WO2018012185A1

WO2018012185A1 - Laminate body substrate, conductive substrate, method for manufacturing laminate body substrate, method for manufacturing conductive substrate

Info

Publication number: WO2018012185A1
Application number: PCT/JP2017/021958
Authority: WO
Inventors: 寛人渡邉
Original assignee: 住友金属鉱山株式会社
Priority date: 2016-07-12
Filing date: 2017-06-14
Publication date: 2018-01-18
Also published as: KR102365980B1; CN109416605B; TW201829177A; JP7049759B2; TWI740970B; KR20190030659A; CN109416605A; JP2018010420A

Abstract

The present invention provides a laminate body substrate provided with a transparent substrate and a laminate body formed on at least one surface of the transparent substrate, wherein the laminate body comprises: an underlying metal layer comprising one or more metals selected from the group of metals consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or an alloy having as a main component one or more metals selected from the abovementioned group of metals; a first blackened layer, disposed on the underlying metal layer, containing oxygen, copper and nickel; and a copper layer. Of the metal components included in the first blackened layer, the ratio of nickel is from 20 mass% to 70 mass%, inclusive.

Description

LAMINATED BOARD, CONDUCTIVE SUBSTRATE, METHOD FOR PRODUCING LAMINATED SUBSTRATE, METHOD FOR PRODUCING CONDUCTIVE SUBSTRATE

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

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

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

For this reason, for example, as disclosed in

Patent Documents

2 and 3, it has been studied to use a metal wiring obtained by processing a metal foil such as copper instead of the ITO film wiring. However, for example, when copper is used for the metal wiring, since copper has a metallic luster, there is a problem that the visibility of the display decreases due to reflection.

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

Japanese Unexamined Patent Publication No. 2003-151358 Japanese Unexamined Patent Publication No. 2011-018194 Japanese Unexamined Patent Publication No. 2013-0669261

By the way, the conductive substrate provided with the metal wiring on the transparent base material is obtained by etching the metal layer so as to obtain a desired wiring pattern after obtaining the laminate substrate in which the metal layer is formed on the surface of the transparent base material. It is obtained by forming a metal wiring. In addition, the conductive substrate having the blackened layer and the metal wiring on the transparent base material is obtained by obtaining a laminate substrate in which the blackened layer and the metal layer are laminated in that order on the surface of the transparent base material, and then the desired wiring. It is obtained by forming the metal wiring by etching the blackened layer and the metal layer so as to form a pattern.

By etching the blackened layer and the metal layer, for example, as shown in FIG. 1A, the blackened layer 2 patterned on the transparent substrate 1 and the metal wiring 3 patterned with the metal layer are stacked. The conductive substrate can be made. In this case, the width W _A of the blackening layer 2 patterned into, it is preferable that the width W _B of the metal wire 3 substantially the same.

However, there is a problem that the reactivity with the etching solution is greatly different between the metal layer and the blackened layer. That is, if the metal layer and the blackened layer are simultaneously etched, one of the layers cannot be etched into the target shape as shown in FIG. 1A.

For example, as compared with the metal layer, if the etch rate of the blackening layer is much slower, as shown in FIG. 1B, a patterned on the transparent substrate 1 was blackened layer 2 having a width (bottom width) W _A but it may be larger than the width W _B of the metal wire 3 is a metal layer patterned. Then, so-called side etching occurs in which the side surface of the metal wiring 3 is etched. For this reason, the cross-sectional shape of the metal wiring 3 is likely to be a trapezoid with a wide base, and if the etching is performed until the electrical insulation between the metal wirings 3 is ensured, the wiring pitch width becomes too wide.

In comparison with the metal layer, if the etch rate of the blackening layer is faster significantly, the patterned black layer 2 having a width as shown in FIG. 1C (bottom width) W _A width W of the metal wires 3 There is a case where a state smaller than _B , that is, so-called undercut occurs. Such undercuts are generated, depending on the degree, the width W _B of a predetermined metal wiring 3, an adhesion width of the transparent substrate 1, a blackening layer 2 patterned bottom width W _A However, if the ratio of the contact width decreases more than necessary, there is a problem that sufficient wiring contact strength cannot be obtained.

Furthermore, even if the etching rate of the blackened layer is made equal to the etching rate of the metal layer, the etching residue of the blackened layer exists on the surface of the transparent substrate exposed after etching, that is, the opening is visually yellow. I could see it.

In view of the above problems of the prior art, an object of the present invention is to provide a laminate substrate that includes a copper layer and a blackened layer, and can simultaneously etch the copper layer and the blackened layer.

In order to solve the above problems, the present invention
A transparent substrate;
A laminate formed on at least one surface side of the transparent substrate,
The laminate is
Mainly composed of one or more metals selected from the metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or selected from the metal group. A base metal layer made of an alloy as a component;
A first blackening layer disposed on the base metal layer and containing oxygen, copper, and nickel;
A copper layer,
Provided is a laminate substrate in which the proportion of nickel is 20% by mass or more and 70% by mass or less in the metal component contained in the first blackened layer.

According to the present invention, it is possible to provide a laminate substrate that includes a copper layer and a blackened layer and can simultaneously etch the copper layer and the blackened layer.

Explanatory drawing at the time of etching a metal layer and a blackening layer simultaneously in the conventional conductive substrate. Explanatory drawing at the time of etching a metal layer and a blackening layer simultaneously in the conventional conductive substrate. Explanatory drawing at the time of etching a metal layer and a blackening layer simultaneously in the conventional conductive substrate. Sectional drawing of the laminated body board | substrate which concerns on embodiment of this invention. Sectional drawing of the laminated body board | substrate which concerns on embodiment of this invention. Sectional drawing of the laminated body board | substrate which concerns on embodiment of this invention. Sectional drawing of the laminated body board | substrate which concerns on embodiment of this invention. The top view of the electroconductive board | substrate provided with the mesh-shaped wiring which concerns on embodiment of this invention. Sectional drawing in the AA 'line of FIG. Explanatory drawing of an undercut amount ratio. Explanatory drawing of a roll-to-roll sputtering apparatus.

Hereinafter, an embodiment of a laminate substrate, a conductive substrate, a laminate substrate manufacturing method, and a conductive substrate manufacturing method of the present invention will be described.
(Laminated substrate, conductive substrate)
The laminate substrate of the present embodiment can include a transparent substrate and a laminate formed on at least one surface side of the transparent substrate. The laminate is made of one or more metals selected from the metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or 1 selected from the above metal group. A base metal layer made of an alloy containing at least different kinds of metals as a main component, a first blackening layer disposed on the base metal layer and containing oxygen, copper, and nickel, and a copper layer. Can do.

And the ratio of nickel can be 20 mass% or more and 70 mass% or less among the metal components contained in a 1st blackening layer.

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

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

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

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

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

Next, the laminate will be described. A laminated body is formed in the at least one surface side of a transparent base material, and can have a base metal layer, a 1st blackening layer, and a copper layer.

Here, the copper layer will be described first.

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

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

When the copper layer is made thicker, it is preferable to use the wet plating method after forming the copper thin film layer by the dry plating method. That is, 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 plating layer can be formed by a wet plating method using the copper thin film layer as a power feeding layer. In this case, the copper layer has a copper thin film layer and a copper plating layer.

Since the copper layer can be formed directly on the transparent substrate or the blackened layer without using an adhesive by forming the copper layer only by the dry plating method or by combining the dry plating method and the wet plating method as described above. 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 electrical resistance value, the wiring width, etc. of the wiring. In particular, the copper layer preferably has a thickness of 50 nm or more, more preferably 60 nm or more, and even more preferably 150 nm or more so that electricity flows sufficiently. The upper limit value of the thickness of the copper layer is not particularly limited. However, when the copper layer is thick, side etching occurs because etching takes time when performing etching to form a wiring, and the resist peels off during the etching. Etc. are likely to occur. For this reason, it is preferable that the thickness of a copper layer is 5000 nm or less, and it is more preferable that it is 3000 nm or less. In addition, when a 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 base metal layer will be described.

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

In addition, the inventors of the present invention initially studied a method of forming a copper oxide layer obtained by oxidizing a part of the copper layer as a blackened layer capable of suppressing light reflection on the surface of the copper layer. And when a part of copper layer was oxidized and it was set as the blackening layer, it discovered that the non-stoichiometric copper oxide and the copper which are not oxidized may be contained in the blackening layer concerned.

When simultaneously etching the copper layer and the blackened layer of the laminate substrate provided with the copper layer and the blackened layer, for example, an etchant capable of etching the copper layer can be suitably used as the etchant. According to the study by the inventors of the present invention, when the blackened layer contains non-stoichiometric copper oxide, the copper layer tends to be eluted into an etchable solution.

Thus, when the blackened layer contains a non-stoichiometric copper oxide that easily elutes with respect to the etching solution, the blackened layer is highly reactive with the etching solution, and compared with the copper layer, The etching rate is greatly increased. For this reason, when the copper layer and the blackened layer were simultaneously etched, the blackened layer was likely to be undercut.

Therefore, the inventors of the present invention include a copper layer and a blackened layer, and with the same etching solution, the copper layer and the blackened layer are formed in one step into an undercut and an opening. The present invention was completed by intensively studying a laminate substrate that can be etched while suppressing the generation of the blackening layer residue.

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

The relationship between the base metal layer and the first blackening layer is that when etching is performed with the same etching solution, the base metal layer is a layer having a higher reactivity to the etching solution than the first blackening layer. can do. That is, the base metal layer is more easily dissolved in the etchant than the first blackening layer, and in other words, the base metal layer can be a layer that is easily etched. By making the base metal layer a layer having a higher reactivity to the etchant than the first blackening layer, generation of etching residues on the surface of the transparent substrate exposed after the etching can be suppressed. As described above, the etching property of the base metal layer affects the etching property of the first blackening layer.

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

As described above, the first blackening layer can contain copper and nickel as metal components. Moreover, although the metal component which a 1st blackening layer contains can also be comprised only from copper and nickel, even in this case, it is not limited only to copper and nickel. For example, the first blackened layer may further contain 1% by mass or less of inevitable impurities as a 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 can contain, for example, at least part of copper, non-stoichiometric copper oxide in which nickel is oxidized, or nickel oxide. Even when the first blackened layer contains non-stoichiometric copper oxide as described above, the first blackened layer also contains a nickel component at the same time, so there is almost no difference in reactivity with the etching solution from the copper layer. Can be. In particular, from the viewpoint of sufficiently suppressing the reactivity of the first blackening layer with respect to the etching solution as compared with the base metal layer, the first blackening layer preferably contains a non-stoichiometric oxide of nickel.

The amount of oxygen contained in the first blackened layer is not particularly limited. However, the amount of oxygen contained in the first blackened layer and the second blackened layer to be described later affects the light reflectance of the laminate substrate and a conductive substrate manufactured using the laminate substrate. There is a case. For this reason, the first blackened layer is formed according to the degree of light reflectance required in the laminated substrate or a conductive substrate manufactured using the laminated substrate, the color tone of the first blackened layer, and the like. It is preferable to select the amount of oxygen contained, and further the amount of oxygen to be added when forming the first blackening layer.

The proportion of nickel in the metal component contained in the first blackened layer is not particularly limited, but the proportion of nickel in the metal component contained in the first blackened layer is 20% by mass or more and 70% by mass. The following is preferable. The ratio of nickel in the metal component contained in the first blackened layer is the total content of metal components in the blackened layer, for example, the total content of copper and nickel is 100% by mass. The ratio of nickel is shown.

This is because, by setting the ratio of nickel to 20% by mass or more of the metal component contained in the first blackening layer, the base metal layer does not contain non-stoichiometric oxide such as non-stoichiometric oxide of nickel, This is because a sufficient difference in reactivity with respect to the etching solution, that is, a difference in reaction rate can be secured.

However, if the proportion of nickel in the metal component contained in the first blackened layer exceeds 70% by mass, the nickel is excessive and it may be difficult to etch the first blackened layer. That is, the dissolution rate of the first blackened layer in the etching solution is slower than that of the copper layer, and there is a possibility that the first blackened layer that can be etched simultaneously with the copper layer cannot be obtained. For this reason, as above-mentioned, it is preferable that the ratio of nickel is 70 mass% or less among the metal components contained in a 1st blackening layer.

Further, among the metal components contained in the first blackened layer, the ratio of nickel is 20% by mass or more and 70% by mass or less, so that the wavelength of the laminated substrate and the conductive substrate formed from the laminated substrate is 400 nm. The average of the regular reflectance of light having a wavelength of 700 nm or less can be assuredly reduced to 55% or less. For this reason, even when the conductive substrate is used for applications such as a touch panel, a decrease in the visibility of the display can be suppressed.

As will be described later, by measuring the average reflectance of light having a wavelength of 400 nm or more and 700 nm or less on the surface of the first blackened layer through the transparent substrate by setting the thickness of the base metal layer to 5 nm or less. When calculated, it can be more reliably set to 55% or less, which is preferable.

On the other hand, the base metal layer is made of one or more metals selected from the metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or selected from the above metal group It can be set as the layer which consists of an alloy which has a 1 or more types of metal as a main component.

However, in the base metal layer, for example, 1% by mass or less of unavoidable impurities may exist as a metal component.

Moreover, the alloy which has as a main component one or more types of metals selected from the said metal group is an alloy which contains most one or more types of metals selected from the said metal group by mass ratio in a metal component. It means that there is. Hereinafter, the same description in this specification has the same meaning. Such an alloy may be an alloy made of one or more kinds of metals selected from the above metal group.

The base metal layer is particularly preferably made of any one of Cu, Ni—Cu alloy, and Ni—Cr alloy containing 7 mass% or less of Cr. Here, in the Ni—Cr alloy, the Cr content can be greater than zero. It is preferable that the base metal layer is made of any of the above metals (alloys) because the reactivity with the etching solution can be made particularly higher than that of the first blackening layer.

In addition, since oxygen is not added when forming the base metal layer, the metal component constituting the base metal layer exists as a metal and is not an indefinite ratio of oxide.

As described above, since the base metal layer does not contain oxygen, the base metal layer is etched using a non-stoichiometric oxide of a metal element constituting the base metal layer, specifically, for example, a non-stoichiometric oxide of nickel. It can be set as the structure which does not contain the component which is hard to melt | dissolve in a liquid.

As described so far, the base metal layer can contain a predetermined metal and can be configured not to contain oxygen. Meanwhile, the first blackening layer may contain oxygen, copper, and nickel.

For this reason, the base metal layer and the first blackening layer included in the laminate substrate according to the present embodiment cause a difference in reactivity with the etching solution, and the base metal layer has the first blackening as described above. The reactivity with the etching solution can be made higher than that of the layer. Moreover, the reactivity with respect to the etching liquid of a 1st blackening layer and a copper layer shall be a thing with little difference.

According to the laminate substrate of this embodiment, since the base metal layer is easily etched as described above, when the laminate substrate is patterned, for example, the etching residue of the blackened layer on the surface of the transparent substrate Can be suppressed. For example, even if a blackened layer residue such as the first blackened layer is generated on the base metal layer, the base metal layer can be easily removed by etching. This is because the residue of the blackening layer can also be removed from above. And since the etching residue of a blackening layer can be decreased, the decreasing rate of the total light transmittance of the transparent base material exposed by the etching, in other words, the decreasing rate of the total light transmittance of the opening can be suppressed.

However, since the reactivity of the base metal layer to the etching solution is high, there is a concern that undercut may occur if only the base metal layer is provided. However, in the multilayer substrate of this embodiment, the first blackening layer that is harder to etch than the base metal layer is disposed on the base metal layer, and the base metal layer is covered with the first blackening layer. For this reason, if the first blackening layer is not removed by etching, the underlying metal layer is not removed by etching, so that occurrence of undercut can be reliably suppressed. Furthermore, as described above, since the base metal layer is easily etched, the etching residue of the blackened layer hardly remains on the surface of the transparent substrate after the etching.

In particular, from the viewpoint of suppressing the occurrence of undercut, and from the viewpoint of suppressing the average regular reflectance of light having a wavelength of 400 nm to 700 nm on the surface of the first blackened layer, the thickness of the base metal layer is 5 nm or less. It is preferable.

The lower limit of the thickness of the underlying metal layer is not particularly limited, but the thickness of the underlying metal layer is also present in order to allow the underlying metal layer to exist as a film and from the viewpoint of sufficiently improving the etching property of the first blackening layer. The thickness is preferably 1.5 nm or more.

Further, the thickness of the first blackening layer is not particularly limited, and can be arbitrarily selected according to, for example, the degree of suppressing the reflection of light 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 blackening layer functions as a layer that suppresses reflection of light on the surface of the copper layer, but when the thickness of the first blackening layer is thin, reflection of light by the copper layer is sufficiently suppressed. There are cases where it is impossible On the other hand, as described above, the reflection of light on the surface of the copper layer can be more reliably suppressed by setting the thickness of the first blackened layer to 20 nm or more.

The upper limit of the thickness of the first blackened layer is not particularly limited, but the time required for film formation and the time required for etching when forming the wiring are increased even if the thickness is increased more than necessary, and the cost is increased. Will lead to an increase. For this reason, the thickness of the first blackening layer is preferably 70 nm or less, and more preferably 50 nm or less.

As described above, since the multilayer substrate of the present embodiment has the predetermined base metal layer and the first blackened layer, the copper layer and the first blackened layer can be etched simultaneously. it can.

It should be noted that the copper layer and the first blackened layer can be etched at the same time by using the same etching solution to cause the copper layer and the first blackened layer to be undercut in one step and the opening. This means that etching can be performed while suppressing the generation of the residue of the blackened layer.

However, in the multilayer substrate of the present embodiment, the copper layer and the first blackened layer can be processed with different etching liquids, and the etching liquid and the first blackened film that can selectively remove the copper layers. It is also possible to produce a conductive substrate having finer fine metal wires by selectively using an etching solution that can selectively remove a layer. Even when using different etching solutions in this way, in particular, the underlying metal layer is more reactive with the etching solution than the first blackening layer, so that fine metal wires can be formed on the surface of the transparent substrate without any blackening layer residue. Is possible.

The method for forming the base metal layer disposed on the laminate substrate of the present embodiment is not particularly limited. The base metal layer is preferably formed by a dry film formation method such as sputtering. In the case where the base metal layer is formed by a sputtering method, the film can be formed while supplying an inert gas used as a sputtering gas into the chamber by using a target of a metal component constituting the base metal layer. Further, oxygen is not added to the sputtering gas when forming the base metal layer.

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

When forming the first black layer by sputtering, for example, a copper-nickel alloy target may be used while supplying oxygen gas in addition to the inert gas used as the sputtering gas in the chamber. it can.

When a copper-nickel alloy target is used during sputtering in the formation of the first blackened layer, the proportion of nickel in the metal component contained in the copper-nickel alloy, for example, copper and nickel, is 20 mass% or more and 70 It is preferable that it is below mass%. This is because the ratio of nickel in the metal components contained in the first blackened layer to be formed, for example, copper and nickel, and the copper-nickel alloy target used in forming the blackened layer is copper. This is because the ratio of nickel in copper and nickel contained in the nickel alloy is the same.

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

In addition, it does not specifically limit as an inert gas at the time of forming a 1st blackening layer and a base metal layer, For example, argon gas and xenon gas can be used, However, Argon gas is used suitably. be able to. The first blackening layer can also contain one or more components selected from hydrogen and carbon in addition to oxygen as components other than the metal component. For this reason, the gas for forming the first blackening layer contains one or more kinds of gases selected from water vapor, carbon monoxide gas, and carbon dioxide gas, in addition to oxygen gas and inert gas. Also good.

As described above, when the first blackening layer is formed by the sputtering method while supplying the inert gas, oxygen gas, and the like to the chamber, the ratio of the inert gas supplied to the chamber and the oxygen gas is as follows. It is not limited. It can be arbitrarily selected according to the reflectance of light required for the laminate substrate and the conductive substrate, the degree of color tone of each blackened layer, and the like.

Further, the laminate substrate of the present embodiment can further have a second blackened layer in addition to the first blackened layer. In this case, the laminate further has a second blackened layer. The second blackening layer can be provided on the surface of the copper layer. That is, the copper layer is disposed between the first blackened layer and the second blackened layer, and can be sandwiched between the first blackened layer and the second blackened layer. When the second blackening layer is provided, the configuration of the second blackening layer is not particularly limited, and for example, a configuration different from that of the first blackening layer may be employed. In addition, the second blackened layer can be configured to contain the same components as the first blackened layer. Specifically, the second blackening layer can contain, for example, oxygen and copper. The second blackened layer can further contain nickel, and can also contain oxygen, copper, and nickel.

The second blackening layer can be composed of one layer, but can also be a multilayer structure, for example, a structure having a layer containing copper as a metal component and a layer containing copper and nickel as metal components You can also

And it is preferable that the ratio of nickel is 0 mass% or more and 70 mass% or less among the metal components in a 2nd blackened layer, for example, copper, or copper and nickel, in a 2nd blackened layer. This is because when the second blackening layer contains copper as the metal component, and optionally further contains nickel, the total content of copper and nickel as the metal component is 100% by mass. This is because if the ratio exceeds 70% by mass, nickel is excessive and etching of the second blackened layer may be difficult.

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

Further, when the second blackened layer has a multilayer structure as described above, the total thickness is preferably in the above range.

The method for forming the second blackened layer is not particularly limited, but it is preferable to form the second blackened layer by a dry film forming method such as a sputtering method in the same manner as the first blackened layer.

When the second blackened layer is formed by sputtering, for example, a copper target or a copper-nickel alloy target is used while supplying oxygen gas in addition to the inert gas used as the sputtering gas in the chamber. Can be membrane.

When a copper-nickel alloy target is used during sputtering in forming the second blackened layer, the proportion of nickel in the copper-nickel alloy, for example, copper and nickel, is greater than 0% by mass. It is preferable that it is 70 mass% or less.

Since the sputtering gas for forming the second blackened layer by sputtering can be selected in the same manner as in the case of forming the first blackened layer, description thereof is omitted here.

In the laminate substrate of the present embodiment, the base metal layer, the first blackened layer, and the copper layer, and in some cases, the second blackened layer can be further laminated on the transparent substrate as described later. By patterning the underlying metal layer, the first blackened layer, and the copper layer, and in some cases, the second blackened layer, a conductive substrate can be obtained.

For this reason, the copper wiring layer and the underlying metal wiring layer of the conductive substrate obtained from the laminated substrate of the present embodiment, and the blackened wiring layers are respectively the copper layer and the underlying metal layer of the laminated substrate of the present embodiment. And the characteristics of each blackened layer are maintained.

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

As described above, the laminate substrate of this embodiment can have a transparent base material, and a laminate having a base metal layer, a first blackening layer, and a copper layer. Note that, as described above, the laminate may further have a second blackened layer.

At this time, the order in which the copper layer and the respective blackened layers are arranged on the transparent substrate and the number of the layers are particularly limited except that the first blackened layer is provided on the base metal layer in the laminate. is not. That is, for example, two layers of the copper layer, the base metal layer, and the first blackening layer can be laminated on at least one surface side of the transparent substrate. Further, a plurality of copper layers and / or first blackened layers can be formed as long as the base metal layer and the first blackened layer are laminated in that order in the laminated body.

However, when placing the copper layer and the blackened layer in the stack, the blackened layer is placed on the surface of the copper layer where the light reflection is particularly desired to be suppressed in order to suppress the reflection of light on the copper layer surface. It is preferable that they are arranged.

In particular, it is more preferable to have a laminated structure in which the blackened layer is formed on the surface of the copper layer. Specifically, for example, the laminated body has a second blackened layer as the blackened layer in addition to the first blackened layer. 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 can be laminated in this order from the transparent substrate side.

When the second blackening layer is provided, a multi-layer structure can be used as described above, but whether to make a multi-layer structure or a single layer may be appropriately selected and is not particularly limited.

Also, the second blackened layer can be configured similarly to the first blackened layer, for example, or can be configured differently from the first blackened layer. That is, the second blackening layer can be a layer containing oxygen and copper, or can be a layer containing oxygen, copper, and nickel. For this reason, it is preferable that the ratio of nickel is 0 mass% or more and 70 mass% or less among the metal components in a 2nd blackening layer. This is because when the second blackening layer contains copper as the metal component, and optionally further contains nickel, the total content of copper and nickel as the metal component is 100% by mass. This is because if the ratio exceeds 70% by mass, etching of the second blackened layer may be difficult.

Specific examples of the configuration of the laminate substrate according to this embodiment will be described below with reference to FIGS. 2A, 2B, 3A, and 3B. 2A, FIG. 2B, FIG. 3A and FIG. 3B are cross-sectional views of the laminate substrate of the present embodiment in a plane parallel to the lamination direction of the transparent base material, the copper layer, the base metal layer, and the first blackening layer. An example is shown.

For example, as in the laminated substrate 10A shown in FIG. 2A, the base metal layer 12, the first blackened layer 13, and the copper layer 14 are laminated one by one on the one surface 11a side of the transparent base material 11 one by one. be able to. That is, the base metal layer 12 provided on the surface of the transparent substrate 11, the first blackening layer 13 provided on the surface of the base metal layer 12, and the copper layer 14 provided on the surface of the first blackening layer 13. It can be set as the structure provided.

Further, as in the laminated substrate 10B shown in FIG. 2B, the

base metal layers

12A and 12B, the first metal layer 12A, the

second metal layer

12B, 1

blackening layer

13A, 13B and

copper layer

14A, 14B can be laminated | stacked one layer at a time in that order.

Further, as described above, in the laminate substrate of the present embodiment, the second blackening layer is provided in addition to the base metal layer, the first blackening layer, and the copper layer on at least one surface side of the transparent base material 11. You can also. For example, as in the laminate 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 are formed on one surface 11a side of the transparent base material 11. 15 can be stacked in that order.

Thus, as the blackening layer, the base metal layer 12, the first blackening layer 13, and the second blackening layer 15 are provided, and the copper layer 14 includes the first blackening layer 13, the second blackening layer 15, By arranging between them, reflection of light incident from the upper surface side and the lower surface side of the copper layer 14 can be more reliably suppressed.

In this case as well, a configuration in which a copper layer, a base metal layer, a first blackening layer, and a second blackening layer are laminated on both surfaces of the transparent substrate 11 can be adopted. Specifically, as in the laminate substrate 20B shown in FIG. 3B, the

base metal layers

12A and 12B are provided on the one surface 11a side and the other surface (the other surface) 11b side of the transparent base material 11, respectively. The

first blackening layers

13A and 13B, the

copper layers

14A and 14B, and the second blackening layers 15A and 15B can be stacked in this order.

In addition, the manufacturing method of the 2nd blackening layer 15 (15A, 15B) is not specifically limited. For example, the second blackening layer 15 (15A, 15B) may be a blackening layer containing oxygen and copper. Further, the second blackening layer 15 (15A, 15B) may be a blackening layer containing oxygen, copper, and nickel similarly to the first blackening layer 13 (13A, 13B). For this reason, it can be made into the layer which contains the same component as a 1st blackening layer, or a metal component contained partially, and a 1st blackening layer and a 2nd blackening layer are the same means. Can be manufactured.

In the configuration example of FIGS. 2B and 3B in which a copper layer, a base metal layer, and a blackening layer are laminated on both surfaces of the transparent base material 11, the transparent base material 11 serves as a symmetrical surface and the upper and lower sides of the transparent base material 11 are aligned. Although the example which arrange | positioned so that the laminated | stacked layer might become symmetrical was shown, it is not limited to the form which concerns.

For example, in FIG. 3B, the base metal layer 12A, the first blackening layer 13A, and the copper layer 14A are stacked in that order in the same manner as the configuration of FIG. It can be in the form. The configuration on the other surface (the other surface) 11b side is such that the base metal layer 12B, the first blackened layer 13B, the copper layer 14B, and the second blackened layer 15B are stacked in that order. As an alternative, the layers laminated on the top and bottom of the transparent substrate 11 may be asymmetrical.

The degree of light reflection of the laminate substrate of the present embodiment is not particularly limited. For example, the average regular reflectance of light having a wavelength of 400 nm to 700 nm is preferably 55% or less, and 40% or less. It is more preferable that it is 30% or less. This is because when the average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 55% or less, for example, when the laminate substrate of this embodiment is used as a conductive substrate for a touch panel, the visibility of the display is reduced. It is because it can suppress especially.

The regular reflectance of the laminate substrate can be measured by irradiating the base metal layer or the blackened layer with light. That is, measurement can be performed by irradiating light from the blackened layer side of the blackened layer and the copper layer included in the laminate substrate. Specifically, for example, when the base metal layer 12, the first blackening layer 13, and the copper layer 14 are laminated in this order on one surface 11 a of the transparent substrate 11 as shown in FIG. 2A, the base metal layer 12 can be irradiated with light. Thus, it can measure by irradiating light with respect to the surface of the base metal layer 12 from the surface 11b side of the transparent base material 11.

The average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less means an average value of measurement results when the regular reflectance is measured by changing the wavelength within a range of 400 nm or more and 700 nm or less. Yes. In the measurement, the width for changing the wavelength is not particularly limited. For example, it is preferable to measure the light in the wavelength range by changing the wavelength every 10 nm, and changing the wavelength every 1 nm to change the wavelength in the wavelength range. More preferably, the measurement is performed on light.

As will be described later, the laminated substrate can be formed into a conductive substrate by forming a thin metal wire by wiring a copper layer, a base metal layer, and a blackened layer by etching. The regular reflectance of light on the conductive substrate is the regular reflectance on the surface on the light incident side of the base metal layer or the blackened layer disposed on the outermost surface when the transparent substrate is removed. means.

For this reason, it is preferable that the measured value in the portion where the copper layer, the base metal layer, and the blackened layer remain satisfies the above range in the case of the conductive substrate after the etching treatment.

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

The conductive substrate of the present embodiment can include a transparent base material and fine metal wires formed on at least one surface side of the transparent base material. The thin metal wire is made of one or more kinds of metals selected from the metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or 1 selected from the above metal group A base metal wiring layer made of an alloy containing at least a metal as a main component, a first blackened wiring layer provided on the base metal wiring layer and containing oxygen, copper, and nickel; a copper wiring layer; It can be set as the laminated body provided with. Moreover, the ratio of nickel can be 20 mass% or more and 70 mass% or less among the metal components contained in a 1st blackening wiring layer.

The conductive substrate of this embodiment can be obtained, for example, by wiring the above-described laminated substrate. Therefore, the copper wiring layer, the base metal wiring layer, and the first blackened wiring layer are the same as the copper layer, the base metal layer, and the first blackened wiring layer, respectively, except that they are patterned by etching. Can have a configuration.

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

The underlying metal wiring layer is made of one or more kinds of metals selected from the metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or selected from the above metal group. In addition, it can be a layer made of an alloy mainly composed of one or more kinds of metals. However, for example, an inevitable impurity of 1% by mass or less may exist as a metal component in the base metal wiring layer.

In particular, the base metal wiring layer is more preferably made 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 not particularly limited, but is preferably 1.5 nm or more and 5 nm or less.

The first blackened wiring layer can contain copper and nickel as metal components, and the proportion of nickel in the metal components contained in the first blackened wiring layer is 20% by mass or more and 70% by mass or less. Is preferred.

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

In the conductive substrate of the present embodiment, a copper wiring layer, a base metal wiring layer, a first blackened wiring layer, and, in some cases, a second blackened wiring layer are provided on the transparent substrate. The black wiring layer such as the first black wiring layer can suppress the reflection of light by the copper wiring layer. Therefore, by providing the blackened wiring layer, it is possible to have good display visibility when used for a touch panel or the like, for example.

The conductive substrate of this embodiment can be preferably used as a conductive substrate for a touch panel, for example. In this case, the conductive substrate has a wiring pattern formed by providing an opening in the copper layer, the base metal layer, the first blackened layer, and in some cases the second blackened layer in the above-described laminate substrate. It can be set as the structure which has. More preferably, it can be set as the structure provided with the mesh-shaped wiring pattern.

The conductive substrate on which the wiring pattern having the opening is formed includes the copper layer, the base metal layer, the first blackened layer, and, in some cases, the second blackened layer of the multilayer substrate described above. Can be obtained by etching. And it can be set as the electroconductive board | substrate which has a mesh-shaped wiring pattern, for example by a two-layer metal fine wire. A specific configuration example is shown in FIG.

FIG. 4 shows a conductive substrate 30 having a mesh-like wiring pattern in the stacking direction of a copper wiring layer, a base metal wiring layer, a first blackened wiring layer, and in some cases a second blackened wiring layer. The figure seen from the upper surface side is shown. 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 drawing, and a copper wiring layer 34A parallel to the Y-axis direction. The

copper wiring layers

34A and 34B can be formed by etching the above-described laminated substrate. The upper and / or lower surfaces of the

copper wiring layers

34A and 34B are not shown with a base metal wiring layer and a first blackening. A wiring layer or the like is formed. In addition, the base metal wiring layer, the first blackened wiring layer, and the like are on the main surface of the transparent substrate 11, that is, on a surface parallel to the surface on which the copper wiring layers 34A, 34B, etc. of the transparent substrate 11 are laminated. Etching is performed so that the cross-sectional shape is substantially the same as that of 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 structural example of arrangement | positioning with the transparent base material 11 and a copper wiring layer is shown in FIG. FIG. 5 is a cross-sectional view taken along the line AA ′ of FIG.

For example, as shown in FIG. 5, copper wiring layers 34 </ b> A and 34 </ b> B may be disposed on the upper and lower surfaces of the transparent substrate 11, respectively. In the case of the conductive substrate shown in FIG. 5, the base

metal wiring layers

32A and 32B and the first blackened

wiring layers

33A and 33B are arranged on the transparent substrate 11 side of the

copper wiring layers

34A and 34B. Yes. The base

metal wiring layers

32A and 32B and the first blackened

wiring layers

33A and 33B have substantially the same cross-sectional shape as that of the

copper wiring layers

34A and 34B in a plane parallel to the main surface of the transparent substrate 11. Can do.

Further, as shown in FIG. 5, the second blackened

wiring layers

35A and 35B can be disposed on the surface of the

copper wiring layers

34A and 34B opposite to the transparent substrate 11. In this case, the second blackened

wiring layers

35A and 35B can have substantially the same cross-sectional shape as that of the

copper wiring layers

34A and 34B in a plane parallel to the main surface of the transparent substrate 11.

That is, in the conductive substrate shown in FIG. 5, as described so far, the fine metal wires are formed on the underlying

metal wiring layers

32A and 32B, the first blackened

wiring layers

33A and 33B, and the

copper wiring layers

34A and 34B. In addition, the second blackened

wiring layers

35A and 35B can be provided. The

copper wiring layers

34A and 34B can have a configuration arranged between the first blackened

wiring layers

33A and 33B and the second blackened

wiring layers

35A and 35B.

The second blackened wiring layer can be formed by etching the second blackened layer described above. For this reason, the second blackened wiring layer can have the same configuration as the second blackened layer described above except that it is patterned by etching.

Specifically, the second blackened wiring layer can contain, for example, oxygen and copper. In some cases, nickel may be further contained. That is, the second blackened wiring layer can contain copper and oxygen, or copper, nickel, and oxygen. In the second blackened wiring layer, it is preferable that the proportion of nickel in the metal component in the second blackened wiring layer is 0% by mass or more and 70% by mass or less. Here, the metal component in the second blackened wiring layer is copper when the second blackened wiring layer contains copper and oxygen, and the second blackened wiring layer is the first blackened wiring layer. Similarly, when oxygen, copper and nickel are contained, copper and nickel are obtained.

Further, the second blackened wiring layer can also have a multilayer structure, for example, a structure having a layer containing copper as a metal component and a layer containing copper and nickel as metal components.

Although the thickness of the second blackened wiring layer is not particularly limited, for example, the lower limit value can be 5 nm or more. Further, the upper limit is preferably, for example, 70 nm or less, and more preferably 50 nm or less. When the second blackened wiring layer has a multilayer structure, the total thickness is preferably within the above range.

In addition, although the example which provided the 2nd blackening wiring layer in addition to the base metal wiring layer and the 1st blackening wiring layer was shown here, it is not limited to the said form. For example, a conductive substrate having only the first blackened wiring layer can be used as the blackened layer.

The conductive substrate having the mesh-like wiring shown in FIG. 4 includes, for example,

copper layers

14A and 14B,

base metal layers

12A and 12B, and first black on both sides of the transparent base 11 as shown in FIGS. 2B and 3B. It can form from the laminated body board | substrate provided with the formation layers 13A and 13B.

For example, the conductive substrate provided with the first blackened wiring layer and the second blackened wiring layer as the blackened wiring layer shown in FIG. 5 may be formed from the multilayer substrate shown in FIG. 3B. it can.

Therefore, an example in which the laminated substrate of FIG. 3B is used will be described.

First, the base metal layer 12A, the first blackened layer 13A, the copper layer 14A, and the second blackened layer 15A on the one surface 11a side of the transparent substrate 11 are arranged in a plurality of lines parallel to the Y-axis direction in FIG. 3B. Etching is performed so that the pattern is arranged at a predetermined interval along the X-axis direction. Note that the Y-axis direction in FIG. 3B indicates a direction perpendicular to the paper surface. Further, the X-axis direction in FIG. 3B means a direction parallel to the width direction of each layer.

Then, the base metal layer 12B, the first blackened layer 13B, the copper layer 14B, and the second blackened layer 15B on the other surface 11b side of the transparent substrate 11 are arranged in a plurality of parallel to the X-axis direction in FIG. 3B. Etching is performed so that the linear patterns are arranged at predetermined intervals along the Y-axis direction.

The conductive substrate having the mesh-like wiring shown in FIGS. 4 and 5 can be formed by the above operation. Note that the etching of both surfaces of the transparent substrate 11 can be performed simultaneously. That is, the

base metal layers

12A and 12B, the first blackened

layers

13A and 13B, the

copper layers

14A and 14B, and the second blackened

layers

15A and 15B may be etched simultaneously.

Further, the same structure as that of the conductive substrate shown in FIG. 5 except that the second blackened

wiring layers

35A and 35B are not obtained by performing etching in the same manner using the laminate substrate shown in FIG. 2B. A conductive substrate having the following can be formed.

The conductive substrate having the mesh-like wiring shown in FIG. 4 can be formed by using two stacked substrates shown in FIG. 2A or FIG. 3A. The case where the conductive substrate of FIG. 3A is used will be described as an example. For the two conductive substrates shown in FIG. 3A, the base metal layer 12, the first blackened layer 13, the copper layer 14, and the second blackened plate are respectively provided. The layer 15 is etched so that a plurality of linear patterns parallel to the X-axis direction are arranged at predetermined intervals along the Y-axis direction. Then, the conductive substrate having mesh-like wiring is obtained by bonding the two conductive substrates so that the linear patterns formed on the respective conductive substrates intersect with each other by the etching process. be able to. The surface to be bonded when the two conductive substrates are bonded is not particularly limited.

For example, for the two conductive substrates, the structure shown in FIG. 5 can be obtained by bonding the surfaces 11b of the transparent base material 11 in FIG.

Note that the width of the fine metal wires and the distance between the fine metal wires in the conductive substrate having the mesh-like wiring shown in FIG. 4 are not particularly limited, and for example, according to the electrical resistance value required for the fine metal wires, etc. Can be selected.

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

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

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

In the configuration example shown in FIG. 6, undercutting may occur 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 upper surface of the blackened layer. When undercut occurs in the configuration example shown in FIG. 6, the width (W ₂ ) of the blackened wiring layer 61 in contact with the transparent substrate 11 which is the bottom width of the fine metal wire is the black width where the pattern width of the fine metal wire is obtained. It becomes narrower than the width (W ₁ ) of the copper wiring layer 62 formed on the patterned wiring layer 61.

In this case, the undercut amount ratio is expressed by the equation (W ₁ −W ₂ ) / 2W ₁ by the bottom width (W ₂ ) of the fine metal wire and the pattern width (W ₁ ) of the fine metal wire.

In the conductive substrate of the present embodiment, as described above, for example, the base metal wiring layer, the first blackened wiring layer, and the copper wiring layer can be laminated in this order from the transparent base material 11 side. When the conductive substrate has such a configuration, the combination of the base metal wiring layer and the first blackened wiring layer is regarded as the blackened wiring layer 61 in FIG. it can be the width of the layer and the bottom width W ₂ of the above-mentioned thin metal wires. Also, the width of the copper wiring layer may be a pattern width W ₁ of the metal thin wire.

The undercut amount ratio preferably has a relationship of (W ₁ −W ₂ ) / 2W ₁ ≦ 0.075. This is because the undercut amount ratio satisfies the above relationship, and it can be said that the blackened layer and the copper layer are simultaneously etched and patterned into a desired pattern. It is because it is preferable also from a viewpoint which raises.

FIG. 4 and FIG. 5 so far show examples in which a mesh-like wiring pattern is formed by combining linear metal thin wires, but the present invention is not limited to such a form, and the metal thin wires constituting the wiring pattern are It can be of any shape. For example, the shape of the fine metal wires constituting the mesh-like wiring pattern can be changed to various shapes such as jagged lines (zigzag straight lines) so that moire (interference fringes) does not occur between the images on the display. .

The conductive substrate of the present embodiment is formed by wiring the above-described laminate substrate and providing openings in the base metal layer, the blackened layer such as the first blackened layer, and the copper layer in the laminate substrate. A wiring pattern. For this reason, the opening part which exposes a transparent base material is provided between the metal fine wires contained in a wiring pattern.

And the decreasing rate from the average of the transmittance | permeability of the light with a wavelength of 400 nm or more and 700 nm or less of this opening part from the average of the transmittance | permeability of the light with a wavelength of 400 to 700 nm of a transparent base material is 3.0% or less. Is preferred.

This is because the average reduction rate of light having a wavelength of 400 nm or more and 700 nm or less of the opening is 3.0% from the average of transmittance of light having a wavelength of 400 nm or more and 700 nm or less of the transparent base material used for the laminate substrate. This is because when the content exceeds 50%, the transparent base material may appear yellow when visually observed. The reduction rate exceeds 3.0% when the base metal layer is not provided. When the first blackened layer and the copper layer are etched, the etching rate of the first blackened layer is low and the first blackened layer is low. This is because the blackened layer and the copper layer cannot be etched simultaneously. Therefore, as described above, it is necessary to provide a base metal layer that is more easily etched than the first blackened layer.

In addition, the degree of light reflection of the conductive substrate of the present embodiment is not particularly limited. For example, the average regular reflectance of light having a wavelength of 400 nm to 700 nm is preferably 55% or less. % Or less is more preferable, and it is further more preferable that it is 30% or less. This is because, when the average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 55% or less, for example, when it is used as a conductive substrate for a touch panel, a reduction in display visibility can be particularly suppressed.

The conductive substrate having a mesh-like wiring composed of the two-layer wiring of the present embodiment described so far can be preferably used as a conductive substrate for a projected capacitive touch panel, for example.
(Manufacturing method of laminate substrate, manufacturing method of conductive substrate)
Next, the structural example of the manufacturing method of the laminated body board | substrate of this embodiment is demonstrated.

The manufacturing method of the laminated body board | substrate of this embodiment can have the following processes.
A transparent base material preparation step for preparing a transparent base material.
The laminated body formation process which forms a laminated body in the at least one surface side of a transparent base material.
And the said laminated body formation process can include the following steps.
Mainly composed of one or more metals selected from the metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, W, or selected from the above metal group. A base metal layer forming step of forming a base metal layer by a base metal layer film forming means for depositing a base metal layer made of an alloy as a component.
A first blackening layer forming step of forming a first blackening layer by a first blackening layer forming means for depositing a first blackening layer containing oxygen, copper, and nickel on the base metal layer;

A copper layer forming step of forming a copper layer by a copper layer forming means for depositing the copper layer.
And it is preferable to implement a base metal layer formation step and a 1st blackening layer formation step in a pressure-reduced atmosphere. Moreover, it is preferable that the ratio of nickel is 20 mass% or more and 70 mass% or less among the metal components contained in a 1st blackening layer.

Hereinafter, the manufacturing method of the multilayer substrate according to the present embodiment will be described, but the description thereof is omitted because the configuration can be the same as that of the above-described multilayer substrate except for the points described below.

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

Therefore, the copper layer forming step, the base metal layer forming step, and the first blackened layer forming step are the same except that the first blackened layer forming step is performed immediately after the base metal layer forming step. It does not specifically limit about the order to implement and the frequency | count of implementing. Therefore, it can be carried out at an arbitrary number of times according to the structure of the laminated substrate to be formed.

The transparent base material preparation step is a step of preparing a transparent base material composed of, for example, a polymer film that transmits visible light or a glass substrate, and the specific operation is not particularly limited. For example, it can be cut into an arbitrary size as necessary for use in the subsequent steps and steps. In addition, since what can be used suitably as a polymer film which permeate | transmits visible light is already stated, description is abbreviate | omitted here.

Next, the laminate forming process will be described. The laminated body forming step is a step of forming a laminated body on at least one surface side of the transparent substrate, and can include a base metal layer forming step, a first blackened layer forming step, and a copper layer forming step. . Each step will be described below.

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

The base metal layer forming step includes at least one surface of the transparent substrate made of one or more kinds of metals selected from a metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W. Or forming a base metal layer by a base metal layer forming means for depositing a base metal layer made of an alloy containing one or more kinds of metals selected from the metal group as a main component.

In the first blackening layer forming step, the first blackening layer is formed by a first blackening layer film forming unit that deposits a first blackening layer containing oxygen, copper, and nickel on the base metal layer. Is a step of forming.

The base metal layer film forming means in the base metal layer forming step and the first black layer forming film forming means in the first black layer forming step are not particularly limited, but are preferably dry plating methods.

In addition, the laminated body board | substrate of this embodiment can also have a 2nd blackening layer, and a laminated body formation process can have a 2nd blackening layer formation step in this case. In the second blackened layer forming step, the second blackened layer can be formed by the second blackened layer forming means for depositing the second blackened layer. The second blackening layer film forming means is not particularly limited, but is preferably a dry plating method.

The dry plating method that can be suitably used in the above-described base metal layer forming step, the first blackened layer forming step, and the second blackened layer forming step is not particularly limited. A sputtering method or an ion plating method can be used. In particular, it is more preferable to use a sputtering method because it is easy to control the composition and thickness of the base metal layer and the blackened layer. That is, it is preferable that the base metal layer film forming unit and the first blackening layer film forming unit be a sputtering film forming method. When the second blackened layer is also formed, the second blackened layer forming means is preferably a sputtering film forming method. That is, the first black layer forming means and the second black layer forming means for forming the black layer are preferably formed by sputtering.

The base metal layer, the first blackened layer, and in some cases, the second blackened layer can be suitably formed using, for example, the roll-to-roll sputtering apparatus 70 shown in FIG.

FIG. 7 shows a configuration example of the roll-to-roll sputtering apparatus 70. The roll-to-roll sputtering apparatus 70 includes a casing 71 that houses most of the components. 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 may be any shape depending on the device accommodated therein, the installation location, the pressure resistance performance, and the like. It can be. For example, the shape of the housing 71 can be a cylindrical shape. However, in order to remove residual gas not related to film formation at the start of film formation, it is preferable that the inside of the casing 71 can be depressurized to 1 Pa or less, more preferably 10 ⁻³ Pa or less, more preferably 10 ⁻⁴ Pa or less. More preferably, it can be done. In addition, it is not necessary that the entire inside of the casing 71 can be reduced to the above pressure, and it can be configured such that only the lower region in the drawing where the can roll 73 (described later) where sputtering is performed can be reduced to the above pressure. .

Inside the casing 71 are an unwinding roll 72, a can roll 73, sputtering cathodes 74a to 74d, a front feed roll 75a, and a rear feed roll for supplying a substrate for forming the first blackened layer or the second blackened layer. 75b, tension rolls 76a and 76b, and a winding roll 77 can be arranged. In addition to the above rolls, guide rolls 78a to 78h, a heater 79, and the like are optionally provided on the transport path of the base material on which the base metal layer, the first blackened layer, and the second blackened layer are formed. You can also.

The unwinding roll 72, the can roll 73, the front feed roll 75a, and the winding roll 77 can be provided with power by a servo motor. The unwinding roll 72 and the winding roll 77 are preferably configured such that the tension balance of the base material on which the copper thin film layer is formed is maintained by torque control using a powder clutch or the like.

Although the structure of the can roll 73 is not particularly limited, for example, the surface thereof is finished with hard chrome plating, and a coolant and a heating medium supplied from the outside of the casing 71 are circulated inside the can roll 73 so that the temperature can be adjusted to a constant temperature. It is preferable that it is comprised.

The tension rolls 76a and 76b are preferably finished with hard chrome plating and provided with a tension sensor, for example. The front feed roll 75a, the rear feed roll 75b, and the guide rolls 78a to 78h are preferably finished with hard chrome plating.

It is preferable that the sputtering cathodes 74a to 74d are of a magnetron cathode type so as to face the can roll 73. The size of the sputtering cathodes 74a to 74d is not particularly limited, but the width direction dimension of the base metal layer for forming the sputtering cathodes 74a to 74d, the first blackening layer, etc. It is preferably wider than the width of the substrate on which the first blackening layer or the like is formed.

The base material on which the base metal layer, the first blackening layer, and the like are formed is conveyed through a roll-to-roll sputtering apparatus 70 that is a roll-to-roll vacuum film forming apparatus. A base metal layer, a first blackening layer, and the like are formed on the can roll 73 when passing through positions facing the sputtering cathodes 74a to 74d. A configuration example of a procedure when the first blackening layer is formed using the roll-to-roll sputtering apparatus 70 will be described.

First, a copper-nickel alloy target is mounted on the sputtering cathodes 74a to 74d, and the inside of the casing 71 in which the base material for forming the first blackening layer is set on the unwinding roll 72 is evacuated by the

vacuum pumps

80a and 80b. . In addition, it is preferable that the ratio of nickel is 20 mass% or more and 70 mass% or less among the metal components contained in the 1st blackening layer to form, for example, copper and nickel. For this reason, the copper-nickel alloy target used for forming the first blackened layer also preferably has a nickel content of 20% by mass or more and 70% by mass or less among copper and nickel.

Then, an inert gas, for example, a sputtering gas composed of argon and oxygen can be introduced into the casing 71 by the gas supply means 81. The configuration of the gas supply unit 81 is not particularly limited, but can have a gas storage tank (not shown). Further, mass flow controllers (MFC) 811a and 811b and

valves

812a and 812b are provided for each gas type between the gas storage tank and the casing 71 so that the supply amount of each gas into the casing 71 can be controlled. Can be configured. Although FIG. 7 shows an example in which two sets of mass flow controllers and valves are provided, the number to be installed is not particularly limited, and the number to be installed can be selected according to the number of gas types to be used.

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

In addition, as the inert gas and the oxygen gas, premixed gases can be supplied into the casing 71. However, the inert gas and the oxygen gas are individually supplied to the casing 71, and each gas has a desired partial pressure in the casing 71. The supply amount and pressure can also be adjusted so that Further, the sputtering gas is not limited to a gas composed of an inert gas and oxygen as described above, and further includes one or more kinds of gases selected from water vapor, carbon monoxide gas, and carbon dioxide gas. May be included.

In this state, while discharging the substrate from the unwinding roll 72 at a speed of, for example, about 0.5 m to 10 m / min, power is supplied from a sputtering DC power source connected to the sputtering cathodes 74a to 74d to perform sputtering discharge. I do. Thereby, a desired 1st blackening layer can be continuously formed on a base material.

In addition to the above, various members can be arranged in the roll-to-roll sputtering apparatus 70 as necessary. For example,

pressure gauges

83a and 83b for measuring the pressure in the casing 71 and vent

valves

84a and 84b can be provided.

The base metal layer is made of one or more kinds of metals selected from the metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W instead of the copper-nickel alloy target, or In the case of the first blackened layer described above, except that an alloy target composed mainly of one or more metals selected from the above metal group is attached to the sputtering cathodes 74a to 74d and oxygen is not added to the sputtering gas. The film can be formed in the same manner as described above.

The base metal layer is more preferably made of any one of Cu, Ni—Cu alloy, and Ni—Cr alloy containing 7 mass% or less of Cr. For this reason, it is preferable to form a base metal layer using a target corresponding to these compositions.

Further, as described above, the multilayer substrate of the present embodiment can have a second blackened layer in addition to the base metal layer and the first blackened layer. As described above, when forming the second blackened layer, a target corresponding to the target composition of the second blackened layer, for example, a copper target or a copper-nickel alloy target is mounted on the sputtering cathodes 74a to 74d. Except for this, the film can be formed in the same manner as in the case of the first blackening layer described above.

And it is preferable to implement a base metal layer formation step and a 1st blackening layer formation step in a pressure-reduced atmosphere. In addition, when the second blackened layer forming step is performed, it is preferable that the second blackened layer forming step is similarly performed in a reduced pressure atmosphere.

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 forming means for depositing copper, that is, copper.

In the copper layer forming step, it is preferable to form a copper thin film layer using a dry plating method. Moreover, when making a copper layer thicker, it is preferable to form a copper plating layer further using a wet plating method after forming a copper thin film layer by a dry plating method.

Therefore, the copper layer forming step can include a step of forming a copper thin film layer by, for example, a dry plating method. 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 feeding layer. .

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

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

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

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

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

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

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

First, a copper target is mounted on the sputtering cathodes 74a to 74d, and the inside of the casing 71 in which the base material for forming the copper thin film layer is set on the unwinding roll 72 is evacuated by the

vacuum pumps

80a and 80b.

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

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

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

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

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

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

So far, each process and step included in the manufacturing method of the multilayer substrate of the present embodiment has been described.

In the laminate substrate obtained by the method for producing a laminate substrate according to this embodiment, the copper layer preferably has a thickness of 50 nm or more, more preferably 60 nm or more, as in the above-described laminate substrate. More preferably, it is 150 nm or more. The upper limit value 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 a 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 not particularly limited, but is preferably 1.5 nm or more and 5 nm or less.

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

When the second blackening layer is provided, the thickness thereof is not particularly limited, but the lower limit can be set to 5 nm or more, for example. Further, the upper limit is preferably, for example, 70 nm or less, and more preferably 50 nm or less. As described above, the second blackened layer may have a multilayer structure, and in this case, the total thickness of the plurality of layers constituting the second blackened layer is preferably in the above range.

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

Using the laminate substrate obtained by the laminate substrate manufacturing method of the present embodiment, a conductive substrate having a wiring pattern having openings in the copper layer, the base metal layer, and the first blackening layer is formed. be able to. More preferably, the conductive substrate can be configured to include mesh-like wiring.

The conductive substrate manufacturing method according to the present embodiment includes etching the base metal layer, the first blackening layer, and the copper layer of the multilayer substrate obtained by the above-described method for manufacturing a multilayer substrate. It is possible to have an etching process for forming a wiring pattern having a fine metal wire that is a laminate including a wiring layer, a first blackened wiring layer, and a copper wiring layer. And the opening part can be formed in a base metal layer, a 1st blackening layer, and a copper layer by the etching process which concerns.

In the etching step, for example, first, a resist having an opening corresponding to a portion to be removed by etching is formed on the outermost surface of the multilayer substrate. For example, in the case of the multilayer substrate shown in FIG. 2A, a resist can be formed on the exposed surface A of the copper layer 14 disposed on the multilayer substrate. Note that a method for forming a resist having an opening corresponding to a portion to be removed by etching is not particularly limited. For example, the resist can be formed by a photolithography method.

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

2B, when a copper layer and a blackened layer are arranged on both surfaces of the transparent substrate 11, resists having openings of predetermined shapes are formed on the surface A and the surface B of the laminate substrate, respectively. The

underlying metal layers

12A and 12B, the

first blackening layers

13A and 13B, and the

copper layers

14A and 14B formed on both surfaces of the transparent substrate 11 may be etched simultaneously. In addition, the

base metal layers

12A and 12B, the first blackened

layers

13A and 13B, and the

copper layers

14A and 14B formed on both sides of the transparent base material 11 can be subjected to an etching process on one 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 can be etched.

The 1st blackening layer formed with the manufacturing method of the laminated substrate of this embodiment shows the reactivity with respect to the etching liquid similar to a copper layer. Further, the base metal layer has a higher reactivity with the etching solution than the first blackened layer. For this reason, the etching solution used in the etching step is not particularly limited, and an etching solution generally used for etching the copper layer can be preferably used.

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

The etching solution can be used at room temperature, but can also be used by heating in order to increase the reactivity, for example, heated to 40 ° C. or more and 50 ° C. or less.

Since the specific form of the mesh-like wiring obtained by the above-described etching process is as described above, the description thereof is omitted here.

2A and 3A, the two laminated substrates having the base metal layer, the first blackening layer, and the copper layer on one surface side of the transparent base material 11 shown in FIG. After that, in the case where two conductive substrates are bonded to form a conductive substrate having a mesh-like wiring, a step of bonding the conductive substrates can be further provided. In this case, a method for bonding the two conductive substrates is not particularly limited, and the bonding can be performed using, for example, an optical adhesive (OCA) or the like.

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

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

In the above, the laminated substrate of this embodiment, the electroconductive board | substrate, the manufacturing method of a laminated body board | substrate, and the manufacturing method of an electroconductive board | substrate were demonstrated. Such a laminate substrate or a laminate substrate obtained by the laminate substrate manufacturing method includes a copper layer and a blackening layer such as a first blackening layer, and simultaneously etches the copper layer and the blackening layer. Processing can be performed. And since a copper layer and a blackening layer can be etched simultaneously, the copper wiring layer and blackening wiring layer of a desired shape can be formed easily.

Further, by providing a blackened wiring layer such as the first blackened wiring layer, reflection of light by the copper wiring layer can be suppressed. For example, when a conductive substrate for a touch panel is used, a decrease in visibility is suppressed. can do. For this reason, it can be set as the electroconductive board | substrate which has favorable visibility by providing a blackening wiring layer.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited to these Examples.
(Evaluation methods)
(1) Regular reflectance The regular reflectance was measured for the laminate substrates produced in the following examples and comparative examples.

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

In each example, a laminate substrate having the structure of FIG. 3A was produced. The reflectance was measured through the transparent base material 11 on one surface 12a of the base metal layer 12 facing the transparent base material 11 in FIG. 3A. The incident angle was set to 5 °, and irradiation was performed with light having a wavelength ranging from 400 nm to 700 nm. In addition, the light irradiated to the laminate substrate is subjected to regular reflectance measurement with respect to light of each wavelength by changing the wavelength every 1 nm within a wavelength range of 400 nm to 700 nm, and the average of the measurement results is calculated as the conductivity. The average of the regular reflectance of the substrate was used. In Table 1, the reflectance is shown.
(2) the undercut amount ratio undercut amount ratio of thin metal wires, each of the embodiments, the cross section of the wire of the conductive substrate prepared in Comparative Example was observed by SEM, the bottom of the pattern width W ₁ and the metal thin wires of the metal thin wires It was calculated to determine the width W _2. Note that the pattern width W _{1 of} the fine metal wire and the bottom width W ₂ of the fine metal wire are as already described with reference to FIG.
(3) Reduction rate of total light transmittance of opening part The total light transmittance was measured about the opening part between the metal fine wires which expose the transparent base material of the electroconductive board | substrate produced by each Example and the comparative example.

The measurement was performed by installing an integrating sphere attachment device on the ultraviolet-visible spectrophotometer when measuring the regular reflectance. The irradiated light is measured for the transmittance of each wavelength light by changing the wavelength every 1 nm within the wavelength range of 400 nm to 700 nm, and the average of the measurement results is the total light of the opening of the conductive substrate. The average transmittance was used.

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

And the average of the total light transmittance of the opening part of the conductive substrate produced in each Example and Comparative Example is the decrease rate from the average of the total light transmittance of the transparent base material, the total light transmittance of the opening part The reduction rate was calculated.
(Sample preparation conditions)
As examples and comparative examples, laminate substrates and conductive substrates were produced under the conditions described below, and evaluation was performed by the above-described evaluation method.
[Example 1]
A laminate substrate having the structure shown in FIG. 3A was produced.
(Transparent substrate preparation process)
First, the transparent base material preparation process was implemented.

Specifically, a transparent substrate made of optical polyethylene terephthalate resin (PET) having a width of 500 mm and a thickness of 100 μm was prepared.
(Laminate formation process)
Next, the laminated body formation process was implemented.

As the laminated body forming step, a base metal layer forming step, a first blackened layer forming step, a copper layer forming step, and a second blackened layer forming step were performed. This will be specifically described below.
(1) Base metal layer formation step First, a base metal layer formation step was performed.

The prepared transparent substrate was set in the roll-to-roll sputtering apparatus 70 shown in FIG. Further, a copper target (manufactured by Sumitomo Metal Mining Co., Ltd.) was attached to the sputtering cathode 74a. Since the underlying metal layer was thin, a copper target was set only on one sputtering cathode 74a, and no target was set on the other sputtering cathodes 74b to 74d.

Then, the heater 79 of the roll-to-roll sputtering apparatus 70 was heated to 100 ° C., the transparent base material was heated, and water contained in the base material was removed.

Subsequently, after the inside of the casing 71 was evacuated to 1 × 10 ⁻⁴ Pa by the

vacuum pumps

80a and 80b, the argon gas was introduced into the casing 71 by the gas supply means 81 so that the flow rate of argon gas was 240 sccm. . And while conveying a transparent base material from the unwinding roll 72 at the speed of 2 m / m, electric power is supplied from the DC power source for sputtering connected to the sputtering cathode 74a, sputtering discharge is performed, and a desired material is formed on the transparent base material. A base metal layer was formed. By this operation, a base metal layer was formed on the transparent substrate so as to have a thickness of 2 nm.
(2) First Blackened Layer Formation Step Next, a first blackened layer formation step was performed.

In the first blackening layer forming step, the target mounted on the sputtering cathodes 74a to 74d is a copper-nickel alloy target (manufactured by Sumitomo Metal Mining Co., Ltd.), and the inside of the casing 71 is exhausted to 1 × 10 ⁻⁴ Pa. Thereafter, argon gas and oxygen gas are supplied into the casing 71 of the roll-to-roll sputtering apparatus 70 by the gas supply means 81 so that the argon gas flow rate is 240 sccm and the oxygen gas flow rate is 80 sccm. The first blackening layer has a thickness of 20 nm on the upper surface of the base metal layer in the same manner as in the case of the base metal layer except that power is supplied from a DC power supply for sputtering connected to the sputtering cathodes 74a to 74d. It formed so that it might become.

In addition, as a base material, the base material layer formation step WHEREIN: The base material which formed the base metal layer on the transparent base material was used, and the 1st blackening layer was formed into a film on the base metal layer.

As a 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 step Then, the copper layer formation step was implemented.

In the copper layer forming step, the target attached to the sputtering cathodes 74a to 74d is changed to a copper target (manufactured by Sumitomo Metal Mining Co., Ltd.), the inside of the casing 71 is evacuated, and then the casing 71 of the roll-to-roll sputtering apparatus 70 is used. A copper layer having a thickness of 200 nm was formed on the upper surface of the first blackened layer in the same manner as the first blackened layer except that only argon gas was introduced therein.

In addition, as a base material which forms a copper layer, the base metal layer and the 1st blackening layer were formed in that order on the transparent base material by the base metal layer formation step and the 1st blackening layer formation step. A substrate was used.
(4) Second Blackening Layer Formation Step Subsequently, a second blackening layer formation step was performed.

In the second blackening layer forming step, the base metal layer forming step, the first blackening layer forming step, and the copper layer forming step are performed on the transparent base material on the base metal layer, the first blackening layer, and the copper. A second blackened layer was formed in the same manner as in the first blackened layer forming step except that a base material in which layers were formed in that order was used.

The average regular 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-described procedure, and the average regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less was 54%.

Moreover, after measuring the regular reflectance of the obtained laminate substrate, an etching process was performed to produce a conductive substrate.

In the etching step, first, a resist having an opening corresponding to a portion to be removed by etching was formed on the surface C in FIG. 3A of the manufactured laminate substrate. And it immersed for 1 minute in the etching liquid which consists of 10 mass% of ferric chloride, 10 mass% of hydrochloric acid, and the remainder with water, and produced the electroconductive board | substrate.

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

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

In the second blackened layer forming step, the oxygen supply amount is changed from the conditions in the first embodiment as in the first blackened layer forming step of the present embodiment.

The evaluation results are shown in Table 1.
[Examples 3 to 7]
Composition of the sputtering target used when forming the base metal layer, the thickness of the base metal layer, the supply amount of oxygen supplied into the housing when forming the first black layer and the second black layer The composition of the copper-nickel alloy target, which is a sputtering target used when forming the first black layer and the second black layer, and the thicknesses of the first black layer and the second black layer are shown. A laminate substrate and a conductive substrate were produced and evaluated in the same manner as in Example 1 except for the points changed as shown in FIG.

In the second blackened layer forming step, the amount of oxygen supplied into the housing during the film formation and the composition of the copper-nickel alloy target were carried out in the same manner as in the first blackened layer forming step of each example. The conditions are changed from those in Example 1. In each embodiment, the second blackened layer is formed to have the same thickness as the first blackened layer.

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

The evaluation results are shown in Table 1.
[Comparative Example 1]
A laminate substrate and a conductive substrate were prepared and evaluated in the same manner as in Example 3 except that the base metal layer was not formed.

The evaluation results are shown in Table 1.
[Comparative Example 2]
A laminate substrate and a conductive substrate were prepared and evaluated in the same manner as in Example 3 except that the thickness of the base metal layer was 1 nm.

The evaluation results are shown in Table 1.
[Comparative Example 3]
A laminate substrate and a conductive substrate were prepared and evaluated in the same manner as in Example 3 except that the thickness of the base metal layer was 6 nm.

The evaluation results are shown in Table 1.
[Comparative Example 4]
The oxygen supply amount supplied into the housing when forming the first blackening layer and the second blackening layer, and the sputtering target used when forming the first blackening layer and the second blackening layer. A laminate substrate and a conductive substrate were prepared and evaluated in the same manner as in Example 1 except that the composition of the copper-nickel alloy target was changed as shown in Table 1.

The evaluation results are shown in Table 1.
[Comparative Example 5]
The thickness of the base metal layer is 3 nm, the supply amount of oxygen supplied into the housing when forming the first blackened layer and the second blackened layer, the first blackened layer, and the second blackened layer Example 1 except that the composition of the copper-nickel alloy target, which is the sputtering target used to form the layers, and the thickness of the first and second blackened layers were 25 nm. A laminate substrate and a conductive substrate were prepared and evaluated.

Evaluation results are shown in Table 1.

According to the results shown in Table 1, in Examples 1 to 7, the undercut amount ratio of the fine metal wire was 0.075 or less, and the reduction rate of the total light transmittance of the opening was 3.0% or less. It was. That is, it was confirmed that the base metal layer, the first blackened layer, the copper layer, and the second blackened layer can be etched simultaneously.

This is because the ratio of nickel is 20% by mass or more and 70% by mass or less among the copper and nickel contained in the sputtering target used for forming the first blackened layer, and the first blackened layer formed is formed. This is considered to be due to the similar composition. That is, it is considered that the reactivity of the first blackening layer with respect to the etching solution can be made equal to that of the copper layer.

And about the foundation | substrate metal layer, since it was made the layer containing a predetermined metal which does not contain oxygen, the reactivity with respect to an etching liquid could be made higher than a 1st blackening layer, Therefore The residue of a blackening layer Is considered to have been removed without leaving on the transparent substrate.

On the other hand, in Comparative Example 1, it was confirmed that the decrease rate of the total light transmittance of the opening exceeded 3.0%. This is presumably because a blackened layer residue was formed on the transparent substrate because the base metal layer was not formed. In Table 1, with respect to the undercut ratio, “etching residue” means that the etching residue of the blackened layer was confirmed in the opening.

Thus, it was confirmed that in Comparative Example 1 having no base metal layer, the first blackened layer and the copper layer could not be etched simultaneously.

In Comparative Example 2, the base metal layer is as thin as 1 nm, and there is a part where the base metal layer is not formed. In this part, the first blackening layer is formed directly on the transparent substrate, and thus etching residue is generated. did.

In Comparative Example 3, it was confirmed that the base metal layer was thick and the reflection by the base metal layer was large, and the average regular reflectance of the obtained laminate substrate was as extremely high as 61%.

In Comparative Example 4, since the proportion of nickel contained in the copper-nickel alloy target when forming the first blackened layer and the second blackened layer was as low as 11% by mass, the regular reflectance of the obtained laminate substrate was It was confirmed that the average of was very high at 60%.

In Comparative Example 5, the ratio of nickel contained in the copper-nickel alloy target at the time of forming the first blackened layer and the second blackened layer is as high as 80% by mass. When performing, the etching rate of the first blackened layer and the second blackened layer was very slow, so it is considered that undercut occurred.

Although the laminated body substrate, the conductive substrate, the manufacturing method of the laminated body substrate, and the manufacturing method of the conductive substrate have been described in the above embodiments and examples, the present invention is not limited to the above embodiments and examples. Various modifications and changes are possible within the scope of the gist of the present invention described in the claims.

This application claims priority based on Japanese Patent Application No. 2016-137717 filed with the Japan Patent Office on July 12, 2016. The entire contents of Japanese Patent Application No. 2016-137717 are incorporated herein by reference. Incorporate.

10A, 10B, 20A, 20B Laminate substrate 11

Transparent base material

12, 12A, 12B Underlying

metal layer

13, 13A, 13B First blackened

layer

14, 14A,

14B Copper layer

15, 15A, 15B Second blackened layer 30

Conductive substrates

32A, 32B Underlying metal wiring layers 33A, 33B First blackened

wiring layers

34A, 34B, 62 Copper wiring layers 35A, 35B Second blackened wiring layers

Claims

A transparent substrate;
A laminate formed on at least one surface side of the transparent substrate,
The laminate is
Mainly composed of one or more metals selected from the metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or selected from the metal group. A base metal layer made of an alloy as a component;
A first blackening layer disposed on the base metal layer and containing oxygen, copper, and nickel;
A copper layer,
The laminated body board | substrate whose ratio of nickel is 20 mass% or more and 70 mass% or less among the metal components contained in a said 1st blackening layer.
The laminate further has a second blackening layer,
The copper layer is disposed between the first blackened layer and the second blackened layer,
The second blackening layer contains oxygen and copper,
The laminate substrate according to claim 1, wherein a ratio of nickel is 0% by mass or more and 70% by mass or less in the metal component in the second blackening layer.
The laminate substrate according to claim 1 or 2, wherein a thickness of the base metal layer is 1.5 nm or more and 5 nm or less.
The laminate substrate according to any one of claims 1 to 3, wherein the base metal layer is made of any one of Cu, Ni-Cu alloy, and Ni-Cr alloy containing 7 mass% or less of Cr.
The laminate substrate according to any one of claims 1 to 4, wherein the average regular reflectance of light having a wavelength of 400 nm to 700 nm is 55% or less.
A transparent substrate;
A thin metal wire formed on at least one surface side of the transparent substrate,
The thin metal wire is
Mainly composed of one or more metals selected from the metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or selected from the metal group. A base metal wiring layer made of an alloy as a component;
A first blackened wiring layer disposed on the base metal wiring layer and containing oxygen, copper, and nickel;
A laminate comprising a copper wiring layer,
The electroconductive board | substrate whose ratio of nickel is 20 to 70 mass% among the metal components contained in the said 1st blackening wiring layer.
The thin metal wire further has a second blackened wiring layer,
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,
The conductive substrate according to claim 6, wherein a 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.
The conductive substrate according to claim 6 or 7, wherein a thickness of the base metal wiring layer is 1.5 nm or more and 5 nm or less.
The conductive substrate according to any one of claims 6 to 8, wherein the base metal wiring layer is made of any one of Cu, Ni-Cu alloy, and Ni-Cr alloy containing 7 mass% or less of Cr.
An opening that exposes the transparent substrate is provided between the thin metal wires,
The average decrease in the transmittance of light having a wavelength of not less than 400 nm and not more than 700 nm of the opening is 3.0% or less from the average of the transmittance of light having a wavelength of not less than 400 nm and not more than 700 nm of the transparent substrate. The conductive substrate according to any one of 6 to 9.
A transparent substrate preparation step of preparing a transparent substrate;
A laminate forming step of forming a laminate on at least one surface side of the transparent substrate,
The laminate forming step includes
Mainly composed of one or more metals selected from the metal group consisting of Cu, Ni, Cr, Ti, Al, Fe, Co, Mo, V, and W, or selected from the metal group. A base metal layer forming step of forming a base metal layer by a base metal layer film forming means for depositing a base metal layer made of an alloy as a component;
A first blackening layer forming step of forming a first blackening layer by a first blackening layer forming means for depositing a first blackening layer containing oxygen, copper, and nickel on the base metal layer;
A copper layer forming step of forming a copper layer by a copper layer film forming means for depositing a copper layer,
The base metal layer forming step and the first blackened layer forming step are performed in a reduced pressure atmosphere, and the proportion of nickel in the metal component contained in the first blackened layer is 20% by mass to 70% by mass. A method for manufacturing a laminated substrate.
The method for manufacturing a laminate substrate according to claim 11, wherein the base metal layer film forming means and the first blackening layer film forming means are sputtering film forming methods.
The method for manufacturing a laminate substrate according to claim 11 or 12, wherein a thickness of the base metal layer is 1.5 nm or more and 5 nm or less.
The method for manufacturing a multilayer substrate according to any one of claims 11 to 13, wherein the base metal layer is made of any one of Cu, Ni-Cu alloy, and Ni-Cr alloy containing 7 mass% or less of Cr.
The method for manufacturing a laminate substrate according to any one of claims 11 to 14, wherein the thickness of the first blackening layer is 20 nm or more.
The base metal layer, the first blackening layer, and the copper layer of the multilayer substrate obtained by the method for manufacturing a multilayer substrate according to any one of claims 11 to 15 are etched to form a base An etching step of forming a wiring pattern having a thin metal wire that is a laminate including a metal wiring layer, a first blackened wiring layer, and a copper wiring layer;
The manufacturing method of the electroconductive board | substrate which forms an opening part in the said base metal layer, the said 1st blackening layer, and the said copper layer by the said etching process.
The method for producing a conductive substrate according to claim 16, wherein an average of regular reflectance of light having a wavelength of 400 nm or more and 700 nm or less of the obtained conductive substrate is 55% or less.