TWI740970B - Laminated body substrate, conductive substrate, manufacturing method of laminated body substrate, and conductive substrate manufacturing method - Google Patents

Abstract

Provided is a laminated body substrate comprising: a transparent base material; and a laminated body formed on at least one surface side of the transparent base material, the laminated body comprising: selected from the group consisting of Cu, Ni, Cr, Ti, Al, Fe, A base metal layer composed of one or more metals of the metal group consisting of Co, Mo, V, and W, or an alloy composed of one or more metals selected from the metal group as the main component; arranged on the base metal layer, And a first blackened layer containing oxygen, copper, and nickel; and a copper layer in which the ratio of nickel in the metal components contained in the first blackened layer is 20% by mass or more and 70% by mass or less.

Description

Laminated body substrate, conductive substrate, manufacturing method of laminated body substrate, and conductive substrate manufacturing method

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

As disclosed in Patent Document 1, a transparent conductive film for touch panels has conventionally been used in which ITO (Indium Oxide Indium Oxide) is formed on the surface of a transparent substrate such as a transparent polymer film. Tin) film.

On the other hand, in recent years, displays with touch panels have been increasing in size. Correspondingly, conductive substrates such as transparent conductive films for touch panels are also seeking to increase in size. However, since ITO has a high resistance value, there is a problem that it cannot cope with the increase in the area of the conductive substrate.

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

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

<Prior Technical Literature> <Patent Literature>

Patent Document 1: Japanese Patent Application Publication No. 2003-151358

Patent Document 2: Japanese Patent Application Publication No. 2011-018194

Patent Document 3: Japanese Patent Application Publication No. 2013-069261

On the other hand, a conductive substrate with metal wiring on a transparent substrate is formed by etching the metal layer into a desired wiring pattern after obtaining a laminate substrate with a metal layer formed on the surface of the transparent substrate. Obtained by wiring. In addition, a conductive substrate having a blackened layer and metal wiring on a transparent substrate is obtained by obtaining a laminate substrate in which a blackened layer and a metal layer are sequentially laminated on the surface of the transparent substrate, and then the blackened layer and The metal layer is obtained by etching into a desired wiring pattern to form a metal wiring.

By etching the blackened layer and the metal layer, for example, as shown in FIG.性substrate. In this case, the width W _A is preferably black and the metal layer 2 is patterned wiring width W _B 3 are formed substantially the same.

However, there is a problem that the reactivity of the metal layer and the blackened layer with respect to the etching solution is very different. In other words, if the metal layer and the blackened layer are to be etched at the same time, there will be a problem that one of the layers cannot be etched into the target shape shown in FIG. 1A.

For example, when the etching rate of the blackened layer is significantly slower than that of the metal layer, as shown in FIG. 1B, the width (bottom width) W _A of the patterned blackened layer 2 on the transparent substrate 1 may become _{It is larger than the width W B} of the metal wiring 3 which is a patterned metal layer. In addition, so-called side etching in which the side surface of the metal wiring 3 is etched occurs. Therefore, the cross-sectional shape of the metal wiring 3 tends to become a trapezoid that expands outward, and if etching is performed to ensure electrical insulation between the metal wirings 3, the wiring pitch width becomes too wide.

In addition, when compared to the etching rate significantly rapid blackening layer and the metal layer, and sometimes 1C, blackening layer patterned into a width (bottom width) W _A 2 becomes higher than the metal wiring 3 When the width W _B is smaller, a so-called undercut occurs. When such an undercut occurs, depending on the degree, the width W _{B of the predetermined metal wiring 3 will exist, and the bottom width W A} of the patterned blackened layer 2 as the adhesion width of the transparent substrate 1 becomes smaller. If the ratio of the adhesive width is reduced to more than necessary, it is not possible to obtain sufficient wiring adhesive strength.

Furthermore, even if the etching rate of the blackened layer is the same as the etching rate of the metal layer, there may be etching residues of the blackened layer on the transparent substrate exposed after etching, that is, on the surface of the opening, and the opening is visible. It looks like a yellow situation.

In view of the above-mentioned problems of the prior art, an object of the present invention is to provide a laminate substrate having a copper layer and a blackened layer, and can simultaneously perform etching treatment on the copper layer and the blackened layer.

In order to solve the above-mentioned problems, the present invention provides a laminated body substrate comprising: a transparent base material; and a laminated body formed on at least one surface side of the transparent base material; , Ti, Al, Fe, Co, Mo, V, W composed of metal group consisting of one or more metals, or a base metal layer composed of an alloy mainly composed of one or more metals selected from the metal group; On the base metal layer, a first blackened layer containing oxygen, copper, and nickel; and a copper layer; among the metal components contained in the first blackened layer, the ratio of nickel is 20% by mass or more and 70% by mass the following.

According to the present invention, it is possible to provide a laminate substrate which has a copper layer and a blackened layer, and can simultaneously perform etching treatment on the copper layer and the blackened layer.

10A, 10B, 20A, 20B‧‧‧Laminate substrate

11‧‧‧Transparent substrate

12, 12A, 12B‧‧‧Base metal layer

13, 13A, 13B‧‧‧The first black layer

14, 14A, 14B‧‧‧copper layer

15, 15A, 15B‧‧‧Second black layer

30‧‧‧Conductive substrate

32A, 32B‧‧‧Base metal wiring layer

33A, 33B‧‧‧The first black wiring layer

34A, 34B, 62‧‧‧Copper wiring layer

35A, 35B‧‧‧Second blackened wiring layer

FIG. 1A is an explanatory diagram of a case where a metal layer and a blackened layer are simultaneously etched in a conventional conductive substrate.

FIG. 1B is an explanatory diagram of a case where the metal layer and the blackened layer are simultaneously etched in a conventional conductive substrate.

FIG. 1C is an explanatory diagram of a case where the metal layer and the blackened layer are simultaneously etched in a conventional conductive substrate.

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

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

Fig. 3A is a cross-sectional view of a laminate substrate according to an embodiment of the present invention.

Fig. 3B is a cross-sectional view of the laminate substrate according to the embodiment of the present invention.

Fig. 4 is a plan view of a conductive substrate having mesh wiring according to an embodiment of the present invention.

Fig. 5 is a cross-sectional view taken along the line A-A' of Fig. 4.

Fig. 6 is an explanatory diagram of the undercut amount ratio.

Fig. 7 is an explanatory diagram of a roll-to-roll sputtering device.

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

(Laminate substrate, conductive substrate)

The laminate substrate of the present embodiment may have a transparent base material and a laminate formed on at least one surface side of the transparent base material. In addition, the laminate may have a base metal layer, a first blackened layer, and a copper layer, the base metal layer being selected from a metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W The first blackened layer is arranged on the base metal layer and contains oxygen, copper, and nickel.

In addition, the ratio of nickel in the metal components contained in the first blackening layer may be 20% by mass or more and 70% by mass or less.

In addition, the laminated body substrate in this embodiment is a board|substrate which has a copper layer or a blackened layer before patterning on the surface of a transparent base material. In addition, the conductive substrate is a wiring substrate having a copper wiring layer or a blackened wiring layer patterned and provided in a wiring shape on the surface of a transparent base material.

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

The transparent substrate is not particularly limited, and it is preferable to use a polymer film or a glass substrate that transmits visible light.

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

The thickness of the transparent substrate is not particularly limited, and it can be arbitrarily selected according to the required intensity when used as a conductive substrate, light transmittance, and the like. As the thickness of the transparent substrate, for example, it can be 10 μm or more and 250 μm or less. In particular, when used for touch panel applications, the thickness is preferably 20 μm or more and 200 μm or less, and more preferably 20 μm or more and 120 μm or less. In the case of use for a touch panel, for example, when the use of reducing the thickness of the entire display is particularly sought, the thickness of the transparent substrate is preferably 20 μm or more and 100 μm or less.

Next, the laminate will be described. The laminate may be formed on at least one surface side of the transparent substrate, and may have a base metal layer, a first blackened layer, and a copper layer.

Here, the copper layer will be described first.

The copper layer is also not particularly limited. In order to reduce the light transmittance, it is preferable not to arrange an adhesive between the copper layer and the transparent substrate, or between the copper layer and the blackened layer. In other words, it is preferable to form the copper layer directly on the upper surface of other components.

Since the copper layer is directly formed on the upper surface of other components, the copper thin film layer can be formed by dry plating methods such as sputtering, ion plating, or vapor deposition, and the copper thin film layer can be used as the copper layer.

In addition, when thickening the copper layer, it is preferable to use a wet plating method after forming the copper thin film layer by a dry plating method. In other words, for example, a copper thin film layer can be formed by a dry plating method on a transparent substrate or a blackened layer, and the copper thin film layer can be used as a power supply layer to form a copper plating layer by a wet plating method. At this time, 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 substrate or the blackened layer without using an adhesive by using only the dry plating method or the combination of the dry plating method and the wet plating method to form the copper layer, so it is preferable .

The thickness of the copper layer is not particularly limited, and when the copper layer is used as a wiring, it can be arbitrarily selected according to the resistance value of the wiring, the wiring width, and the like. The thickness of the copper layer is preferably 50 nm or more, more preferably 60 nm or more, and still more preferably 150 nm or more, so that the current can flow particularly sufficiently. The upper limit of the thickness of the copper layer is not particularly limited. However, if the copper layer becomes thicker, when etching is performed for wiring formation, side etching may occur due to the time required for etching, and resist peeling may easily occur during etching. The problem. Therefore, the thickness of the copper layer is preferably 5000 nm or less, and more preferably 3000 nm or less. In addition, when the copper layer has a copper thin film layer and a copper plating layer as mentioned above, it is preferable that the sum total of the thickness of a copper thin film layer and the thickness of a copper plating layer is the said range.

Next, the first blackening layer and the underlying metal layer will be described.

Since the copper layer has metallic luster, if only the copper wiring layer that etches the copper layer is formed on the transparent substrate, the copper will reflect light as described above. For example, when used as a wiring substrate for a touch panel, There is a problem of reduced visibility of the display. Therefore, the method of providing the blackened layer has been studied. However, sometimes the blackened layer does not have sufficient reactivity to the etching solution, and it is difficult to simultaneously etch the copper layer and the blackened layer into a desired shape, or blackening occurs. The problem of layer etching residue.

In addition, the inventors of the present invention first studied a method of forming a layer that oxidizes a part of the copper layer into copper oxide as a blackened layer capable of suppressing light reflection on the surface of the copper layer. It has also been found that when a part of the copper layer is oxidized and used as a blackened layer, the blackened layer sometimes contains non-stoichiometric copper oxide or unoxidized copper.

When the copper layer and the blackened layer of the laminate substrate having the copper layer and the blackened layer are simultaneously etched, as the etching liquid, for example, an etching liquid capable of etching the copper layer can be preferably used. Furthermore, according to the research of the inventor of the present invention, when the blackened layer contains non-stoichiometric copper oxide, it is easily dissolved in an etching solution capable of etching the copper layer.

As a result, when the blackened layer contains non-stoichiometric copper oxide that is easily eluted from the etching solution, the blackened layer has higher reactivity with the etching solution, and the etching speed of the blackened layer is greatly changed compared with the copper layer. quick. Therefore, when the copper layer and the blackened layer are simultaneously etched, the blackened layer is likely to become an undercut.

Therefore, for the copper layer and the blackened layer, the copper layer and the blackened layer can be etched in one procedure with the same etching solution, and the occurrence of undercuts and the occurrence of blackened layer residues for the openings can be suppressed at the same time The inventor of the present invention conducted intensive research on the laminate substrate and completed the present invention.

The first blackened layer included in the laminate substrate of the present embodiment is provided on the base metal layer provided on the surface of the transparent base material, that is, is provided on the surface of the base metal layer.

In addition, regarding the relationship between the base metal layer and the first blackened layer, when the same etching solution is used for etching, the base metal layer may be a layer having higher reactivity with respect to the etching solution than the first blackened layer. That is, the base metal layer can be more easily dissolved in the etching solution than the first blackened layer. In other words, the base metal layer can be a layer that is easy to etch. By forming the base metal layer as a layer having higher reactivity with respect to the etching solution than the first blackening layer, it is possible to suppress the generation of etching residue on the surface of the transparent substrate exposed after etching. In this way, the etching property of the base metal layer will affect the etching property of the first blackened layer.

Specifically, in addition to oxygen and copper, the first blackened layer included in the laminate substrate of the present embodiment may also include a nickel component that is difficult to dissolve in the etching solution.

As described above, the first blackened layer may contain copper and nickel as metal components. In addition, the metal component contained in the first blackened layer may be composed only of copper and nickel, and even in this case, it is not limited to copper and nickel. For example, in the first blackened layer, unavoidable impurities of 1% by mass or less may also be present as the metal component.

The first blackening layer only needs to contain oxygen, copper, and nickel, and the state in which each component is contained is not particularly limited. The first blackening layer may contain, for example, non-stoichiometric copper oxide or nickel oxide in which at least a part of copper or nickel is oxidized. Even in the case where the first blackened layer contains non-stoichiometric copper oxide as described above, since the first blackened layer also contains nickel at the same time, it is possible to form a second layer with almost the same reactivity to the etching solution as the copper layer. A blackened layer. In particular, from the viewpoint of sufficiently suppressing the reactivity of the first blackened layer with respect to the etching solution compared with the base metal layer, it is preferable that the first blackened layer contains a non-stoichiometric oxide of nickel.

In addition, the amount of oxygen contained in the first blackening layer is not particularly limited. However, the amount of oxygen contained in the first blackened layer or the second blackened layer described later may affect the light reflectivity of the laminate substrate or the conductive substrate produced using the laminate substrate. Therefore, it is preferable to select the amount of oxygen contained in the first blackened layer according to the degree of light reflectance required by the laminate substrate or the conductive substrate made using the laminate substrate, or the hue of the first blackened layer. , And the amount of oxygen added when forming the first blackened layer.

The ratio of nickel in the metal component contained in the first blackened layer is not particularly limited, but it is preferable that the ratio of nickel in the metal component contained in the first blackened layer is 20% by mass or more and 70% by mass the following. It should be noted that the ratio of nickel in the metal components contained in the first blackened layer means when the total content of the metal components in the blackened layer, for example, the total content of copper and nickel is 100% by mass The ratio of nickel at the time.

The reason is that by setting the ratio of nickel in the metal components contained in the first blackened layer to 20% by mass or more, it is possible to sufficiently ensure that it is compatible with non-stoichiometric oxides such as non-stoichiometric oxides that do not contain nickel. The difference in the reactivity to the etching solution between the underlying metal layers, that is, the difference in the reaction speed.

However, if the ratio of nickel in the metal component contained in the first blackened layer exceeds 70% by mass, there is a possibility that nickel will become excessive and etching of the first blackened layer will become difficult. That is, the dissolution rate of the first blackened layer with respect to the etching solution is slower than that of the copper layer, and it may not be possible to form the first blackened layer that can be etched simultaneously with the copper layer. Therefore, as described above, it is preferable that the ratio of nickel in the metal component contained in the first blackening layer is 70% by mass or less.

In addition, by setting the ratio of nickel in the metal component contained in the first blackening layer to 20% by mass or more and 70% by mass or less, a laminate substrate and a conductive substrate formed from the laminate substrate can be used The average value of the specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less is more reliably reduced to 55% or less. Therefore, even when the conductive substrate is used for applications such as a touch panel, it is possible to suppress the decrease in visibility of the display, which is also preferable in this point.

It should be noted that, as will be described later, by setting the thickness of the base metal layer to 5 nm or less, when the light with a wavelength of 400 nm or more and 700 nm or less on the surface of the first blackened layer transmitted through the transparent substrate is mirrored When the average reflectance is measured and calculated, it can be more reliably set to 55% or less, which is preferable.

On the other hand, the base metal layer may be composed of one or more metals selected from the group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or may be composed of one or more metals selected from the group of metals. A layer composed of an alloy composed of more than one metal as the main component.

However, in the base metal layer, unavoidable impurities of 1% by mass or less may also be present as a metal component.

In addition, an alloy containing one or more metals selected from the metal group as a main component refers to an alloy containing the most one or more metals selected from the metal group in the metal components. Hereinafter, the same description in this specification has the same meaning. The alloy may be an alloy composed of one or more metals selected from the group of metals.

It is more preferable that the base metal layer is particularly composed of any one of Cu, a Ni-Cu alloy, and a Ni-Cr alloy containing 7% by mass or less of Cr. Here, in the Ni-Cr alloy, the content of Cr may be more than zero. When the base metal layer is composed of any of the above-mentioned metals (alloys), the reactivity to the etching solution can be made particularly higher than that of the first blackening layer, which is preferable.

It should be noted that since oxygen is not added when forming the base metal layer, the metal component constituting the base metal layer exists as a metal, not a non-stoichiometric oxide.

In this way, since the underlying metal layer does not contain oxygen, the underlying metal layer can form a non-stoichiometric oxide that does not contain the metal elements constituting the underlying metal layer. Specifically, non-stoichiometric oxides such as nickel are difficult to dissolve in The composition of the etching solution.

As described above, the base metal layer may contain a predetermined metal, and may have a structure that does not contain oxygen. On the other hand, the first blackened layer may contain oxygen, copper, and nickel.

Therefore, the base metal layer and the first blackened layer of the laminate substrate of this embodiment can have a difference in reactivity with respect to the etching solution. As described above, the reactivity of the base metal layer with respect to the etching solution can be made higher than that of the first blackened layer. A blackened layer. In addition, there can be almost no difference in the reactivity of the first blackened layer and the copper layer with respect to the etching solution.

According to the laminate substrate of the present embodiment, since the base metal layer is easily etched as described above, when the laminate substrate is patterned, it is possible to suppress, for example, the occurrence of etching residues on the blackened layer on the surface of the transparent base material. The reason is that even if residues of the blackened layer such as the first blackened layer are generated on the underlying metal layer, the underlying metal layer can be easily removed by etching. Therefore, the underlying metal layer can be removed at the same time as the blackened layer. The residue of the chemical layer is also removed from the transparent substrate. In addition, 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, that is, the reduction rate of the total light transmittance of the opening can be suppressed.

However, since the base metal layer has high reactivity with respect to the etching solution, if only the base metal layer is provided, undercuts may occur. However, in the laminate substrate of this embodiment, the first blackened layer, which is more difficult to be etched than the underlying metal layer, is arranged on the underlying metal layer, and the underlying metal layer is covered by the first blackened layer. Therefore, if the first blackened layer is not removed by etching, the underlying metal layer will not be removed by etching, so the occurrence of undercuts can be reliably suppressed. Furthermore, as described above, since the underlying metal layer is easily etched, it is difficult for the etching residue of the blackened layer to remain on the surface of the etched transparent substrate.

In particular, from the viewpoint of suppressing the occurrence of undercuts, and from the viewpoint of suppressing the average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less on the surface of the first blackening layer, the thickness of the base metal layer is preferably 5 nm the following.

It should be noted that the lower limit of the thickness of the base metal layer is also not particularly limited. Since the base metal layer exists as a film, it is also preferred from the viewpoint of sufficiently improving the etching properties of the first blackened layer. The thickness of the metal layer is 1.5 nm or more.

In addition, the thickness of the first blackening layer is not particularly limited. For example, it can be arbitrarily selected according to the degree of suppression of light reflection on the surface of the copper layer.

In particular, the lower limit of the thickness of the first blackening layer is preferably 20 nm or more.

As described above, the first blackened layer functions as a layer that suppresses the reflection of light on the surface of the copper layer. When the thickness of the first blackened layer is thin, sometimes the light reflection by the copper layer cannot be sufficiently suppressed. . In contrast, as described above, by setting the thickness of the first blackened layer to be 20 nm or more, it is possible to reliably suppress the reflection of light on the surface of the copper layer.

The upper limit of the thickness of the first blackened layer is not particularly limited. Even if it is thicker than necessary, the time required for film formation or the time required for etching during wiring formation will become longer, incurring cost. rise. Therefore, the thickness of the first blackening layer is preferably 70 nm or less, and more preferably 50 nm or less.

As described above, in the laminate substrate of the present embodiment, since the predetermined base metal layer and the first blackened layer are provided, the copper layer and the first blackened layer can be etched at the same time.

It should be noted that being able to etch the copper layer and the first blackened layer at the same time means that the copper layer and the blackened layer can be etched in one procedure with the same etching solution, and at the same time, it can suppress the occurrence of undercuts and the openings. Part of the blackened layer residue occurs.

However, in the laminate substrate of this embodiment, the copper layer and the first blackened layer may be wired with different etching solutions, or an etching solution capable of selectively removing the copper layer and an etching solution capable of selectively removing the copper layer may be used separately. The etching solution of the first blackened layer is removed, and a conductive substrate with finer metal fine wires is produced. Even if the etching solution is used separately, especially since the base metal layer is more reactive to the etching solution than the first metal layer, it is possible to form fine metal wires without a blackened layer on the surface of the transparent substrate. The residue.

There is no particular limitation on the film formation method of the base metal layer arranged on the laminate substrate of the present embodiment. The base metal layer is preferably formed by a dry film forming method such as a sputtering method. When the base metal layer is formed by a dry film formation method, a target of the metal component constituting the base metal layer can be used to form the film while supplying an inert gas as a sputtering gas into the chamber. In addition, no oxygen was added to the sputtering gas when forming the underlying metal layer.

The method of forming the first blackened layer arranged on the laminate substrate of the present embodiment is not particularly limited. The first blackened layer is preferably formed by a dry film forming method such as a sputtering method.

When the first blackened layer is formed by the sputtering method, for example, a copper-nickel alloy target can be used, and the film can be formed while supplying an inert gas used as a sputtering gas and oxygen into the chamber.

In the formation of the first blackened layer, in the case of using a copper-nickel alloy target during sputtering, it is preferable that the metal component contained in the copper-nickel alloy, for example, the ratio of nickel in copper and nickel is 20% by mass or more 70% by mass or less. The reason is that the ratio of the metal components contained in the formed first blackened layer, such as nickel in copper and nickel, and the copper-nickel target of the copper-nickel alloy used when forming the blackened layer The ratio of nickel in copper and nickel contained in the alloy is the same.

When the first blackened layer is formed by the sputtering method, there is no particular limitation on the method of adjusting the amount of oxygen supplied into the chamber. For example, a mixed gas in which oxygen and an inert gas are mixed in advance may be used so that the oxygen partial pressure becomes the required partial pressure. In addition, it is also possible to adjust the partial pressure of oxygen in the chamber by simultaneously supplying inert gas and oxygen into the chamber and adjusting the supply amount of each gas. In particular, the latter is preferable because it can adjust the partial pressure of each gas in the chamber as required.

It should be noted that the inert gas when forming the first blackened layer or the underlying metal layer is not particularly limited. For example, argon gas or xenon gas can be used, and argon gas can be preferably used. In addition, as a component other than the metal component, the first blackened layer may contain one or more components selected from hydrogen and carbon in addition to oxygen. Therefore, in addition to oxygen and inert gas, the gas used when forming the first blackened layer may include one or more gases selected from the group consisting of water vapor, carbon monoxide gas, and carbon dioxide gas.

When the first blackened layer is formed by the sputtering method while supplying inert gas, oxygen, etc. into the chamber as described above, there is no limitation on the ratio of the inert gas to the oxygen supplied into the chamber. It can be arbitrarily selected according to the light reflectance required for the laminate substrate or the conductive substrate, the degree of the color tone of each blackening layer, and the like.

In addition, the laminate substrate of the present embodiment may have a second blackened layer in addition to the first blackened layer. At this time, the layered body further has a second blackened layer. The second blackening layer may be provided on the surface of the copper layer. In other words, the copper layer may be arranged between the first blackened layer and the second blackened layer, and may be in a state of being sandwiched between the first blackened layer and the second blackened layer. When it has a second blackening layer, the structure of the second blackening layer is not particularly limited, and for example, it may be a structure different from that of the first blackening layer. In addition, the second blackened layer may have a structure containing the same components as the first blackened layer. Specifically, the second blackening layer may contain oxygen and copper, for example. In addition, the second blackened layer may further contain nickel, or may contain oxygen, copper, and nickel.

Although the second blackening layer may be composed of one layer, it may have a multiple layer structure. For example, it may be a structure having a layer containing copper as a metal component and a layer containing copper and nickel as a metal component.

In addition, for the second blackened layer, it is preferable that the metal component in the second blackened layer, for example, copper, or the ratio of nickel in copper and nickel, is 0% by mass or more and 70% by mass or less. The reason is that when the second blackening layer contains copper and sometimes nickel as a metal component, when the total content of copper and nickel as the metal component is 100% by mass, if the ratio of nickel exceeds 70% by mass %, nickel will be excessive, and etching of the second blackened layer may become difficult.

The thickness of the second blackening layer is not particularly limited, and for example, the lower limit may be 5 nm or more. In addition, the upper limit is preferably set to 70 nm or less, and more preferably 50 nm or less, for example.

In addition, when the second blackened layer has a multiple-layer structure as described above, it is preferable that the total thickness thereof is in the above-mentioned range.

The film formation method of the second blackened layer is not particularly limited, but it is preferably formed by a dry film formation method such as a sputtering method, similarly to the first blackened layer.

When the second blackened layer is formed by the sputtering method, for example, a copper target or a copper-nickel alloy target can be used, and the film can be formed while supplying an inert gas used as a sputtering gas and oxygen into the chamber.

In the formation of the second blackened layer, when a copper-nickel alloy target is used during sputtering, it is preferable that the ratio of the metal component contained in the copper-nickel alloy, for example, nickel in copper and nickel, is greater than 0% by mass and 70% by mass or less.

Regarding the sputtering gas when forming the second blackened layer by the sputtering method, since it can be selected in the same manner as in the case of forming the first blackened layer, the description is omitted here.

In the laminate substrate of this embodiment, as will be described later, a base metal layer, a first blackened layer, and a copper layer may be laminated on a transparent base material, and a second blackened layer may be laminated in some cases. The conductive substrate is formed by patterning the underlying metal layer, the first blackened layer, the copper layer, and the second blackened layer that may be included.

Therefore, the copper wiring layer, the base metal wiring layer, and each blackened wiring layer of the conductive substrate obtained from the laminate substrate of the present embodiment maintain the copper layer, the base metal layer, and the copper layer of the laminate substrate of the present embodiment, respectively. The characteristics of each blackened layer.

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

As described above, the laminate substrate of the present embodiment may have a transparent base material, and a laminate having a base metal layer, a first blackened layer, and a copper layer. It should be noted that, as described above, the layered body may further have a second blackening layer.

At this time, except for providing the first blackened layer on the underlying metal layer in the laminate, the order of arranging the copper layer and each blackened layer on the transparent substrate or the number of layers is not particularly limited. In other words, for example, two copper layers, an underlying metal layer, and a first blackened layer may be laminated on at least one surface side of the transparent substrate. In addition, as long as the underlying metal layer and the first blackened layer are laminated in the order of the underlying metal layer and the first blackened layer in the laminate, a plurality of copper layers and/or the first blackened layer may be formed.

However, when the copper layer and the blackened layer are arranged in the laminate, in order to suppress the reflection of light on the surface of the copper layer, it is preferable to arrange the blackened layer on the surface of the copper layer on which light reflection is to be particularly suppressed.

Particularly, it is more preferable to have a build-up structure in which a blackened layer is formed on the surface of the copper layer. Specifically, for example, the laminate may have a second blackened layer as the blackened layer in addition to the first blackened layer, and the copper layer may be arranged between the first blackened layer and the second blackened layer. . More specifically, for example, the base metal layer, the first blackened layer, the copper layer, and the second blackened layer may be laminated in this order from the transparent substrate side.

When the second blackening layer is provided, it may have a multiple-layer structure as described above, and the multiple-layer structure or the formation of one layer may be appropriately selected, and it is not particularly limited.

In addition, the second blackened layer may have the same structure as the first blackened layer, or may have a different structure from the first blackened layer. In other words, the second blackening layer may be a layer containing oxygen and copper, or may be a layer containing oxygen, copper, and nickel. Therefore, it is preferable that the ratio of nickel in the metal component in the second blackening layer is 0 mass% or more and 70 mass% or less. The reason is that when the second blackening layer contains copper and sometimes nickel as a metal component, when the total content of copper and nickel as the metal component is 100% by mass, if the ratio of nickel exceeds 70% by mass %, the etching of the second blackened layer may become difficult.

A specific example of the structure of the laminate substrate of the present embodiment will be described below using FIGS. 2A, 2B, 3A, and 3B. 2A, FIG. 2B, FIG. 3A, and FIG. 3B show examples of cross-sectional views on a surface parallel to the stacking direction of the transparent base material, the copper layer, the base metal layer, and the blackened layer of the laminate substrate of the present embodiment.

For example, in the laminate substrate 10A shown in FIG. 2A, the base metal layer 12, the first blackened layer 13, and the copper layer 14 may be sequentially laminated on the one surface 11a side of the transparent base material 11. That is, it can be formed to have a base metal layer 12 provided on the surface of the transparent substrate 11, a first blackened layer 13 provided on the surface of the base metal layer 12, and copper provided on the surface of the first blackened layer 13. Layer 14 structure.

In addition, as shown in FIG. 2B of the conductive substrate 10B, the base metal layers 12A, 12B, and the first blackened layer 13A may be respectively provided on one surface 11a side and the other surface (other surface) 11b side of the transparent base material 11. , 13B, and the copper layers 14A, 14B are sequentially stacked layer by layer.

In addition, as described above, the laminate substrate of the present embodiment may be provided with a second blackened layer in addition to the base metal layer, the first blackened layer, and the copper layer on at least one surface side of the transparent base material 11. For example, in the base substrate 20A shown in FIG. 3A, the base metal layer 12, the first blackened layer 13, the copper layer 14, and the second blackened layer 15 may be sequentially laminated on one surface 11a side of the transparent base material 11. .

By having the base metal layer 12, the first blackened layer 13 and the second blackened layer 15 as blackened layers in this way, and the copper layer 14 is arranged between the first blackened layer 13 and the second blackened layer 15, It is possible to more reliably suppress the reflection of light incident from the upper surface side and the lower surface side of the copper layer 14.

At this time, it may be a structure in which a copper layer, an underlying metal layer, a first blackened layer, and a second blackened layer are laminated on both surfaces of the transparent base material 11. Specifically, as shown in FIG. 3B, the conductive substrate 20B can be laminated on one surface 11a side and the other surface (other surface) 11b side of the transparent base material 11, respectively, and base metal layers 12A, 12B, and the first black The blackened layers 13A, 13B, the copper layers 14A, 14B, and the second blackened layers 15A, 15B.

In addition, the manufacturing method of the 2nd blackening layer 15 (15A, 15B) is not specifically limited. For example, the second blackened layer 15 (15A, 15B) may be a blackened layer containing oxygen and copper. In addition, the second blackened layer 15 (15A, 15B) may be a blackened layer containing oxygen, copper, and nickel similarly to the first blackened layer 13 (13A, 13B). Therefore, the first blackened layer may contain the same composition as the first blackened layer, or a part of the layer may contain a different metal composition, and the first blackened layer and the second blackened layer may be manufactured by the same method.

In the two-area copper layer, base metal layer, and blackened layer of the transparent substrate 11, the structural examples of FIGS. 2B and 3B show that the transparent substrate 11 is symmetrically arranged up and down on the transparent substrate 11 with the transparent substrate 11 as a symmetry plane. There are examples of laminated layers, but it is not limited to this form.

For example, in FIG. 3B, the structure on the one surface 11a side of the transparent base material 11 may be a form in which the underlying metal layer 12A, the first blackened layer 13A, and the copper layer 14A are sequentially laminated as in the structure of FIG. 2B. In addition, the configuration on the side of the other surface (other surface) 11b may be such that the underlying metal layer 12B, the first blackened layer 13B, the copper layer 14B, and the second blackened layer 15B are laminated in this order, so that the upper and lower sides of the transparent substrate 11 The laminated layers have an asymmetric structure.

The degree of light reflection of the laminate substrate of the present embodiment is not particularly limited. For example, the average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, more preferably 40% or less, and still more preferably 30% or less. The reason is that when the average value of the specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less is 55% or less, for example, the laminate substrate of this embodiment can be used as a conductive substrate for a touch panel. Suppress the decrease in visibility of the display.

The specular reflectance of the laminate substrate can be measured by irradiating the base metal layer or the blackened layer with light. That is, it can be measured by irradiating light from the side of the blackening layer among the blackening layer and the copper layer included in the laminate substrate. Specifically, for example, when the underlying metal layer 12, the first blackened layer 13, and the copper layer 14 are sequentially laminated on one surface 11a of the transparent substrate 11 as shown in FIG. 2A, the underlying metal layer 12 may be irradiated with light. In the method, the surface of the base metal layer 12 is irradiated with light from the surface 11b side of the transparent substrate 11 to perform the measurement.

In addition, the average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less refers to the average value of the measurement results when the specular reflectance is measured by changing the wavelength in the range of 400 nm or more and 700 nm or less. In the measurement, the width of the wavelength change is not particularly limited. For example, it is preferable to change the wavelength every 10 nm to measure the light in the above-mentioned wavelength range, and it is more preferable to change the wavelength every 1 nm to measure the light in the above-mentioned wavelength range.

It should be noted that, as described below, the copper layer, the base metal layer, and the blackened layer may be etched to perform wiring processing on the laminate substrate to form thin metal wires and form a conductive substrate. The specular reflectance of light in the conductive substrate refers to the specular reflectance on the light incident side of the base metal layer or the blackened layer arranged on the outermost surface except for the transparent base material.

Therefore, in the case of a conductive substrate that has undergone an etching treatment, it is preferable that the measured value on the portion where the copper layer, the base metal layer, and the blackened layer are left satisfies the above-mentioned range.

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

The conductive substrate of the present embodiment may have a transparent base material and thin metal wires formed on at least one surface side of the transparent base material. In addition, the thin metal wire may be a laminate. The laminate includes one or more metals selected from the group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or one or more metals selected from the group of metals A base metal wiring layer composed of an alloy as a main component; a first blackened wiring layer arranged on the base metal wiring layer and containing oxygen, copper, and nickel; and a copper wiring layer. In addition, the ratio of nickel in the metal components contained in the first blackened wiring layer may be 20% by mass or more and 70% by mass or less.

The conductive substrate of the present embodiment can be obtained, for example, by performing wiring processing on the above-mentioned laminate substrate. Therefore, except for patterning by etching, the copper wiring layer, the base metal wiring layer, and the first blackened wiring layer may each have the same structure as the copper layer, the base metal layer, and the first blackened wiring layer.

That is, the thickness of the copper wiring layer is preferably 50 nm or more, more preferably 60 nm or more, and even more preferably 150 nm or more. The upper limit of the thickness of the copper wiring layer is not particularly limited, but it is preferably 5000 nm or less, and more preferably 3000 nm or less.

In addition, the underlying metal wiring layer may be composed of one or more metals selected from the group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or may be composed of a metal selected from the group of metals. A layer composed of an alloy mainly composed of one or more metals. However, for example, in the underlying metal wiring layer, unavoidable impurities of 1% by mass or less may also be present as a metal component.

The base metal wiring layer is more preferably composed of any one of Cu, Ni-Cu alloy, and Ni-Cr alloy containing 7 mass% or less of Cr.

The thickness of the underlying metal wiring layer is also not particularly limited, but it is preferably 1.5 nm or more and 5 nm or less.

The first blackened wiring layer may contain copper and nickel as metal components, and the ratio of nickel in the metal components contained in the first blackened wiring layer is preferably 20% by mass or more and 70% by mass or less.

The thickness of the first blackened wiring layer is not particularly limited, and its lower limit is preferably 20 nm or more. In addition, the upper limit of the thickness of the first blackened wiring layer is not particularly limited, but it is preferably 70 nm or less, and more preferably 50 nm or less.

In addition, in the conductive substrate of the present embodiment, a copper wiring layer, a base metal wiring layer, and a first blackened wiring layer are provided on a transparent base material, and a second blackened wiring layer may be provided on the transparent base material. The wiring layer or the like blackens the wiring layer, so that the reflection of light generated by the copper wiring layer can be suppressed. Therefore, by providing a blackened wiring layer, for example, when it is used for a touch panel or the like, it is possible to have good visibility of the display.

The conductive substrate of this embodiment can be used as, for example, a conductive substrate for touch panels. At this time, the conductive substrate may have a wiring pattern formed by providing openings on the copper layer, the base metal layer, the first blackened layer, and sometimes the second blackened layer in the laminate substrate. Structure. More preferably, it may have a structure with a net-shaped wiring pattern.

The conductive substrate on which the wiring pattern provided with the opening is formed can be obtained by etching the copper layer, the base metal layer, the first blackened layer, and the second blackened layer that may be included in the above-mentioned laminated substrate. In addition, for example, two layers of thin metal wires can be used to form a conductive substrate having a mesh-like wiring pattern. The specific structure is shown in Figure 4 for example.

4 is a view showing a conductive substrate 30 having a net-like wiring pattern viewed from the upper surface side in the lamination direction of the copper wiring layer, the base metal wiring layer, the first blackened layer, and sometimes the second blackened layer picture. The conductive substrate 30 shown in FIG. 4 has a transparent base material 11, a plurality of copper wiring layers 34B parallel to the X-axis direction in the figure, and a plurality of copper wiring layers 34A parallel to the Y-axis direction in the figure. It should be noted that the copper wiring layers 34A, 34B can be formed by etching the above-mentioned laminate substrate, and an unshown base metal wiring is formed on the upper and/or lower surfaces of the copper wiring layers 34A, 34B. Layer and the first blackened layer, etc. In addition, with regard to the underlying metal wiring layer and the first blackened layer, the surface parallel to the main surface of the transparent substrate 11, that is, the surface parallel to the surface of the transparent substrate 11 on which the copper wiring layers 34A, 34B, etc. are laminated The upper cross-sectional shape is etched so as to be approximately the same shape as the copper wiring layers 34A and 34B.

The arrangement of the transparent substrate 11 and the copper wiring layers 34A and 34B is not particularly limited. The configuration example of the arrangement of the transparent substrate 11 and the copper wiring layer is shown in FIG. 5. Fig. 5 corresponds to a cross-sectional view taken along the line A-A' in Fig. 4.

For example, as shown in FIG. 5, copper wiring layers 34A and 34B may be arranged on the upper and lower surfaces of the transparent base material 11, respectively. It should be noted that in the case of the conductive substrate shown in FIG. 5, base metal wiring layers 32A, 32B and first blackened wiring layers 33A, 33B are arranged on the transparent substrate 11 side of the copper wiring layers 34A, 34B . For the base metal wiring layers 32A, 32B and the first blackened wiring layers 33A, 33B, the cross-sectional shape of the surface parallel to the main surface of the transparent base 11 can be formed into the copper wiring layers 34A, 34B substantially the same shape.

In addition, as shown in FIG. 5, the second blackened wiring layers 35A, 35B may be arranged on the surface of the copper wiring layers 34A, 34B on the opposite side of the transparent base material 11. At this time, for the second blackened wiring layers 35A, 35B, the cross-sectional shape of the surface parallel to the main surface of the transparent base 11 may be formed to be approximately the same shape as the copper wiring layers 34A, 34B.

That is, in the conductive substrate shown in FIG. 5, as described above, in addition to the base metal wiring layers 32A, 32B, the first blackened wiring layers 33A, 33B, and the copper wiring layers 34A, 34B, the thin metal wires may also It further has second blackened wiring layers 35A and 35B. In addition, the copper wiring layers 34A, 34B may have a structure arranged between the first blackened wiring layers 33A, 33B and the second blackened wiring layers 35A, 35B.

The second blackened wiring layer can be formed by etching the above-mentioned second blackened layer. Therefore, except for patterning by etching, the second blackened wiring layer may have the same structure as the second blackened layer described above.

Specifically, the second blackened wiring layer may contain oxygen and copper, for example. In addition, nickel may be further contained in some cases. That is, the second blackened wiring layer may contain copper and oxygen, or copper, nickel, and oxygen. In addition, for the second blackened wiring layer, it is preferable that the ratio of nickel in the metal component in the second blackened wiring layer is 0% by mass or more and 70% by mass or less. It should be noted that the metal component in the second blackened wiring layer here is copper when the second blackened wiring layer contains copper and oxygen, and when the second blackened wiring layer is the same as the first blackened wiring layer When the ground contains oxygen, copper and nickel, it is copper and nickel.

In addition, the second blackened wiring layer may have a plural-layer structure, and for example, may have a structure having a layer containing copper as a metal component and a layer containing copper and nickel as a metal component.

The thickness of the second blackened wiring layer is not particularly limited, and for example, the lower limit may be 5 nm or more. In addition, the upper limit is preferably 70 nm or less, and more preferably 50 nm or less, for example. When the second blackened layer is formed into a plural-layer structure, it is preferable that the total thickness thereof is in the above-mentioned range.

It should be noted that the example in which the second blackened wiring layer is provided in addition to the base metal wiring layer and the first blackened wiring layer is shown here, but it is not limited to this form. For example, as the blackened layer, a conductive substrate having only the first blackened wiring layer may be used.

The conductive substrate with mesh wiring shown in FIG. 4 can be formed by, for example, having copper layers 14A, 14B, base metal layers 12A, 12B, and a first blackening layer on both sides of a transparent substrate 11 as shown in FIGS. 2B and 3B. The laminate substrate of the layers 13A and 13B is formed.

It should be noted that, for example, the conductive substrate having the first blackened wiring layer and the second blackened wiring layer as the blackened wiring layer shown in FIG. 5 may be formed of the laminate substrate shown in FIG. 3B.

Therefore, the case of forming using the laminate substrate shown in FIG. 3B will be described as an example.

First, a plurality of linear patterns parallel to the Y-axis direction in FIG. 3B are arranged at predetermined intervals along the X-axis direction. The layer 13A, the copper layer 14A, and the second blackened layer 15A are etched. It should be noted that the Y-axis direction in FIG. 3B refers to a direction perpendicular to the paper surface. In addition, the X-axis direction in FIG. 3B refers to a direction parallel to the width direction of each layer.

Next, a plurality of linear patterns parallel to the X-axis direction in FIG. 3B are arranged at predetermined intervals along the Y-axis direction. The etching layer 13B, the copper layer 14B, and the second blackening layer 15B are etched.

Through the above operations, a conductive substrate with mesh wiring as shown in FIGS. 4 and 5 can be formed. It should be noted that both sides of the transparent substrate 11 may be etched at the same time. That is, the etching of the base metal layers 12A, 12B, the first blackened layers 13A, 13B, the copper layers 14A, 14B, and the second blackened layers 15A, 15B can be performed at the same time.

In addition, except that it does not have the second blackened wiring layers 15A, 15B, the laminate substrate shown in FIG. 2B can be etched in the same manner to form a conductive substrate having the same structure as the conductive substrate shown in FIG. 5 Substrate.

The conductive substrate with mesh wiring shown in FIG. 4 can also be formed using two conductive substrates shown in FIG. 2A or FIG. 3A. Taking the case of using the conductive substrate of FIG. 3A as an example for description, for the two conductive substrates shown in FIG. 3A, a plurality of linear patterns parallel to the X-axis direction are spaced along the Y-axis direction. The base metal layer 12, the first blackened layer 13, the copper layer 14, and the second blackened layer 15 are etched in a manner of arranging at predetermined intervals. Next, by aligning the directions so that the linear patterns formed on the respective conductive substrates by the above-mentioned etching process cross each other, and bonding the two conductive substrates together, a conductive substrate with mesh wiring can be formed. The bonding surface when bonding two conductive substrates is not particularly limited.

For example, for two conductive substrates, the surface 11b of the transparent base material 11 in FIG. 3A on which the copper layer 14 and the like are not laminated can be bonded to each other to form the structure shown in FIG. 5.

It should be noted that the width of the thin metal wires or the distance between the thin metal wires in the conductive substrate with mesh wiring shown in FIG. 4 is not particularly limited, and can be selected according to the required resistance value of the thin metal wires, for example.

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

Here, the undercut amount ratio will be described using FIG. 6. 6 shows a cross-sectional view of a conductive substrate in which a blackened wiring layer 61 and a copper wiring layer 62 are sequentially laminated on a transparent base material 11 along the direction in which the blackened wiring layer and the copper wiring layer are stacked. It should be noted that, in FIG. 6, an example in which a thin metal wire is composed of a blackened wiring layer 61 and a copper wiring layer 62 is shown.

When the etching rate of the layer in contact with the transparent substrate among the layers constituting the conductive substrate is faster than the etching rate of the layer formed on the layer in contact with the transparent substrate, the layer in contact with the transparent substrate may sometimes The pattern width may be narrower than the pattern width of the layer formed on the layer in contact with the transparent substrate. That is, undercuts sometimes occur.

In the structural example shown in FIG. 6, when 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 blackened layer, undercuts may occur. _{When undercutting occurs in the structural example shown in FIG. 6, the width (W 2} ) of the blackened wiring layer 61 in contact with the transparent substrate 11 as the bottom width of the thin metal wire will be larger than the pattern width of the thin metal wire. _{The width (W 1} ) of the copper wiring layer 62 on the blackened wiring layer 61 is narrower.

At this time, the undercut amount ratio is expressed by the formula _{(W 1} -W ₂ )/2W _{1 based on the bottom width (W 2} ) of the thin metal wire and the pattern width (W ₁ ) of the thin metal wire.

It should be noted that, in the conductive substrate of the present embodiment, as described above, for example, an underlying metal wiring layer, a first blackened wiring layer, and a copper wiring layer may be laminated in this order from the transparent base material 11 side. When the conductive substrate has this form, the layer where the base metal wiring layer and the first blackened wiring layer are combined can be regarded as the blackened wiring layer 61 in FIG. 6, and the base metal wiring layer in contact with the transparent base 11 The width of is the base width W _{2 of the} thin metal wire. In addition, the width of the copper wiring layer may be the pattern width W ₁ of the aforementioned thin metal wires.

In addition, the undercut amount ratio preferably has a relationship of (W ₁ -W ₂ )/2W ₁ ≦0.075. The reason is that by making the undercut amount ratio satisfy the above relationship, the blackened layer and the copper layer can be simultaneously etched and patterned into a desired pattern, and from the viewpoint of improving the adhesion between the transparent substrate 11 and the thin metal wires It's also better to see.

Up to now, FIGS. 4 and 5 show examples in which linear metal thin wires are combined to form a mesh-shaped wiring pattern. However, it is not limited to this form, and the metal thin wires constituting the wiring pattern may have any shape. For example, it is also possible to form the shape of the thin metal wires constituting the mesh wiring pattern into zigzag curved lines (zigzag straight lines) so as not to generate moiré (interference rings) between the image on the display. shape.

The conductive substrate of the present embodiment is formed by performing wiring processing on the above-mentioned laminate substrate, and providing openings on the base metal layer, the first blackened layer, and other blackened layers in the laminate substrate, and the copper layer. Wiring pattern. Therefore, openings exposing the transparent base material are provided between the thin metal wires included in the wiring pattern.

In addition, the reduction rate of the average value of the light transmittance of the opening having a wavelength of 400 nm or more and 700 nm or less from the average value of the light transmittance of the transparent substrate having a wavelength of 400 nm or more and 700 nm or less is preferably 3.0% or less.

The reason is that if the average value of the light transmittance of the above-mentioned opening with a wavelength of 400 nm or more and 700 nm or less is greater than 3.0%, when the transparent substrate is visually observed, it sometimes looks as if it changes color to yellow. For the above reduction rate of more than 3.0%, it is because the etching speed of the first blackened layer is slow when the first blackened layer and the copper layer are etched when the base metal layer is not provided, and the first blackened layer cannot be etched at the same time. And the copper layer is etched. Therefore, as described above, it is necessary to provide a base metal layer that is easier to be etched than the first blackened layer.

The degree of light reflection of the conductive substrate of the present embodiment is not particularly limited. For example, the average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, more preferably 40% or less, and still more preferably 30% or less. The reason is that when the average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 55% or less, even when it is used as a conductive substrate for a touch panel, it is possible to particularly suppress the decrease in visibility of the display.

The conductive substrate of the present embodiment described above, which has mesh wiring composed of two layers of wiring, can be preferably used, for example, as a conductive substrate for a projection-type capacitive touch panel.

(Manufacturing method of laminate substrate, manufacturing method of conductive substrate)

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

The manufacturing method of the laminated body board|substrate of this embodiment can have the following procedures.

A transparent substrate preparation procedure for preparing a transparent substrate.

A layered body forming process of forming a layered body on at least one surface side of a transparent substrate.

In addition, the layered body forming procedure may include the following steps.

The use of stacking is composed of more than one metal selected from the metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or is mainly composed of more than one metal selected from the metal group The base metal layer forming method of the base metal layer composed of the alloy of the components is the base metal layer forming step of forming the base metal layer.

A first blackened layer forming step of forming a first blackened layer on the base metal layer by a first blackened layer film forming method of depositing a first blackened layer containing oxygen, copper, and nickel.

A copper layer forming step of forming a copper layer using a copper layer film forming method of depositing a copper layer.

In addition, the base metal layer forming step and the first blackening layer forming step are preferably performed in a reduced pressure atmosphere. In addition, the ratio of nickel in the metal components contained in the first blackened layer is preferably 20% by mass or more and 70% by mass or less.

Hereinafter, the manufacturing method of the laminated body substrate of the present embodiment will be described, and the parts other than the following description may have the same structure as in the case of the above-mentioned laminated body substrate, so the description thereof will be omitted.

As described above, the laminate substrate of the present embodiment may include a transparent base material, and a laminate having a copper layer and each blackened layer. At this time, except for providing the first blackened layer on the underlying metal layer in the laminate, the order in which the copper layer and the blackened layer are arranged on the transparent substrate or the number of layers is not particularly limited. In other words, for example, a plurality of copper layers, an underlying metal layer, and a first blackened layer may be laminated on at least one surface side of the transparent substrate, respectively.

Therefore, with the exception of the first blackened layer forming step immediately after the base metal layer forming step, there is no special order and number of times for the above-mentioned copper layer forming step, base metal layer forming step, and first blackened layer forming step. limited. Therefore, it can be implemented in an arbitrary number of times and time depending on the structure of the laminated body substrate to be formed.

The transparent substrate preparation procedure may be, for example, a procedure of preparing a transparent substrate composed of a polymer film or a glass substrate that transmits visible light, and the specific operation is not particularly limited. For example, it can be cut into any size as needed for the following procedures and steps. It should be noted that the film suitable for use as a polymer film for transmitting visible light has already been described above, so its description is omitted here.

Next, the layered body formation procedure will be described. The layered body formation procedure is a procedure of forming a layered body on at least one surface side of the transparent substrate, and may include a base metal layer forming step, a first blackened layer forming step, and a copper layer forming step. The steps are described below.

First, the step of forming the underlying metal layer and the step of forming the first blackened layer will be described.

The base metal layer forming step is to deposit one or more metals selected from the metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or from a metal group selected from the metal group. A method for forming a base metal layer of a base metal layer composed of an alloy mainly composed of one or more metals is a step of forming a base metal layer on at least one surface side of a transparent substrate.

In addition, the first blackened layer forming step is a step of forming the first blackened layer on the base metal layer by the first blackened layer film forming method of depositing the first blackened layer containing oxygen, copper, and nickel.

The base metal layer forming method in the base metal layer forming step and the first blackened layer forming method in the first black layer forming step are not particularly limited, but a dry plating method is preferred.

It should be noted that the laminated body substrate of this embodiment may also have a second blackened layer, and in this case, the laminated body forming procedure may have a second blackened layer forming step. In the second blackening layer forming step, the second blackening layer may be formed by a second blackening layer film forming method of depositing the second blackening layer. The method for forming the second blackened layer is not particularly limited, but a dry plating method is preferred.

The dry plating method that can be preferably used in the above-mentioned base metal layer formation step, the first blackened layer formation step, or the second blackened layer formation step is not particularly limited, and a sputtering method or ionization method can be used in a reduced pressure atmosphere. Plating method. In particular, since it is easy to control the composition or thickness of the base metal layer or the blackened layer, it is more preferable to use the sputtering method. That is, the base metal layer forming method and the first blackened layer forming method are preferably sputtering film forming methods. In addition, when the second blackened layer is also formed, the second blackened layer forming method is preferably a sputtering film forming method. That is, the first blackened layer film forming method and the second blackened layer film forming method of forming a blackened layer are preferably sputtering film forming methods.

The base metal layer, the first blackened layer, and the second blackened layer that may be included can be preferably formed using a roll-to-roll sputtering apparatus 70 shown in FIG. 7, for example.

FIG. 7 shows an example of the structure of the roll-to-roll sputtering device 70. The roll-to-roll sputtering device 70 has a housing 71 that houses most of its constituent parts. In FIG. 7, the shape of the housing 71 is shown as a rectangular parallelepiped shape, but the shape of the housing 71 is not particularly limited, and can be any shape according to the device contained therein, installation location, pressure resistance, and the like. For example, the shape of the housing 71 may be a cylindrical shape. However, in order to remove residual gas unrelated to film formation at the beginning of film formation, the inside of the housing 71 can preferably be reduced to 1 Pa or less, more preferably to 10 ^-3 Pa or less, and even more preferably to 10 ^-4 Pa below. It should be noted that it is not necessary that the entire interior of the housing 71 can be decompressed to the above-mentioned pressure, and it may be configured such that only sputtering is performed in the lower area in the figure where the can roll 73 described later is arranged. Reduce pressure to the above pressure.

In the housing 71, the unwinding roller 72 for supplying the base material for forming the first black layer or the second black layer, the can roller 73, the sputtering cathode 74a to 74d, and the forward feed roller 75a can be arranged. , Rear feed roller 75b, tension rollers 76a, 76b, take-up roller 77. In addition, in addition to the above-mentioned rollers, guide rollers 78a to 78h or heating can be arbitrarily provided on the transport path of the substrate for forming the base metal layer, the first blackened layer or the second blackened layer.器79 etc.

The unwinding roller 72, the can roller 73, the forward material roller 75a, and the winding roller 77 may have power generated by a servo motor. It is preferable that the unwind roller 72 and the take-up roller 77 be capable of maintaining the tension balance of the base material for forming the copper thin film layer by torque control of a powder clutch or the like.

The structure of the can roll 73 is not particularly limited. For example, it is preferably configured such that the surface is made of a hard chromium plating layer, and the coolant or heating agent supplied from the outside of the housing 71 is circulated in the interior to adjust the temperature to a certain level.

The tension rollers 76a and 76b preferably have a surface made of hard chromium plating and have a tension sensor, for example. In addition, it is also preferable that the surface of the forward feed roller 75a, the rear feed roller 75b, or the guide rollers 78a to 78h is made of hard chromium plating.

The sputtering cathodes 74a to 74d are preferably magnetron cathodes and are disposed facing the tank roller 73. As shown in FIG. The size of the sputtering cathodes 74a to 74d is not particularly limited. It is preferable that the size of the substrate in the width direction of the sputtering cathodes 74a to 74d for forming the base metal layer or the first blackened layer is wider than the size of the substrate. The width of the substrate used to form the base metal layer or the first blackened layer.

The base material for forming the base metal layer, the first blackened layer, or the like is transported in a roll-to-roll sputtering device 70 that is a roll-to-roll vacuum film forming device. Next, when passing on the can roll 73 and facing the positions of the sputtering cathodes 74a to 74d, the underlying metal layer, the first blackened layer, or the like is formed into a film. A configuration example of the procedure in the case of forming the first blackened layer into a film using the roll-to-roll sputtering device 70 will be described.

First, the copper-nickel alloy target is mounted on the sputtering cathodes 74a to 74d, and vacuum pumps 80a, 80b are used to evacuate the housing 71 on which the base material for forming the first black layer is provided on the unwinding roller 72. . In addition, it is preferable that the ratio of the metal component contained in the formed 1st blackening layer, for example, nickel in copper and nickel is 20 mass% or more and 70 mass% or less. Therefore, even for the copper-nickel alloy target used when forming the first blackened layer, the ratio of nickel in copper and nickel is preferably 20% by mass or more and 70% by mass or less.

After that, the gas supply unit 81 may be used to introduce a sputtering gas composed of an inert gas such as argon and oxygen into the housing 71. It should be noted that the structure of the gas supply unit 81 is not particularly limited, and a gas storage tank not shown may be provided. In addition, it can be configured to provide mass flow controllers (MFC) 811a, 811b and valves 812a, 812b for each gas between the gas storage tank and the housing 71, and the supply amount of each gas to the housing 71 can be adjusted. control. Fig. 7 shows an example in which two sets of mass flow controllers and valves are provided. However, the number of installations is not particularly limited, and the number of installations can be selected according to the number of gas types used.

At this time, it is preferable to adjust the flow rate of the sputtering gas and the opening degree of the pressure regulating valve 82 provided between the vacuum pump 80b and the housing 71 so that the inside of the housing 71 is maintained, for example, 0.13 Pa or more and 13 Pa or less, and the film formation is performed .

It should be noted that the gas mixed with inert gas and oxygen may be supplied into the casing 71, or separately supplied to the casing 71, and each gas in the casing 71 may be subjected to a desired partial pressure. The supply volume and pressure are adjusted. In addition, the sputtering gas is not limited to the above-mentioned gas composed of inert gas and oxygen, and may further include one or more gases selected from the group consisting of water vapor, carbon monoxide gas, and carbon dioxide gas.

In this state, while transporting the substrate from the unwinding roller 72 at a speed of, for example, about 0.5 m or more and 10 m or less per minute, the sputtering DC power supply connected to the sputtering cathodes 74a to 74d is used to supply power and perform sputtering discharge. . Thereby, the desired first blackened layer can be continuously formed on the substrate.

It should be noted that in the roll-to-roll sputtering device 70, various components other than the above-mentioned components may be arranged as needed. For example, pressure gauges 83a, 83b, and exhaust valves 84a, 84b for measuring the pressure in the housing 71 may be provided.

For the base metal layer, in addition to being composed of one or more metals selected from the group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or composed of one or more metals selected from the group of metals The target of the alloy with the metal as the main component is mounted on the sputtering cathode 74a to 74d instead of the part of the copper-nickel alloy target and the part where oxygen is not added to the sputtering gas. It can be the same as the case of the first blackened layer described above. The film formation is performed 地地.

It should be noted that the base metal layer is more preferably composed of any one of Cu, a Ni-Cu alloy, and a Ni-Cr alloy containing 7% by mass or less of Cr. Therefore, it is preferable to use a target corresponding to this composition to form a base metal layer.

In addition, as described above, the laminate substrate of the present embodiment may have a second blackened layer in addition to the base metal layer and the first blackened layer. In this way, when forming the second blackened layer, in addition to mounting a target corresponding to the composition of the second blackened layer, such as a copper target or a copper-nickel alloy target, on the sputtering cathodes 74a to 74d, Film formation is performed in the same manner as in the case of the above-mentioned first blackened layer.

In addition, the base metal layer forming step and the first blackening layer forming step are preferably performed in a reduced pressure atmosphere. In addition, when the second blackened layer forming step is performed, the second blackened layer forming step is also preferably performed under a reduced pressure atmosphere in the same manner.

Next, the copper layer forming step will be described.

In the copper layer forming step, a copper layer can be formed on at least one surface side of the transparent substrate by a copper layer deposition method, that is, a copper layer forming method of copper.

In the copper layer forming step, a dry plating method is preferably used to form the copper thin film layer. In addition, when the copper layer is further thickened, it is preferable to further form the copper plating layer by the wet plating method after forming the copper thin film layer by the dry plating method.

Therefore, the copper layer forming step may include, for example, a step of forming a copper thin film layer by a dry plating method. In addition, 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 power supply layer.

Therefore, the above-mentioned copper layer film forming method is not limited to one film forming method, and a plurality of film forming methods may be used in combination.

As described above, by using only the dry plating method, or a combination of dry plating and wet plating to form the copper layer, the copper layer can be directly formed on the transparent substrate or the blackened layer without using an adhesive. good.

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

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

In particular, as a dry plating method for forming a copper thin film layer, it is more preferable to use a sputtering method from the viewpoint of easy thickness control. That is, at this time, as a method of forming a copper layer by depositing a copper layer in the copper layer forming step, a sputtering film forming method (sputtering film forming method) can be preferably used.

The copper thin film layer can be preferably formed using a roll-to-roll sputtering device 70 shown in FIG. 7, for example. It should be noted that the structure of the roll-to-roll sputtering device 70 has been described above, and therefore the description thereof is omitted here.

Hereinafter, the steps of forming the copper thin film layer will be described using the case of using a roll-to-roll sputtering apparatus as an example.

The procedure in the case of forming a copper thin film layer using the roll-to-roll sputtering apparatus 70 will be described.

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

After that, a sputtering gas such as an inert gas such as argon can be introduced into the casing 71 by the gas supply unit 81.

In addition, when supplying sputtering gas into the housing 71 by the gas supply unit 81, it is preferable to adjust the flow rate of the sputtering gas and the opening of the pressure regulating valve 82 provided between the vacuum pump 80b and the housing 71 so that The inside of the device is maintained at, for example, 0.13 Pa or more and 1.3 Pa or less, and film formation is performed.

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

In addition, as described above, a copper layer (copper plating layer) can be further formed by 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 dry plating may be used as the power supply layer. At this time, as a method of forming a copper layer by depositing copper in the copper layer forming step, an electroplating method can be preferably used.

The conditions in the process of forming the copper plating layer by wet plating with the copper thin film layer as the power supply layer, that is, the conditions of the electroplating treatment are not particularly limited, and various conditions according to conventional methods may be adopted. For example, a copper plating layer can be formed by supplying a substrate on which a copper thin film layer is formed into a plating tank in which a copper plating solution is placed, and controlling the current density or the transport speed of the substrate.

So far, the respective procedures and steps included in the method of manufacturing the laminate substrate of the present embodiment have been described.

For the laminate substrate obtained by the method of manufacturing the laminate substrate of this embodiment, 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, similarly to the above-mentioned laminate substrate. 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. In addition, when the copper layer has a copper thin film layer and a copper plating layer as mentioned above, it is preferable that the sum total of the thickness of a copper thin film layer and the thickness of a copper plating layer is the said range.

The thickness of the underlying metal layer is also not particularly limited, but it is preferably 1.5 nm or more and 5 nm or less.

The thickness of the first blackened wiring layer is also not particularly limited, and its lower limit is preferably 20 nm or more. In addition, the upper limit of the thickness of the first blackened layer is not particularly limited, but is preferably 70 nm or less, and more preferably 50 nm or less.

When the second blackening is provided, the thickness is not particularly limited, and for example, the lower limit is preferably 5 nm or more. In addition, the upper limit is preferably 70 nm or less, and more preferably 50 nm or less, for example. It should be noted that, as described above, the second blackened layer may also have a multiple-layer structure. In this case, it is preferable that the total thickness of the plurality of layers constituting the second blackened layer is in the above-mentioned range.

For the laminate substrate obtained by the method of manufacturing the laminate substrate of the present embodiment, the average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, more preferably 40% or less, and still more preferably 30 %the following.

The multilayer substrate obtained by the manufacturing method of the multilayer substrate of the present embodiment can be formed into a conductive substrate with a wiring pattern formed with openings in the copper layer, the base metal layer, and the first blackened layer. The conductive substrate may further preferably have a structure having mesh-shaped wiring.

The manufacturing method of the conductive substrate of the present embodiment may have an etching process for etching the underlying metal layer, the first blackened layer, and the copper layer of the multilayer substrate obtained by the above-mentioned manufacturing method of the multilayer substrate, A wiring pattern having thin metal wires as a laminate is formed, and the laminate includes a base metal wiring layer, a first blackened wiring layer, and a copper wiring layer. In addition, with this etching process, openings can be formed in the underlying metal layer, the first blackened layer, and the copper layer.

In the etching process, for example, first, a resist is formed on the outermost surface of the laminate substrate, and the resist has an opening corresponding to a portion to be removed by etching. For example, in the case of the laminate substrate shown in FIG. 2A, a resist may be formed on the surface A that exposes the copper layer 14 arranged on the laminate substrate. In addition, the formation method of the resist which has the opening part corresponding to the part to be removed by etching is not specifically limited, For example, it can form by a photolithography method.

Next, by supplying an etching solution from the upper surface of the resist, etching of the underlying metal layer 12, the first blackened layer 13, and the copper layer 14 can be performed.

It should be noted that when the copper layer and the blackened layer are arranged on both sides of the transparent base material 11 as shown in FIG. 2B, the surface A and the surface B of the laminate substrate can be respectively formed with openings having predetermined shapes. The etching agent is used to simultaneously etch the underlying metal layers 12A, 12B, the first blackened layers 13A, 13B, and the copper layers 14A, 14B formed on both surfaces of the transparent substrate 11. In addition, the base metal layers 12A, 12B, the first blackened layers 13A, 13B, and the copper layers 14A, 14B formed on both sides of the transparent substrate 11 may also be etched side by side. That is, for example, after the base metal layer 12A, the first blackened layer 13A, and the copper layer 14A are etched, the base metal layer 12B, the first blackened layer 13B, and the copper layer 14B may be etched.

The first blackened layer formed in the manufacturing method of the laminate substrate of the present embodiment exhibits the same reactivity to the etching solution as the copper layer. In addition, the reactivity of the base metal layer to the etching solution is higher than that of the first blackening layer. Therefore, the etching liquid used in the etching process is not particularly limited, and etching liquids generally used for copper layer etching can be preferably used.

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

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

Since the specific form of the mesh wiring obtained by the above-mentioned etching process has already been described, its description is omitted here.

In addition, after the two laminate substrates having a base metal layer, a first blackened layer, and a copper layer on one surface side of the transparent base material 11 shown in FIGS. 2A and 3A are provided to the etching process to form a conductive substrate In the case of bonding two conductive substrates to form a conductive substrate with mesh wiring, a procedure for bonding the conductive substrate may be further provided. At this time, the method of bonding the two conductive substrates is not particularly limited. For example, optical adhesive (OCA) or the like can be used for bonding.

It should be noted that the average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, and more preferably 40% or less for the conductive substrate obtained by the method for producing a laminate substrate of this embodiment. , More preferably 30% or less.

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

The manufacturing method of the multilayer substrate, the conductive substrate, the multilayer substrate, and the manufacturing method of the conductive substrate of the present embodiment have been described above. This laminate substrate or the laminate substrate obtained by the method of manufacturing the laminate substrate has blackened layers such as a copper layer and a first blackened layer, and can simultaneously perform etching treatment on the copper layer and the blackened layer. In addition, since the copper layer and the blackened layer can be etched at the same time, the copper wiring layer and the blackened wiring layer of a desired shape can be easily formed.

In addition, by providing a blackened layer such as a first blackened layer, it is possible to suppress the reflection of light generated by the copper wiring layer, and for example, when used as a conductive substrate for a touch panel, it is possible to suppress a decrease in visibility. Therefore, by providing a blackened wiring layer, a conductive substrate with good visibility can be formed.

<Example>

Hereinafter, the present invention will be described in detail using the examples and comparative examples of the present invention, but the present invention is not limited to these examples.

(Evaluation method)

(1) Specular reflectivity

The specular reflectance was measured for the laminate substrate produced in each of the following examples and comparative examples.

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

In each example, a laminate substrate having the structure of FIG. 3A was produced, and the reflectance was measured by passing through the transparent substrate 11 on one surface 12a of the base metal layer 12 in FIG. 3A facing the transparent substrate 11. It is implemented by irradiating light with a wavelength of 400 nm or more and 700 nm or less at an incident angle of 5°. It should be noted that for the light irradiated to the laminate substrate, the wavelength is changed every 1 nm within the wavelength range of 400 nm or more and 700 nm or less, and the specular reflectance is measured for each wavelength of light, and the average value of the measurement results is the The average value of the specular reflectance of the conductive substrate. It should be noted that it is expressed as reflectance in Table 1.

(2) The undercut amount ratio of thin metal wires

Regarding the undercut amount ratio, the cross-section of the wiring of the conductive substrate produced in each of the Examples and Comparative Examples was observed using SEM, and the pattern width W _{1 of the} thin metal wire and the bottom width W _{2 of the} thin metal wire were calculated. It should be noted that the pattern width W _{1 of the} thin metal wire and the bottom width W _{2 of the} thin metal wire are as described above using FIG. 6.

(3) Reduction rate of total light transmittance of the opening

The total light transmittance was measured for the openings between the thin metal wires of the transparent base material of the conductive substrates prepared in the respective examples and comparative examples.

The measurement is performed by installing an integrating sphere accessory device in the ultraviolet-visible spectrophotometer when measuring the reflectance of the specular surface. Regarding the irradiated light, the wavelength is changed every 1 nm in the range of 400nm to 700nm, and the transmittance for each wavelength is changed, and the average of the measurement results is the total light transmittance of the opening of the conductive substrate average value.

In addition, the average value of the total light transmittance was measured in advance for the transparent base material used in the production of the laminate substrate in the same manner.

In addition, the reduction rate of the average value of the total light transmittance of the openings of the conductive substrates produced in the respective examples and comparative examples and the reduction rate of the average value of the total light transmittance from the transparent substrate were calculated as the openings The reduction rate of total light transmittance.

(Conditions for sample preparation)

As an example and a comparative example, a laminated body substrate and a conductive substrate were produced under the following conditions, and they were evaluated by the above-mentioned evaluation method.

[Example 1]

A laminate substrate having the structure shown in FIG. 3A was produced.

(Transparent substrate preparation procedure)

First, perform a transparent substrate preparation procedure.

Specifically, a transparent substrate made of polyethylene terephthalate resin (PET) for optics with a width of 500 mm and a thickness of 100 μm was prepared.

(Layered body formation procedure)

Next, a layered body formation process is implemented.

As the layered body formation procedure, a base metal layer formation step, a first blackened layer formation step, a copper layer formation step, and a second blackened layer formation step were performed. This will be specifically described below.

(1) Steps for forming base metal layer

First, the base metal layer forming step is performed.

The prepared transparent substrate was set in the roll-to-roll sputtering apparatus 70 shown in FIG. 7. In addition, a copper target (manufactured by Sumitomo Metal Mining Co., Ltd.) was attached to the sputtering cathode 74a. It should be noted that, since the base metal layer is thin, a copper target is set on only one sputtering cathode 74a, and no targets are set on the other sputtering cathodes 74b to 74d.

Next, the heater 79 of the roll-to-roll sputtering device 70 is heated to 100° C. to heat the transparent substrate to remove moisture contained in the substrate.

Next, after evacuating the inside of the casing 71 to 1×10 ^-4 Pa by the vacuum pumps 80 a and 80 b, the gas supply unit 81 introduces argon into the casing 71 at a flow rate of 240 sccm. Next, while transporting the transparent substrate from the unwinding roller 72 at a speed of 2 m per minute, power is supplied from the sputtering DC power supply connected to the sputtering cathode 74a, and sputtering discharge is performed to form a desired film on the transparent substrate. The base metal layer. Through this operation, a base metal layer with a thickness of 2 nm was formed on the transparent substrate.

(2) The first blackening layer formation step

Next, the first blackening layer forming step is performed.

In the first blackening layer formation step, except that the targets mounted on the sputtering cathodes 74a to 74d are set as copper-nickel alloy targets (manufactured by Sumitomo Metal Mining Co., Ltd.), the inside of the casing 71 is exhausted to 1×10 ^{After -4} Pa, use the gas supply unit 81 to introduce argon and oxygen into the casing 71 of the roll-to-roll sputtering device 70 at a flow rate of argon gas of 240 sccm and a flow rate of oxygen gas of 80 sccm. The sputtering DC power supply connected to ~74d supplies power, and the first blackened layer with a thickness of 20 nm is formed on the upper surface of the base metal layer in the same manner as in the case of the base metal layer.

It should be noted that, as the base material, a base metal layer formed on a transparent base material in the base metal layer forming step was used, and the first blackened layer was formed on the base metal layer.

In addition, as the copper-nickel alloy target, as shown in Table 1, a target containing 20% by mass of Ni and 80% by mass of Cu was used.

(3) Copper layer formation steps

Next, a copper layer forming step is implemented.

In the copper layer formation step, except that the targets mounted on the sputtering cathodes 74a to 74d are changed to copper targets (manufactured by Sumitomo Metal Mining Co., Ltd.), the inside of the casing 71 is exhausted, and then the roll-to-roll sputtering device In the case 71 of 70, except for introducing only argon gas, a copper layer with a thickness of 200 nm is formed on the upper surface of the first blackened layer as in the case of the first blackened layer.

It should be noted that, as a base material for forming the copper layer, a base metal layer and a first blackened layer are sequentially formed on a transparent base material in the base metal layer forming step and the first blackened layer forming step.

(4) The second blackening layer formation step

Next, a second blackening layer forming step is performed.

In the second blackening layer forming step, in addition to using the base metal layer forming step, the first blackening layer forming step, and the copper layer forming step, the base metal layer, the first blackening layer, and the copper layer are sequentially formed on the transparent substrate. Except for the base material of the copper layer, the first blackened layer is formed in the same manner as in the case of the first blackened layer.

When the average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less of the produced laminate substrate was measured by the above procedure, the average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less was 54%.

In addition, after measuring the specular reflectance of the obtained laminate substrate, an etching process was performed to produce a conductive substrate.

In the etching process, first, a resist having an opening corresponding to a portion to be removed by etching is formed on the surface C in FIG. 3A of the produced laminate substrate. Next, it was immersed in an etching solution composed of 10% by mass of ferric chloride, 10% by mass of hydrochloric acid, and the remainder of water for 1 minute to produce a conductive substrate.

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

The evaluation results are shown in Table 1.

[Example 2]

Except that the supply amount of oxygen introduced into the casing when forming the first black layer and the second black layer was changed as shown in Table 1, a laminate substrate and a conductive substrate were produced in the same manner as in Example 1, and were carried out. Evaluation.

It should be noted that, in the second blackened layer forming step, the oxygen supply amount was changed according to the conditions in Example 1, as in the first blackened layer forming step of this embodiment.

The evaluation results are shown in Table 1.

[Example 3~Example 7]

In addition to the composition of the sputtering target used when forming the base metal layer, the thickness of the base metal layer, and the amount of oxygen supplied into the housing when forming the first black layer and the second black layer, as The composition of the copper-nickel alloy target of the sputtering target used when forming the first black layer and the second black layer and the thickness of the first black layer and the second black layer were changed as shown in Table 1. In the same manner as in Example 1, a laminate substrate and a conductive substrate were produced and evaluated.

It should be noted that even in the second blackened layer forming step, the amount of oxygen supplied into the housing during film formation was changed according to the conditions in Example 1, similarly to the first blackened layer forming step of each example. Supply amount and composition of copper-nickel alloy target. In addition, in each example, the second blackened layer was formed into a film so as to have the same thickness as the first blackened layer.

As the sputtering target when forming the underlying metal layer, as shown in Table 1, in Example 5, a target containing 60% by mass of Ni and 40% by mass of Cu was used. In addition, in Example 6, a target containing 7 mass% of Cr and 93 mass% of Ni was used.

The evaluation results are shown in Table 1.

[Comparative Example 1]

Except that the base metal layer was not formed, a laminate substrate and a conductive substrate were produced in the same manner as in Example 3 and evaluated.

The evaluation structure is shown in Table 1.

[Comparative Example 2]

Except that the thickness of the base metal layer was 1 nm, a laminate substrate and a conductive substrate were produced in the same manner as in Example 3 and evaluated.

The evaluation structure is shown in Table 1.

[Comparative Example 3]

Except that the thickness of the base metal layer was 6 nm, a laminate substrate and a conductive substrate were produced in the same manner as in Example 3 and evaluated.

The evaluation structure is shown in Table 1.

[Comparative Example 4]

In addition to the amount of oxygen supplied into the housing when forming the first black layer and the second black layer, it is used as a sputtering target used when forming the first black layer and the second black layer. Except that the composition of the copper-nickel alloy target was changed as shown in Table 1, a laminate substrate and a conductive substrate were produced in the same manner as in Example 1, and evaluated.

The evaluation structure is shown in Table 1.

[Comparative Example 5]

Except that the thickness of the base metal layer is 3nm, the amount of oxygen supplied into the housing when forming the first black layer and the second black layer is used as the Except that the composition of the copper-nickel alloy target of the sputtering target and the thickness of the first blackened layer and the second blackened layer were 25 nm, a laminate substrate and a conductive substrate were produced in the same manner as in Example 1, and evaluated .

The evaluation structure is shown in Table 1.

According to the results shown in Table 1, in Examples 1 to 7, the undercut amount ratio of the thin metal wires 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 can be confirmed that the base metal layer, the first blackened layer, the copper layer, and the second blackened layer can be etched at the same time.

The reason is that the ratio of nickel in copper and nickel contained in the sputtering method used when forming the first blackened layer is 20% by mass or more and 70% by mass or less. The same composition is also present in the layers. That is, it is considered that the reason is that the reactivity of the first blackened layer with respect to the etching solution can be made the same reactivity as the copper layer.

Furthermore, it is considered that by making the base metal layer a layer containing a predetermined metal that does not contain oxygen, the reactivity of the base metal layer with respect to the etching solution can be made higher than that of the first blackening layer, so that the residue of the blackening layer can be removed. It does not remain on the transparent substrate.

In contrast, it can be confirmed that the reduction rate of the total light transmittance of the opening of Comparative Example 1 exceeded 3.0%. It is considered that the reason is that since the base metal layer is not formed, residues of the blackened layer are generated on the transparent substrate. In addition, regarding the undercut ratio in Table 1, the "etch residue" refers to an etching residue in which the blackened layer can be confirmed in the opening.

In this way, it was confirmed that the first blackened layer and the copper layer could not be etched at the same time with respect to the comparative example 1 which did not have the base metal layer.

In Comparative Example 2, the base metal layer was as thin as 1 nm, and there was a part where the base metal layer was not formed. In this part, the first blackened layer was directly formed on the transparent substrate, which resulted in etching residue. .

In Comparative Example 3, the base metal layer was thin, and the reflection caused by the base metal layer became large. It can be confirmed that the average value of the specular reflectance of the obtained laminate substrate became very high, which was 61%.

In Comparative Example 4, since the ratio of nickel contained in the copper-nickel alloy target when the first blackened layer and the second blackened layer were formed was as low as 11% by mass, it could be confirmed that the obtained laminate substrate The average value of the specular reflectance becomes very high, at 60%.

In Comparative Example 5, since the ratio of nickel contained in the copper-nickel alloy target when the first blackened layer and the second blackened layer were formed was very high, 80% by mass, when etching was performed to form a conductive substrate Since the etching speed of the first blackened layer and the second blackened layer is very slow, it is considered that undercutting will occur.

As mentioned above, although the manufacturing method of a laminated body substrate, a conductive substrate, a laminated body substrate, and the manufacturing method of a conductive substrate were demonstrated based on embodiment, an Example, etc., this invention is not limited to the said embodiment, an example, etc.. Various modifications and changes can be made within the scope of the gist of the present invention described in the scope of the patent application.

This application claims priority based on Japanese Patent Application No. 2016-137717 filed with the Japan Patent Office on July 12, 2016. The entire content of the Japanese Patent Application No. 2016-137717 is incorporated by reference. Included in this international application.

10A‧‧‧Laminate substrate

11‧‧‧Transparent substrate

11a‧‧‧One side

11b‧‧‧The other side

12‧‧‧Base metal layer

13‧‧‧The first black layer

14‧‧‧Copper layer

Claims (17)

A laminated body substrate comprising: a transparent base material; and a laminated body formed on at least one surface side of the transparent base material; the laminated body comprising: selected from the group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co A base metal layer composed of one or more metals of the metal group consisting of, Mo, V, and W, or a base metal layer composed of an alloy mainly composed of one or more metals selected from the metal group; arranged on the base metal layer, and A first blackened layer containing oxygen, copper, and nickel; and a copper layer; among the metal components contained in the first blackened layer, the ratio of nickel is 20% by mass to 70% by mass. For example, the laminate substrate of item 1 of the scope of patent application, wherein the laminate further has a second blackened layer, the copper layer is disposed between the first blackened layer and the second blackened layer, and the second blackened layer The oxidation layer contains oxygen and copper, and among the metal components in the second blackening layer, the ratio of nickel is 0% by mass or more and 70% by mass or less. For example, the laminate substrate of item 1 or 2 of the scope of patent application, wherein the thickness of the base metal layer is 1.5 nm or more and 5 nm or less. Such as the laminate substrate of the first or second patent application, wherein the base metal layer is composed of any one of Cu, a Ni-Cu alloy, and a Ni-Cr alloy containing 7% by mass or less of Cr. For example, in the laminated substrate of the first or second patent application, the average value of the specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less is 55% or less. A conductive substrate comprising: a transparent substrate; and thin metal wires formed on at least one surface side of the transparent substrate; the thin metal wires are a laminate, and the laminate includes: A base metal wiring layer composed of one or more metals of a metal group consisting of Ti, Al, Fe, Co, Mo, V, and W, or an alloy composed of one or more metals selected from the metal group as a main component; On the underlying metal wiring layer, a first blackened wiring layer containing oxygen, copper, and nickel; and a copper wiring layer; among the metal components contained in the first blackened wiring layer, the ratio of nickel is 20% by mass Above 70% by mass. For example, the conductive substrate of item 6 of the scope of patent application, wherein the thin metal wire further has a second blackened wiring layer, and the copper wiring layer is disposed between the first blackened wiring layer and the second blackened wiring layer, The second blackened wiring layer contains oxygen and copper, and the ratio of nickel in the metal component in the second blackened wiring layer is 0% by mass or more and 70% by mass or less. For example, the conductive substrate of item 6 or 7 of the scope of patent application, wherein the thickness of the underlying metal wiring layer is 1.5 nm or more and 5 nm or less. For example, the conductive substrate of item 6 or 7 in the scope of the patent application, wherein the base metal wiring layer is composed of any one of Cu, Ni-Cu alloy, and Ni-Cr alloy containing 7% by mass or less of Cr. For example, the conductive substrate of item 6 or 7 in the scope of the patent application, wherein an opening is provided between the thin metal wires to expose the transparent substrate, and the average value of the light transmittance of the opening with a wavelength of 400nm or more and 700nm or less The reduction rate of the average value of the transmittance of light with a wavelength of 400 nm or more and 700 nm or less from the transparent substrate is 3.0% or less. A method for manufacturing a laminate substrate, comprising: a transparent substrate preparation process for preparing a transparent substrate; and a laminate forming process for forming a laminate on at least one side of the transparent substrate, the laminate forming process including: The following base metal layer forming method forms the base metal layer forming step of the base metal layer, the base metal layer forming method is: stacking is selected from Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V The base metal layer is composed of one or more metals of the metal group composed of W, or an alloy composed of one or more metals selected from the metal group as the main component; the first blackening by depositing oxygen, copper, and nickel A first blackened layer forming method of forming a first blackened layer on the base metal layer; and a copper layer forming step of forming a copper layer by a copper layer forming method of depositing a copper layer; The base metal layer forming step and the first blackened layer forming step are performed under a reduced pressure atmosphere, and the ratio of nickel in the metal component contained in the first blackened layer is 20% by mass or more and 70% by mass or less. For example, the method for manufacturing a laminate substrate according to the 11th patent application, wherein the base metal layer forming method and the first blackened layer forming method are sputtering film forming methods. For example, the method for manufacturing a laminate substrate according to item 11 or 12 of the scope of patent application, wherein the thickness of the base metal layer is 1.5 nm or more and 5 nm or less. The method for manufacturing a laminate substrate according to the 11th or 12th patent application, wherein the base metal layer is composed of any one of Cu, a Ni-Cu alloy, and a Ni-Cr alloy containing 7% by mass or less of Cr. For example, in the method for manufacturing a laminate substrate of item 11 or 12 in the scope of patent application, the thickness of the first blackened layer is 20 nm or more. A method for manufacturing a conductive substrate, comprising: an etching process, which compares the base metal layer and the second layer of a laminate substrate obtained by the method for manufacturing a laminate substrate according to any one of the 11th to 15th patent applications. A blackened layer and the copper layer are etched to form a wiring pattern of thin metal wires with a laminate. The laminate includes a base metal wiring layer, a first blackened wiring layer, and a copper wiring layer; An opening is formed on the base metal layer, the first blackened layer and the copper layer. The method for manufacturing a conductive substrate according to the 16th patent application, wherein the obtained conductive substrate has an average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less of 55% or less.

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