TWI716534B - Conductive substrate - Google Patents

Abstract

A conductive substrate is provided, which includes a transparent substrate, a metal layer formed on at least one surface of the transparent substrate, and a blackened layer formed on the metal layer, the blackened layer containing nickel monomer and nickel oxide , Nickel hydroxide and copper.

Description

Conductive substrate

The present invention relates to a conductive substrate.

The electrostatic capacitance type touch panel detects the change in electrostatic capacitance caused when an object approaches the panel surface, and converts the position information of the approaching object on the panel surface into an electrical signal. The conductive substrate used for the capacitive touch panel is arranged on the surface of the display. Therefore, the material of the conductive layer of the conductive substrate is required to have low reflectivity and difficult to identify.

Therefore, as a material for the conductive layer of the conductive substrate for a touch panel, a material with low reflectivity and difficult to be recognized is used, and the material is formed on a transparent substrate or a transparent film.

For example, Patent Document 1 discloses a conventionally used transparent conductive film for touch panels, in which an ITO (indium oxide-tin) film is formed as a transparent conductive film on a polymer film.

Here, in recent years, displays equipped with touch panels have tended to have larger screens, and accordingly, conductive substrates such as transparent conductive films for touch panels have also been required to have larger areas. However, since ITO has a high resistance value, there is a problem that it cannot cope with the enlargement of the conductive substrate.

In this regard, in order to suppress the resistance of the conductive substrate, a method of using copper mesh wiring as a conductive layer and blackening the surface of the copper mesh wiring has been proposed.

For example, Patent Document 2 discloses a method for manufacturing a thin-film touch panel sensor, which includes: forming a protective layer on a copper thin film supported by the thin film; and by photolithography, At least process the protective layer into striped wiring patterns and lead out wiring patterns; remove the exposed copper film by etching to form striped copper wiring and lead out copper wiring; blacken the copper wiring A step of.

However, the method of blackening the copper wiring after the striped copper wiring is formed by etching and adopted in Patent Document 2 has a problem in terms of productivity due to an increase in manufacturing steps.

In this regard, the inventors of the present invention have studied the formation of a conductive substrate having a desired wiring pattern by etching the metal layer and the blackened layer for a conductive substrate on which a metal layer and a blackened layer are formed on a transparent substrate. It is possible to reduce manufacturing steps and obtain a highly productive conductive substrate manufacturing method.

<Prior Technical Literature>

<Patent Literature>

Patent Document 1: (Japan) JP 2003-151358 A

Patent Document 2: (Japan) JP 2013-206315 A

However, the reactivity of the metal layer and the blackened layer to the etching solution is sometimes greatly different. Therefore, if the metal layer and the blackened layer are etched at the same time, sometimes one of the layers cannot be etched into the target shape, or the uneven etching in the plane may cause dimensional deviation, so the metal layer and the black layer cannot be etched. The chemical layer is simultaneously etched.

In view of the above-mentioned historical technical problems, one aspect of the present invention aims to provide a conductive substrate having a metal layer and a blackened layer that can be etched simultaneously.

In order to solve the above problems, one aspect of the present invention provides a conductive substrate, which includes a transparent substrate, a metal layer formed on at least one surface of the transparent substrate, a blackened layer formed on the metal layer, and the black The chemical layer contains nickel monomer, nickel oxide, nickel hydroxide and copper.

According to one aspect of the present invention, it is possible to provide a conductive substrate having a metal layer and a blackened layer that can be etched at the same time.

10A, 10B, 20A, 20B, 30‧‧‧Conductive substrate

11‧‧‧Transparent substrate

12, 12A, 12B‧‧‧Metal layer

13, 13A, 13B, 32A, 32B‧‧‧Blackening layer

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

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

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

2B is a cross-sectional view of the conductive substrate according to the embodiment of the present invention.

Fig. 3 is a plan view of a conductive substrate having grid-shaped wiring according to an embodiment of the present invention.

Fig. 4A is a cross-sectional view taken along the line A-A' of Fig. 3.

Fig. 4B is a cross-sectional view taken along the line A-A' of Fig. 3.

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

(Conductive substrate)

The conductive substrate of this embodiment may have a transparent base material, a metal layer formed on at least one surface of the transparent base material, and a blackened layer formed on the metal layer. In addition, the blackened layer may contain nickel monomer, nickel oxide, nickel hydroxide, and copper.

Here, the conductive substrate in the present embodiment includes a substrate having a metal layer and a blackened layer on the surface of a transparent base material before patterning the metal layer, etc., and a substrate after patterning the metal layer, that is, wiring. Substrate. The conductive substrate after patterning the metal layer and the blackened layer includes an area of the transparent base material that is not covered by the metal layer or the like, so it can transmit light and constitute a transparent conductive substrate.

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

The transparent substrate is not particularly limited, and an insulator film or a glass substrate that can transmit visible light can be preferably used.

As the insulator film that can transmit visible light, for example, a polyamide-based film, a polyethylene terephthalate-based film, and polyethylene naphthalate can be preferably used. Resin films such as cycloolefin film, cycloolefin film, polyimide film, polycarbonate film, etc. In particular, as a material for an insulator film that can transmit visible light, it is more preferable to use PET (polyethylene terephthalate), COP (cycloolefin copolymer), PEN (polyethylene naphthalate), Polyimide, polyamide, polycarbonate, etc.

The thickness of the transparent substrate is not particularly limited, and it can be arbitrarily selected according to the required strength, electrostatic capacity, light transmittance, and the like when used as a conductive substrate. The thickness of the transparent substrate may be, for example, 10 μm or more and 200 μm or less. Especially when used for touch panel applications, the thickness of the transparent substrate is preferably 20 μm or more and 120 μm or less, and more preferably 20 μm or more and 100 μm or less. When used for touch panel applications, for example, when used for applications that require reduction in the overall thickness of the display, the thickness of the transparent substrate is preferably 20 μm or more and 50 μm or less.

The transparent substrate preferably has a high total light transmittance, for example, the total light transmittance is preferably 30% or more, more preferably 60% or more. When the total light transmittance of the transparent substrate is in the above range, for example, when it is used for touch panel applications, the visibility of the display can be sufficiently ensured.

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

Hereinafter, the metal layer will be described.

There is no particular limitation on the material constituting the metal layer, and a material suitable for conductivity can be selected. Copper has good electrical properties and is easy to be etched. Therefore, copper is preferably used as the material constituting the metal layer. That is, the metal layer preferably contains copper.

When the metal layer contains copper, the material constituting the metal layer is preferably composed of, for example, Cu and at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Mn, Co, and W A copper alloy or a material containing copper and one or more metals selected from the above-mentioned metals. In addition, the metal layer may be a copper layer made of copper.

The method of forming the metal layer is not particularly limited. However, in order to avoid a decrease in the light transmittance of the exposed portion of the transparent base material of the patterned conductive substrate, it is better not to arrange an adhesive between other members and the metal layer. That is, it is preferable to form a metal layer directly on the upper surface of another member. Here, for example, a metal layer can be formed and arranged on the upper surface of the following adhesion layer or transparent substrate. Therefore, it is preferable to form and arrange the metal layer directly on the upper surface of the adhesion layer or the transparent substrate.

Since the metal layer is directly formed on the other member, the metal layer preferably has a metal thin film layer formed by a dry plating method. The dry plating method is not particularly limited, and for example, a vapor deposition method, a sputtering method, an ion plating method, etc. can be used. The sputtering method is particularly easy to control the film thickness, so the sputtering method is preferably used.

In addition, when it is desired to further increase the thickness of the metal layer, after the metal thin film layer is formed by the dry plating method, the metal plating layer can be laminated by the wet plating method. Specifically, for example, a metal thin film layer can be formed by a dry plating method on a transparent substrate or an adhesion layer, and the metal thin film layer can be used as a power supply layer, and a plating method, which is one of wet plating methods, can be used to form the metal plating layer.

Here, in the case where only the above-mentioned dry plating method is used to form the metal layer, the metal layer may be composed of a metal thin film layer. In addition, when a dry plating method and a wet plating method are combined to form a metal layer, a metal thin film layer and a metal plating layer may constitute the metal layer.

As described above, the metal layer can be formed using only the dry plating method or a combination of the dry plating method and the wet plating method. Therefore, the metal layer can be directly formed and arranged on the transparent substrate or the adhesion layer without using an adhesive.

The thickness of the metal layer is not particularly limited, and can be arbitrarily selected according to the amount of current supplied to the wiring when the metal layer is used as the wiring, the wiring width, and the like.

However, as the metal layer becomes thicker, more etching time is required to form a wiring pattern by etching, and side etching is prone to occur, and problems such as difficulty in forming thin lines sometimes arise. Therefore, the thickness of the metal layer is preferably 5 μm or less, and more preferably 3 μm or less.

In particular, from the viewpoint of reducing the resistance value of the conductive substrate to provide sufficient current, for example, the thickness of the metal layer is preferably 50 nm or more, more preferably 60 nm or more, and even more preferably 150 nm or more.

Here, when the metal layer has a metal thin film layer and a metal plating layer as described above, the total thickness of the thickness of the metal thin film layer and the thickness of the metal plating layer is preferably within the above range.

Regardless of whether the metal layer is composed of a metal thin film layer or has a metal thin film layer and a metal plating layer, the thickness of the metal thin film layer is not particularly limited, for example, it is preferably 50 nm or more and 700 nm the following.

Hereinafter, the blackened layer will be described.

The metal layer has metallic luster. Therefore, if only the metal layer is etched on a transparent substrate to form wiring, the wiring will reflect light. For example, when it is used in a wiring substrate for a touch panel, the display will be recognizable. Reduce the problem. Therefore, the method of setting the black layer has been studied. However, the reactivity of the metal layer and the blackened layer to the etching solution is sometimes greatly different. If the metal layer and the blackened layer are etched at the same time, the metal layer or the blackened layer cannot be etched into the desired shape, or There are problems such as size deviation. Therefore, in the conventionally studied conductive substrates, it is necessary to etch the metal layer and the blackened layer in different steps, and it is difficult to etch the metal layer and the blackened layer in one step at the same time.

In this regard, the inventors of the present invention have studied a blackened layer that can be etched simultaneously with the metal layer, that is, it has good reactivity to the etching solution, and when the metal layer is etched simultaneously, a pattern of a predetermined shape can be obtained, which can suppress A blackened layer with dimensional deviation. As a result, it was found that the blackened layer containing nickel alone, nickel oxide, nickel hydroxide, and copper allows the blackened layer to exhibit approximately the same reactivity with the etching solution as the metal layer, and completed the present invention.

As described above, the blackened layer of the conductive substrate of this embodiment may contain nickel alone, nickel oxide, nickel hydroxide, and copper.

Here, the state of copper contained in the blackened layer is not particularly limited, and, for example, copper in the form of a copper single body and/or a copper compound may be contained. As a copper compound, copper oxide, copper hydroxide, etc. are mentioned, for example.

Therefore, the blackening layer contains, for example, a single nickel, a nickel oxide, and a nickel hydroxide, and may also contain one or more selected from metallic copper, copper oxide, and copper hydroxide that is a single copper.

As described above, when the blackened layer contains nickel oxide and nickel hydroxide, the blackened layer becomes a color capable of suppressing light reflection on the surface of the metal layer, and can function as a blackened layer.

In addition, by containing, for example, copper in the form of a copper monomer and/or a copper compound, the blackened layer can have the same reactivity to the etching solution as the metal layer. Therefore, even when the metal layer and the blackened layer are etched at the same time, both layers can be etched into a target shape, and the uniform etching can be performed in the plane, thereby suppressing dimensional deviation. That is, the metal layer and the blackened layer can be simultaneously etched.

The ratio of each component contained in the blackening layer is not particularly limited, and can be arbitrarily selected according to the degree of suppression of light reflection required for the conductive substrate, the degree of reactivity with the etching solution, and the like. However, from the viewpoint of sufficiently improving the reactivity to the etching solution, for example, regarding the blackened layer, the number of nickel atoms calculated from the Ni 2P spectrum and Cu LMM spectrum measured by X-ray photoelectron spectroscopy (XPS) is 100 In this case, the ratio of the number of copper atoms is preferably 5 or more and 90 or less. That is, when nickel and copper contained in the blackened layer are ratio of the number of atoms, when nickel is 100, copper is preferably 5 or more and 90 or less. When the number of nickel atoms is 100, the ratio of the number of copper atoms is more preferably 7 or more and 90 or less, and still more preferably 7 or more and 65 or less.

Here, the number of nickel atoms refers to the total number of nickel atoms contained in the blackened layer, and it contains not only nickel alone but also nickel that forms compounds such as nickel oxide.

In addition, regarding the blackened layer, the nickel contained in the blackened layer calculated by peak separation analysis of the Ni 2P spectrum measured by XPS, that is, when the number of atoms of metallic nickel is 100, the nickel constituting the nickel oxide The number of atoms is preferably 25 or more and 280 or less, and the number of nickel atoms constituting the nickel hydroxide is preferably 10 or more and 220 or less. The reason is that when the blackened layer contains nickel oxide and nickel hydroxide in a predetermined ratio relative to the metal nickel, the blackened layer can be particularly suitable for suppressing the metal layer. The color of the light reflection on the surface.

Here, as described above, when XPS is used to measure the blackened layer, in order to be able to analyze the internal state, for example, it is preferable to first remove the 10 nm portion of the outermost surface of the blackened layer by Ar ion etching or the like, and then perform the measurement.

The method for forming the blackened layer is not particularly limited, and any method can be selected as long as it is a method capable of forming a blackened layer containing the above-mentioned components. Here, the wet method is easy to control the composition of the blackened layer containing the above-mentioned components, and therefore, the wet method is preferably used.

As the wet method, an electroplating method is particularly preferred.

Regarding the blackening plating solution used when forming the blackening layer film by the electroplating method, it is sufficient to prepare a blackening plating solution capable of forming the blackening layer having the above-mentioned composition, and the composition is not particularly limited. For example, a blackening plating solution containing nickel ions, copper ions, and a pH adjuster can be preferably used.

The concentration of each component in the blackening plating solution is not particularly limited, and can be arbitrarily selected according to the degree of suppression of light reflection on the surface of the metal layer required for the blackening layer to be formed.

For example, the nickel ion concentration in the blackening plating solution is preferably 2.0 g/l or more, and more preferably 3.0 g/l or more. The reason is that by setting the nickel ion concentration in the blackening plating solution to 2.0 g/l or more, the blackening layer can be made into a color particularly suitable for suppressing light reflection on the surface of the metal layer, thereby suppressing the reflectance of the conductive substrate. .

The upper limit of the nickel ion concentration in the blackening plating solution is not particularly limited. For example, it is preferably 20.0 g/l or less, and more preferably 15.0 g/l or less. The reason is that by setting the nickel ion concentration in the blackening bath to 20.0g/l or less, it is possible to suppress the excessive nickel content in the blackened layer formed and prevent the surface of the blackened layer from becoming a shiny nickel-plated surface. Therefore, the reflectance of the conductive substrate can be suppressed.

In addition, the copper ion concentration in the blackening plating solution is preferably 0.005 g/l or more, and more preferably 0.008 g/l or more. The reason is that when the copper ion concentration in the blackening plating solution is 0.005g/l or more, the blackening layer can be made into a color particularly suitable for suppressing light reflection on the surface of the metal layer, and the effect of the blackening layer on the etching solution is improved. With its reactivity, it can also be patterned into a desired shape when the blackened layer is etched together with the metal layer.

The upper limit of the copper ion concentration in the blackening plating solution is not particularly limited. For example, it is preferably 4.0 g/l or less, and more preferably 1.02 g/l or less. The reason is that by setting the copper ion concentration in the blackening plating solution to 4.0 g/l or less, it is possible to prevent the formed blackening layer from becoming too reactive to the etching solution, making the blackening layer particularly suitable for suppressing metal The color of light reflection on the layer surface can suppress the reflectance of the conductive substrate.

When preparing the blackening plating solution, the method of supplying nickel ions and copper ions is not particularly limited, and for example, they can be supplied in a salt state. For example, sulfamic acid (sulfamic acid) salt or sulfate can be suitably used. Here, regarding the type of salt, the same type of salt may be used for each metal element, or different types of salt may be used at the same time. Specifically, for example, the same type of salt such as nickel sulfate and copper sulfate can be used to prepare a blackening plating solution. In addition, for example, different kinds of salts such as nickel sulfate and copper sulfamate may be used together to prepare a blackening plating solution.

In addition, as the pH adjuster, an alkali metal hydroxide can be preferably used. The reason is that by using an alkali metal hydroxide as a pH adjuster, it is possible to reduce the reflectance of a conductive substrate having a blackened layer formed using the blackened plating solution. The reason why the use of alkali metal hydroxide as a pH adjuster can reduce the reflectance of a conductive substrate having a blackened layer formed by using this blackened plating solution is not clear, but it is presumed to be supplied to the blackened plating solution. The hydroxide ion in it can promote the precipitation of nickel oxide. By promoting the precipitation of nickel oxide, the blackened layer can be made It becomes a color particularly suitable for suppressing light reflection on the surface of the metal layer. Therefore, the reflectance of the conductive substrate having the blackened layer can be particularly suppressed.

As the alkali metal hydroxide as the pH adjuster, for example, one or more selected from sodium hydroxide, potassium hydroxide, and lithium hydroxide can be used. In particular, the alkali metal hydroxide as a pH adjuster is more preferably one or more selected from sodium hydroxide and potassium hydroxide. The reason is that sodium hydroxide and potassium hydroxide are particularly easy to obtain and have advantages in terms of cost.

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

The reason is that by setting the pH of the blackening plating solution to 4.0 or higher, when the blackening plating solution is used to form a blackening layer, it is possible to more reliably suppress the occurrence of color unevenness in the blackening layer, and it is possible to form an extremely low light Blackened layer of reflected color. In addition, by setting the pH of the blackening plating solution to 5.2 or less, it is possible to suppress the precipitation of part of the blackening plating solution components.

In addition, the blackening bath may also contain a complexing agent. As the complexing agent, for example, sulfamic acid can be preferably used. When the blackening plating solution contains sulfamic acid, a blackening layer whose color is particularly suitable for suppressing light reflection on the surface of the metal layer can be formed.

The content of the complexing agent in the blackening plating solution is not particularly limited, and it can be arbitrarily selected according to the degree of suppression of reflectance required for the formed blackening layer.

For example, in the case of using sulfamic acid as the complexing agent, the concentration of sulfamic acid in the blackening bath is not particularly limited. For example, it is preferably 1 g/l or more and 50 g/l or less, and more preferably 5 g/l or more and 20 g Below /l. The reason is that by setting the concentration of sulfamic acid to 1 g/l or more, the blackened layer can be made into a color particularly suitable for suppressing light reflection on the surface of the metal layer, and the reflectance of the conductive substrate can be suppressed. In addition, even if excessive sulfamic acid is added, the reflection of the conductive substrate is suppressed Since the effect of the rate is not improved, it is preferably 50 g/l or less as described above.

The thickness of the blackening layer is not particularly limited, and can be arbitrarily selected according to the degree of light reflection suppression required for the conductive substrate, and the like.

The thickness of the blackening layer is preferably 30 nm or more, and more preferably 50 nm or more, for example. The blackened layer has a function of suppressing light reflection by the metal layer, and when the thickness of the blackened layer is too thin, the light reflection of the metal layer may not be sufficiently suppressed. In this regard, by setting the thickness of the blackening layer to be 30 nm or more, the reflection on the surface of the metal layer can be suppressed more reliably, so it is preferably 30 nm or more.

In addition, the upper limit of the thickness of the blackened layer is not particularly limited. However, an unnecessary increase in thickness will lead to an increase in the time required for etching when forming the wiring, which will increase the cost. Therefore, the thickness of the blackening layer is preferably 120 nm or less, and more preferably 90 nm or less.

In addition to the above-mentioned transparent base material, metal layer, and blackened layer, other arbitrary layers may be provided on the conductive substrate. For example, an adhesive layer can be provided.

Hereinafter, a configuration example of the adhesive 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, when the metal layer is directly formed on the transparent substrate, the metal layer may peel off from the transparent substrate during the manufacturing process or during use.

In contrast, in the conductive substrate of the present embodiment, in order to improve the adhesion between the transparent base material and the metal layer, an adhesion layer may be arranged on the transparent base material. That is, it is also possible to constitute a conductive substrate provided with an adhesion layer between the transparent base material and the metal layer.

By disposing the adhesive layer between the transparent base material and the metal layer, the adhesiveness between the transparent base material and the metal layer can be improved, and the metal layer can be prevented from peeling off the transparent base material.

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

The material constituting the adhesive layer is not particularly limited, and it can be based on the adhesive force of the transparent substrate and the metal layer, the degree of light reflection suppression required on the surface of the metal layer, or relative to the environment in which the conductive substrate is used (for example, humidity or temperature). ) The degree of stability, etc., can be selected arbitrarily.

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

Here, the adhesion layer may also contain a metal alloy of at least two metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. In this case, the adhesion layer may still contain one or more elements selected from carbon element, oxygen element, hydrogen element, and nitrogen element. At this time, as a metal alloy containing at least two metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn, Cu-Ti- Fe alloy or 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, and it is preferable to form the film by a dry plating method. As the dry plating method, for example, a sputtering method, an ion plating method, or a vapor deposition method can be preferably used. When the adhesion layer is formed by the dry method, the sputtering method is more preferable in consideration of the ease of controlling the film thickness. Here, as described above, one or more elements selected from carbon element, oxygen element, hydrogen element, and nitrogen element may be added to the adhesion layer. In this case, the reactive sputtering method can be preferably used.

To make the adhesive layer contain one or more elements selected from carbon element, oxygen element, hydrogen element, and nitrogen element, in the environment when the adhesive layer is formed A gas of one or more elements selected from the group consisting of element, oxygen element, hydrogen element, and nitrogen element can add these elements to the adhesion layer. For example, use carbon monoxide gas and/or carbon dioxide gas when adding carbon to the adhesive layer, use oxygen when adding oxygen, use hydrogen and/or water when adding hydrogen, and use nitrogen when adding nitrogen , Can be added to the environment during dry plating in advance.

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

By forming the adhesive layer by the dry plating method as described above, the adhesiveness between the transparent substrate and the adhesive layer can be improved. In addition, the adhesive layer may contain, for example, a metal as its main component, so the adhesiveness with the metal layer is also high. Therefore, by disposing the adhesion layer between the transparent base material and the metal layer, it is possible to suppress the peeling of the metal layer.

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

When the adhesion layer functions 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. However, if the thickness exceeds the necessary thickness, the time required for film formation and the time required for etching during wiring formation are prolonged, resulting in an increase in cost. Therefore, as described above, the thickness of the adhesion layer is preferably 50 nm or less, more preferably 35 nm or less, and still more preferably 33 nm or less.

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

As described above, the conductive substrate of this embodiment may have a transparent base material, a metal layer, and a blackened layer. In addition, layers such as an adhesive layer can be arbitrarily provided.

A specific configuration example will be described below with reference to FIGS. 1A, 1B, 2A, and 2B. 1A, FIG. 1B, FIG. 2A, and FIG. 2B illustrate cross-sectional views of the conductive substrate of the present embodiment on a plane parallel to the laminating direction of the transparent base material, the metal layer, and the blackened layer.

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

Specifically, for example, a conductive substrate 10A shown in FIG. 1A may be laminated on one surface 11a side of the transparent base material 11 with one layer each of the metal layer 12 and the blackened layer 13 in this order. In addition, like the conductive substrate 10B shown in FIG. 1B, on one surface 11a side and the other surface (the other surface) 11b side of the transparent base material 11, metal layers 12A and 12B may be sequentially laminated and blackened, respectively. Layers 13A and 13B each have one layer.

In addition, a structure in which, for example, an adhesive layer is provided as an arbitrary layer may be configured. In this case, for example, an adhesive layer, a metal layer, and a blackened layer may be formed in order from the transparent substrate side on at least one surface of the transparent substrate.

Specifically, for example, the conductive substrate 20A shown in FIG. 2A may have the adhesion layer 14, the metal layer 12, and the blackened layer 13 laminated in this order on the one surface 11a side of the transparent base material 11.

In this case, an adhesion layer, a metal layer, and a blackened layer may be laminated on both surfaces of the transparent base material 11. Specifically, as shown in FIG. 2B, the conductive substrate 20B can be laminated on one surface 11a side and the other surface 11b side of the transparent base material 11, respectively, and the adhesion layers 14A and 14B, the metal layers 12A and 12B, and the blackened layer 13A and 13B.

In addition, Figures 1B and 2B show that the transparent substrate is laminated with metal on both sides In the case of a layer and a blackened layer, the transparent substrate 11 is used as a symmetry plane, and the layers laminated on the upper and lower sides of the transparent substrate 11 are symmetrically arranged. However, the present invention is not limited to this form. For example, in FIG. 2B, the structure on the side 11a of the transparent substrate 11 may be the same as that in FIG. 1B, without the adhesion layer 14A, but a form in which the metal layer 12A and the blackened layer 13A are sequentially laminated , The layers laminated on the upper and lower sides of the transparent substrate 11 have an asymmetric structure.

In addition, in the conductive substrate of the present embodiment, by providing the metal layer and the blackening layer on the transparent base material, light reflection by the metal layer can be suppressed, and the reflectance of the conductive substrate can be suppressed.

The degree of reflectivity of the conductive substrate of this embodiment is not particularly limited. For example, in order to improve the visibility of the display when used as a conductive substrate for a touch panel, it is preferable to have reflectivity. For example, the average reflectance of light having a wavelength of 400 nm or more and 700 nm or less is preferably 15% or less, and more preferably 10% or less.

The reflectance can be measured by irradiating light to the blackened layer of the conductive substrate and measuring it. Specifically, for example, as shown in FIG. 1A, when the metal layer 12 and the blackened layer 13 are sequentially laminated on one surface 11a side of the transparent substrate 11, the blackened layer 13 can be irradiated with light. The surface A of the blackened layer 13 is irradiated with light and measured. During the measurement, light with 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, 1 nm in wavelength as described above, and the average of the measured values can be used as the reflectance of the conductive substrate .

The conductive substrate of this embodiment can be preferably used as a conductive substrate for touch panels. In this case, the conductive substrate may have a structure with grid-like wiring.

By etching the metal layer and the blackened layer of the conductive substrate of the present embodiment described above, a conductive substrate having grid-like wiring can be obtained.

For example, grid-like wiring can be formed from two layers of wiring. The specific configuration is shown in Figure 3 for example. FIG. 3 shows a view of the conductive substrate 30 having grid-like wiring viewed from the upper side in the lamination direction of the metal layer and the like. In order to make the wiring pattern easy to understand, the transparent base material and the patterning of the metal layer are omitted. Layers other than the formed wirings 31A and 31B. In addition, wiring 31B visible through the transparent substrate 11 is also shown.

The conductive substrate 30 shown in FIG. 3 includes a transparent base 11, a plurality of wirings 31A parallel to the Y-axis direction in the figure, and wirings 31B parallel to the X-axis direction. Here, wirings 31A and 31B are formed by etching the metal layer, and a blackened layer (not shown) is formed on the upper and/or lower surfaces of the wirings 31A and 31B. In addition, the blackened layer is etched into the same shape as the wirings 31A and 31B.

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

First, as shown in FIG. 4A, wirings 31A and 31B may be arranged on the upper and lower surfaces of the transparent substrate 11, respectively. Here, in FIG. 4A, the blackened layers 32A and 32B etched into the same shape as the wiring are arranged on the upper surface of the wiring 31A and the lower surface of the wiring 31B.

In addition, as shown in FIG. 4B, a set of transparent substrates 11 can be used, and wirings 31A and 31B are arranged on the upper and lower surfaces of one transparent substrate 11 sandwiched therebetween, and one wiring 31B is arranged between the transparent substrates 11. In this case, blackened layers 32A and 32B etched into the same shape as the wiring are arranged on the upper surfaces of the wirings 31A and 31B. Here, as described above, in addition to the metal layer and the blackened layer, an adhesion layer may be provided. Therefore, in either case of FIGS. 4A and 4B, for example, an adhesive layer may be provided between the wiring 31A and/or the wiring 31B and the transparent base material 11. When providing an adhesive layer, it is preferable to also etch the adhesive layer into the same shape as the wiring 31A, 31B.

For example, using a conductive substrate with metal layers 12A and 12B, and blackened layers 13A and 13B provided on both sides of a transparent substrate 11 as shown in FIG. 1B, it is possible to form a mesh as shown in FIGS. 3 and 4A. Conductive substrate for grid wiring.

Taking the case of forming using the conductive substrate of FIG. 1B as an example, first, the metal layer 12A and the blackened layer 13A on the side of one surface 11a of the transparent substrate 11 are etched to form a predetermined distance along the X axis. A plurality of linear patterns arranged at intervals and parallel to the Y-axis direction in FIG. 1B. Here, the X-axis direction in FIG. 1B indicates a direction parallel to the width direction of each layer. In addition, the Y-axis direction in FIG. 1B indicates the direction perpendicular to the paper surface in FIG. 1B.

Then, the metal layer 12B and the blackened layer 13B on the other surface 11b side of the transparent substrate 11 are etched to form a plurality of pieces arranged in parallel with the X-axis direction in Figure 1B at predetermined intervals along the Y-axis direction Linear pattern.

Through the above operations, it is possible to form a conductive substrate having grid-like wiring as shown in FIGS. 3 and 4A. In addition, both sides of the transparent substrate 11 can be etched at the same time. That is, the metal layers 12A and 12B and the blackened layers 13A and 13B can be simultaneously etched. In addition, by performing the same etching using the conductive substrate shown in FIG. 2B, it is also possible to produce a conductive substrate having an adhesive layer between the wiring 31A, 31B and the transparent substrate 11 as shown in FIG. 4A. The layer is patterned to have the same shape as the wirings 31A and 31B.

By using two conductive substrates as shown in FIG. 1A or FIG. 2A, it is possible to form a conductive substrate with grid-like wiring as shown in FIG. 3. Take the case of using two conductive substrates as shown in FIG. 1A as an example for description. Two conductive substrates as shown in FIG. 1A are respectively etched on the metal layer 12 and the blackened layer 13 to form A plurality of linear patterns arranged in parallel to the X-axis direction at predetermined intervals along the Y-axis direction. Then, will pass the above The linear patterns formed on the respective conductive substrates by the etching process are arranged in a direction crossing each other, and two conductive substrates are bonded together, so that a conductive substrate with grid-like wiring can be obtained. When bonding two conductive substrates, the bonding surface is not particularly limited. For example, the surface A in FIG. 1A where the metal layer 12 etc. are laminated and the other surface 11b in FIG. 1A where the metal layer 12 and the like are not laminated can be bonded to obtain the structure shown in FIG. 4B.

In addition, for example, the surfaces of the non-laminated metal layer 12 and the like on the transparent substrate 11, that is, the other surface 11b in FIG. 1A, may be attached to each other to obtain a cross-sectional structure as shown in FIG. 4A.

In addition, by replacing the conductive substrate shown in FIG. 1A with the conductive substrate shown in FIG. 2A, it can also be made as shown in 4A and 4B to provide an adhesive layer between the wiring 31A and 31B and the transparent base material 11. The conductive substrate is patterned to have the same shape as the wiring 31A and 31B.

The width of the wiring and the distance between the wirings of the conductive substrate with grid-like wiring as shown in FIGS. 3, 4A and 4B are not particularly limited. For example, they can be selected according to the amount of current flowing through the wiring. .

Here, the conductive substrate according to the present embodiment has a blackened layer containing nickel alone, nickel oxide, nickel hydroxide, and copper, and when patterning is performed by simultaneously etching the blackened layer and the copper layer , It is also possible to image the blackened layer and the copper layer into a desired shape. Specifically, for example, wiring with a wiring width of 10 μm or less can be formed. Therefore, the conductive substrate of the present embodiment preferably includes wiring with a wiring width of 10 μm or less. The lower limit of the wiring width is not particularly limited, and it may be 3 μm or more, for example.

In addition, FIG. 3, FIG. 4A, and FIG. 4B show the combination of linear wiring to An example of forming a grid-like wiring (wiring pattern), but the present embodiment is not limited to this, and the wiring constituting the wiring pattern may have any shape. For example, the shape of the wires constituting the grid-like wiring pattern may be various shapes such as zigzag curved lines (z-shaped straight lines) to prevent moiré (interference patterns) from occurring between the surface images of the display.

The conductive substrate having the grid-shaped wiring composed of the above-mentioned two-layer wiring can be preferably used as, for example, a conductive substrate for a touch panel of a projection type capacitance system.

According to the conductive substrate of the present embodiment described above, the metal layer formed on at least one surface of the transparent substrate has a laminated structure of a blackened layer. In addition, since the blackened layer contains nickel alone, nickel oxide, nickel hydroxide, and copper, when patterning is performed by etching the metal layer and the blackened layer, the blackened layer is easily formed by patterning The desired shape.

In addition, the blackened layer contained in the conductive substrate of the present embodiment can sufficiently suppress light reflection on the surface of the metal layer, thereby obtaining a conductive substrate with low reflectance. In addition, when used in applications such as touch panels, the visibility of the display can be improved.

(Method of manufacturing conductive substrate)

Hereinafter, a configuration example of the manufacturing method of the conductive substrate of this embodiment will be described.

The manufacturing method of the conductive substrate of this embodiment may include the following steps.

In the metal layer forming step, a metal layer is formed on at least one surface of the transparent substrate.

The blackening layer forming step is to form a blackening layer on the metal layer.

In addition, in the blackening layer forming step, a blackening layer containing nickel alone, nickel oxide, nickel hydroxide, and copper can be formed.

Hereinafter, the manufacturing method of the conductive substrate of this embodiment is demonstrated concretely.

Here, the manufacturing method of the conductive substrate of this embodiment can be suitably used for manufacturing the said conductive substrate. In addition, except for the content described below, the same structure as the above-mentioned conductive substrate can be adopted, and therefore a part of the description is omitted.

The transparent base material used for the metal layer forming step may be prepared in advance. The type of transparent substrate used here is not particularly limited, and transparent substrates such as insulator films (resin films) and glass substrates capable of transmitting visible light described above can be preferably used. It is also possible to pre-cut the transparent substrate to any size as needed.

In addition, as described above, the metal layer preferably has a metal thin film layer. In addition, the metal layer may also have a metal thin film layer and a metal plating layer. Therefore, the metal layer forming step may include, for example, a step of forming a metal thin film layer by a dry plating method. In addition, the metal layer forming step may further include a step of forming a metal thin film layer by a dry plating method, and a step of using the metal thin film layer as a power supply layer to form a metal plating layer by an electroplating method which is one of wet plating methods.

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, etc. can be used. In addition, as the vapor deposition method, a vacuum vapor deposition method can be preferably used. Since the sputtering method is particularly easy to control the film thickness, it is more preferable to use the sputtering method as the dry plating method used in the step of forming the metal thin film layer.

Hereinafter, the steps of forming the metal plating layer will be described. Regarding the conditions in the step of forming the metal plating layer by the wet plating method, that is, the conditions of the electroplating treatment are not particularly limited, and conditions in common methods may be adopted. For example, a substrate on which a metal thin film layer is formed can be placed in a plating tank containing a metal plating solution, and by controlling the current density and the transport speed of the substrate, the metal plating layer can be formed.

Hereinafter, the steps of forming the blackened layer will be described.

In the blackening layer forming step, a blackening layer containing nickel monomer, nickel oxide, nickel hydroxide, and copper can be formed.

The blackened layer can be formed by a wet method. Specifically, for example, a metal layer can be used as a power supply layer, and a blackened layer is formed on the metal layer by an electroplating method in the above-mentioned plating tank containing a blackened plating solution. By using the metal layer as the power supply layer and forming the blackened layer by the electroplating method, the blackened layer can be formed on the entire surface of the metal layer opposite to the transparent substrate.

The blackening plating solution has been explained in the previous section, and the details are omitted here.

In the manufacturing method of the conductive substrate of this embodiment, in addition to the above-mentioned steps, arbitrary steps may be implemented.

For example, if it is desired to form an adhesive layer between the transparent base material and the metal layer, the adhesive layer forming step may be performed to form the adhesive layer on the surface of the transparent base material where the metal layer is to be formed. In the case of performing the adhesion layer forming step, the metal layer forming step may be performed after the adhesion layer forming step. In the metal layer forming step, it may be formed on the transparent substrate on which the adhesion layer has been formed after this step. Metal film layer.

In the step of forming the adhesive layer, the method of forming the adhesive layer is not particularly limited, and it is preferable to form the film by a dry plating method. As the dry plating method, for example, a sputtering method, an ion plating method, or a vapor deposition method can be preferably used. When the adhesive layer is formed by a dry method, it is easy to control the film thickness, so it is more preferable to use a sputtering method. In addition, as described above, one or more elements selected from carbon element, oxygen element, hydrogen element, and nitrogen element may be added to the adhesion layer. In this case, it is more preferable to use a reactive sputtering method.

The conductive substrate obtained by the manufacturing method of the conductive substrate of this embodiment The board can be used for various applications such as touch panels. In addition, when used in various applications, it is preferable to pattern the metal layer and the blackened layer contained in the conductive substrate of the present embodiment. Moreover, when providing an adhesive layer, it is preferable to pattern an adhesive layer also. For example, the metal layer and the blackened layer can be patterned according to the desired wiring pattern, and the adhesion layer can also be patterned according to the situation. It is preferable to pattern the metal layer and the blackened layer in the same shape, and the adhesion layer can also be patterned according to the situation. Patterning is also performed.

Therefore, the manufacturing method of the conductive substrate of the present embodiment may include a patterning step of patterning the metal layer and the blackened layer. In addition, when the adhesion layer is formed, the patterning step may be a step of patterning the adhesion layer, the metal layer, and the blackened layer.

The specific order of the patterning step is not particularly limited, and it can be implemented in any order. For example, as shown in FIG. 1A, in the case of a conductive substrate 10A on which a metal layer 12 and a blackened layer 13 are laminated on a transparent base material 11, a mask placement step can be performed first, and the surface of the blackened layer 13 A configures a mask with a desired pattern. Next, an etching step may be performed to provide an etching solution to the surface A on the blackened layer 13, that is, the side where the mask is disposed.

The etching solution used in the etching step is not particularly limited. However, the blackened layer formed by the manufacturing method of the conductive substrate of the present embodiment has approximately the same reactivity with the etching solution as the metal layer. Therefore, the etching solution used in the etching step is not particularly limited, and the etching solution generally used when etching the metal layer can be preferably used.

As the etching solution, for example, a mixed aqueous solution containing one or more selected from 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. In order to improve the reactivity, it can also be used by heating. For example, it can be used by heating to 40°C or more and 50°C or less.

In addition, as shown in FIG. 1B, a conductive substrate 10B having metal layers 12A and 12B, and blackened layers 13A and 13B laminated on one surface 11a and the other surface 11b of the transparent substrate 11 can also be patterned step. In this case, for example, a mask arrangement step in which a mask having a desired pattern is arranged on the surface A and the surface B on the blackened layers 13A and 13B can be performed. Next, an etching step of supplying an etching solution to the surface A and the surface B on the blackened layers 13A and 13B, that is, the side where the mask is arranged, may be performed.

The pattern formed in the etching step is not particularly limited, and it may have any shape. For example, in the case of the conductive substrate 10A shown in FIG. 1A, the metal layer 12 and the blackened layer 13 can be formed in a pattern including a plurality of straight lines or zigzag curved lines (z-shaped straight lines) as described above.

In addition, in the case of the conductive substrate 10B shown in FIG. 1B, the metal layer 12A and the metal layer 12B may form a grid-like wiring pattern. In this case, it is preferable to perform patterning separately so that the blackened layer 13A has the same shape as the metal layer 12A, and the blackened layer 13B has the same shape as the metal layer 12B.

In addition, for example, after patterning the metal layer 12 and the like of the conductive substrate 10A in the patterning step, a lamination step of laminating two or more patterned conductive substrates may be performed. At the time of lamination, for example, the layers are laminated so that the patterns of the metal layers of the respective conductive substrates intersect, so that a laminated conductive substrate having grid-like wiring can be obtained.

The method of fixing two or more laminated conductive substrates is not particularly limited. For example, it can be fixed with an adhesive or the like.

Obtained by the above-mentioned manufacturing method of the conductive substrate of the present embodiment The conductive substrate has a structure in which a blackened layer is laminated on a metal layer formed on at least one surface of a transparent substrate. Furthermore, since the blackened layer contains nickel alone, nickel oxide, nickel hydroxide, and copper, as described above, when patterning is performed by etching the metal layer and the blackened layer, it is easy to pattern the blackened layer into The desired shape.

In addition, the blackened layer contained in the conductive substrate obtained by the method of manufacturing the conductive substrate of the present embodiment can sufficiently suppress light reflection on the surface of the metal layer, and a conductive substrate with low reflectance can be obtained. Therefore, when used for applications such as a touch panel, the visibility of the display can be improved.

[Example]

The following description is based on specific examples and comparative examples, but the present invention is not limited to these examples.

(Evaluation method)

The samples prepared in the following experimental examples were evaluated by the following methods.

(1) Composition analysis of the blackened layer

An X-ray photoelectron spectrometer (manufactured by PHI, model: QuantaSXM) was used to analyze the composition of the blackened layer. Among them, the X-ray source used monochromatic Al (1486.6 eV).

As detailed below, in each of the following experimental examples, a conductive substrate having the structure of FIG. 1A was produced. Here, the exposed surface A of the blackened layer 13 in FIG. 1A was subjected to Ar ion etching, and the Ni 2P spectrum and the Cu LMM spectrum of the interior 10 nm away from the outermost surface were measured. Based on the obtained spectrum, the ratio of the number of copper atoms when the number of nickel atoms contained in the blackened layer is 100 was calculated. Here, Table 1 shows the results in terms of the ratio of metal components.

In addition, according to the peak separation analysis of the Ni 2P spectrum, the content of the blackened layer was calculated When the number of atoms of metallic nickel is 100, the number of nickel atoms constituting the nickel oxide and the number of nickel atoms constituting the nickel hydroxide. Here, Table 1 shows the results in terms of the ratio of nickel components.

(2) Reflectance measurement

The reflectance measurement unit was set on an ultraviolet visible spectrophotometer (Model: UV-2600 manufactured by Shimadzu Corporation) and measured.

As described below, a conductive substrate having the structure shown in FIG. 1A was produced in each experimental example. Therefore, when the reflectance measurement is performed, the surface A of the blackened layer 13 of the conductive substrate 10A shown in FIG. 1A is set at an incident angle of 5° and a light receiving angle of 5°, and the wavelength is irradiated at an interval of 1 nm from 400 nm to 700 nm. Measure the regular reflectance of the light, and use the average value as the reflectance (average reflectance) of the conductive substrate.

(3) Etching characteristics

First, a dry film protective layer (Hitachi Chemical RY3310) was pasted on the surface of the blackened layer of the conductive substrate obtained in the following experimental example by the lamination method. Then, UV exposure was performed with a photomask, and the protective layer was dissolved with a 1% sodium carbonate aqueous solution and developed. Through the above, a sample having a pattern in which the width of the protective layer is changed in units of 0.5 μm in the range of 3.0 μm or more and 10.0 μm or less is produced. That is, 15 kinds of linear patterns with protective layer widths of 3.0 μm, 3.5 μm, 4.0 μm ‧ ‧ 9.5 μm, 10.0 μm, etc., were formed in units of 0.5 μm.

Then, the sample was immersed in an etching solution at 30° C. composed of 10% by weight of sulfuric acid and 3% by weight of hydrogen peroxide for 40 seconds, and peeled off with an aqueous sodium hydroxide solution to remove the dry film protective layer.

The obtained sample was observed under a microscope of 200 times, and the minimum value of the wiring width of the metal wiring remaining on the conductive substrate was obtained.

After the protective layer is peeled off, the smaller the minimum value of the wiring width of the metal wiring remaining on the conductive substrate, or the less dissolved residues around the formed metal wiring, it means the reactivity of the copper layer and the blackened layer to the etching solution The closer to the same level. Here, the minimum value of the wiring width of the remaining metal wiring was 3 μm or more and 10 μm or less, and the case where no dissolved residue was seen around the formed metal wiring was evaluated as "○". In addition, the minimum value of the remaining metal wiring was 3 μm or more and 10 μm or less, and a part of the dissolved residue remained around the formed metal wiring, but it was evaluated as "△" when there was no obstacle in actual use. In the case where it was not dissolved in the etching solution and the metal wiring with a wiring width of 10 μm or less could not be formed, it was evaluated as unacceptable "×". The case of "○" or "△" can be regarded as a conductive substrate having a metal layer and a blackened layer that can be etched at the same time, and can be evaluated as a pass.

Here, Table 2 shows "○", "△", and "×" as the evaluation results.

(Conditions for sample preparation)

A conductive substrate was produced under the conditions described below, and evaluated according to the above-mentioned evaluation method. Experimental example 1 to experimental example 10 are all examples.

[Experimental example 1]

A conductive substrate having the structure shown in FIG. 1A was produced.

(Metal layer forming step)

A copper layer as a metal layer was formed on one surface of a long transparent substrate made of polyethylene terephthalate resin (PET) with a length of 300 m, a width of 250 mm, and a thickness of 100 μm. In addition, a transparent substrate made of polyethylene terephthalate resin used as a transparent substrate was evaluated for total light transmittance by the method specified in JIS K 7361-1, and the result was 97%.

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

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

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

In the metal thin film layer forming step, first, the above-mentioned transparent base material whose water has been removed by preheating to 60° C. is set in the cavity of the sputtering device.

Next, exhaust the chamber to reduce the pressure to 1×10 ^-3 Pa, and then introduce argon to make the pressure in the chamber 1.3 Pa.

Electricity was supplied to a copper target previously set on the cathode of the sputtering device, and a copper thin film layer with a thickness of 0.7 μm was formed on one surface of the transparent substrate.

Then, in the metal plating layer forming step, a copper plating layer was formed as the metal plating layer. The copper plating layer was formed by the electroplating method, and the thickness of the copper plating layer was 0.3 μm.

By performing the above metal thin film layer forming step and metal plating layer forming step, a copper layer with a thickness of 1.0 μm was formed as a metal layer.

The substrate prepared by the metal layer forming step and having a copper layer with a thickness of 1.0 μm formed on a transparent substrate was immersed in 20 g/l sulfuric acid for 30 sec, and washed, and the following blackened layer forming step was implemented.

(Blackening layer formation step)

In the blackening layer forming step, a blackening plating solution is used and an electroplating method is used to form a blackening layer on one surface of the copper layer.

In addition, as the blackening plating solution, a plating solution containing nickel ions, copper ions, sulfamic acid, and sodium hydroxide was prepared. By adding nickel sulfate 6 hydrate and copper sulfate 5 hydrate to the blackening bath, Provides nickel ions and copper ions.

Then, each component was added and prepared so that the concentration of nickel ions in the blackening plating solution became 5 g/l, the concentration of copper ions became 0.03 g/l, and the concentration of sulfamic acid became 11 g/l.

In addition, an aqueous sodium hydroxide solution was added to the blackening plating solution to adjust the pH of the blackening plating solution to 4.9.

In the blackening layer forming step, electroplating was performed under the conditions of a blackening bath temperature of 40°C, a current density of 0.10 A/dm ² , and a plating time of 400 sec to form a blackening layer.

The thickness of the formed blackening layer was 70 nm.

For the conductive substrate obtained through the above steps, the component analysis, reflectance and etching characteristics of the blackened layer described above were evaluated. The results are shown in Table 1.

[Experimental example 2-Experimental example 10]

In each experimental example, the nickel ion concentration, copper ion concentration, current density and plating time in the blackening bath during the formation of the blackening layer are shown in Table 1. Under the same conditions as in Experimental Example 1, a conductive substrate was produced and evaluated. The results are shown in Table 1.

【Table 1】

From the results shown in Table 1, it was confirmed that in Experimental Example 1 to Experimental Example 10, the blackened layer contained nickel alone, nickel oxide, nickel hydroxide, and copper.

In addition, the evaluation result of the etching characteristics is "○" or "△", confirming These conductive substrates have a metal layer and a blackened layer that can be etched at the same time.

In particular, according to the atomic ratio of nickel to copper contained in the blackened layer, in Experimental Example 1-8 where copper is 7 or more and 90 or less when nickel is 100, it is confirmed that the etching characteristic is "○" and the reflectance is also 10% or less. Therefore, in the conductive substrates of Experimental Example 1 to Experimental Example 8, it was confirmed that the reactivity of the metal layer and the blackened layer to the etching solution were particularly similar, and had a blackened layer that can particularly suppress light reflection on the surface of the metal layer.

The conductive substrate has been described above based on the embodiment and the examples, but the present invention is not limited to the above-mentioned embodiment and examples. Various modifications and changes can be made within the scope of the gist of the present invention described in the scope of the patent application.

This application claims priority based on patent application No. 2016-016603 filed with the Japan Patent Office on January 29, 2016, and cites the entire content of patent application No. 2016-016603.

A‧‧‧surface

10A‧‧‧Conductive substrate

11‧‧‧Transparent substrate

11a‧‧‧One side of transparent substrate 11

11b‧‧‧The other side of transparent substrate 11

12‧‧‧Metal layer

13‧‧‧Black layer

Claims (3)

A conductive substrate comprising: a transparent substrate; a metal layer formed on at least one surface of the transparent substrate; and a blackened layer formed on the metal layer, the blackened layer containing nickel monomer, nickel oxide The metal layer contains copper, nickel hydroxide and copper. For example, the conductive substrate of the first item in the scope of the patent application, wherein the nickel and copper contained in the blackened layer are based on the atomic ratio. When the nickel is 100, the copper is 5 to 90. For example, the conductive substrate of the first or second item of the scope of patent application, wherein there is an adhesion layer between the transparent base material and the metal layer.

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