a thickness of 0.2 μm was performed on one surface of the transparent substrate.

Next, a copper plating layer is formed in the copper plating layer forming step. The copper plating layer is a film formed by a copper plating layer having a thickness of 0.3 μm by electroplating.

By performing the above copper thin film layer forming step and copper plating layer forming step, a copper layer having a thickness of 0.5 μm was formed as the copper layer.

The substrate having the copper layer having a thickness of 0.5 μm formed on the transparent substrate prepared in the copper layer forming step was immersed in 20 g/l of sulfuric acid for 30 seconds, and the following blackening layer formation step was carried out after the cleaning. .

(blackening layer forming step)

In the blackening layer forming step, a blackening layer was formed on one surface of the copper layer by using the blackening plating solution of the above experimental example and electrolytic plating. In the blackening layer forming step, electrolytic plating is performed under the conditions of a blackening bath temperature of 40 ° C, a current density of 0.2 A/dm ² , and a plating time of 100 sec (sec). This forms a blackening layer.

The film thickness of the formed blackening layer was 70 nm.

The above-described reflectance and etching characteristics were evaluated for the conductive substrate obtained by the above steps. The results are shown in Tables 2 and 3. It should be noted that Table 2 is etched. The evaluation results of the properties, Table 3 shows the evaluation results of the reflectance.

In Tables 2 and 3, the positions corresponding to the numbers of the experimental examples shown in Table 1 indicate the results of the respective experimental examples. For example, the positions of the nickel ion concentration represented by the experimental example 1 in Table 1 of 2.0 g/l and the copper ion concentration of 0.005 g/l are also shown in Table 2 and Table 3 as the results of Experimental Example 1.

[Experimental Example 2 to Experimental Example 24]

When the blackening plating solution was prepared, the same procedure as in Experimental Example 1 was carried out except that the nickel ion concentration and the copper ion concentration in the blackening plating solution were changed to the values shown in Table 1. The modulation of the blackening bath.

In addition, for example, in the case of Experimental Example 2, the concentration of nickel ions was 3.0 g/l, and the concentration of copper ions was 0.005 g/l.

In addition, a conductive substrate was produced and evaluated in the same manner as in Experimental Example 1, except that the blackening plating solution prepared in each experimental example was used in the formation of the blackening layer.

The results are shown in Tables 2 and 3.

[Experimental Example 25]

When the blackening plating solution was prepared, a blackening plating solution was prepared in the same manner as in Experimental Example 8, except that ammonia water was used instead of sodium hydroxide.

Specifically, a blackening plating solution containing nickel ions, copper ions, amide sulfuric acid, and ammonia is prepared.

Further, each component was added and prepared so that the nickel ion concentration in the blackening plating solution was 9.9 g/L, the copper ion concentration was 0.05 g/L, and the amide sulfuric acid concentration was 11 g/L.

Further, ammonia water was added to the blackening plating solution to adjust the pH of the blackening plating solution to 5.0.

In addition, a conductive substrate was produced and evaluated in the same manner as in Experimental Example 1, except that the blackening plating solution was used in the formation of the blackening layer.

As a result, the etching property was evaluated as ○, and the reflectance was 55.1%.

It was confirmed that a conductive substrate in which a blackened layer was formed using the blackening plating solution of Experimental Example 1 to Experimental Example 21 containing nickel ions, copper ions, and a pH adjuster and the pH adjuster was an alkali metal hydroxide was confirmed. The minimum value of the wiring width of the pattern of the metal wiring remaining after the etching is 10 μm or less. Therefore, there is blackening which is formed by using these blackening plating solutions. In the case of the conductive substrate of the layer, when the blackened layer and the copper layer were etched together, it was confirmed that the conductive substrate could be patterned into a desired shape. In addition, it has been confirmed that the average value (reflectance) of the regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 55.0% or less.

On the other hand, in Experimental Example 22 to Experimental Example 24 as comparative examples, it was confirmed that there was no pattern of metal wiring having a wiring width of 10 μm. Therefore, when the blackening layer was formed using these blackening plating solutions and etched together with the copper layer, it was confirmed that it was difficult to pattern the blackened layer into a desired shape.

In the conductive substrate in which the blackening layer was formed as the blackening plating solution of the experimental example 25 of the comparative example, the minimum value of the wiring width of the pattern of the metal wiring remaining after the etching was 10 μm or less. Therefore, in the case of the conductive substrate having the blackened layer formed by using the blackening plating solution, when the blackening layer and the copper layer are etched together, it is confirmed that the conductive substrate can be patterned. shape. However, it has also been confirmed that the average value (reflectance) of the regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is extremely high, as high as 55.1%. The blackening plating solution of the experimental example 25 is a blackening plating solution having the same configuration as that of Experimental Example 8 except that ammonia water is used instead of sodium hydroxide. However, the blackening plating solution having the same configuration as that of Experimental Example 8 is used. In the conductive substrate in which the blackened plating solution was formed into a blackened layer, it was confirmed that the reflectance was 4.3%, which was much lower than that of Experimental Example 25. By using an alkali metal hydroxide as a pH adjuster for the blackening plating solution, it is possible to use light having a wavelength of 400 nm or more and 700 nm or less of the conductive substrate formed by using the blackening plating solution. The average value (reflectance) of the regular reflectance is suppressed to be low.

The method for producing the blackening plating solution and the conductive substrate has been described above based on the embodiments, the examples, and the like. However, the present invention is not limited to the above-described embodiments, examples, and the like. Various modifications and changes can be made without departing from the spirit and scope of the invention.

The present application claims priority to Japanese Patent Application No. 2016-016598, filed on Jan. 29,,,,,,,,,,

10A‧‧‧Electrically conductive substrate

11‧‧‧Transparent substrate

11a‧‧‧ a surface

11b‧‧‧Other surface

12‧‧‧ copper layer

13‧‧‧Blackening layer

A‧‧‧ surface

X, Y‧‧‧X-axis, Y-axis

Claims (4)

A blackening plating solution comprising: nickel ions, copper ions and a pH adjusting agent, wherein the pH adjusting agent is an alkali metal hydroxide. The blackening plating solution according to the first aspect of the invention, wherein the pH adjusting agent is one or more selected from the group consisting of sodium hydroxide and potassium hydroxide. The blackening plating solution according to claim 1 or 2, wherein the pH is 4.0 or more and 5.2 or less, the nickel ion concentration is 2.0 g/l or more and 20.0 g/l or less, and the copper ion concentration is 0.005 g/l. Above and below 1.02g/l. A method for producing a conductive substrate, comprising: a copper layer forming step of forming a copper layer on at least one surface of the transparent substrate; and a blackening layer forming step on which the patent application ranges 1 to 3 are used The blackening plating solution of any one of the items forms a blackening layer.