JP6932908B2 - Laminated board, conductive board, method of manufacturing laminated board, method of manufacturing conductive board - Google Patents

Description

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

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

By the way, in recent years, the screen size of a display provided with a touch panel has been increasing, and in response to this, a large area of a conductive substrate such as a transparent conductive film for a touch panel is required. However, since ITO has a high electric resistance value, there is a problem that it cannot cope with a large area of the conductive substrate.

Therefore, for example, as disclosed in Patent Documents 2 and 3, it is considered to use a metal wiring processed with a metal foil such as copper instead of the wiring of the ITO film. However, when copper is used for metal wiring, for example, since copper has a metallic luster, there is a problem that the visibility of the display is lowered due to reflection.

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

Japanese Unexamined Patent Publication No. 2003-151358 Japanese Unexamined Patent Publication No. 2011-018194 Japanese Unexamined Patent Publication No. 2013-069261

By the way, in a conductive substrate provided with metal wiring on a transparent substrate, after obtaining a laminated substrate in which a metal layer is formed on the surface of the transparent substrate, the metal layer is etched so as to obtain a desired wiring pattern. Obtained by forming metal wiring. Further, in the conductive substrate having the blackening layer and the metal wiring on the transparent base material, the desired wiring is obtained after obtaining a laminated substrate in which the blackening layer and the metal layer are laminated in this order on the surface of the transparent base material. It is obtained by etching the blackening layer and the metal layer so as to form a pattern to form a metal wiring.

By etching the blackening layer and the metal layer, for example, as shown in FIG. 1A, the blackening layer 2 patterned on the transparent substrate 1 and the metal wiring 3 in which the metal layer is patterned. Can be a conductive substrate in which and is laminated. In this case, the width W _A of the blackening layer 2 patterned into, it is preferable that the width W _B of the metal wire 3 substantially the same.

However, there is a problem that the reactivity to the etching solution is significantly different between the metal layer and the blackening layer. That is, when trying to etch the metal layer and the blackening layer at the same time, there is a problem that one of the layers cannot be etched into the desired shape as shown in FIG. 1 (a).

For example, as compared with the metal layer, if the etch rate of the blackening layer is much slower, as shown in FIG. 1 (b), patterned blackening layer 2 having a width (bottom width) W _A is the pattern reduction has been in some cases greater than the width W _B of the metal wire 3 is a metal layer. Then, the side surface of the metal wiring 3 is etched, so-called side etching occurs. Therefore, the cross-sectional shape of the metal wiring 3 tends to be a trapezoid with a wide hem, and if etching is performed until the electrical insulation between the metal wirings 3 is secured, the wiring pitch width becomes too wide.

In comparison with the metal layer, if the etch rate of the blackening layer is faster significantly, the Figure 1 patterned blackening layer 2 having a width as shown in (c) (bottom width) W _A metal wiring 3 state of becomes smaller than the width W _B, undercut may occur. Such undercuts are generated, depending on the degree, the width W _B of a predetermined metal wiring 3, an adhesion width of the transparent substrate 1, a blackening layer 2 patterned bottom width W _A There is a problem that sufficient wiring adhesion strength cannot be obtained when the ratio of the adhesion width is lowered more than necessary.

Further, even if the etching rate of the blackened layer is adjusted to the etching rate of the metal layer, the etching residue of the blackened layer is present on the surface of the transparent substrate exposed after etching, that is, the opening, and the opening looks yellow visually. Sometimes.

In view of the above problems of the prior art, an object of the present invention is to provide a laminated substrate including a copper layer and a blackening layer that can be etched at the same time.

In order to solve the above problems, the present invention
With a transparent base material
A laminate formed on at least one surface side of the transparent base material is provided.
The laminate is
A first blackening layer containing nitrogen and copper,
A second blackening layer provided on the first blackening layer and containing oxygen, copper, and nickel,
With a copper layer
With a third blackening layer ,
The thickness of the first blackening layer is 5 nm or more and 15 nm or less.
Copper contained in the second blackened layer, and among the nickel state, and are percentage 11 mass% to 60 mass% of nickel,
The copper layer is arranged between the second blackening layer and the third blackening layer.
The third blackening layer contains copper, a layer containing nitrogen, a layer containing copper, nitrogen, and oxygen, or oxygen and at least copper as a metal component, and the metal component. ratio of nickel to provide one of the layers der Ru laminate substrate layer is 70 mass% or more 0% by weight of.

According to the present invention, it is possible to provide a laminated substrate including a copper layer and a blackening layer that can be etched at the same time.

Explanatory drawing when the metal layer and the blackening layer are etched at the same time in the conventional conductive substrate. Sectional drawing of the laminated body substrate which concerns on embodiment of this invention. Sectional drawing of the laminated body substrate which concerns on embodiment of this invention. Top view of a conductive substrate provided with mesh-like wiring according to an embodiment of the present invention. FIG. 4 is a cross-sectional view taken along the line AA'of FIG. Explanatory drawing of undercut amount ratio. Explanatory drawing of a roll-to-roll sputtering apparatus.

Hereinafter, an embodiment of a laminated substrate, a conductive substrate, a method for manufacturing a laminated substrate, and a method for manufacturing a conductive substrate of the present invention will be described.
(Laminated substrate, conductive substrate)
The laminated body substrate of the present embodiment can include a transparent base material and a laminated body formed on at least one surface side of the transparent base material. Further, the laminate is provided on the first blackening layer containing nitrogen and copper, the first blackening layer, and the second blackening layer containing oxygen, copper, and nickel, and copper. Layers and can be provided. The proportion of nickel in the copper and nickel contained in the second blackening layer can be 11% by mass or more and 60% by mass or less.

The laminated substrate in the present embodiment is a substrate having a copper layer or a blackening layer before patterning on the surface of the transparent substrate. Further, the conductive substrate is a wiring board having a copper wiring layer or a blackened wiring layer which is patterned into a wiring shape on the surface of a transparent base material.

Here, first, each member included in the laminated body substrate of this embodiment will be described below.

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

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

The thickness of the transparent substrate is not particularly limited, and can be arbitrarily selected according to the strength required for the conductive substrate, the light transmittance, and the like. The thickness of the transparent substrate can be, for example, 10 μm or more and 250 μm or less. In particular, when used for a touch panel application, it is preferably 20 μm or more and 200 μm or less, and more preferably 20 μm or more and 120 μm or less. When used for a touch panel, for example, especially in an application where it is required to reduce the thickness of the entire display, the thickness of the transparent base material is preferably 20 μm or more and 100 μm or less.

Next, the laminated body will be described. The laminate is formed on at least one surface side of the transparent base material, and can have a first blackening layer, a second blackening layer, and a copper layer. In addition, when the blackening layer included in the laminated body substrate is collectively referred to, it is also simply referred to as "blackening layer" below.

Here, the copper layer will be described first.

The copper layer is also not particularly limited, but it is preferable not to dispose an adhesive between the copper layer and the transparent base material or between the copper layer and the blackening layer in order not to reduce the light transmittance. That is, it is preferable that the copper layer is directly formed on the upper surface of the other member.

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

When the copper layer is made thicker, it is preferable to use a wet plating method after forming a copper thin film layer by a dry plating method. That is, for example, a copper thin film layer can be formed on a transparent base material or a blackened layer by a dry plating method, and the copper thin film layer can be used as a feeding layer to form a copper plating layer by a wet plating method. In this case, the copper layer has a copper thin film layer and a copper plating layer.

As described above, the copper layer can be formed directly on the transparent base material or the blackened layer without using an adhesive by forming the copper layer only by the dry plating method or by combining the dry plating method and the wet plating method. preferable.

The thickness of the copper layer is not particularly limited, and when the copper layer is used as the wiring, it can be arbitrarily selected according to the electric resistance value of the wiring, the wiring width, and the like. In particular, the thickness of the copper layer is preferably 50 nm or more, more preferably 60 nm or more, and even more preferably 150 nm or more so that sufficient electricity can flow. The upper limit of the thickness of the copper layer is not particularly limited, but when the copper layer becomes thick, side etching occurs because etching takes time when etching is performed to form wiring, and the resist is peeled off in the middle of etching. Etc. are likely to occur. Therefore, the thickness of the copper layer is preferably 5000 nm or less, and more preferably 3000 nm or less. When the copper layer has the copper thin film layer and the copper plating layer as described above, the total of the thickness of the copper thin film layer and the thickness of the copper plating layer is preferably in the above range.

Next, the blackening layer will be described.

Since the copper layer has a metallic luster, the copper reflects light as described above only by forming the copper wiring layer which is the wiring obtained by etching the copper layer on the transparent base material, and is used as a wiring board for a touch panel, for example. In this case, there is a problem that the visibility of the display is lowered. Therefore, a method of providing a blackening layer has been studied, but the blackening layer may not have sufficient reactivity with an etching solution, and the copper layer and the blackening layer are simultaneously etched into a desired shape. This was difficult, and there was a problem that an etching residue of the blackened layer was generated.

In addition, the inventors of the present invention initially used a method of forming a copper oxide layer obtained by oxidizing a part of the copper layer or nitriding a part of the copper layer as a blackening layer capable of suppressing light reflection on the surface of the copper layer. The method of forming the copper nitride layer was examined. When a part of the copper layer is oxidized to form a blackened layer, the blackened layer may contain an indefinite ratio of copper oxide or unoxidized copper, or copper. It has been found that when a part of the layer is nitrided to form a blackened layer, the blackened layer may contain an indefinite ratio of copper nitride or unnitrided copper.

When the copper layer and the copper layer of the laminated substrate provided with the blackening layer and the blackening layer are simultaneously etched, for example, an etching solution capable of etching the copper layer can be preferably used as the etching solution. Then, according to the study by the inventors of the present invention, when the blackened layer contains an indefinite ratio of copper oxide or an indefinite ratio of copper nitride, the copper layer is made into an etching solution capable of etching. Easy to elute.

As described above, when the blackened layer contains a copper oxide having an indefinite ratio that is easily eluted with respect to the etching solution, the blackened layer has high reactivity with the etching solution, and the blackened layer has a higher reactivity than the copper layer. Etching speed is significantly increased. Therefore, when the copper layer and the blackening layer are etched at the same time, the blackening layer tends to be undercut.

Therefore, the inventors of the present invention suppress the generation of undercuts in the copper layer and the blackening layer and the generation of the residue of the blackening layer in the openings by using the same etching solution in one step. At the same time, the blackened layer that can be etched was studied diligently to complete the present invention.

The blackening layer of the laminated substrate of the present embodiment has a multi-layer structure, and has at least a two-layer structure, and is provided on the first blackening layer and the first blackening layer, that is, on the surface of the first blackening layer. It is provided with a second blackening layer to be formed.

Then, when etching is performed with the same etching solution, the first blackening layer can be a layer having higher reactivity to the etching solution than the second blackening layer. That is, the first blackening layer is more easily dissolved in the etching solution than the second blackening layer, and in other words, the first blackening layer can be a layer that is easily etched.

Specifically, the second blackening layer of the laminated substrate of the present embodiment can contain a nickel component that is difficult to dissolve in an etching solution, in addition to oxygen and copper. On the other hand, the first blackening layer can be configured not to contain a nickel component that is difficult to dissolve in the etching solution.

The first blackening layer can contain at least nitrogen and copper. Further, the first blackening layer may further contain oxygen. The second blackening layer can contain oxygen, copper, and nickel. Further, it is desirable that the second blackening layer contains copper as an essential metal species and contains 89% by mass or less.

Therefore, there is a difference in the reactivity of the blackened layer of the laminated substrate of the present embodiment with respect to the etching solution, and as described above, the first blackened layer reacts more with the etching solution than the second blackened layer. It can be highly sex. Further, the reactivity of the second blackening layer to the etching solution can be such that the etching can be performed at the same time as the copper layer. The fact that the reactivity of the etching solution of the second blackening layer can be etched at the same time as the copper layer includes that the reactivity of the second blackening layer to the etching solution may be lower than that of the copper layer. The thickness of the second blackening layer can be much thinner than the thickness of the copper layer. For example, even if the reactivity of the second blackening layer to the etching solution is lower than that of the copper layer, it is sufficient that the second blackening layer has reactivity to be etched at the same time as the copper layer.

According to the laminated substrate of the present embodiment, since the first blackening layer is easily etched as described above, it is possible to reduce the etching residue of the blackening layer on the surface of the transparent substrate, for example. Since the etching residue of the blackened layer can be reduced, the reduction rate of the total light transmittance of the transparent substrate exposed by etching, in other words, the reduction rate of the total light transmittance of the opening can be suppressed to a small value.

However, since the first blackening layer has high reactivity with the etching solution, there is a concern that undercut may occur if only the first blackening layer is used as the blackening layer. However, in the laminated substrate of the present embodiment, since the second blackening layer is arranged on the first blackening layer, the first blackening layer is less likely to be etched than the first blackening layer. It is covered with a chemical layer.

Therefore, if the second blackening layer is not removed by etching, the first blackening layer is not removed by etching, so that the occurrence of undercut can be reliably suppressed. Further, as described above, since the first blackening layer is easily etched, the etching residue of the blackening layer is unlikely to remain on the surface of the transparent substrate after etching.

As described above, in the laminated substrate of the present embodiment, the copper layer and the blackening layer can be etched at the same time.

The fact that the copper layer and the blackening layer can be etched at the same time means that the copper layer and the blackening layer can be undercut and blackened to the opening by the same etching solution in one step. This means that etching can be performed while suppressing the generation of layer residues.

However, in the laminated substrate of the present embodiment, it is possible to perform wiring processing with an etching solution different from the copper layer and the blackening layer, and the etching solution and the blackening layer capable of selectively removing the copper layer are selectively selected. It is also possible to produce a conductive substrate having finer fine metal wires by properly using an etching solution that can be removed. In particular, since the first blackening layer has higher reactivity to the etching solution than the second blackening layer, fine metal fine wires can be formed on the surface of the transparent substrate without the residue of the blackening layer.

As described above, it is desirable that the first blackening layer contains copper as a metal species, and the metal species contained in the first blackening layer may be composed of only copper, but is limited to copper only. It's not something. For example, the first blackening layer may further contain 1% by mass or less of unavoidable impurities as a metal species.

The first blackening layer may further contain oxygen in addition to nitrogen and copper. Further, the state in which each component is contained in the first blackening layer is not particularly limited. For example, at least a part of copper may be nitrided or oxidized, and an indefinite ratio oxide may be contained in the first blackening layer in addition to the indefinite ratio copper nitride.

Further, as described above, it is desirable that the second blackening layer contains copper and nickel as metal species, and the metal species contained in the second blackening layer may be composed of only copper and nickel. It is not limited to copper and nickel. For example, the second blackening layer may further contain 1% by mass or less of unavoidable impurities as a metal species.

The second blackening layer may also contain oxygen, copper, and nickel, and the state in which each component is contained is not particularly limited. For example, at least a part of copper or nickel may be oxidized to form an indefinite ratio of copper oxide or nickel oxide, which may be contained in the blackening layer.

This is because the second blackening layer of the laminated substrate of the present embodiment contains nickel, so that even if the blackening layer contains an indefinite ratio of copper oxide, the reactivity with the etching solution is the copper layer. This is because it can be almost the same as. Therefore, in the laminated substrate of the present embodiment, the copper layer and the blackening layer can be etched at the same time.

The second blackening layer preferably does not contain nitrogen except when it contains nitrogen as an unavoidable impurity. When the second blackening layer contains nitrogen, the reactivity to the etching solution differs between the blackening layer and the copper layer, although it depends on the copper content and nickel content in the metal species. This is because it may not be possible to etch the blackening layer and the copper layer together.

The amount of nitrogen and oxygen contained in the first blackening layer and the amount of oxygen contained in the second blackening layer are not particularly limited. However, the amount of oxygen contained in each blackening layer may affect the light reflectance of the laminated substrate or the conductive substrate produced by using the laminated substrate. Therefore, depending on the degree of light reflectance required for the laminated substrate and the conductive substrate produced by using the laminated substrate, the color tone of the blackened layer, and the like, the nitrogen contained in the blackened layer may be increased. It is preferable to select the amount of oxygen, and further, the amount of oxygen to be added when forming the blackening layer.

The proportion of nickel in the copper and nickel contained in the second blackening layer is not particularly limited, but the proportion of nickel in the copper and nickel contained in the second blackening layer is 11% by mass or more and 60. It is preferably mass% or less. The proportion of nickel indicates the proportion when the total content of copper and nickel in the blackened layer is 100% by mass.

This is because the proportion of nickel in the copper and nickel contained in the second blackening layer is 11% by mass or more, so that the difference in reactivity with the etching solution from the first blackening layer containing no nickel, that is, This is because the difference in reaction rate can be sufficiently secured.

However, if the proportion of nickel in the copper and nickel contained in the second blackening layer exceeds 60% by mass, the nickel is excessive and the etching of the second blackening layer may become difficult. That is, the dissolution rate of the second blackening layer in the etching solution is slower than that of the copper layer, and there is a possibility that the second blackening layer that can be etched at the same time as the copper layer cannot be formed. Therefore, as described above, the proportion of nickel in the copper and nickel contained in the second blackening layer is preferably 60% by mass or less.

Further, by setting the proportion of nickel among the copper and nickel contained in the second blackening layer to 11% by mass or more and 60% by mass or less, the wavelength of the laminated substrate and the conductive substrate formed from the laminated substrate The average specular reflectance of light of 400 nm or more and 700 nm or less can be 55% or less. Therefore, even when this conductive substrate is used for a touch panel or the like, deterioration of the visibility of the display can be suppressed, which is also preferable in this respect.

In the laminated substrate of the present embodiment, the first blackening layer, the second blackening layer, and the copper layer can be laminated on the transparent base material as described later, and these first and second blackening layers can be laminated. A conductive substrate can be obtained by patterning the layer and the copper layer.

Therefore, the copper wiring layer and each blackened wiring layer of the conductive substrate obtained from the laminated substrate of this embodiment maintain the characteristics of the copper layer and each blackened layer of the laminated substrate of this embodiment, respectively. Will be done.

The film forming method of each blackening layer arranged on the conductive substrate of the present embodiment is not particularly limited. The blackened layer is preferably formed by, for example, a dry film forming method such as a sputtering method.

When each blackening layer is formed by a sputtering method, for example, a copper target is used to form a first blackening layer, and a copper-nickel alloy target is used to form a second blackening layer. In addition to the inert gas used as the sputtering gas, the film can be formed while supplying nitrogen gas or oxygen gas into the chamber.

When a copper-nickel alloy target is used during sputtering in the formation of the second blackening layer, the proportion of nickel in the copper and nickel contained in the copper-nickel alloy is 11% by mass or more and 60% by mass or less. It is preferable to have. This is contained in the copper-nickel alloy of the ratio of nickel to the copper and nickel contained in the blackening layer to be formed and the target of the copper-nickel alloy used when forming the blackening layer. This is because the ratio of nickel to copper and nickel is the same.

When each blackening layer is formed by the sputtering method, the method of adjusting the supply amount of nitrogen gas or oxygen gas supplied into the chamber is not particularly limited. For example, a mixed gas in which nitrogen gas and / or oxygen gas and an inert gas are mixed in advance so that the partial pressure of nitrogen or the partial pressure of oxygen becomes a desired partial pressure can also be used. Further, by simultaneously supplying an inert gas and nitrogen gas and / or oxygen gas into the chamber and adjusting the supply amount of each gas, the partial pressure of the nitrogen gas and / or the partial pressure of the oxygen gas in the chamber is adjusted. Can also be adjusted. In particular, the latter is preferable because the partial pressure of each gas in the chamber can be adjusted as needed.

The inert gas for forming each blackening layer is not particularly limited, and for example, argon gas or xenon gas can be used, but argon gas can be preferably used. In addition to oxygen, each blackening layer may also contain one or more components selected from hydrogen and carbon as components other than the metal species. Therefore, the gas for forming each blackening layer includes one or more kinds of gases selected from water vapor, carbon monoxide gas, and carbon dioxide gas, in addition to nitrogen gas, oxygen gas, and inert gas. You may be.

When each blackening layer is formed by the sputtering method while supplying the inert gas, nitrogen gas, and oxygen gas to the chamber as described above, the inert gas, nitrogen gas, and oxygen supplied into the chamber are formed. The ratio with gas is not limited. It can be arbitrarily selected according to the light reflectance required for the laminated substrate or the conductive substrate, the degree of color tone of each blackened layer, and the like.

The total thickness of each blackening layer formed in the laminated substrate of the present embodiment is not particularly limited, and may be arbitrarily selected depending on, for example, the degree of suppressing light reflection on the surface of the copper layer. Can be done.

The total of the thickness of the first blackening layer and the thickness of the second blackening layer preferably has a lower limit of, for example, 10 nm or more, and more preferably 15 nm or more.

As described above, the blackening layer functions as a layer that suppresses the reflection of light on the surface of the copper layer, but when the thickness of the blackening layer is thin, the reflection of light by the copper layer may not be sufficiently suppressed. .. On the other hand, as described above, by setting the total thickness of the first blackening layer and the second blackening layer to 10 nm or more, the reflection of light on the surface of the copper layer can be suppressed more reliably.

The upper limit of the total of the thickness of the first blackening layer and the thickness of the second blackening layer is not particularly limited, but even if it is made thicker than necessary, the time required for film formation and the wiring are formed. The time required for etching at that time becomes long, which leads to an increase in cost. Therefore, the total thickness of the first blackening layer and the thickness of the second blackening layer is preferably 70 nm or less, and more preferably 50 nm or less.

The thickness of the first blackening layer is preferably 5 nm or more and 15 nm or less. This is because the reflectance of the laminated substrate can be sufficiently suppressed by setting the thickness of the first blackening layer to 5 nm or more. However, since the first blackening layer is easily etched, if the thickness of the first blackening layer exceeds 15 nm, undercut may occur depending on the etching conditions such as the etching time. Therefore, as described above, 15 nm. The following is preferable.

On the other hand, the thickness of the second blackening layer can be appropriately selected so that the total thickness of the first blackening layer and the second blackening layer is within the above range.

Further, the laminated substrate of the present embodiment may have a third blackening layer in addition to the first blackening layer and the second blackening layer. When the third blackening layer is provided, the structure of the third blackening layer is not particularly limited, and can be, for example, the same structure as the first blackening layer and / or the second blackening layer.

That is, the third blackening layer can contain, for example, nitrogen and copper. In some cases, oxygen can be further contained. Further, the third blackening layer can contain oxygen, copper and nickel. Therefore, the third blackening layer is either a layer containing copper and nitrogen, a layer containing copper, nitrogen and oxygen, or a layer containing oxygen and at least copper as a metal component. Can be a layer of.

Further, when the third blackening layer is a layer containing oxygen and at least copper as a metal component, the proportion of nickel in the metal component in the third blackening layer is 0% by mass or more and 70% by mass or less. Is preferable. The metal component in the third blackening layer here is copper when the third blackening layer contains copper and oxygen as in the case of the first blackening layer, and the third blackening layer is When copper, nickel and oxygen are contained in the same manner as in the second blackening layer, it becomes copper and nickel. Further, the third blackening layer may have a multi-layer structure as described later, and has, for example, a structure having a layer containing copper as a metal component and a layer containing copper and nickel as metal components. You can also.

The film thickness of the third blackening layer is not particularly limited, but for example, the lower limit value can be 5 nm or more. The upper limit is preferably, for example, 70 nm or less, and more preferably 50 nm or less.

Next, a configuration example of the laminated substrate of the present embodiment will be described.

As described above, the laminate substrate of the present embodiment can have a transparent substrate and a laminate having a copper layer and each blackening layer. At this time, the order in which the copper layer and each blackening layer are arranged on the transparent base material and the number of the layers are particularly limited except that the second blackening layer is provided on the first blackening layer in the laminated body. It's not something. That is, for example, two layers of a copper layer, a first blackening layer, and a second blackening layer can be laminated on at least one surface side of the transparent base material. Further, a plurality of copper layers and / or blackening layers can be formed as long as the first blackening layer and the second blackening layer are laminated in this order in the laminated body.

However, when arranging the copper layer and the blackening layer in the laminated body, in order to suppress the reflection of light on the surface of the copper layer, the blackening layer is formed on the surface of the copper layer where the reflection of light is particularly desired to be suppressed. It is preferably arranged.

In particular, it is more preferable that the blackening layer has a laminated structure formed on the surface of the copper layer. Specifically, for example, the laminated body has a third blackening layer in addition to the first and second blackening layers. It has a blackening layer, and the copper layer can be configured to be arranged between the second blackening layer and the third blackening layer. More specifically, for example, the first blackening layer, the second blackening layer, the copper layer, and the third blackening layer can be laminated in this order from the transparent substrate side. The third blackening layer contains copper, a layer containing nitrogen, a layer containing copper, nitrogen, and oxygen, or oxygen and at least copper as a metal component, and the metal component. It can be any layer in which the proportion of nickel is 0% by mass or more and 70% by mass.

When the third blackening layer is provided, it may be appropriately selected whether the third blackening layer has a multi-layer structure or is composed of a single blackening layer, and is not particularly limited. For example, for the purpose of matching the color tone of the blackening layer having a multi-layer structure including the first blackening layer and the second blackening layer with the third blackening layer, the third blackening layer is referred to as the first blackening layer. It is also possible to have a multi-layer structure having the second blackening layer.

Further, the third blackening layer may have the same structure as the first blackening layer or the second blackening layer, for example. That is, the third blackening layer is either a layer containing copper and nitrogen, a layer containing copper, nitrogen and oxygen, or a layer containing oxygen and at least copper as a metal component. Can be layers. When the third blackening layer is a layer containing oxygen and at least copper as a metal component, the proportion of nickel in the metal component in the third blackening layer is 0% by mass or more and 70% by mass or less. Is preferable. This is because when the third blackening layer contains copper as a metal component and, in some cases, nickel, and the total content of copper and nickel is 100% by mass, the proportion of nickel is 70% by mass. This is because if it exceeds%, nickel is excessive and the etching of the third blackening layer may become difficult.

A specific configuration example of the laminated substrate of the present embodiment will be described below with reference to FIGS. 2 and 3. 2 and 3 show an example of a cross-sectional view of the laminated substrate of the present embodiment on a plane parallel to the laminating direction of the transparent base material, the copper layer, and the blackened layer. For example, as in the laminated substrate 10A shown in FIG. 2A, the first blackening layer 131, the second blackening layer 132, and the copper layer 12 are further formed on one surface 11a side of the transparent base material 11. It can be laminated one by one in that order. That is, the first blackening layer 131 provided on the surface of the transparent base material 11, the second blackening layer 132 provided on the surface of the first blackening layer 131, and copper provided on the surface of the second blackening layer 132. It can be configured to include the layer 12.

Further, as in the laminated substrate 10B shown in FIG. 2B, the first blackening layer is formed on one surface 11a side of the transparent base material 11 and the other surface (the other surface) 11b side, respectively. 131A, 131B, the second blackening layers 132A, 132B, and the copper layers 12A, 12B can be laminated layer by layer in that order.

Further, as described above, the laminated substrate of the present embodiment is continuously provided with a blackening layer other than the first blackening layer and the second blackening layer on at least one surface side of the transparent base material 11. It is also possible to have a plurality of blackening layers that are not laminated. For example, as in the laminated substrate 20A shown in FIG. 3A, the first blackening layer 131, the second blackening layer 132, and the copper layer 12 are formed on one surface 11a side of the transparent base material 11. The third blackening layer 133 and the third blackening layer 133 can be laminated in that order.

As described above, the blackening layer includes the first blackening layer 131, the second blackening layer 132, and the third blackening layer 133, and the copper layer 12 is the second blackening layer 132 and the third blackening layer. By arranging it between the copper layer 12 and the copper layer 12, it is possible to more reliably suppress the reflection of light incident on the upper surface side and the lower surface side of the copper layer 12.

Also in this case, a copper layer, a first blackening layer, a second blackening layer, and a third blackening layer can be laminated on both sides of the transparent base material 11. Specifically, as in the laminated substrate 20B shown in FIG. 3B, the first black is formed on one surface 11a side of the transparent base material 11 and the other surface (the other surface) 11b side, respectively. The chemical layers 131A and 131B, the second blackening layers 132A and 132B, the copper layers 12A and 12B, and the third blackening layers 133A and 133B can be laminated in this order.

The method for producing the third blackening layer 133 (133A, 133B) is not particularly limited. For example, the second blackening layer 132 (132A, 132B) and the third blackening layer 133 (133A, 133B) can both be a blackening layer containing oxygen, copper, and nickel. It can be manufactured by the same manufacturing method. In addition, the third blackening layer 133 (133A, 13)
3B) can be a blackening layer containing nitrogen and copper together with the first blackening layer 131 (131A, 131B), and can be manufactured by the same manufacturing method.

In the configuration examples of FIGS. 2 (b) and 3 (b) in which a copper layer and a blackening layer are laminated on both sides of the transparent base material 11, the transparent base material 11 is used as a symmetrical plane. An example is shown in which the vertically laminated layers are arranged symmetrically, but the present invention is not limited to this form.

For example, in FIG. 3B, the configuration of one surface 11a side of the transparent base material 11 is the same as the configuration of FIG. 2B, that is, the first blackening layer 131A, the second blackening layer 132A, and copper. The layers 12A can be laminated in that order. Then, in the configuration on the other surface (the other surface) 11b side, the first blackening layer 131B, the second blackening layer 132B, the copper layer 12B, and the third blackening layer 133B are laminated in that order. As the above-mentioned form, the layers laminated on the upper and lower sides of the transparent base material 11 may have an asymmetrical structure.

The degree of light reflection of the laminated substrate of the present embodiment is not particularly limited, but for example, the average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, preferably 40% or less. Is more preferable, and 30% or less is further preferable. This reduces the visibility of the display when the average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 55% or less, for example, even when the laminated substrate of the present embodiment is used as a conductive substrate for a touch panel. This is because it can be particularly suppressed.

The specular reflectance of the laminated substrate can be measured by irradiating the blackened layer with light. That is, among the blackened layer and the copper layer contained in the laminated substrate, the measurement can be performed by irradiating light from the blackened layer side. Specifically, for example, when the first blackening layer 131, the second blackening layer 132, and the copper layer 12 are laminated in this order on one surface 11a of the transparent base material 11 as shown in FIG. 2A, the first blackening is performed. The surface of the first blackening layer 131 can be irradiated with light from the surface 11b side of the transparent base material 11 so that the layer 131 can be irradiated with light.

Further, the average of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less means the average value of the measurement results when the measurement is performed by changing the wavelength within the range of 400 nm or more and 700 nm or less. At the time of measurement, the width in which the wavelength is changed is not particularly limited, but for example, it is preferable to change the wavelength every 10 nm to measure light in the above wavelength range, and change the wavelength every 1 nm to change the wavelength in the above wavelength range. It is more preferable to make measurements on light.

As will be described later, the laminated substrate can be made into a conductive substrate by forming fine metal wires by wiring the copper layer and the blackened layer by etching. The specular reflectance of light in the conductive substrate means the specular reflectance of the blackened layer arranged on the outermost surface on the surface on the side where light is incident, when the transparent base material is removed.

Therefore, in the case of the conductive substrate after the etching treatment, it is preferable that the measured value at the portion where the copper layer and the blackening layer remain satisfies the above range.

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

The conductive substrate of the present embodiment can include a transparent base material and a thin metal wire formed on at least one surface side of the transparent base material. The thin metal wire is provided on the first blackened wiring layer containing nitrogen and copper, and the second blackened wiring layer containing oxygen, copper, and nickel. It can be a laminate provided with a copper wiring layer. Further, the proportion of nickel in the copper and nickel contained in the second blackened wiring layer can be 11% by mass or more and 60% by mass or less.

The first blackened wiring layer contains at least nitrogen and copper, and may further contain oxygen. Further, it is desirable that the second blackened wiring layer contains copper as an essential metal species and contains 89% by mass or less of the contained metal species.

The conductive substrate of the present embodiment can be obtained, for example, by wiring the above-mentioned laminated substrate. Further, in the conductive substrate of the present embodiment, since the copper wiring layer and the blackened wiring layer having a multi-layer structure are provided on the transparent base material, it is possible to suppress the reflection of light by the copper wiring layer. can. Therefore, by providing the blackened wiring layer, it is possible to have good visibility of the display when used for a touch panel or the like, for example.

The conductive substrate of this embodiment can be preferably used as, for example, a conductive substrate for a touch panel. In this case, the conductive substrate may have a wiring pattern formed by providing openings in the copper layer and the blackening layer in the above-mentioned laminated substrate. More preferably, the configuration may include a mesh-like wiring pattern.

The conductive substrate on which the wiring pattern having the openings is formed can be obtained by etching the copper layer, the first blackening layer, and the second blackening layer of the laminated substrate described above. can. Then, for example, a conductive substrate having a mesh-like wiring pattern can be obtained by using two layers of thin metal wires. A specific configuration example is shown in FIG.

FIG. 4 shows a view of the conductive substrate 30 having a mesh-like wiring pattern as viewed from the upper surface side in the stacking direction of the copper wiring layer, the first blackened wiring layer, and the second blackened wiring layer. .. The conductive substrate 30 shown in FIG. 4 has a transparent base material 11, a plurality of copper wiring layers 31B parallel to the X-axis direction in the figure, and a copper wiring layer 31A parallel to the Y-axis direction. The copper wiring layers 31A and 31B can be formed by etching the above-mentioned laminated substrate, and the first blackened wiring layer and the second black wiring layer (not shown) are not shown on the upper surface and / or the lower surface of the copper wiring layers 31A and 31B. A blackened wiring layer is formed. Further, the first blackened wiring layer and the second blackened wiring layer are formed on a surface parallel to the main surface of the transparent base material 11, that is, a surface parallel to the surface on which the copper wiring layers 31A, 31B, etc. of the transparent base material 11 are laminated. Is etched so that the cross-sectional shape of is substantially the same as that of the copper wiring layers 31A and 31B.

The arrangement of the transparent base material 11 and the copper wiring layers 31A and 31B is not particularly limited. FIG. 5 shows a configuration example of the arrangement of the transparent base material 11 and the copper wiring layer. FIG. 5 corresponds to a cross-sectional view taken along the line AA'of FIG.

For example, as shown in FIG. 5, copper wiring layers 31A and 31B may be arranged on the upper and lower surfaces of the transparent base material 11, respectively. In the case of the conductive substrate shown in FIG. 5, the first blackened wiring layers 321A and 321B and the second blackened wiring layers 322A and 322B are arranged on the transparent base material 11 side of the copper wiring layers 31A and 31B. Has been done. The first blackened wiring layers 321A and 321B and the second blackened wiring layers 322A and 322B can have substantially the same cross-sectional shape on the main surface of the transparent base material 11 as the copper wiring layers 31A and 31B. ..

Further, as shown in FIG. 5, the third blackened wiring layers 323A and 323B can be arranged on the surface of the copper wiring layers 31A and 31B opposite to the transparent base material 11. In this case, the cross-sectional shape of the third blackened wiring layers 323A and 323B on the surface parallel to the main surface of the transparent base material 11 can be substantially the same as that of the copper wiring layers 31A and 31B.

That is, in the conductive substrate shown in FIG. 5, as described above, the thin metal wires are formed on the first blackened wiring layers 321A and 321B and the second blackened wiring layers 322A and 322B as the blackening layer. In addition, it can further have a third blackened wiring layer 323A, 323B. The copper wiring layers 31A and 31B can have a configuration arranged between the second blackened wiring layers 322A and 322B and the third blackened wiring layers 323A and 323B.

The third blackened wiring layer can be formed by etching the above-mentioned third blackened wiring layer. Therefore, the third blackened wiring layer can have the same configuration as the above-mentioned third blackened wiring layer except that it is patterned by etching. Therefore, the third blackened wiring layer can have the same configuration as, for example, the first blackened wiring layer and / or the second blackened wiring layer.

Specifically, the third blackened wiring layer can contain, for example, copper and oxygen. In some cases, nickel can be further contained. That is, the third blackened wiring layer can contain copper and oxygen, or copper, nickel, and oxygen. That is, the third blackened wiring layer contains a wiring layer containing copper and nitrogen, a wiring layer containing copper, nitrogen and oxygen, or oxygen and at least copper as a metal component. It can be any wiring layer of the wiring layer.

When the third blackened wiring layer is a layer containing oxygen and at least copper as a metal component, the proportion of nickel in the metal component in the third blackened wiring layer is 0% by mass or more and 70% by mass. % Or less is preferable.

The metal component in the third blackened wiring layer here is copper when the third blackened wiring layer contains copper and nitrogen in the same manner as the first blackened wiring layer, and is the third blackened wiring layer. When the wiring layer contains copper, nickel, and oxygen as in the case of the second blackened wiring layer, it becomes copper and nickel. Further, the third blackened wiring layer may have a multi-layer structure, and may have, for example, a structure having a layer containing copper as a metal component and a layer containing copper and nickel as metal components.

Although an example in which a third blackened wiring layer is provided in addition to the first blackened wiring layer and the second blackened wiring layer is shown here, the present invention is not limited to this form. For example, as the blackening layer, a conductive substrate having only a first blackening layer and a second blackening wiring layer can be used.

The conductive substrate having the mesh-like wiring shown in FIG. 4 has, for example, copper layers 12A and 12B on both sides of the transparent base material 11 and a first blackening layer as shown in FIGS. 2 (b) and 3 (b). It can be formed from a laminated substrate including 131A and 131B and second blackening layers 132A and 132B.

For example, the conductive substrate provided with the first blackened wiring layer, the second blackened wiring layer, and the third blackened wiring layer shown in FIG. 5 is the laminated substrate shown in FIG. 3 (b). Can be formed from.

Therefore, a case of forming using the laminated substrate of FIG. 3B will be described as an example.

First, the copper layer 12A, the first blackening layer 131A, the second blackening layer 132A, and the third blackening layer 133A on the one surface 11a side of the transparent base material 11 are parallel to each other in the Y-axis direction in FIG. 3 (b). A plurality of linear patterns are etched so as to be arranged at predetermined intervals along the X-axis direction. The Y-axis direction in FIG. 3B refers to a direction perpendicular to the paper surface. Further, the X-axis direction in FIG. 3B means a direction parallel to the width direction of each layer.

Then, the copper layer 12B, the first blackening layer 131B, the second blackening layer 132B, and the third blackening layer 133B on the other surface 11b side of the transparent base material 11 are arranged in the X-axis direction in FIG. 3 (b). Etching is performed so that a plurality of linear patterns parallel to the above are arranged at predetermined intervals along the Y-axis direction.

By the above operation, the conductive substrate having the mesh-like wiring shown in FIGS. 4 and 5 can be formed. Both sides of the transparent base material 11 can be etched at the same time. That is, the copper layers 12A and 12B, the first blackening layers 131A and 131B, the second blackening layers 132A and 132B, and the third blackening layers 133A and 133B may be etched at the same time.

Further, by performing the same etching using the laminated substrate shown in FIG. 2 (b), the conductivity shown in FIGS. 4 and 5 is shown except that the third blackened wiring layer 323A and 323B are not provided. A conductive substrate having the same configuration as that of the sex substrate can be formed.

The conductive substrate having the mesh-like wiring shown in FIG. 4 can also be formed by using two laminated substrates shown in FIGS. 2 (a) or 3 (a). Explaining the case where the conductive substrate of FIG. 2A is used as an example, the copper layer 12, the first blackening layer 131, and the second black are described for the two conductive substrates shown in FIG. 2A, respectively. The chemical layer 132 is etched so that a plurality of linear patterns parallel to the X-axis direction are arranged at predetermined intervals along the Y-axis direction. Then, the two conductive substrates are laminated so that the linear patterns formed on the conductive substrates by the etching process are oriented so as to intersect each other to obtain a conductive substrate having mesh-like wiring. be able to. The surface to be bonded when the two conductive substrates are bonded is not particularly limited.

For example, the two conductive substrates can be configured as shown in FIG. 5 by laminating the surfaces 11b of the transparent substrate 11 in FIG. 2A on which the copper layers 12 and the like are not laminated. ..

The width of the thin metal wires and the distance between the thin metal wires in the conductive substrate having the mesh-like wiring shown in FIG. 4 are not particularly limited, and depend on, for example, the electric resistance value required for the thin metal wires. Can be selected.

However, it is preferable that the following undercut amount ratio is within a predetermined range so that the transparent base material and the fine metal wire have sufficient adhesion.

Here, the undercut amount ratio will be described with reference to FIG. FIG. 6 is a cross-sectional view of a conductive substrate in which a blackened wiring layer 61 and a copper wiring layer 62 are laminated in this order on a transparent base material 11 in a plane along the stacking direction of the blackened wiring layer and the copper wiring layer. Is shown. Note that FIG. 6 shows an example in which the blackened wiring layer 61 is one layer and the copper wiring layer 62 is one layer to form a thin metal wire.

When the layer in contact with the transparent substrate has a higher etching rate than the layer formed on the upper surface of the layer in contact with the transparent substrate among the layers constituting the conductive substrate, the pattern width of the layer in contact with the transparent substrate is increased. It may be narrower than the pattern width of the layer formed on the layer in contact with the transparent substrate. That is, undercut may occur.

In the configuration example shown in FIG. 6, if the etching rate of the blackened layer in contact with the transparent substrate is faster than the etching rate of the copper layer formed on the upper surface of the blackened layer, undercut may occur. _{When undercut occurs in the configuration example shown in FIG. 6, the width (W 2} ) of the blackened wiring layer 61 in contact with the transparent base material 11, which is the bottom width of the thin metal wire, is black, which is the pattern width of the thin metal wire. It is narrower than _{the width (W 1} ) of the copper wiring layer 62 formed on the chemical wiring layer 61.

In this case, the undercut amount ratio, and the thin metal wire bottom width _{(W 2),} by a pattern width of the metal thin wire _{(W 1),} the formula of _{(W 1 -W 2) / 2W} 1.

The undercut amount ratio preferably has a relationship _{of (W 1} − W ₂ ) / 2 W _{1 ≦ 0.075.} It can be said that the undercut amount ratio satisfies the above relationship, so that the blackening layer and the copper layer can be etched at the same time and patterned in a desired pattern, and the adhesion between the transparent base material 11 and the fine metal wire can be said to be achieved. This is because it is also preferable from the viewpoint of enhancing.

Up to this point, FIGS. 4 and 5 have shown examples in which linear metal wires are combined to form a mesh-like wiring pattern, but the present invention is not limited to this form, and the metal wires constituting the wiring pattern are not limited to this. It can have any shape. For example, the shape of the thin metal wire forming the mesh-like wiring pattern can be changed to various shapes such as a jaggedly bent line (zigzag straight line) so that moire (interference fringes) does not occur between the image and the display image. ..

The conductive substrate of the present embodiment has a wiring pattern formed by wiring the above-mentioned laminated substrate and providing openings in the copper layer and the blackening layer of the laminated substrate. Therefore, an opening for exposing the transparent base material is provided between the thin metal wires included in the wiring pattern.

The reduction rate of the average transmittance of light having a wavelength of 400 nm or more and 700 nm or less of the opening from the average transmittance of light having a wavelength of 400 nm or more and 700 nm or less of the transparent substrate is 3.0% or less. Is preferable.

This is because the average reduction rate of the light transmittance of the opening having a wavelength of 400 nm or more and 700 nm or less from the average of the light transmittance of the transparent substrate used for the laminated substrate having a wavelength of 400 nm or more and 700 nm or less is 3.0. This is because if it exceeds%, the transparent substrate may be discolored to yellow when visually observed. When the reduction rate exceeds 3.0%, it is a case where the first blackening layer is not provided, and the etching rate of the second blackening layer when etching the second blackening layer and the copper layer. This is because the second blackening layer and the copper layer cannot be etched at the same time. Therefore, as described above, it is necessary to provide a first blackening layer that is more easily etched than the second blackening layer.

The degree of light reflection of the conductive substrate of the present embodiment is not particularly limited, but for example, the average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less. It is more preferably% or less, and further preferably 30% or less. This is because when the average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 55% or less, deterioration of the visibility of the display can be particularly suppressed even when used as a conductive substrate for a touch panel, for example.

The conductive substrate having the mesh-like wiring composed of the two-layer wiring of the present embodiment described so far can be preferably used as, for example, a conductive substrate for a projection type capacitance type touch panel.

(Manufacturing method of laminated substrate, manufacturing method of conductive substrate)
Next, a configuration example of the method for manufacturing the laminated substrate of the present embodiment will be described.

The method for manufacturing a laminated substrate of the present embodiment can have the following steps.
A transparent base material preparation step for preparing a transparent base material.
A laminate forming step of forming a laminate on at least one surface side of a transparent substrate.
The laminate forming step can include the following steps.
A copper layer forming step of forming a copper layer by a copper layer forming means for depositing copper.
And nitrogen, the first blackened layer forming step of forming a first black layer by the first blackened layer forming means for depositing the first blackened layer containing copper.
A second blackening layer that deposits a second blackening layer containing oxygen, copper, and nickel on the first blackening layer. A second blackening layer that forms a second blackening layer by means of forming a second blackening layer. Formation step.

The first blackening layer forming step and the second blackening layer forming step are preferably carried out in a reduced pressure atmosphere. Further, it is preferable that the proportion of nickel in the copper and nickel contained in the second blackening layer is 11% by mass or more and 60% by mass or less.

The first blackening layer may further contain oxygen in addition to nitrogen and copper. Further, it is desirable that the second blackening layer contains 89% by mass or less of the metal species containing copper as an essential metal species.

The method for manufacturing the laminated substrate of the present embodiment will be described below, but the description is omitted because the same configuration as that of the above-mentioned laminated substrate can be obtained except for the points described below.

As described above, the laminate substrate of the present embodiment can have a transparent substrate and a laminate having a copper layer and each blackening layer. At this time, the order in which the copper layer and each blackening layer are arranged on the transparent base material and the number of the layers are particularly limited except that the second blackening layer is provided on the first blackening layer in the laminated body. It's not something. That is, for example, a plurality of layers of the copper layer, the first blackening layer, and the second blackening layer can be laminated on at least one surface side of the transparent base material.

Therefore, the copper layer forming step, the first blackening layer forming step, and the second blackening layer forming step are the points where the second blackening layer forming step is carried out immediately after the first blackening layer forming step. Other than the above, the order of implementation and the number of implementations are not particularly limited. Therefore, it can be carried out at an arbitrary number of times and at an arbitrary timing according to the structure of the laminated substrate to be formed.

The step of preparing the transparent base material is, for example, a step of preparing a transparent base material composed of a polymer film that transmits visible light, a glass substrate, or the like, and the specific operation is not particularly limited. For example, it can be cut to an arbitrary size as needed for use in each subsequent step or step. Since the materials that can be suitably used as the polymer film that transmits visible light have already been described, the description thereof will be omitted here.

Next, the laminate forming step will be described. The laminate forming step is a step of forming a laminate on at least one surface side of the transparent base material, and has a first blackening layer forming step, a second blackening layer forming step, and a copper layer forming step. Can be done. Each step will be described below.

First, the first blackening layer forming step and the second blackening layer forming step will be described.

In the first blackening layer forming step, the first blackening layer is formed by the first blackening layer film forming means for depositing the first blackening layer containing nitrogen and copper on at least one surface side of the transparent base material. This is the step of forming a film.
In the first blackening layer forming step, a first blackening layer containing nitrogen and copper and further containing oxygen is formed on at least one surface side of the transparent base material by the first blackening layer forming means. It may be deposited to form a first blackening layer containing nitrogen, copper and oxygen.

Further, in the second blackening layer forming step, the second blackening is performed by the second blackening layer forming means for depositing the second blackening layer containing oxygen, copper and nickel on the first blackening layer. This is a step of forming a chemical layer.

A first blackening layer forming means for depositing a first blackening layer containing nitrogen and copper in the first blackening layer forming step, and oxygen, copper, and nickel in the second blackening layer forming step. The second blackening layer forming means for depositing the second blackening layer containing the above is not particularly limited, but a dry plating method is desirable.

The laminated body substrate of the present embodiment may also have a third blackening layer, and in this case, the laminated body forming step may have a third blackening layer forming step. In the third blackening layer forming step, the third blackening layer can be formed by the third blackening layer forming means for depositing the third blackening layer. The third blackening layer film forming means is not particularly limited, but a dry plating method is preferable.

The dry plating method is not particularly limited, but a sputtering method and an ion plating method can be used in a reduced pressure atmosphere. In particular, it is more preferable to use the sputtering method because the composition and thickness of the blackened layer can be easily controlled. That is, it is preferable that the first blackening layer film forming means and the second blackening layer forming means are a sputtering film forming method. Further, when the third blackened layer is also formed, it is preferable that the third blackened layer forming means is a sputtering film forming method.

The first blackening layer, the second blackening layer, and the like can be suitably formed by using, for example, the roll-to-roll sputtering apparatus 70 shown in FIG. 7.

FIG. 7 shows a configuration example of the roll-to-roll sputtering apparatus 70. The roll-to-roll sputtering apparatus 70 includes a housing 71 that houses most of its components. Although the shape of the housing 71 is shown as a rectangular parallelepiped shape in FIG. 7, the shape of the housing 71 is not particularly limited, and any shape is arbitrary depending on the device to be housed inside, the installation location, the pressure resistance performance, and the like. Can be. For example, the shape of the housing 71 may be a cylindrical shape.

However, in order to remove residual gas that is not related to film formation at the start of film formation, it is preferable that the inside of the housing 71 can be depressurized to 1 Pa or less, more preferably ^{10 -3 Pa or less, and 10 -4} Pa or less. It is even more preferable to be able to. It is not necessary that the entire inside of the housing 71 can be depressurized to the above pressure, and it is also possible to configure the housing 71 so that only the lower region in the figure in which the can roll 73, which will be described later, is arranged can be depressurized to the above pressure. ..

In the housing 71, the unwinding roll 72, the can roll 73, the sputtering cathodes 74a to 74d, the front feed roll 75a, and the rear feed roll for supplying the base material for forming the first blackening layer or the second blackening layer. 75b, tension rolls 76a, 76b, and take-up roll 77 can be arranged. In addition to the above rolls, guide rolls 78a to 78h, a heater 79, and the like can be optionally provided on the transport path of the base material on which the first blackening layer or the second blackening layer is formed.

The unwinding roll 72, the can roll 73, the front feed roll 75a, and the winding roll 77 can be provided with power by a servomotor. It is preferable that the unwinding roll 72 and the winding roll 77 maintain the tension balance of the base material on which the copper thin film layer is formed by torque control by a powder clutch or the like.

The configuration of the can roll 73 is also not particularly limited, but for example, the surface thereof is finished with hard chrome plating, and a refrigerant or a hot medium supplied from the outside of the housing 71 circulates inside the can roll 73, so that the temperature can be adjusted to a constant temperature. It is preferable that the structure is as follows.

It is preferable that the tension rolls 76a and 76b have, for example, a surface finished with hard chrome plating and provided with a tension sensor. Further, it is preferable that the surfaces of the front feed roll 75a, the rear feed roll 75b, and the guide rolls 78a to 78h are finished with hard chrome plating.

It is preferable that the sputtering cathodes 74a to 74d are arranged so as to face the canroll 73 in a magnetron cathode type. The size of the sputtering cathodes 74a to 74d is not particularly limited, but the widthwise dimension of the base material on which the first blackening layer or the second blackening layer of the sputtering cathodes 74a to 74d is formed is the opposite first blackening layer. Alternatively, it is preferably wider than the width of the base material on which the second blackening layer is formed.

The base material for forming the first blackening layer or the second blackening layer is conveyed in the roll-to-roll sputtering apparatus 70, which is a roll-to-roll vacuum film forming apparatus. Then, the first blackening layer or the second blackening layer is formed on the canroll 73 when passing through the positions facing the sputtering cathodes 74a to 74d. A configuration example of the procedure when the second blackening layer is formed by using the roll-to-roll sputtering apparatus 70 will be described.

First, the copper-nickel alloy target is attached to the sputtering cathodes 74a to 74d, and the inside of the housing 71 in which the base material for forming the blackening layer is set on the unwinding roll 72 is evacuated by the vacuum pumps 80a and 80b. The proportion of nickel in the copper and nickel contained in the formed second blackening layer is preferably 11% by mass or more and 60% by mass or less. Therefore, also for the copper-nickel alloy target used when forming the second blackening layer, it is preferable that the proportion of nickel in copper and nickel is 11% by mass or more and 60% by mass or less.

After that, a sputtering gas composed of an inert gas such as argon and oxygen can be introduced into the housing 71 by the gas supply means 81. The configuration of the gas supply means 81 is not particularly limited, but a gas storage tank (not shown) may be provided. Then, mass flow controllers (MFCs) 811a, 811b, 811c and valves 812a, 812b, 812c are provided between the gas storage tank and the housing 71 for each gas type, and the amount of each gas supplied into the housing 71 is measured. It can be configured to be controllable. FIG. 7 shows an example in which two sets of a mass flow controller and a valve are provided, but the number of installations is not particularly limited, and the number of installations can be selected according to the number of gas types to be used.

At this time, the flow rate of the sputtering gas and the opening degree of the pressure adjusting valve 82 provided between the vacuum pump 80b and the housing 71 are adjusted to keep the inside of the housing 71 at, for example, 0.13 Pa or more and 13 Pa or less. It is preferable to carry out the film formation.

Although the inert gas and the oxygen gas can be supplied into the housing 71 in advance, they are individually supplied to the housing 71, and the respective gases in the housing 71 have a desired partial pressure. The supply amount and pressure can be adjusted so as to be. Further, the sputtering gas is not limited to a gas composed of an inert gas and an oxygen gas as described above, but one or more kinds of gases selected from water vapor, carbon monoxide gas, and carbon dioxide gas can be used. It may also be included.

In this state, while transporting the base material from the unwinding roll 72 at a speed of, for example, 0.5 m or more and 10 m or less per minute, power is supplied from the DC power source for sputtering connected to the sputtering cathodes 74a to 74d for sputtering discharge. I do. As a result, a desired second blackening layer can be continuously formed on the base material.

In addition to the above, various members can be arranged in the roll-to-roll sputtering apparatus 70 as needed. For example, pressure gauges 83a and 83b for measuring the pressure inside the housing 71 and vent valves 84a and 84b may be provided.

The first blackening layer is different from the point where the copper target is attached to the sputtering cathodes 74a to 74d instead of the copper-nickel alloy target, and the point where a gas composed of an inert gas, a nitrogen gas, and an oxygen gas is used as the sputtering gas. Can be formed in the same manner as in the case of the second blackening layer described above.

Further, as described above, the laminated substrate of the present embodiment may have a third blackening layer in addition to the first blackening layer and the second blackening layer. In this way, when the third blackening layer is formed, the above-mentioned second blackening layer is described except that the target corresponding to the target composition of the third blackening layer is attached to the sputtering cathodes 74a to 74d. The film can be formed in the same manner as in the case of.

The first blackening layer forming step and the second blackening layer forming step are preferably carried out in a reduced pressure atmosphere. Further, when the third blackening layer forming step is performed, it is preferable to carry out the step in a reduced pressure atmosphere as well.

Next, the copper layer forming step will be described.

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

In the copper layer forming step, it is preferable to form a copper thin film layer by using a dry plating method. When the copper layer is made thicker, it is preferable to form a copper thin film layer by a dry plating method and then further form a copper plating layer by a wet plating method.

Therefore, the copper layer forming step can include, for example, a step of forming a copper thin film layer by a dry plating method. Further, the copper layer forming step may include a step of forming a copper thin film layer by a dry plating method and a step of forming a copper plating layer by a wet plating method using the copper thin film layer as a feeding layer. ..

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

As described above, the copper layer can be formed directly on the transparent base material or the blackened layer without using an adhesive by forming the copper layer only by the dry plating method or by combining the dry plating method and the wet plating method. preferable.

As described above, in the copper layer forming step, the copper thin film layer can be formed by, for example, a dry plating method.

The dry plating method is not particularly limited, but a sputtering method, an ion plating method, a vapor deposition method, or the like can be preferably used in a reduced pressure atmosphere.

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

The copper thin film layer can be suitably formed by using, for example, the roll-to-roll sputtering apparatus 70 shown in FIG. 7. Since the configuration of the roll-to-roll sputtering apparatus 70 has already been described, the description thereof will be omitted here.

The process of forming the copper thin film layer will be described below by taking the case of using a roll-to-roll sputtering apparatus as an example.

A procedure for forming a copper thin film layer using the roll-to-roll sputtering apparatus 70 will be described.

First, the copper target is attached to the sputtering cathodes 74a to 74d, and the inside of the housing 71 in which the base material for forming the copper thin film layer is set on the unwinding roll 72 is evacuated by the vacuum pumps 80a and 80b.

After that, an inert gas, for example, a sputtering gas such as argon can be introduced into the housing 71 by the gas supply means 81.

Then, when the sputtering gas is supplied into the housing 71 by the gas supply means 81, the flow rate of the sputtering gas and the opening degree of the pressure adjusting valve 82 provided between the vacuum pump 80b and the housing 71 are adjusted. Then, it is preferable to keep the inside of the apparatus at, for example, 0.13 Pa or more and 1.3 Pa or less to carry out the film formation.

In this state, while transporting the base material from the unwinding roll 72 at a speed of, for example, 1 m or more and 20 m or less per minute, electric power is supplied from a DC power source for sputtering connected to the sputtering cathodes 74a to 74d to perform sputtering discharge. As a result, a desired copper thin film layer can be continuously formed on the base material.

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

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

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

Up to this point, each step and step included in the method for manufacturing the laminated substrate of the present embodiment has been described.

In the laminate substrate obtained by the method for producing a laminate substrate of the present embodiment, the copper layer preferably has a thickness of 50 nm or more, more preferably 60 nm or more, similarly to the laminate substrate described above. , 150 nm or more is more preferable. The upper limit of the thickness of the copper layer is not particularly limited, but the thickness of the copper layer is preferably 5000 nm or less, and more preferably 3000 nm or less. When the copper layer has the copper thin film layer and the copper plating layer as described above, the total of the thickness of the copper thin film layer and the thickness of the copper plating layer is preferably in the above range.

The total thickness of the first blackening layer and the thickness of the second blackening layer is not particularly limited, but the lower limit is preferably, for example, 10 nm or more, and more preferably 15 nm or more. preferable.

The upper limit of the total of the thickness of the first blackening layer and the thickness of the second blackening layer is preferably 70 nm or less, and more preferably 50 nm or less.

The thickness of the first blackening layer is preferably 5 nm or more and 15 nm or less.

On the other hand, the thickness of the second blackening layer can be appropriately selected so that the total thickness of the first blackening layer and the second blackening layer is within the above range.

The film thickness of the third blackening layer can be, for example, a lower limit of 5 nm or more. The upper limit is preferably, for example, 70 nm or less, and more preferably 50 nm or less.

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

A conductive substrate in which a wiring pattern having openings in the copper layer, the first blackening layer, and the second blackening layer is formed by using the laminated substrate obtained by the method for manufacturing a laminated substrate of the present embodiment. Can be. The conductive substrate can be more preferably configured with mesh-like wiring.

In the method for manufacturing a conductive substrate according to the present embodiment, the copper layer, the first blackening layer, and the second blackening layer of the laminated substrate obtained by the above-mentioned manufacturing method for the laminated substrate are etched. It is possible to have an etching step of forming a wiring pattern having a fine metal wire which is a laminated body including a copper wiring layer, a first blackened wiring layer, and a second blackened wiring layer. Then, by this etching step, openings can be formed in the copper layer, the first blackening layer, and the second blackening layer.

In the etching step, for example, first, a resist having an opening corresponding to a portion to be removed by etching is formed on the outermost surface of the laminated substrate. For example, in the case of the laminated substrate shown in FIG. 2A, a resist can be formed on the exposed surface A of the copper layer 12 arranged on the laminated substrate. The method of forming a resist having an opening corresponding to the portion to be removed by etching is not particularly limited, but it can be formed by, for example, a photolithography method.

Next, by supplying the etching solution from the upper surface of the resist, the copper layer 12, the first blackening layer 131, and the second blackening layer 132 can be etched.

When the copper layer and the blackening layer are arranged on both sides of the transparent base material 11 as shown in FIG. 2B, a resist having openings having a predetermined shape on the surface A and the surface B of the laminated substrate, respectively. The copper layer, the first blackening layer, and the second blackening layer formed on both sides of the transparent base material 11 may be etched at the same time. Further, the copper layer, the first blackening layer, and the second blackening layer formed on both sides of the transparent base material 11 can be etched on one side at a time. That is, for example, after etching the copper layer 12A, the second blackening layer 132A, and the first blackening layer 131A, the copper layer 12B, the second blackening layer 132B, and the first blackening layer 131B are etched. You can also.

The second blackening layer formed by the method for producing a laminated substrate of the present embodiment exhibits the same reactivity with an etching solution as the copper layer. Further, the first blackening layer has higher reactivity with this etching solution than the second blackening layer. Therefore, the etching solution used in the etching step is not particularly limited, and an etching solution generally used for etching the copper layer can be preferably used.

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

The etching solution can be used at room temperature, but it can also be used by heating it in order to enhance the reactivity, for example, it can be used by heating it to 40 ° C. or higher and 50 ° C. or lower.

Since the specific form of the mesh-shaped wiring obtained by the etching step described above is as described above, the description thereof will be omitted here.

Further, two laminated substrates having a copper layer, a first blackening layer, and a second blackening layer on one surface side of the transparent base material 11 shown in FIGS. 2A and 3A are provided. When two conductive substrates are bonded together to form a conductive substrate having mesh-like wiring after being subjected to an etching step to form a conductive substrate, a step of bonding the conductive substrates can be further provided. At this time, the method of bonding the two conductive substrates is not particularly limited, and for example, they can be bonded using an optical adhesive (OCA) or the like.

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

This is when the average specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less is 55% or less.
For example, even when it is used as a conductive substrate for a touch panel, it is possible to particularly suppress a decrease in visibility of the display.

The method for manufacturing the laminated substrate, the conductive substrate, the laminated substrate, and the method for manufacturing the conductive substrate of the present embodiment have been described above. According to the laminate substrate or the laminate substrate obtained by the method for producing the laminate substrate, the copper layer and the blackening layer show substantially the same reactivity with respect to the etching solution. Therefore, it is possible to provide a laminated substrate provided with a copper layer and a blackening layer that can be etched at the same time. Since the copper layer and the blackened layer can be etched at the same time, the copper wiring layer and the blackened wiring layer having a desired shape can be easily formed.

Further, by providing the blackened wiring layer, it is possible to suppress the reflection of light by the copper wiring layer, and it is possible to suppress the deterioration of visibility when, for example, a conductive substrate for a touch panel is used. Therefore, by providing the blackened wiring layer, it is possible to obtain a conductive substrate having good visibility.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited to these Examples.

(Evaluation method)
(1) Specular reflectance The specular reflectance was measured for the laminated substrates produced in each of the following Examples and Comparative Examples.

The measurement was carried out by installing a reflectance measurement unit on an ultraviolet-visible spectrophotometer (model: UV-2550 manufactured by Shimadzu Corporation).

In each example, a laminated substrate having the structure shown in FIG. 3A was produced, but the reflectance was measured with respect to the 131a surface of the first blackening layer 131 facing the transparent base material 11 in FIG. 3A. The light was irradiated through the transparent substrate 11 with an incident angle of 5 ° and a wavelength in the range of 400 nm or more and 700 nm or less. The light irradiating the laminated substrate has a wavelength of 400 nm or more and 700 nm or less, and the specular reflectance is measured for the light of each wavelength by changing the wavelength in 1 nm or less, and the average of the measurement results is the conductivity. It was taken as the average of the specular reflectance of the substrate. In addition, it is shown as a reflectance in Table 1.

(2) the undercut amount ratio undercut amount ratio of thin metal wires, each of the embodiments, the cross section of the wire of the conductive substrate prepared in Comparative Example was observed by SEM, the bottom of the pattern width W ₁ and the metal thin wires of the metal thin wires The width W ₂ was calculated. The pattern width W _{1 of} the thin metal wire and the bottom width W ₂ of the thin metal wire are as already described with reference to FIG.

(3) Decrease rate of total light transmittance of the opening The total light transmittance was measured for the opening between the thin metal wires exposing the transparent base material of the conductive substrate produced in each Example and Comparative Example.

The measurement was performed by installing an integrating sphere attachment device on the ultraviolet-visible spectrophotometer when the specular reflectance was measured. The irradiated light has a wavelength in the range of 400 nm or more and 700 nm or less, and the transmittance is measured for the light of each wavelength by changing the wavelength every 1 nm, and the average of the measurement results is the total light beam of the opening of the conductive substrate. The average transmittance was used.

In addition, the average of all light transmittances was measured in the same manner for the transparent substrate used in manufacturing the laminated substrate in advance.

Then, the total light transmittance of the opening, which is the reduction rate of the average of the total light transmittance of the opening of the conductive substrate produced in each Example and the comparative example from the average of the total light transmittance of the transparent substrate. The rate of decrease was calculated.

(Sample preparation conditions)
As Examples and Comparative Examples, a laminated substrate and a conductive substrate were produced under the conditions described below, and evaluated by the above-mentioned evaluation method.
[Example 1]
A laminated substrate having the structure shown in FIG. 3A was produced.

(Transparent substrate preparation process)
First, a transparent substrate preparation step was carried out. Specifically, a transparent substrate made of polyethylene terephthalate resin (PET) for optics having a width of 500 mm and a thickness of 100 μm was prepared.

(Laminate body forming process)
Next, a laminate forming step was carried out. As a laminate forming step, a first blackening layer forming step, a second blackening layer forming step, a copper layer forming step, and a third blackening layer forming step were carried out. This will be described in detail below.

(1) First blackening layer forming step First, the first blackening layer forming step was carried out.

The prepared transparent substrate was set in the roll-to-roll sputtering apparatus 70 shown in FIG. Further, copper targets (manufactured by Sumitomo Metal Mining Co., Ltd.) were attached to the sputtering cathodes 74a to 74d. Then, the heater 79 of the roll-to-roll sputtering apparatus 70 was heated to 100 ° C. to heat the transparent base material, and the water contained in the base material was removed.

Subsequently, after the inside of the housing 71 is ^{exhausted to 1 × 10 -4} Pa by the vacuum pumps 80a and 80b, the flow rate of argon gas is 240 sccm, the flow rate of nitrogen gas is 40 sccm, and the flow rate of oxygen gas is 20 sccm by the gas supply means 81. Then, the argon gas, the nitrogen gas and the oxygen gas were introduced into the housing 71. Then, while transporting the transparent base material from the unwinding roll 72 at a speed of 2 m / min, electric power is supplied from the DC power source for sputtering connected to the sputtering cathodes 74a to 74d, and sputtering discharge is performed on the transparent base material. A desired first blackening layer was continuously formed. By this operation, a first blackening layer was formed on the transparent substrate so as to have a thickness of 10 nm.

(2) Second blackening layer forming step Next, a second blackening layer forming step was carried out.

In the second blackening layer forming step, the target attached to the sputtering cathodes 74a to 74d is a copper-nickel alloy target (manufactured by Sumitomo Metal Mining Co., Ltd.), nitrogen gas is not introduced, and the flow rate of oxygen gas is 40 sccm. The second blackening layer was formed in the same manner as in the first blackening layer forming step except for the above points. As the base material, a base material in which the first blackening layer is formed on the transparent base material is used in the first blackening layer forming step, and the second blackening layer is formed on the first blackening layer. ing.

As the copper-nickel alloy target, as shown in Table 1, a target containing 11% by mass of Ni and 89% by mass of Cu was used. By this operation, a second blackening layer was formed on the first blackening layer so as to have a thickness of 10 nm.

(3) Copper layer forming step Subsequently, a copper layer forming step was carried out.

In the copper layer forming step, the target mounted on the sputtering cathode is changed to a copper target (manufactured by Sumitomo Metal Mining Co., Ltd.), the inside of the housing 71 is exhausted, and then argon is inside the housing 71 of the roll-to-roll sputtering apparatus 70. A copper layer having a thickness of 200 nm was formed on the upper surface of the second blackening layer in the same manner as in the case of the first blackening layer except that only the gas was introduced.

As the base material for forming the copper layer, the first blackening layer and the second blackening layer are formed on the transparent base material in the first blackening layer forming step and the second blackening layer forming step. The base materials formed in that order were used.

(4) Third blackening layer forming step Subsequently, a third blackening layer forming step was carried out. In the third blackening layer forming step, the first blackening layer forming step, the second blackening layer forming step, and the copper layer forming step are performed on the transparent substrate, and the first blackening layer and the second blackening layer are formed. The third blackened layer was formed in the same manner as in the second blackened layer forming step except that the base material in which the layers and the copper layers were formed in that order was used and the film thickness was set to 20 nm.

When the average specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less was measured by the above procedure, the average specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less was 55%.

Further, after measuring the specular reflectance of the obtained laminated substrate, an etching step was performed to prepare a conductive substrate.

In the etching step, first, a resist having an opening corresponding to a portion to be removed by etching was formed on the surface C in FIG. 3A of the produced laminated substrate. Then, a conductive substrate was prepared by immersing it in an etching solution consisting of 10% by mass of ferric chloride, 10% by mass of hydrochloric acid, and water as the balance for 1 minute.

For the produced conductive substrate, the undercut amount ratio of the thin metal wire and the total light transmittance of the opening were measured.

The evaluation results are shown in Table 1.
[Example 2]
A laminated substrate and a conductive substrate were produced in the same manner as in Example 1 except that the amount of oxygen supplied into the housing when the second blackening layer was formed was changed as shown in Table 1. And evaluated.

In the third blackening layer forming step as well, the oxygen supply amount is changed from the conditions in Example 1 as in the second blackening layer forming step of this example.

The evaluation results are shown in Table 1.
[Example 3]
The supply amounts of nitrogen and oxygen supplied into the housing when the first blackening layer was formed were changed as shown in Table 1, and the sputtering target used when the second blackening layer was formed. A laminated substrate and a conductive substrate were prepared and evaluated in the same manner as in Example 1 except that the composition of the copper-nickel alloy target was changed as shown in Table 1.
[Example 4, Example 5]
The laminated substrate and the laminated substrate and the same as in Example 1 except that the composition of the copper-nickel alloy target, which is the sputtering target used for forming the second blackened layer, was changed as shown in Table 1. A conductive substrate was prepared and evaluated.
[Example 6]
The amount of nitrogen and oxygen supplied into the housing when the first blackening layer was formed was changed as shown in Table 1, and the sputtering target used when the second blackening layer was formed. A laminated substrate and a conductive substrate were prepared and evaluated in the same manner as in Example 1 except that the composition of the copper-nickel alloy target was changed as shown in Table 1.
[Example 7]
The amount of oxygen supplied into the housing when the first blackening layer was formed was changed as shown in Table 1, and the sputtering target used when the second blackening layer was formed. , A laminated substrate and a conductive substrate were prepared and evaluated in the same manner as in Example 1 except that the composition of the copper-nickel alloy target was changed as shown in Table 1.

Also in the third blackening layer forming step, the composition of the copper-nickel alloy target is changed from the composition in Example 1 as in the second blackening layer forming step of each example.

The evaluation results are shown in Table 1.
[Comparative Example 1]
The composition and film thickness of the copper-nickel alloy target, which is the sputtering target used when forming the second blackening layer without forming the first blackening layer, were changed as shown in Table 1. A laminated substrate and a conductive substrate were prepared and evaluated in the same manner as in Example 1 except for the above.

Also in the third blackening layer forming step, the composition of the copper-nickel alloy target is changed from the composition in Example 1 as in the second blackening layer forming step of this comparative example.

The evaluation results are shown in Table 1.
[Comparative Example 2]
The point that the supply amount of nitrogen and oxygen supplied into the housing when the first blackening layer was formed without forming the second blackening layer was changed as shown in Table 1, and the first blackening layer. The third blackening layer forming step was carried out under the same conditions as the first blackening layer forming step, and the same as in Example 1 except that the third blackening layer was formed. A laminated substrate and a conductive substrate were prepared and evaluated.

The evaluation results are shown in Table 1.
[Comparative Example 3]
The supply amounts of nitrogen and oxygen supplied into the housing when the first blackening layer was formed were changed as shown in Table 1, and the first blackening layer and the second blackening layer were formed. The composition of the sputtering target used for filming was changed as shown in Table 1, and the third blackening layer forming step was carried out in the same manner as the first blackening layer forming step, and the third blackening layer was formed. A laminated substrate and a conductive substrate were prepared and evaluated in the same manner as in Example 1 except for the point where the above was formed.
[Comparative Example 4]
The points where the film thicknesses of the first blackening layer and the second blackening layer were set to 4 nm each, the composition of the sputtering target used when forming the first blackening layer and the second blackening layer, and the composition of the sputtering target. The points where the film thickness was changed as shown in Table 1, the film thickness of the third blackening layer was set to 8 nm, and the third blackening layer forming step was the second blackening layer forming step of this comparative example except for the film thickness. The same conditions as in Example 1 were carried out, and a laminated substrate and a conductive substrate were prepared and evaluated in the same manner as in Example 1 except that the third blackening layer was formed.

The evaluation results are shown in Table 1.

表１に示した結果によると、実施例１〜実施例７は、いずれも正反射率が５５％以下であり、良好な視認性を有することが確認された。また、実施例１〜実施例７は、いずれも金属細線のアンダーカット量比率が０．０７５以下、開口部の全光線透過率の減少率が３．０％以下となった。すなわち、銅層と、第１黒化層と、第２の黒化層とを同時にエッチングできることを確認できた。

According to the results shown in Table 1, it was confirmed that all of Examples 1 to 7 had a specular reflectance of 55% or less and had good visibility. Further, in each of Examples 1 to 7, the undercut amount ratio of the thin metal wire was 0.075 or less, and the reduction rate of the total light transmittance of the opening was 3.0% or less. That is, it was confirmed that the copper layer, the first blackening layer, and the second blackening layer can be etched at the same time.

This is because the proportion of nickel in the copper and nickel contained in the sputtering target used when forming the second blackening layer is 11% by mass or more and 60% by mass or less, and the blackening layer formed on the film has a nickel content of 11% by mass or more and 60% by mass or less. It is probable that the composition was the same. That is, it is considered that the reactivity of the second blackening layer with the etching solution could be made equivalent to that of the copper layer.

It is considered that the first blackening layer had higher reactivity to the etching solution than the second blackening layer by forming the layer containing nitrogen and copper, and could be removed without leaving a residue.

On the other hand, in Comparative Example 1, it was confirmed that the reduction rate of the total light transmittance of the opening exceeded 3.0%, and the etching rate of the blackened layer was slower than that of the copper layer. ..

Further, in Comparative Example 2, the specular reflectance exceeded 55%, and a decrease in visibility was confirmed.

In Comparative Example 2, the undercut amount ratio of the thin metal wire was 0.12, which greatly exceeded 0.075, and it was confirmed that the etching rate of the blackened layer was faster than that of the copper layer.

As described above, in Comparative Examples 1 and 2 having only one of the first blackening layer and the second blackening layer, the first blackening layer and the second blackening layer cannot be etched at the same time as the copper layer. Was confirmed.

10A, 10B, 20A, 20B Laminated substrate 11 Transparent base material 12, 12A, 12B Copper layers 131, 131A, 131B First blackening layer 132, 132A, 132B Second blackening layer 133, 133A, 133B Third blackening Layer 30 Conductive substrates 31A, 31B, 62 Copper wiring layers 321A, 321B First blackened wiring layer 322A, 322B Second blackened wiring layer 323A, 323B Third blackened wiring layer

Claims (12)

With a transparent base material
A laminate formed on at least one surface side of the transparent base material is provided.
The laminate is
A first blackening layer containing nitrogen and copper,
A second blackening layer provided on the first blackening layer and containing oxygen, copper, and nickel,
With a copper layer
With a third blackening layer ,
The thickness of the first blackening layer is 5 nm or more and 15 nm or less.
Copper contained in the second blackened layer, and among the nickel state, and are percentage 11 mass% to 60 mass% of nickel,
The copper layer is arranged between the second blackening layer and the third blackening layer.
The third blackening layer contains copper, a layer containing nitrogen, a layer containing copper, nitrogen, and oxygen, or oxygen and at least copper as a metal component, and the metal component. any layer der Ru laminate substrate layer proportion of nickel is 70 mass% or more 0% by weight of. The laminated substrate according to claim 1, wherein the first blackening layer further contains oxygen . The laminated substrate according to claim 1 or 2 , wherein the average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 55% or less. With a transparent base material
A thin metal wire formed on at least one surface side of the transparent base material is provided.
The thin metal wire
A first blackened wiring layer containing nitrogen and copper,
A second blackened wiring layer provided on the first blackened wiring layer and containing oxygen, copper, and nickel, and a second blackened wiring layer.
And the copper wiring layer,
It is a laminated body including a third blackened wiring layer.
Copper contained in the second blackened wiring layers, and among the nickel state, and are percentage 11 mass% to 60 mass% of nickel,
The copper wiring layer is arranged between the second blackened wiring layer and the third blackened wiring layer.
The third blackened wiring layer contains a wiring layer containing copper and nitrogen, a wiring layer containing copper, nitrogen and oxygen, or oxygen and at least copper as a metal component, and one of the wiring layers der Ru conductive substrate wiring layer ratio is 70 mass% or less than 0 wt% nickel of the metal components. The conductive substrate according to claim 4 , wherein the first blackened wiring layer further contains oxygen . An opening for exposing the transparent base material is provided between the thin metal wires.
The claim that the average reduction rate of the light transmittance of the opening having a wavelength of 400 nm or more and 700 nm or less from the average of the light transmittance of the transparent substrate having a wavelength of 400 nm or more and 700 nm or less is 3.0% or less. 4. The conductive substrate according to 4 or 5. The transparent base material preparation process for preparing the transparent base material and
It has a laminate forming step of forming a laminate on at least one surface side of the transparent substrate.
The laminate forming step is
A copper layer forming step of forming a copper layer by a copper layer forming means for depositing copper,
A first blackening layer forming step of forming a first blackening layer by a first blackening layer forming means for depositing a first blackening layer containing nitrogen and copper, and a first blackening layer forming step.
The first blackened layer, and oxygen, copper and a second black to form the second black layer by the second blackened layer forming means for depositing a second blackened layer containing nickel Formation step and
A third blackening layer forming step of forming a third blackening layer in which the copper layer is arranged between the second blackening layer is included.
The first blackening layer forming step and the second blackening layer forming step were carried out in a reduced pressure atmosphere.
The thickness of the first blackening layer is 5 nm or more and 15 nm or less.
Copper contained in the second blackened layer, and among the nickel state, and are percentage 11 mass% to 60 mass% of nickel,
The third blackening layer contains copper, a layer containing nitrogen, a layer containing copper, nitrogen, and oxygen, or oxygen and at least copper as a metal component, and the metal component. any layer der Ru method for producing a laminate substrate layer proportion of nickel is 70 mass% or more 0% by weight of. The method for producing a laminated substrate according to claim 7 , wherein the first blackening layer further contains oxygen. The method for producing a laminated substrate according to claim 7 or 8 , wherein the first blackening layer film forming means and the second blackening layer forming means are a sputtering film forming method. The method for manufacturing a laminated substrate according to any one of claims 7 to 9 , wherein the total thickness of the first blackening layer and the thickness of the second blackening layer is 10 nm or more. The copper layer, the first blackening layer, and the second blackening layer of the laminated substrate obtained by the method for manufacturing a laminated substrate according to any one of claims 7 to 10 are etched. It has an etching step of forming a wiring pattern having metal thin wires which is a laminated body including a copper wiring layer, a first blackened wiring layer, and a second blackened wiring layer.
A method for producing a conductive substrate in which openings are formed in the copper layer, the first blackening layer, and the second blackening layer by the etching step. The method for manufacturing a conductive substrate according to claim 11 , wherein the obtained conductive substrate has an average regular reflectance of 55% or less for light having a wavelength of 400 nm or more and 700 nm or less.

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