TW201901701A - Method for producing transparent conductive substrate, transparent conductive substrate - Google Patents

Abstract

Provided is a method for manufacturing a transparent electroconductive substrate having a patterning process for patterning a laminate which is a constituent of a laminated substrate that includes a transparent substrate and the laminate arranged on at least one side of the transparent substrate and consisting of a first blackening layer containing nickel and copper and an electroconductive layer containing copper that are laminated in the order stated from the transparent substrate side, the patterning process having an electroconductive layer etching step for etching the electroconductive layer with a first etchant with which copper can be dissolved, and a first blackening layer etching step for etching the first blackening layer with a second etchant containing chloride icons and water, the chloride ion concentration of the second etchant being 10 mass% or more in terms of hydrochloric acid.

Description

   Manufacturing method of transparent conductive substrate, transparent conductive substrate   

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

The electrostatic capacity type touch panel detects the change in electrostatic capacity caused by an object close to the surface of the panel, and converts the position information of the close object on the surface of the panel into an electrical signal. The transparent conductive substrate used in the capacitive touch panel is disposed on the surface of the display. Therefore, the wiring material of the transparent conductive substrate needs to have low reflectance and is difficult to be recognized.

For this reason, as a wiring material used in the capacitive touch panel, a material having a low reflectance and hard to be seen is used, and wiring is formed on a transparent substrate or a transparent film. For example, Patent Document 1 discloses a transparent conductive film for a touch panel in which an ITO (indium oxide-tin) film is formed as a transparent conductive film on a polymer film.

In addition, in recent years, a display having a touch panel is becoming larger, and accordingly, a large area of a conductive substrate such as a transparent conductive film for a touch panel is also required. However, if the resistance value of ITO is high and the wiring length is long, the signal will be degraded (degraded), so there is a problem that it is not suitable for a large panel.

For this reason, for example, as described in Patent Documents 2 and 3, it has been studied to use metal wiring such as copper instead of ITO. However, since metal, which is a material of the metal wiring, has a metallic luster, there is a problem in that reflection causes a decrease in visibility of the display.

Therefore, a transparent conductive substrate has been studied in which a blackened layer that suppresses light reflection on the surface of a conductive layer is formed on a conductive layer using a metal material on a transparent substrate, and then the conductive layer and the black The patterned layer is patterned to be a transparent conductive substrate in which a blackened layer is formed on a surface of a metal wiring.

    [Previous Technical Literature]         [Patent Literature]    

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

[Patent Document 2] Japanese Patent Application Laid-Open No. 2011-018194

[Patent Document 3] Japanese Patent Laid-Open No. 2013-069261

The inventors of the present invention have studied a transparent conductive substrate including a blackened layer containing nickel and copper as a transparent conductive substrate capable of suppressing light reflection on the surface of a conductive layer using a metal material, in particular. Specifically, a first blackened layer containing nickel and copper, a conductive layer which is a layer using a metal material containing copper, and a second blackened layer containing nickel and copper are arranged in this order from the transparent substrate side. A multilayer conductive transparent conductive substrate was studied.

In addition, in order to pattern a multilayer substrate on which a multilayer body including a blackened layer and a conductive layer is arranged on a transparent substrate, thereby manufacturing a transparent conductive substrate having a wiring pattern, a resist is first disposed on the surface of the multilayer body. (resist) The resist has an opening having a shape corresponding to a portion to be removed by etching. Then, an etching solution that can simultaneously etch the blackened layer and the conductive layer is supplied, whereby the laminated body including the blackened layer and the conductive layer is etched. Thereafter, the resist was peeled and removed, and a transparent conductive substrate having a wiring pattern was manufactured based thereon. As described above, conventionally, from the viewpoint of productivity, the blackened layer and the conductive layer have been etched with the same etching solution.

However, when the blackening layer and the conductive layer are etched by an etching solution, if the blackening layer connected to the transparent substrate has the above-mentioned structure, the first blackening layer is etched, and a part of it occurs There is a problem that residues are easily caused by dissolution.

In particular, in the case where a transparent conductive substrate is mounted (mounted) on a display in recent years, in order to make the wiring pattern inconspicuous, a blackened layer capable of further suppressing the reflectance of the surface of the conductive layer is required.

In addition, in the case of a blackened layer containing nickel and copper, the reflectance of the surface of the conductive layer can be further suppressed by increasing the content ratio of nickel oxide. However, nickel oxide has low reactivity to an etchant that can simultaneously etch a blackened layer and a conductive layer, for example, an etchant such as ferric chloride, so suppressing the reflectance will cause blackening more easily. The residue of the layer cannot pattern the blackened layer into a desired shape.

In view of the foregoing problems of the prior art, it is an object of the present invention to provide a method for manufacturing a transparent conductive substrate capable of patterning a blackened layer into a desired shape.

In order to solve the above-mentioned problem, in one aspect of the present invention, a method for manufacturing a transparent conductive substrate is provided, which includes a patterning step for patterning a multilayer body of a multilayer substrate, the multilayer substrate including a transparent base. A first blackened layer containing nickel and copper, and a conductive layer containing copper, which are arranged on at least one surface of the transparent substrate and are laminated on the transparent substrate in order from the transparent substrate The steps include: a conductive layer etching step for etching the conductive layer with a first copper-soluble etching solution; and a first etching layer for etching the first blackened layer with a second etching solution containing chloride ions and water. In the blackening layer etching step, the chloride ion concentration of the second etching solution is 10% by mass or more in terms of hydrochloric acid.

According to one aspect of the present invention, a method for manufacturing a transparent conductive substrate capable of patterning a blackened layer into a desired shape can be provided.

10A, 10B‧‧‧Multilayer substrate

11, 11A, 11B, 91, 101‧‧‧ transparent substrate

121, 122‧‧‧Laminated bodies

121A, 122A‧‧‧The first blackened layer

121B, 122B‧‧‧ conductive layer

122C‧‧‧The second blackening layer

71‧‧‧metal thin wire

22, 33, 43, 51A, 51B, 711‧‧‧ conductive wiring layer

23, 34, 44, 52A, 52B, 712, 103‧‧‧ 1st blackened wiring layer

32, 42, 53A, 53B, 92, 102‧‧‧ 2nd blackened wiring layer

70‧‧‧ transparent conductive substrate

L‧‧‧ 1st Blackened Wiring Layer Projection Width

[FIG. 1A] An explanatory diagram of a multilayer substrate.

[FIG. 1B] An explanatory diagram of a multilayer substrate.

[FIG. 2A] An explanatory diagram of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 2B] An explanatory diagram of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 2C] An explanatory diagram of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 2D] An explanatory diagram of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 3A] An explanatory diagram of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 3B] An explanatory diagram of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 3C] An explanatory diagram of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 3D] An explanatory diagram of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 3E] An explanatory diagram of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 4A] An explanatory diagram of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 4B] An explanatory diagram of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 4C] An explanatory diagram of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 4D] An explanatory diagram of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 5] An explanatory diagram of a transparent conductive substrate having mesh-shaped wiring.

[Fig. 6A] A configuration example of a cross-sectional view taken along the line A-A 'in Fig. 5.

[Fig. 6B] A configuration example of a cross-sectional view taken along the line A-A 'in Fig. 5.

[FIG. 7A] An explanatory diagram of a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 7B] An explanatory diagram of a transparent conductive substrate according to an embodiment of the present invention.

[FIG. 8] An electron microscope photograph of a transparent conductive substrate including a lattice-like thin metal wire obtained in Experimental Example 4-1.

[FIG. 9] An electron microscope photograph of a conductive wiring layer portion of a transparent conductive substrate obtained in Experimental Example 7-1.

[FIG. 10] An electron microscope photograph of a conductive wiring layer portion of the transparent conductive substrate obtained in Experimental Example 7-6.

Hereinafter, one embodiment of the manufacturing method of the transparent base material of this invention is demonstrated.

The method for manufacturing a transparent conductive substrate according to this embodiment may include a patterning step of patterning a laminated body of a laminated substrate including a transparent substrate and the laminated body, and the laminated body is disposed on the transparent substrate. On at least one surface, a first blackened layer containing nickel and copper and a conductive layer containing copper are laminated in this order from the transparent substrate side.

In addition, the patterning step may have the following stages.

A conductive layer etching step in which the conductive layer is etched by a first etchant capable of dissolving copper.

A first blackened layer etching step in which the first blackened layer is etched with a second etchant containing chloride ions and water.

The chloride ion concentration of the second etching solution is 10% by mass or more in terms of hydrochloric acid.

Here, first, each member contained in the laminated body substrate used for the manufacturing method of the transparent conductive substrate of this embodiment is demonstrated below.

The transparent base material is not particularly limited, and for example, a resin substrate (resin film) or a glass substrate that can transmit visible light can be preferably used.

As the material of the resin substrate that can transmit visible light, for example, a polyamide resin, a polyethylene terephthalate (PET) resin, a polyethylene naphthalate (PEN) resin, or a cycloolefin can be preferably used Resins such as resins, polyimide (PI) resins, and polycarbonate (PC) resins. In particular, as the material of the resin substrate that can transmit visible light, polyamine, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), and COP (cycloolefin polymerization) are preferably used. Materials), polyamide, polycarbonate, etc.

The thickness of the transparent substrate is not particularly limited, and can be arbitrarily selected according to the strength, capacitance, light transmittance, and the like required as a transparent conductive substrate. The thickness of the transparent substrate may be, for example, 10 μm or more and 200 μm or less. Especially in the case of use for a touch panel, the thickness of the transparent substrate is preferably 20 μm or more and 120 μm or less, and more preferably 20 μm or more and 100 μm or less. In the case of use for a touch panel, for example, in the case where the thickness of the entire display needs to be reduced, the thickness of the transparent substrate is preferably 20 μm or more and 50 μm or less.

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

The total light transmittance of the transparent substrate can be evaluated by a method specified in JIS K 7361-1.

Next, a laminated body is demonstrated.

In the method for manufacturing a transparent conductive substrate according to this embodiment, a laminate of a laminate substrate having a "transparent substrate" and a "laminate disposed on at least one surface of a transparent substrate" is patterned ( patterning) to form a transparent conductive substrate having a desired wiring pattern.

As described above, the laminated body may have a structure in which a first blackened layer containing nickel and copper and a conductive layer containing copper are laminated in this order from the transparent substrate side from the transparent substrate side. In addition, as described later, the laminated body may further include a second blackening layer containing nickel and copper on a surface of the conductive layer opposite to the surface opposite to the first blackening layer.

The conductive layer need only contain copper (Cu), and other components are not particularly limited. It can be arbitrarily selected according to the resistance value etc. required for a transparent conductive substrate. The conductive layer is preferably, for example, Cu and Ni (nickel), Mo (molybdenum), Ta (tantalum), Ti (titanium), V (vanadium), Cr (chromium), Fe (iron), Mn (manganese), Co ( Cobalt), and a copper alloy of at least one element selected from the element group of W (tungsten), or a material containing Cu and at least one element selected from the element group. Alternatively, the conductive layer may be made of a copper layer made of copper.

The method for forming the conductive layer on the transparent substrate is not particularly limited, but in order not to reduce the light transmittance, it is preferable that no adhesive is disposed between the conductive layer and the first blackened layer. That is, the conductive layer is preferably formed directly on the upper surface of the first blackened layer.

In order to form a conductive layer directly on the upper surface of the first blackening layer, the conductive layer preferably has a conductive thin film layer. The conductive layer may include a conductive thin film layer and a conductive plating layer.

For example, a conductive thin film layer may be formed on the first blackened layer by a dry plating method, and the conductive thin film layer may be used as a conductive layer. Accordingly, the conductive layer can be formed directly on the first blackened layer without interposing an adhesive. In addition, as a dry plating method, it is preferable to use a sputtering method, a vapor deposition method, an ion plating method, etc., for example.

In addition, when the film thickness of the conductive layer is increased, the conductive thin film layer may be used as a power supply layer, and the conductive plating layer may be formed by, for example, an electroplating method, which is a type of wet plating method. Conductive layer of conductive plating. Since the conductive layer has a conductive thin film layer and a conductive plating layer, in this case, the conductive layer can be directly formed without interposing an adhesive on the first blackened layer.

The thickness of the conductive layer is not particularly limited. When the conductive layer is patterned for use as a wiring, it can be arbitrarily selected according to the magnitude of the current supplied to the wiring, the width of the wiring, and the like.

However, if the conductive layer becomes thick, when the conductive layer is etched in order to pattern the laminated body, the time required for etching is long, so side etching is likely to occur, and there are cases where it is difficult to form thin lines. Problem situation. For this reason, the thickness of the conductive layer is preferably 5 μm or less, and more preferably 3 μm or less.

In addition, in particular, from the viewpoint of reducing the resistance value of the transparent conductive substrate to sufficiently supply a current, for example, the thickness of the conductive layer is preferably 50 nm or more, preferably 60 nm or more, and more preferably 150 nm or more.

In addition, when the conductive layer has the conductive thin film layer and the conductive plating layer as described above, the total of the thickness of the conductive thin film layer and the thickness of the conductive plating layer is preferably within the above range.

The thickness of the conductive thin film layer is not particularly limited in the case where the conductive layer is formed of a conductive thin film layer or in the case of a conductive thin film layer and a conductive plating layer, but it is preferably 50 nm or more and 500 nm or less, for example.

As for the conductive layer, by patterning it into a shape corresponding to a desired wiring pattern, a conductive wiring layer, which is a wiring, can be formed. The pattern shape of the conductive wiring layer is not particularly limited, and it can be formed into a shape corresponding to a wiring pattern required for a transparent conductive substrate.

The conductive wiring layer can be formed by patterning the conductive layer as described above, for example. For this reason, when the conductive layer is composed of a conductive thin film layer, the conductive wiring layer may have a patterned conductive thin film layer. In addition, when the conductive layer has a conductive thin film layer and a conductive plating layer, the conductive wiring layer may include a patterned conductive thin film layer and a patterned conductive plating layer.

The conductive layer can reduce the resistance compared to the conventional ITO used as the material of the conductive layer of the transparent conductive substrate. Therefore, by providing wiring patterned with the conductive layer, the transparency can be reduced Resistance value of a conductive substrate.

Next, the first blackening layer will be described.

When a conductive layer and / or a conductive wiring layer are directly formed on a transparent substrate, there may be cases where the adhesion between the transparent substrate and the conductive layer and / or the conductive wiring layer is insufficient. For this reason, when a conductive layer and / or a conductive wiring layer are directly disposed on the upper surface of a transparent substrate, the conductive layer and / or the conductive wiring layer may be peeled from the transparent substrate during manufacturing or during use. In addition, there is a case where it is necessary to suppress light reflection from the surface of the conductive layer and / or the conductive wiring layer of light incident from the transparent substrate side.

Therefore, in the multilayer substrate used in the method for manufacturing a transparent conductive substrate according to this embodiment, in order to improve the adhesion between the transparent substrate and the conductive layer, the light and the light incident from the transparent substrate side are conductive. Reflection on the surface of the layer is suppressed, and a first blackening layer may be provided between the conductive layer and the transparent substrate.

The first blackening layer may contain nickel and copper, and other components are not particularly limited. However, as described above, in order to suppress light reflection on the surface of the conductive layer, it is preferable to have a color suitable for suppressing such light reflection. Therefore, the first blackening layer preferably contains nickel, copper, and nickel oxide. The first blackened layer may further contain a copper oxide. The nickel oxide and the copper oxide may exist, for example, as an oxide of a composite metal, such as an oxide of a metal containing nickel and copper.

The first blackening layer may be composed of, for example, the above-mentioned nickel, copper, nickel oxide, and copper oxide. In addition, the first blackening layer may contain an arbitrary component. As an arbitrary component, for example, a hydroxide of one or more metals selected from nickel and copper may be contained.

The method of forming the first blackened layer is not particularly limited, but it is preferable to form the film by a dry plating method. As the dry plating method, for example, a sputtering method, an ion plating method, a vapor deposition method, or the like can be preferably used. When the first blackening layer is formed by a dry method, it is more preferable to use a sputtering method from the viewpoint that it is easier to control the film thickness. In addition, as described above, the first blackening layer may further contain an oxide such as nickel oxide. Therefore, oxygen may be added to the environment when the first blackening layer is formed. In this case, it is more preferable to use a reactive sputtering method.

By adding oxygen in advance to the environment when the first blackening layer is formed, oxygen can be added to the first blackening layer to form an oxide.

When the first blackening layer is formed, oxygen is preferably added to an inert gas, for example, as an environment during dry plating. It is not particularly limited as the inert gas, but for example, argon gas can be preferably used.

By forming the first blackened layer by the dry plating method as described above, the adhesion between the transparent substrate and the first blackened layer can be improved. In addition, since the first blackening layer may contain, for example, a metal as a main component, the first blackening layer has high adhesion to the conductive layer. For this reason, by disposing the first blackening layer between the transparent substrate and the conductive layer, peeling of the conductive layer and / or the conductive wiring layer formed by the conductive layer can be suppressed.

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

When the thickness of the first blackening layer is 3 nm or more, light reflection on the surface of the conductive layer is particularly suppressed, which is preferable.

However, if the first blackened layer is too thick, the time required for film formation and / or the time required for etching during patterning of the first blackened layer becomes longer, resulting in an increase in cost. Therefore, as described above, the thickness of the first blackening layer is preferably 50 nm or less, preferably 35 nm or less, and more preferably 33 nm or less.

Next, the second blackening layer will be described.

The multilayer body included in the multilayer body substrate used in the method for manufacturing a transparent conductive substrate according to the present embodiment may further include nickel on the surface of the conductive layer opposite to the surface facing the first blackened layer. And the second blackening layer of copper.

The inclusion of the second blackening layer is preferable because it is possible to suppress light reflection on the surface of the conductive layer on which the first blackening layer is not disposed.

The second blackening layer may contain nickel and copper, and is not particularly limited to other components. As described above, in order to suppress light reflection on the surface of the conductive layer, it is preferable to have a color suitable for suppressing such light reflection. Therefore, the second blackening layer preferably contains nickel, copper, and nickel oxide. The second blackening layer may further contain a copper oxide. The nickel oxide and the copper oxide may exist, for example, as an oxide of a composite metal, such as an oxide of a metal containing nickel and copper.

The second blackening layer may be made of, for example, the above-mentioned nickel, copper, nickel oxide, and copper oxide. In addition, the second blackening layer may contain an arbitrary component. As an arbitrary component, for example, a hydroxide of one or more metals selected from nickel and copper may be contained.

The first blackening layer and the second blackening layer may have the same composition, but may have different compositions. As described above, both the first blackening layer and the second blackening layer may contain nickel and copper. In addition, both the first blackening layer and the second blackening layer may further contain nickel oxide, copper oxide, one or more hydroxides selected from nickel and copper, and the like. Therefore, the first blackening layer and the second blackening layer may contain the same components, and the content ratios may be the same or different. The components contained in the first blackening layer and the second blackening layer may be different.

The method for forming the second blackening layer is not particularly limited, but any method may be selected as long as it can form a method containing nickel and copper. However, it is preferable that the second blackening layer is formed directly without interposing an adhesive on the upper surface of another member such as a conductive layer.

As a method for forming the second blackened layer, for example, a wet plating method and / or a dry plating method can be used. In the case of a wet plating method, for example, a plating method can be used, and in the case of a dry plating method, for example, a sputtering method, an ion plating method, a vapor deposition method, or the like can be used. When a dry plating method is used, it is preferable to use a sputtering method, especially from the viewpoint of easier control of the film thickness.

In addition, as mentioned above, the 2nd blackening layer may contain oxides, such as a nickel oxide. Therefore, when the second blackening layer is formed by a dry plating method, oxygen may be added to the environment at the time of film formation. In this case, a reactive sputtering method may be more preferably used.

By adding oxygen to the environment when the second blackening layer is formed by the dry plating method in advance, oxygen can be added to the second blackening layer to form an oxide.

When the second blackening layer is formed, oxygen is preferably added to, for example, an inert gas as the environment during dry plating. It is not particularly limited as the inert gas, but for example, argon gas can be preferably used.

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

The thickness of the second blackening layer is, for example, preferably 15 nm or more, and more preferably 20 nm or more. When the thickness of the second blackening layer is 15 nm or more, light reflection on the surface of the conductive layer can be reliably suppressed, which is preferable.

In addition, the upper limit value of the thickness of the second blackening layer is not particularly limited, but if it is too thick, the time required for the etching in the patterning step becomes longer, which causes an increase in cost. Therefore, the thickness of the second blackening layer is preferably 70 nm or less, and more preferably 50 nm or less.

Here, the structure of a laminated body substrate is demonstrated using FIG. 1A and FIG. 1B. 1A and 1B are schematic cross-sectional views of a plane parallel to the laminated direction of the transparent substrate and the laminated body.

As shown in FIG. 1A, the multilayer substrate 10A may include a transparent substrate 11 and a multilayer 121 arranged on one surface 11 a of the transparent substrate 11. The laminated body 121 includes a first blackened layer 121A and a conductive layer 121B in this order from the transparent substrate 11 side.

In addition, as shown in FIG. 1B, the multilayer substrate 10B may include a transparent base material 11 and a multilayer body 122 disposed on one surface 11 a of the transparent base material 11. In the case of the laminated body substrate 10B shown in FIG. 1B, the laminated body 122 may have a structure in which a first blackened layer 122A, a conductive layer 122B, and a second blackened layer 122C are laminated in order from the transparent substrate 11 side. .

In addition, in FIG. 1A and FIG. 1B, as a laminated body substrate, the example in which the laminated body was arrange | positioned only on the one surface 11a of the transparent base material 11 was shown, However, It is not limited to this form, It can also be made A multilayer substrate of the multilayer is also arranged on the other surface 11 b of the transparent substrate 11. When the laminated body is also arranged on the other surface 11b of the transparent base material 11, the laminated body arranged above and below the transparent base material 11 may be configured as a symmetrical structure or may be configured as a different structure. For example, in the laminated body substrate 10A shown in FIG. 1A, a first blackened layer 122A may be sequentially disposed on the other surface 11b from the transparent substrate 11 side in the same manner as the laminated body 122 shown in FIG. 1B. A laminated body having a structure in which the conductive layer 122B and the second blackening layer 122C are laminated.

Next, a configuration example of each step and stage of the method for manufacturing a transparent conductive substrate according to this embodiment will be described with reference to the drawings. It should be noted that in the accompanying drawings, the same reference numerals are given to the same members, and a part of the description is omitted.

The method for manufacturing a transparent conductive substrate according to this embodiment may include patterning a multilayer body including a multilayer substrate including a “transparent substrate” and a “layer disposed on at least one surface of the transparent substrate”. step.

2A to 2D show examples of performing a patterning step using the multilayer substrate 10A shown in FIG. 1A. 2A to 2D are schematic cross-sectional views of a surface of the multilayer substrate 10A that is parallel to the stack direction of the transparent substrate 11 and the multilayer 121.

When the patterning step of the method for manufacturing a transparent conductive substrate according to the present embodiment is performed, the surface of the multilayer body 121 of the multilayer substrate 10A may be opposite to the surface 121 a of the multilayer substrate 121 opposite to the transparent substrate 11 in advance. A resist pattern 21 is disposed on the surface 121b. The resist pattern 21 may have an opening portion 21A having a shape corresponding to a portion to be removed in the patterning step of the laminated body 121.

In addition, the patterning step may include a conductive layer etching step of etching the conductive layer with a first etching solution capable of dissolving copper.

By conducting the conductive layer etching step, as shown in FIG. 2B, the conductive layer 121B of the laminated body 121 can be patterned to become the conductive wiring layer 22 that is a wiring. At this time, since the first blackening layer 121A is not substantially etched, as shown in FIG. 2B, the same shape as that before the conductive layer etching step can be maintained.

The first etching solution is not particularly limited as long as it is an etching solution capable of dissolving copper. For example, it is more preferable to use an etching solution containing sulfuric acid, hydrogen peroxide water, hydrochloric acid, copper chloride, and iron chloride. The selected one kind of aqueous solution or a mixed aqueous solution containing two or more kinds selected from the above-mentioned sulfuric acid and the like. The content of each component in the etching solution is not particularly limited. However, it is preferable to adjust the concentration of each component in the first etching solution so that the conductive layer can be selectively etched.

The etchant can be used at room temperature, but in order to improve the reactivity, it can also be used after being heated. For example, it can be used after being heated to 30 ° C or higher and 50 ° C or lower.

Next, a first blackened layer etching step of etching the first blackened layer with a second etchant containing chloride ions and water may be performed.

By performing the first blackening layer etching step, as shown in FIG. 2C, the first blackening layer 121A of the multilayer body 121 that has not been patterned and remains after the conductive layer etching step can be patterned, thereby making it possible to produce The first blackened wiring layer 23 which is a patterned first blackened layer is formed.

In addition, in the first blackening layer etching stage, by using a second etching solution containing chloride ions and water, the first blackening layer containing nickel and copper can be formed in a manner that suppresses the occurrence of residues and has a desired shape. Patterning can suppress the occurrence of side etching of the conductive wiring layer 22.

As the second etching solution, as described above, as long as it contains chloride ions and water, the concentration of each component, other components, and the like are not particularly limited. However, in order to sufficiently improve the reactivity with respect to the first blackened layer, the concentration of chloride ions in the second etching solution is preferably 10% by mass or more in terms of hydrochloric acid. The concentration of chloride ions in terms of hydrochloric acid refers to the concentration calculated when all chloride ions included in the second etching solution are contained in the state of hydrochloric acid (HCl).

The second etching solution preferably contains hydrochloric acid and water. When the second etching solution contains hydrochloric acid and water, the concentration of hydrochloric acid is not particularly limited, but it is preferably 10% by mass or more and 37% by mass or less.

This is because the reactivity with the first blackened layer can be sufficiently improved by setting the concentration of hydrochloric acid to 10% by mass or more. In addition, the concentration of hydrochloric acid that can be easily obtained is about 37% by mass or less, and from the viewpoint of cost and the like, it is preferably 37% by mass or less.

The second etching solution may contain one or more selected from, for example, ferric chloride and copper chloride.

However, if the iron ion concentration and / or copper ion concentration in the second etching solution are too high, there is a possibility that the conductive layer is corroded and / or the conductive wiring layer is formed by patterning the conductive layer. Therefore, the iron ion concentration in the second etching solution is preferably 0.2% by mass or less. The copper ion concentration in the second etching solution is preferably 0.4% by mass or less. In addition, since the 2nd etching liquid can also be set as the structure which does not contain iron ion and / or copper ion, the iron ion concentration may be 0 or more. The copper ion concentration may be 0 or more.

From the above, it can be seen that the second etching solution contains hydrochloric acid and water, the concentration of hydrochloric acid is 10% by mass or more and 37% by mass or less, and the iron ion concentration may be 0.2% by mass or less.

The second etching solution contains, for example, hydrochloric acid and water. The concentration of hydrochloric acid is 10% by mass or more and 37% by mass or less, and the copper ion concentration may be 0.4% by mass or less.

After the patterning step, as shown in FIG. 2D, by stripping and removing the resist pattern 21, a conductive wiring layer 22 having a patterned conductive layer and a blackened layer and a patterned first layer can be obtained. The transparent conductive substrate of the first blackened wiring layer 23 which is a blackened layer.

The method of peeling and removing the resist pattern 21 may be any method depending on the type of the resist used. For example, the resist pattern 21 may be immersed in an aqueous sodium hydroxide solution to swell and peel the resist pattern, thereby removing the resist pattern. .

Between the conductive layer etching step and the first blackened layer etching step of the patterning step, and after the first blackened layer etching step, for example, the laminated body substrate subjected to the patterning process may be washed (washed), etc. . As described above, by performing cleaning after each step of the patterning step, it is possible to prevent the etching solution adhering to the laminated substrate from being carried into the subsequent steps. After the resist pattern is peeled off, washing, drying, etc. may be performed as necessary. In the case of other configuration examples of the patterning step described later, similarly, the laminated body substrate subjected to the patterning process may be cleaned and the like between and / or after each step.

Moreover, the laminated body substrate used for the manufacturing method of the transparent conductive substrate of this embodiment may have a 2nd blackening layer as mentioned above. Hereinafter, a configuration example of the manufacturing method of the transparent conductive substrate of this embodiment in this case will be described using FIGS. 3A to 3E.

As described with reference to FIG. 1B, the multilayer body 122 of the multilayer substrate 10B may further include a second blackening layer containing nickel and copper on the surface of the conductive layer 122B opposite to the surface facing the first blackening layer 122A. Layer 122C.

In this case, as shown in FIG. 3A, a resist pattern 31 may be arranged in advance on a surface 122 b on the side opposite to the surface 122 a of the laminated body 122 of the laminated body substrate 10B opposite to the surface 122 a of the transparent substrate 11. The resist pattern 31 may have an opening portion 31A having a shape corresponding to a portion to be removed in the patterning step of the laminated body 122.

In addition, in the patterning step, as shown in FIG. 3B, before the conductive layer etching step, a second blackening layer etching step of etching the second blackening layer 122C with a second etching solution may be further included.

Since the second etching solution has already been described, its description is omitted here.

By performing the second blackening layer etching step, as shown in FIG. 3B, the second blackening layer 122C of the laminated body 122 can be patterned to serve as a second blackening wiring that is a patterned second blackening layer. Layer 32. Since the conductive layer 122B is not substantially etched by the second etchant, as shown in FIG. 3B, the shape substantially the same as that before the second blackening layer etching step can be maintained.

Thereafter, as in the case of the configuration example described above, a conductive layer etching step of etching the conductive layer 122B with a first etching solution capable of dissolving copper can be performed. Accordingly, as shown in FIG. 3C, the conductive layer 122B can be patterned as the conductive wiring layer 33.

Next, a first blackened layer etching step of etching the first blackened layer 122A with a second etchant containing chloride ions and water may be performed. Accordingly, as shown in FIG. 3D, a first blackened wiring layer 34 that is a patterned first blackened layer can be formed.

Since the conductive layer etching stage and the first blackened layer etching stage have already been described, their descriptions are omitted here.

After the patterning step, as shown in FIG. 3E, by peeling and removing the resist pattern 31, a pattern obtained by patterning the second blackened layer 122C, the conductive layer 122B, and the first blackened layer 122A can be obtained. A transparent conductive substrate of the second blackened wiring layer 32, the conductive wiring layer 33, and the first blackened wiring layer 34.

Hereinafter, referring to FIGS. 4A to 4D, the multilayer body of the multilayer body substrate used in the method for manufacturing a transparent conductive substrate according to the present embodiment further has a surface on the opposite side of the surface of the conductive layer opposite to the first blackened layer. In the case of containing the second blackening layer of nickel and copper, another configuration example of the method for manufacturing the transparent conductive substrate of the present embodiment will be described.

In this case, as shown in FIG. 4A, a resist pattern 41 may be disposed in advance on a surface 122 b on the opposite side of the surface 122 a of the multilayer body 122 of the multilayer substrate 10B that faces the transparent substrate 11. The resist pattern 41 may have an opening portion 41A having a shape corresponding to a portion to be removed in the patterning step of the laminated body 122.

In the conductive layer etching step of the patterning step, as shown in FIG. 4B, the conductive layer 122B and the second blackened layer 122C may be etched by using a first etchant.

As described above, the first etching solution can etch the conductive layer 122B and has low reactivity with the second blackened layer 122C. However, since the second blackening layer 122C is disposed on the conductive layer 122B, the second blackening layer 122C can be similarly etched by etching the conductive layer 122B.

For this reason, the second blackened wiring layer 42 and the conductive wiring layer 43 can be formed by performing a conductive layer etching step.

Since the first etching solution has already been described, its description is omitted here.

Thereafter, as in the case of the configuration example described above, a first blackened layer etching step of etching the first blackened layer 122A with a second etchant containing chloride ions and water may be performed. Accordingly, as shown in FIG. 4C, the first blackened wiring layer 44 can be formed.

Since the first blackening layer etching step has already been described, its description is omitted here.

After the patterning step, as shown in FIG. 4D, by peeling and removing the resist pattern 41, the second blackening layer 122C, the conductive layer 122B, and the first blackening layer 122A can be obtained. A transparent conductive substrate of the second blackened wiring layer 42, the conductive wiring layer 43, and the first blackened wiring layer 44.

In addition, although the example which performed the patterning process using the laminated body substrate in which the laminated body was arrange | positioned only on one surface of the transparent base material 11 was shown so far, it is not limited to this form. For example, the patterning step may be performed using a multilayer substrate in which a multilayer is arranged on one surface of the transparent substrate and the other surface located on the opposite side of the one surface. As for the laminated body arranged on one surface and the laminated body arranged on the other surface, the patterning step may be performed at the same time, or the patterning step may be performed separately.

The pattern formed in the patterning step of the transparent conductive substrate according to this embodiment is not particularly limited, and can be arbitrarily selected according to the application and the like. For example, when used for a touch panel, a transparent conductive substrate having mesh-shaped (lattice) wiring may be required. For this purpose, for example, the conductive layer may be patterned so as to be a grid-shaped conductive wiring layer. In addition, the purpose of providing the first blackening layer and the second blackening layer is to suppress light reflection on the surface of the conductive layer. Therefore, it is preferable to pattern these layers so that they are parallel to the surface of the transparent substrate on which the laminated body is disposed. The cross-sectional shape of the surface is the same as that of the conductive wiring layer.

A configuration example of a transparent conductive substrate having a grid-like wiring will be described. A transparent conductive substrate having a grid-like wiring can be obtained from one transparent conductive substrate, but a transparent conductive substrate having a grid-like wiring can also be obtained by combining two transparent conductive substrates.

Fig. 5 is a plan view of a transparent conductive substrate having a grid-like wiring, and Figs. 6A and 6B each show a configuration example of a cross-sectional view taken along line A-A 'in Fig. 5. In addition, a top view is a figure seen from the upper direction from the direction orthogonal to the surface on which the laminated body of the transparent base material 11 was arrange | positioned. In addition, the description of the first blackened wiring layer and the second blackened wiring layer is omitted in FIG. 5, but the first blackened wiring layer and the second blackened wiring layer are electrically conductive with the arrangement of the transparent substrate 11. The cross-sectional shape of a parallel surface of the wiring layer 51A and the like may have the same shape as that of the adjacent conductive wiring layers 51A and 51B.

In the transparent conductive substrate 50 shown in FIG. 5, a grid-shaped wiring is formed by a linear conductive wiring layer 51A parallel to the Y-axis direction and a linear conductive wiring layer 51B parallel to the X-axis direction.

In addition, as shown in FIG. 6A, a configuration in which a conductive wiring layer 51A is disposed on one surface 11 a of the transparent substrate 11 and a conductive wiring layer 51B is disposed on the other surface 11 b may be adopted. In this case, as shown in FIG. 6A, the first blackened wiring layers 52A and 52B may be disposed on the transparent substrate 11 side of the conductive wiring layers 51A and 51B. A configuration in which the second blackened wiring layers 53A and 53B are arranged on the surfaces of the conductive wiring layers 51A and 51B opposite to the transparent substrate 11 side may be employed. In addition, it is good also as a structure which does not have the 2nd blackening wiring layers 53A and 53B.

The transparent conductive substrate having the structure shown in FIGS. 5 and 6A can be manufactured, for example, by the following steps. First, two laminated substrates having a laminated body disposed on one surface of a transparent substrate are patterned by the above-mentioned patterning step to form a plurality of linear patterns parallel to each other. Next, the direction can be adjusted so that a plurality of linear wirings of the two transparent conductive substrates are in a grid shape, and the other surfaces of the transparent base material on which the laminated body is not disposed are bonded to each other. . In this case, the transparent substrate 11 of Fig. 6A has a structure in which two transparent substrates are bonded together.

In addition, the transparent conductive substrate having the structure shown in FIGS. 5 and 6A can also be manufactured by the following steps. First, a multilayer substrate in which a multilayer is arranged on one surface of the transparent substrate and the other surface opposite to the one surface is prepared. Then, the laminated body disposed on both surfaces of the transparent substrate is patterned in a patterning step so that the conductive wiring layer, which is a wiring of the laminated body, has the same configuration as that of FIGS. 5 and 6A.

In addition, as shown in FIG. 5 and FIG. 6B, a configuration in which the conductive wiring layer 51A is disposed on the transparent substrate 11A and the conductive wiring layer 51B is disposed between the transparent substrate 11A and the transparent substrate 11B may be adopted. In this case, the first blackened wiring layers 52A and 52B may be disposed on the transparent substrates 11A and 11B of the conductive wiring layers 51A and 51B. A configuration in which the second blackened wiring layers 53A and 53B are arranged on the surfaces of the conductive wiring layers 51A and 51B opposite to the transparent substrates 11A and 11B may be employed. In addition, in this case, the structure which does not have the 2nd blackening wiring layers 53A and 53B may be sufficient.

The transparent conductive substrate having the structure shown in FIGS. 5 and 6B can be manufactured, for example, by the following steps. First, two laminated substrates having a laminated body disposed on one surface of a transparent substrate are patterned by the above-mentioned patterning step to form a plurality of linear patterns parallel to each other. Then, the direction is adjusted so that a plurality of linear wirings of the two transparent conductive substrates are in a grid shape, and the other surface of the transparent base material of one transparent conductive substrate without the laminated body and the other transparent conductive material is arranged. The exposed surfaces of the patterned laminates of the substrates can be bonded together to manufacture.

In addition, FIG. 5, FIG. 6A, and FIG. 6B show the example which formed the grid-shaped wiring (wiring pattern) by combining the linear wiring which is a conductive wiring layer, but it is not limited to this form, The wiring constituting the wiring pattern may have any shape. For example, in order not to cause moiré with the image of the display, the shape of the conductive wiring layer constituting the grid-like wiring pattern may be designed as a zigzag line (a zigzag straight line), etc. Of various shapes.

The method for manufacturing a transparent conductive substrate according to this embodiment may further include any step other than the patterning step described above.

For example, before the patterning step, there may be a resist disposing step of disposing a resist on a surface opposite to the surface of the laminated body opposite to the surface of the transparent substrate, that is, the exposed surface.

The resist configuration step may also have the following stages.

A photoresist layer formation stage in which a photoresist layer is formed on the exposed surface.

According to the resist pattern to be formed, the photosensitive resist layer is exposed to ultraviolet rays, and an unexposed portion is developed, thereby forming a resist pattern at a resist pattern forming stage.

In the resist arrangement step, the resist patterns 21, 31, and 41 shown in FIGS. 2A, 3A, and 4A can be formed.

2A, first, a photosensitive resist layer may be formed on the surface 121b on the side opposite to the surface 121a of the laminated body 121 opposite to the transparent substrate 11. The method for forming the photosensitive resist layer is different depending on the type of the resist used, but a method of applying the resist 121 on the surface 121b of the multilayer body 121 to be coated may be used. A method of attaching such as a laminate method and the like.

Next, using a mask or the like, UV exposure is performed according to the resist pattern to be formed, and then, for example, by developing and removing the unexposed portion, a resist pattern can be formed.

The method of developing the photosensitive resist layer is not particularly limited, but examples thereof include a method of immersing in a developing solution such as an aqueous sodium carbonate solution.

Moreover, the manufacturing method of the transparent conductive substrate of this embodiment may have a laminated body substrate manufacturing process, for example.

The multilayer substrate manufacturing step may further include, for example, the following steps.

A first blackened layer forming step of forming a first blackened layer on at least one surface of a transparent substrate.

A conductive layer forming stage in which a conductive layer is formed on the first blackened layer.

In addition, if necessary, there may be a second blackened layer forming step of forming a second blackened layer on the conductive layer.

Examples of specific methods for forming the first blackened layer, the conductive layer, and the second blackened layer have already been described, and thus descriptions thereof are omitted here.

Further, there may be a bonding step of bonding a plurality of transparent conductive substrates after the patterning step as described above to form, for example, a grid-like wiring.

According to the manufacturing method of the transparent conductive substrate of the present embodiment described above, the first blackened layer and the conductive layer that are in contact with the transparent substrate are etched using different etching solutions, thereby suppressing the formation on the transparent substrate. Residue of the first blackened layer. In addition, the side etching of the conductive layer can be suppressed from becoming large.

For this reason, according to the manufacturing method of the transparent conductive substrate of this embodiment, a blackening layer can be patterned into a desired shape.

    [Transparent conductive substrate]    

Next, a configuration example of the transparent conductive substrate according to this embodiment will be described.

In addition, the transparent conductive substrate of this embodiment can be manufactured by the manufacturing method of the transparent conductive substrate mentioned above, for example. For this reason, the description of a part of the items already described is omitted.

In addition, as described above, the first blackened wiring layer, the conductive wiring layer, and the second blackened wiring layer can be patterned by patterning the first blackened layer, the conductive layer, and the second blackened layer, respectively, as described above. form. Therefore, the first blackened wiring layer, the conductive wiring layer, and the second blackened wiring layer may be patterned, and may have the same characteristics as those described in the method for manufacturing a transparent conductive substrate. The first blackened layer, the conductive layer, and the second blackened layer have the same configuration.

The transparent conductive substrate according to this embodiment may include a transparent base material and fine metal wires arranged on at least one surface of the transparent base material.

The thin metal wire may be a laminated body in which a first blackened wiring layer containing nickel and copper and a conductive wiring layer containing copper are laminated in this order from the transparent substrate side.

In addition, when viewed from a direction perpendicular to one surface of the transparent substrate, the protruding width of the first blackened wiring layer protruded from the conductive wiring layer may be 0.5 μm or less.

Here, a transparent conductive substrate according to this embodiment will be described first with reference to FIGS. 7A and 7B. FIG. 7A is a schematic cross-sectional view showing a transparent base material of a transparent conductive substrate according to the present embodiment and a plane parallel to the lamination direction of thin metal wires.

As shown in FIG. 7A, the transparent conductive substrate 70 of the present embodiment may have a structure in which metal thin wires 71 including a first blackened wiring layer 712 and a conductive wiring layer 711 are arranged on at least one surface 11 a of the transparent base material 11.

Here, FIG. 7B shows a case where the transparent conductive substrate 70 shown in FIG. 7A is viewed from a direction perpendicular to the one surface 11 a of the transparent substrate 11, that is, the transparent conductivity is viewed along the block arrow A in the figure. In the case of a substrate, an enlarged view of a region B surrounded by dotted lines (dashed lines).

In the method for manufacturing a transparent conductive substrate, by patterning the first blackened layer and the like as described above, the patterned first blackened wiring layer 712 and the conductive wiring layer 711 can be obtained on the transparent substrate 11. The thin metal wires 71 are laminated. However, in the process of patterning the first blackened layer and the like, a part of the first blackened layer is dissolved and remained, which may cause the first blackened wiring layer 712 to protrude from the conductive wiring layer 711. . For this reason, in the transparent conductive substrate of the present embodiment, the protruding width L of the first blackened wiring layer 712 is preferably 0.5 μm or less.

The extension width L of the first blackened wiring layer 712 is preferably set to 0, so the extension width L of the first blackened wiring layer 712 can be set to 0 or more.

The method of making the protruding width L of the first blackened wiring layer 712 within the above range is not particularly limited, but it can be set to the above range by, for example, the manufacturing method using the above-mentioned transparent conductive substrate.

7A and 7B show an example in which the thin metal wire is composed of the first blackened wiring layer 712 and the conductive wiring layer 711, but the invention is not limited to this configuration. For example, the thin metal wire may further include a second blackened wiring layer containing nickel and copper on a surface of the conductive wiring layer 711 opposite to the surface opposite to the first blackened wiring layer 712.

Although FIG. 7A shows an example in which fine metal wires are arranged on only one surface 11 a of the transparent base material 11, the present invention is not limited to this form. As described with reference to FIG. 6A and the like, a thin metal wire may be disposed on the other surface 11 b of the transparent substrate 11. In this case, the configuration of the layers included in the thin metal wires arranged on one surface 11 a of the transparent substrate 11 and the thin metal wires arranged on the other surface 11 b may be different. For example, a thin metal wire having a first blackened wiring layer and a conductive wiring layer may be arranged on one surface 11a, and a first blackened wiring layer, a conductive wiring layer, and a second blackening may be arranged on the other surface 11b. Thin metal wires on the wiring layer. However, it is preferable that the protruding width of the first blackened wiring layer included in the thin metal wire satisfies the above range.

It should be noted that, when a thin metal wire is disposed on the other surface, the projected width of the first blackened wiring layer protruding from the conductive wiring layer among the thin metal wires on the other surface side is to make the This protrusion is confirmed, and measurement can be performed by observing from the other surface side of the transparent substrate. Generally, one surface of the transparent substrate is parallel to the other surface. Therefore, when measuring the extension width of the first blackened wiring layer on the other surface side, the transparent substrate is from a direction perpendicular to the one surface of the transparent substrate. Observation can also be said to be observed from a direction perpendicular to the other surface of the transparent substrate. In addition, when thin metal wires are disposed on one surface and the other surface of the transparent substrate in this manner, the extension width of the first blackened wiring layer means that the width of the first blackened wiring layer is from the same side as the first blackened layer. The conductive wiring layer, that is, the protruding width of the adjacent conductive wiring layer.

In addition, for example, as described with reference to FIGS. 5, 6A, and 6B, a plurality of conductive wiring layers may be combined to obtain a transparent conductive substrate having grid-shaped wiring.

In addition, in the first blackened wiring layer, the cross-sectional shape of a surface parallel to the surface of the transparent substrate on which the metal thin wires are provided is preferably the same shape as the conductive wiring layer. Therefore, when a conductive substrate having a grid-like wiring is obtained by combining the conductive wiring layers, the first blackened wiring layer included in the transparent conductive substrate is also preferably formed by Combined to form a grid. When the second blackened wiring layer is provided on both surfaces of the transparent substrate, the same applies to the second blackened wiring layer.

In the transparent conductive substrate of this embodiment, by providing the first blackened wiring layer on the surface of the conductive wiring layer, it is possible to improve the adhesion between the transparent substrate and the conductive wiring layer, and to suppress the conductive wiring layer. Reflection on the surface of the first blackened wiring layer side. The degree of light reflection on the surface of the first blackened wiring layer is not particularly limited, but for example, the average value of the reflectance of light having a wavelength of 400 nm to 700 nm in the first blackened wiring layer is preferably 15% or less.

In addition, the average value of the reflectance of the light of the first blackened wiring layer having a wavelength of 400 nm or more and 700 nm or less is preferably an average value of the reflectance of light close to the transparent substrate. For this reason, the lower limit value of the average value of the reflectance of the light of the first blackened wiring layer having a wavelength of 400 nm or more and 700 nm or less can be selected according to the transparent substrate used, and is not particularly limited. For example, when a polyethylene terephthalate resin or the like is used as the transparent substrate, the average reflectance of light having a wavelength of 400 nm or more and 700 nm or less is about 6%. In addition, even if the average value of the reflectance of light having a wavelength of 400 nm or more and 700 nm or less of the first blackened wiring layer is 0, for example, the reflectance of the light with a transparent substrate such as polyethylene terephthalate resin is The difference between the average values can also be as small as about 6%. Therefore, the average value of the reflectance of the first blackened wiring layer having a wavelength of 400 nm or more and 700 nm or less may be, for example, 0 or more.

The measurement of the light reflectance of the first blackened wiring layer can be measured by irradiating the first blackened wiring layer of the transparent conductive substrate with light. Specifically, for example, when the first blackened wiring layer 712 and the conductive wiring layer 711 are sequentially laminated on one surface 11a of the transparent base material 11 as in the case of the transparent conductive substrate 70 shown in FIG. 7A, 1 The blackened wiring layer 712 is irradiated with light, and can be measured by irradiating light to the surface 712a of the first blackened wiring layer 712 through the transparent substrate 11. During the measurement, light having a wavelength of 400 nm or more and 700 nm or less can be irradiated onto the surface 712a of the first blackened wiring layer 712 of the transparent conductive substrate at a wavelength of 1 nm, for example, as described above, and the average value of the measurement is The value is an average value of the reflectance of light having a wavelength of the first blackened wiring of 400 nm or more and 700 nm or less.

The first blackened wiring layer is a layer obtained by patterning the first blackened layer as described above. Therefore, the first blackened layer may be measured and calculated in advance with an average value of the reflectance of light having a wavelength of 400 nm or more and 700 nm or less, and the value may be used as the first blackened wiring layer with a wavelength of 400 nm or more and The average value of the reflectance of light below 700 nm.

    [Example]    

Specific examples and comparative examples will be described below, but the present invention is not limited to these examples.

    [Experimental Example 1]    

As Experimental Examples 1-1 to 1-30, transparent conductive substrates were manufactured. Experimental examples 1-4 to 1-18 are examples, and experimental examples 1-1 to 1-3 and experimental examples 1-19 to 1-30 are comparative examples.

First, a 50 μm-thick polyethylene terephthalate resin (PET) film, which is a transparent substrate, was prepared for the patterning step. The first blackened layer, the conductive layer, and the first Laminated multilayer substrate of 2 blackened layers. The transparent substrate was evaluated for total light transmittance according to the method specified in JIS K 7361-1, and the result was 93%. In the following other experimental examples, the same transparent substrate was also used.

The first blackening layer has a thickness of 0.03 μm and contains nickel, copper, a nickel oxide, and a copper oxide.

As the conductive layer, a copper layer having a thickness of 0.5 μm was used. The conductive layer includes a conductive thin film layer (copper thin film layer) formed by a sputtering method and a conductive plated layer (copper plating layer) formed by a plating method. Hereinafter, the configuration was similarly performed in other experimental examples.

The second blackening layer has a thickness of 0.05 μm and contains nickel, copper, a nickel oxide, and a copper oxide.

Both the first blackened layer and the second blackened layer were formed into a film by a reactive sputtering method using an environment in which oxygen was added to argon. Film formation was performed similarly in other experimental examples below.

For the first blackened layer and the second blackened layer, the same laminated body substrate has the same composition, and three different laminated layers with a reflectance of 12% to 16% on the surface of the first blackened layer are prepared. Body substrate.

In addition, the measurement of the light reflectance on the surface of the first blackened layer is provided by a reflectance measuring unit provided on an ultraviolet visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV-2550). Measurements were performed.

Via the transparent substrate of the laminated substrate produced, the first blackened layer surface was irradiated with a wavelength of 400 nm or more and a wavelength of 700 nm at intervals of 1 nm under conditions of an incident angle of 5 ° and a light reception angle of 5 ° The following light was measured for the normal reflectance, and the average value was used as the reflectance. The reflectance was measured similarly in other experimental examples below. Hereinafter, the average value of the reflectance of light with a wavelength of 400 nm or more and 700 nm or less on the surface of the first blackened layer is also simply referred to as "the reflectance of the surface of the first blackened layer". In addition, there are cases in the table where only "reflectance" is described.

In addition, when the light reflectance on the surface of the first blackened layer is 12% to 16%, among the nickel components contained in the first blackened layer and the second blackened layer, metallic nickel, nickel oxide, or hydroxide The content ratio of nickel is shown in Table 1. The values of 12% and 16% reflectance shown in Table 1 are based on the analysis results of XPS (X-ray Photoelectron Spectroscopy) when the reflectance is 14%, and the first blackening layer is considered. And the amount of oxygen supplied during film formation of the second blackened layer.

In Table 1, for example, the case where the reflectance is 12% means that, for the first blackened layer and the second blackened layer, 50.5% by mass of the nickel component is in the form of metallic nickel, and 49.5% by mass is nickel oxide. (In the form of nickel hydroxide, if applicable).

After the prepared multilayer substrate was cut to an arbitrary size, a resist placement step was performed. Specifically, a photosensitive resist (manufactured by Asahi Kasei Corporation, product name: AQ-1F59) was attached to the surface of the second blackening layer by a lamination method, thereby forming a photosensitive resist layer (photosensitive resist Agent layer formation stage). Thereafter, by exposing the photosensitive resist layer to ultraviolet light and developing the unexposed portion, a resist pattern in a grid pattern was formed (resistor pattern formation stage). In addition, in the resist pattern, the interval between adjacent lines was 0.1 mm, and the width of the lines (resistor width) was 13 μm.

The following patterning step was performed with respect to a multilayer substrate in which a resist pattern was formed on the surface of the second blackening layer. In addition, the laminated body substrate was also cleaned between each step.

As the first etching solution, a ferric chloride solution having a concentration of 25% by mass and a temperature of 30 ° C was prepared. Next, the prepared multilayer substrate was immersed in the first etching solution for 10 seconds, and thus the conductive layer and the second blackened layer were etched (conductive layer etching stage).

Thereafter, as the second etching solution, an aqueous hydrochloric acid solution having a concentration of 5% to 37% by mass, an aqueous solution of nitric acid having a concentration of 10% to 35% by mass, or a concentration of 10% as shown in Table 2 was prepared for each experimental example. A mass% and a 30 mass% sulfuric acid aqueous solution. The second etching solution was used at room temperature (25 ° C). In the second etching solution, the copper ion concentration and the iron ion concentration were both zero.

Next, the laminated substrate after the conductive layer etching stage was immersed in the second etching solution of each experimental example, and the time until the first blackened layer was dissolved, there was no residue on the film, and it was considered to be transparent was performed. Was measured. The evaluation results are shown in Table 2.

〔Table 2〕

From the results shown in Table 2, it was confirmed that, by using a hydrochloric acid aqueous solution containing chloride ions and water and having a chloride ion concentration of 10% by mass or more in terms of hydrochloric acid as the second etching solution, it was possible to reduce ) The first blackened layer is etched for 180 seconds. That is, it was confirmed that the residue of the first blackened layer on the transparent substrate can be suppressed, and the first blackened layer, the conductive layer, and the second blackened layer can be patterned into a desired shape.

It should be noted that the obtained transparent conductive substrate was observed with an SEM (Scanning Electron Microscope, manufactured by Japan Electronics Co., Ltd., Model: JSM-6360LV), and it was confirmed that no matter in Experimental Example 1 -4 ~ In any of Experimental Examples 1-18, the protrusion width of the first blackened wiring layer from the conductive wiring layer was all 0.5 μm or less.

On the other hand, when an aqueous solution of nitric acid and / or sulfuric acid containing no chloride ion was used as the second etching solution, it was confirmed that the first blackened layer could not be completely etched even if it exceeded 180 seconds. The residue of the first blackened layer appeared on the transparent substrate.

    [Experimental Example 2]    

As Experimental Examples 2-1 to 2-6, transparent conductive substrates were manufactured, and the influence of the copper ion concentration in the second etching solution was studied. Experimental examples 2-1 to 2-6 are examples.

First, a 50 μm-thick polyethylene terephthalate resin (PET) film, which is a transparent substrate, was prepared for the patterning step. The first blackened layer, the conductive layer, and the first Laminated multilayer substrate of 2 blackened layers.

The first blackening layer has a thickness of 0.03 μm and contains nickel, copper, a nickel oxide, and a copper oxide.

As the conductive layer, a copper layer having a thickness of 0.5 μm, which was configured in the same manner as in Experimental Example 1, was used.

The second blackening layer has a thickness of 0.05 μm and contains nickel, copper, nickel oxide, and copper oxide.

A multilayer substrate was prepared in which the first blackened layer and the second blackened layer had the same composition and the reflectance on the surface of the first blackened layer was 14%. It should be noted that the composition of the first blackened layer and the second blackened layer is the same as in the case of Experimental Example 1-5.

After the prepared multilayer substrate was cut to an arbitrary size, a resist placement step was performed. Specifically, a photosensitive resist (manufactured by Asahi Kasei Corporation, product name: AQ-1F59) was attached to the surface of the second blackened layer by a lamination method, thereby forming a photosensitive resist layer (photosensitive Resist layer formation stage). Then, by exposing the photosensitive resist layer to ultraviolet rays and developing the unexposed portions, a resist pattern in a grid pattern is formed (resistor pattern formation stage). In addition, in the resist pattern, the interval between adjacent lines was 0.1 mm, and the width of the lines (resistor width) was 13 μm.

The following patterning step was performed with respect to a multilayer substrate in which a resist pattern was formed on the surface of the second blackening layer. The multilayer substrate was also cleaned between steps.

As the second etching solution, an aqueous hydrochloric acid solution having a hydrochloric acid concentration of 25% by mass and a temperature of room temperature (25 ° C) was prepared. In addition, when the second etching solution was prepared, copper chloride was added to the above-mentioned concentration of hydrochloric acid to adjust each experimental example so that the copper ion concentration in the second etching solution was as shown in Table 3. Shown value. The iron ion concentration of the second etching solution used in this experimental example was all zero.

Next, the second blackened layer was etched by immersing the multilayer substrate in a second etching solution for 30 seconds (second blackened layer etching step).

Thereafter, as a first etching solution, a ferric chloride solution having a concentration of 25% by mass and a temperature of 30 ° C was prepared. Then, the laminated body substrate after the end of the second blackening layer etching step was immersed in the first etching solution for 10 seconds, thereby etching the conductive layer (conductive layer etching step).

Next, the first blackened layer was etched using the second etchant used when the second blackened layer was etched in each experimental example (first blackened layer etching step).

Thereafter, the transparent conductive substrate was obtained by immersing in a sodium hydroxide aqueous solution having a concentration of 5% by mass and a temperature of 40 ° C. for 60 seconds to swell, peel, and remove the resist pattern, followed by washing and drying.

In any of the experimental examples, no residue of the first blackened layer occurred on the transparent substrate.

With respect to the obtained transparent conductive substrate, the appearance of the conductive wiring layer was observed, and whether the conductive wiring layer was corroded was visually confirmed. The evaluation results are shown in Table 3.

In Table 3, when the wiring was formed normally, it was evaluated as A, and when a part of the wiring was seen to be thin, it was evaluated as B.

In any of Experimental Examples 2-1 to 2-6, it was confirmed that the first blackened layer, the conductive layer, and the second blackened layer can be patterned into a desired shape. However, it is also confirmed from the results shown in Table 3 that the conductive wiring layer, which is a part of the wiring obtained under the condition that the copper ion concentration in the second etching solution is about 0.5% by mass, can be seen. Thinner. From the above results, it was confirmed that the copper ion concentration in the second etching solution is preferably less than 0.5% by mass, and more preferably 0.4% by mass or less.

It should be noted that the obtained transparent conductive substrate was observed with SEM. From this, it was confirmed that in any of Experimental Example 2-1 to Experimental Example 2-6, the slave layer of the first blackened wiring layer was observed. The protruding width of each of the conductive wiring layers is 0.5 μm or less.

    [Experimental Example 3]    

As Experimental Examples 3-1 to 3-7, transparent conductive substrates were manufactured, and the influence of the iron ion concentration in the second etching solution was examined. Experimental examples 3-1 to 3-7 are examples.

First, the first blackening layer, the conductive layer, and the second A multilayer substrate in which a blackened layer is laminated.

The first blackening layer has a thickness of 0.03 μm and contains nickel, copper, a nickel oxide, and a copper oxide.

As the conductive layer, a copper layer having a thickness of 0.5 μm, which was configured in the same manner as in Experimental Example 1, was used.

The second blackening layer has a thickness of 0.05 μm and contains nickel, copper, a nickel oxide, and a copper oxide.

A multilayer substrate was prepared in which the first blackened layer and the second blackened layer had the same composition and the reflectance on the surface of the first blackened layer was 14%. It should be noted that the composition of the first blackened layer and the second blackened layer is the same as in the case of Experimental Example 1-5.

After the prepared multilayer substrate was cut to an arbitrary size, a resist placement step was performed. Specifically, a photosensitive resist (manufactured by Asahi Kasei Corporation, product name: AQ-1F59) was attached to the surface of the second blackened layer by a lamination method, thereby forming a photosensitive resist layer (photosensitive Resist layer formation stage). Next, by exposing the photosensitive resist layer to ultraviolet rays and developing the unexposed portions, a resist pattern of a grid pattern was formed (resistor pattern formation stage). In addition, in the resist pattern, the interval between adjacent lines was 0.1 mm, and the width of the lines (resistor width) was 13 μm.

The following patterning step was performed on a multilayer substrate in which a resist pattern was formed on the surface of the second blackening layer. Laminate substrate cleaning was also performed between each step.

As the second etching solution, an aqueous hydrochloric acid solution having a hydrochloric acid concentration of 25% by mass and a temperature of room temperature (25 ° C) was prepared. It should be noted that, when the second etching solution was prepared, ferric chloride was added to the above-mentioned concentration of hydrochloric acid, and each experimental example was adjusted in a range of 0 to 0.3% by mass to make the second etching solution The iron ion concentration is the value shown in Table 4. The copper ion concentration of the second etching solution used in this experimental example was all zero.

Next, the second blackened layer was etched by immersing the multilayer substrate in a second etching solution for 30 seconds (second blackened layer etching step).

Thereafter, as a first etching solution, a ferric chloride solution having a concentration of 25% by mass and a temperature of 30 ° C was prepared. Then, the laminated body substrate after the end of the second blackening layer etching step was immersed in the first etching solution for 10 seconds, thereby etching the conductive layer (conductive layer etching step).

Next, the first blackened layer was etched using the second etchant used when the second blackened layer was etched in each experimental example (first blackened layer etching step).

Thereafter, the transparent conductive substrate was obtained by immersing in a sodium hydroxide aqueous solution having a concentration of 5% by mass and a temperature of 40 ° C. for 60 seconds to swell, peel, and remove the resist pattern, followed by washing and drying.

In any of the experimental examples, no residue of the first blackened layer appeared on the transparent substrate.

With respect to the obtained transparent conductive substrate, the appearance of the conductive wiring layer was observed, and whether the conductive wiring layer was corroded was visually confirmed. The evaluation results are shown in Table 4.

In Table 4, when the wiring was formed normally, it was evaluated as A, and when a part of the wiring was seen to be thin, it was evaluated as B.

〔Table 4〕

It was confirmed that the first blackened layer, the conductive layer, and the second blackened layer can be patterned into a desired shape in any of Experimental Examples 3-1 to 3-7. However, it is also confirmed from the results shown in Table 4 that a part of the conductive wiring layer which is a wiring obtained under the condition that the iron ion concentration in the second etching solution is about 0.30% by mass can be seen. Thinner. From the above results, it was confirmed that the iron ion concentration in the second etching solution is preferably less than 0.30% by mass, and more preferably 0.20% by mass or less.

It should be noted that the obtained transparent conductive substrate was observed with an SEM, and it was confirmed that, in any of Experimental Examples 3-1 to 3-7, the slave layer of the first blackened wiring layer was observed. The protruding width of each of the conductive wiring layers is 0.5 μm or less.

    [Experimental Example 4]    

As Experimental Example 4-1 and Experimental Example 4-2, a transparent conductive substrate was manufactured. Both Experimental Example 4-1 and Experimental Example 4-2 are examples.

First, the first blackening layer, the conductive layer, and the second A multilayer substrate in which a blackened layer is laminated.

The first blackening layer has a thickness of 0.03 μm and contains nickel, copper, a nickel oxide, and a copper oxide.

As the conductive layer, a copper layer having a thickness of 0.5 μm, which was configured in the same manner as in Experimental Example 1, was used.

The second blackening layer has a thickness of 0.05 μm and contains nickel, copper, a nickel oxide, and a copper oxide.

A multilayer substrate was prepared in which the first blackened layer and the second blackened layer had the same composition and the reflectance on the surface of the first blackened layer was 14%. It should be noted that the composition of the first blackened layer and the second blackened layer is the same as in the case of Experimental Example 1-5.

After that, a resist placement step was performed. Specifically, a photosensitive resist (manufactured by Asahi Kasei Corporation, product name: AQ-1F59) was attached to the surface of the second blackened layer by a lamination method, thereby forming a photosensitive resist layer (photosensitive Resist layer formation stage).

Next, the photosensitive resist layer is exposed to ultraviolet rays through a glass mask of a specific pattern. For the glass mask used at this time, a glass mask having a resist width of 13 μm after development and a grid pattern having a side length of 100 μm was used.

Thereafter, the unexposed portion was developed by being immersed in a 1% by mass sodium carbonate aqueous solution at 30 ° C. for 60 seconds, thereby forming a resist pattern (resist pattern formation stage).

The following patterning step was performed with respect to a multilayer substrate in which a resist pattern was formed on the surface of the second blackening layer. It should be noted that, in the patterning step, the laminate substrate was also cleaned between the steps.

As the first etching solution, a ferric chloride solution having a concentration of 25% by mass and a temperature of 30C was prepared. Then, the prepared multilayer substrate was immersed in the first etching solution for 10 seconds, and thus the conductive layer and the second blackened layer were etched (conductive layer etching stage).

Next, as the second etching solution, an aqueous hydrochloric acid solution having a concentration shown in Table 5 of 20% by mass (Experimental Example 4-1) or 30% by mass (Experimental Example 4-2) was prepared for each experimental example. In addition, the 2nd etching liquid was used at room temperature (25 degreeC). Regardless of the second etching solution, the copper ion concentration and iron ion concentration are both zero.

Thereafter, the laminated body substrate after the conductive layer etching stage was finished was immersed in the second etching solution of each experimental example for 45 seconds (Experimental Example 4-1) or 20 seconds (Experimental Example 4-2). Etching of the blackened layer (first blackened layer etching step).

Next, after immersing in a sodium hydroxide aqueous solution having a concentration of 5% by mass and a temperature of 40 ° C. for 60 seconds, the resist pattern was swollen, peeled, and removed, and then washed and dried to obtain transparent conductivity. Substrate.

The obtained transparent conductive substrate was observed for the presence or absence of the residue of the first blackened layer using an optical microscope. The observation of the wiring shape (the shape of the conductive wiring layer) and the measurement of the wiring width (the width of the conductive wiring layer) were also performed with an electron microscope.

With regard to the wiring width, the wiring width of four wirings arbitrarily selected was measured, and the average value was used as the wiring width of the transparent conductive substrate.

The evaluation results are shown in Table 5. In addition, FIG. 8 shows an electron microscope photograph of a transparent conductive substrate including fine metal wires in a grid (grid) shape obtained in Experimental Example 4-1.

〔table 5〕

From the results shown in Table 5, it can be confirmed that, in Experimental Example 4-1 and Experimental Example 4-2, the residue of the first blackened layer does not exist, and the grid wiring is good without peeling and / or loss. Etching. That is, it was confirmed that the blackened layer and the conductive layer can be patterned into a desired shape.

It should be noted that the obtained transparent conductive substrate was observed with an SEM, and it was confirmed that in any of Experimental Example 4-1 and Experimental Example 4-2, the slave layer of the first blackened wiring layer was observed. The protruding width of each of the conductive wiring layers is 0.5 μm or less.

    [Experimental Example 5]    

As Experimental Example 5-1 and Experimental Example 5-2, a transparent conductive substrate was manufactured. Both Experimental Example 5-1 and Experimental Example 5-2 are examples.

In the conductive layer etching step, a copper chloride solution having a concentration of 21% by mass and a temperature of 35 ° C. was prepared as the first etching solution, and the prepared multilayer substrate was immersed in the first etching solution for 45 seconds. The conductive layer and the second blackened layer were etched.

In the first blackening layer etching stage, as the second etching solution, a hydrochloric acid concentration of 20% by mass (Experimental Example 5-1) or 30% by mass (Experimental Example 5-2) was prepared for each experimental example. ) Hydrochloric acid aqueous solution, and the immersion time was set to 20 seconds (Experimental Example 5-1) or 10 seconds (Experimental Example 5-2).

A transparent conductive substrate was produced and evaluated in the same manner as in Experimental Example 4 except for the above two points. The results are shown in Table 6.

In addition, the 2nd etching liquid was used at room temperature (25 degreeC). Regardless of the second etching solution, the copper ion concentration and iron ion concentration are both zero.

From the results shown in Table 6, it can be confirmed that, in Experimental Example 5-1 and Experimental Example 5-2, the residue of the first blackened layer does not exist, and the grid wiring is good without peeling and / or loss. Etching. That is, it was confirmed that the blackened layer and the conductive layer can be patterned into a desired shape.

It should be noted that the obtained transparent conductive substrate was observed with an SEM, and it was confirmed that in any of Experimental Example 5-1 and Experimental Example 5-2, the slave layer of the first blackened wiring layer was observed. The protruding width of each of the conductive wiring layers is 0.5 μm or less.

    [Experimental Example 6]    

A transparent conductive substrate was manufactured. Experimental Example 6 is an example.

First, as in the case of Experimental Example 4, a multilayer substrate in which a resist pattern was formed on the surface of the second blackened layer was prepared. Next, the following patterning steps were performed on the multilayer substrate.

As the second etching solution, a 20% by mass hydrochloric acid aqueous solution was prepared. In addition, the 2nd etching liquid was used at room temperature (25 degreeC). Both the copper ion concentration and the iron ion concentration of the second etching solution were zero. After that, the prepared multilayer substrate was immersed in the second etching solution for 45 seconds to perform etching of the second blackened layer (second blackened layer etching step). It should be noted that cleaning was performed after the second blackening layer was etched.

As the first etching solution, a ferric chloride solution having a concentration of 25% by mass and a temperature of 30 ° C was prepared. Next, the laminated body substrate after the second blackened layer etching step was immersed in the first etching solution for 10 seconds, thereby etching the conductive layer (conductive layer etching step). It should be noted that cleaning was performed after the conductive layer was etched.

Thereafter, the laminated body substrate subjected to the conductive layer etching step was immersed in the second etching solution for 45 seconds, whereby the first blackened layer was etched (first blackened layer etching step). It should be noted that cleaning was performed after the first blackened layer was etched.

Next, after immersing in a sodium hydroxide aqueous solution having a concentration of 5% by mass and a temperature of 40 ° C. for 60 seconds, the resist pattern was swollen, peeled and removed, and then washed and dried to obtain transparent conductivity Substrate.

The obtained transparent conductive substrate was evaluated in the same manner as in Experimental Example 4.

The evaluation results are shown in Table 7.

From the results shown in Table 7, it was confirmed that, in this experimental example, no residue of the first blackened layer was present, and good etching of the grid wiring without peeling and / or loss was performed. That is, it was confirmed that the blackened layer and the conductive layer can be patterned into a desired shape.

It should be noted that the obtained transparent conductive substrate was observed by SEM, and it was confirmed that in Experimental Example 6, the protruding width of the first blackened wiring layer from the conductive wiring layer was also 0.5 μm or less.

    [Experimental Example 7]    

As Experimental Examples 7-1 to 7-6, transparent conductive substrates were manufactured. Experimental examples 7-1 to 7-3 are examples, and experimental examples 7-4 to 7-6 are comparative examples.

First, except that the film formation conditions of the blackened layer are adjusted so that the film thicknesses of the first blackened layer and the second blackened layer, and the reflectance of the surface of the first blackened layer are desired values, In Experimental Example 1, the first blackened layer and the conductive layer were sequentially prepared on the one surface of a transparent substrate, namely, a polyethylene terephthalate resin (PET) film having a thickness of 50 μm, for the patterning step. And a second blackened layer on which a laminated body substrate is laminated.

The first blackening layer has a thickness of 0.02 μm and contains nickel, copper, a nickel oxide, and a copper oxide.

As the conductive layer, a copper layer having a thickness of 0.5 μm was used. The conductive layer includes a conductive thin film layer (copper thin film layer) formed by a sputtering method and a conductive plating layer (copper plating layer) formed by a plating method.

The second blackening layer has a thickness of 0.02 μm and contains nickel, copper, a nickel oxide, and a copper oxide.

Both the first blackened layer and the second blackened layer were formed using an environment in which oxygen was added to argon, and were formed by a reactive sputtering method.

For the first blackened layer and the second blackened layer, the same multilayer substrate was prepared with the same composition, and the reflectance of the surface of the first blackened layer was 10%, 14%, and 20%. Laminated substrate. It should be noted that, as shown in Table 8, in Example 7-1 and Example 7-4, a multilayer substrate having a reflectance of 10% on the surface of the first blackened layer was used. In Examples 7-2 and In Experimental Example 7-5, a multilayer substrate having a reflectance of 14% on the surface of the first blackened layer was used. In Experimental Examples 7-3 and 7-6, the reflectance of the surface of the first blackened layer was used. 20% laminate substrate.

For each of the first blackened layer and the second blackened layer, in order to make the surface reflectance of the first blackened layer to the above-mentioned value in each experimental example, the film formation conditions were specifically determined based on a test performed in advance. In other words, the voltage and the environment applied to the nickel-copper alloy palladium were adjusted, and a film was formed.

The reflectance on the surface of the first blackened layer refers to the average value of the reflectance of light having a wavelength of 400 nm or more and 700 nm or less on the surface of the first blackened layer, as described above.

After the prepared multilayer substrate was cut to an arbitrary size, a resist placement step was performed. Specifically, a dry film resist (manufactured by Asahi Kasei Co., Ltd., product name: ATP-053) was attached to the surface of the second blackened layer by a lamination method, thereby forming a photosensitive resist layer (photosensitive Resist layer formation stage). Next, by exposing the photosensitive resist layer to ultraviolet rays and developing the unexposed portions, a resist pattern having a plurality of linear shapes parallel to each other is formed (resistor pattern forming stage). In addition, in the resist pattern, the interval between adjacent lines was 0.1 mm, and the width of the lines (resistor width) was 16 μm.

The following patterning step was performed with respect to a multilayer substrate in which a resist pattern was formed on the surface of the second blackening layer. In addition, the laminated body substrate was cleaned between each step.

In Experimental Examples 7-1 to 7-3, a patterning step was performed under the following conditions.

As the first etching solution, a ferric chloride solution having a concentration of 25% by mass and a temperature of 30 ° C was prepared. Next, the prepared multilayer substrate was immersed in the first etching solution for 10 seconds, and thus the conductive layer and the second blackened layer were etched (conductive layer etching stage).

Thereafter, as a second etching solution, an aqueous hydrochloric acid solution having a concentration of 25% by mass and a temperature of 30 ° C was prepared. Then, the prepared multilayer substrate was immersed in the second etching solution for 20 seconds, thereby performing the etching of the first blackened layer (the first blackened layer etching step). Both the copper ion concentration and the iron ion concentration of the second etching solution were zero.

In Experimental Examples 7-4 to 7-6, a patterning step was performed under the following conditions.

As the first etching solution, a ferric chloride solution having a concentration of 25% by mass and a temperature of 30 ° C was prepared. Next, the prepared multilayer substrate was immersed in the first etching solution for 50 seconds, whereby the first blackened layer, the conductive layer, and the second blackened layer were etched.

In addition, in Experimental Example 7-4 to Experimental Example 7-6, the etching with the 2nd etching liquid was not performed.

After performing the above-mentioned patterning step in each experimental example, immersion in an aqueous sodium hydroxide solution having a concentration of 5% by mass and a temperature of 40 ° C. for 60 seconds to swell, peel, and remove the resist pattern was performed. By washing and drying, a transparent conductive substrate was obtained.

With respect to the obtained transparent conductive substrate, the maximum value of the protruding width L of the first blackened wiring layer protruding from the conductive wiring layer was evaluated using SEM.

The evaluation results are shown in Table 8. In addition, FIGS. 9 and 10 show SEM images of the periphery of the conductive wiring layer of Experimental Example 7-1 and Experimental Example 7-6, respectively.

[Table 8]

It can be confirmed that in Experimental Examples 7-1 to 7-3, the residue of the first blackened layer does not exist, and the conductive wiring layer can be etched well without peeling or loss. In addition, as shown in Table 7, it was also confirmed that in the transparent conductive substrates obtained in Experimental Examples 7-1 to 7-3, the protruding width L of the first blackened wiring layer was 0.5 μm or less. For example, as shown in FIG. 9, it was confirmed that, in the SEM image of the transparent conductive substrate of Experimental Example 7-1, only the transparent base material 91 and the second blackened wiring layer 92 were basically observed, but they were not visible. Projection from the first blackened wiring layer of the conductive wiring layer covered by the second blackened wiring layer 92.

On the other hand, it was confirmed that in Experimental Example 7-4 and Experimental Example 7-5, the first blackened layer was not etched and remained on the entire surface. In addition, it was also confirmed that, in Experimental Example 7-6, the average reflectance of the first blackened layer was high. Therefore, compared with Experimental Example 7-4 and Experimental Example 7-5, the reactivity to the etching solution was relatively low. High, can remove a part. However, as shown in FIG. 10, it was confirmed that the first blackened wiring layer 103 protruded from the conductive wiring layer covered by the second blackened wiring layer 102 disposed on the transparent substrate 101. The maximum value of the protruding width L of the first blackened wiring layer is 0.9 μm.

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

This application claims priority based on Japanese Patent Application No. 2017-105836 filed with the Japan Patent Office on May 29, 2017 and Japanese Patent Application No. 2017-143963 filed with the Japanese Patent Office on July 25, 2017, and will file Japanese Patent Application No. 2017-105836 The contents of No. and Special Will 2017-143963 are all incorporated in this application.

Claims (10)

    A method for manufacturing a transparent conductive substrate, comprising a patterning step, the patterning step patterning a laminated body of a laminated substrate, the laminated substrate comprising a transparent substrate and the laminated body, and the laminated body is arranged on the transparent base On at least one surface of the material, a first blackened layer containing nickel and copper, and a conductive layer containing copper are laminated in this order from the transparent substrate side, and the patterning step includes: A conductive layer etching step in which the conductive layer is etched; and a first blackened layer etching step in which the first blackened layer is etched by a second etchant containing chloride ions and water; The compound ion concentration is 10% by mass or more in terms of hydrochloric acid.         The method for manufacturing a transparent conductive substrate according to claim 1, wherein the layered body further includes a second black containing nickel and copper on a surface of the conductive layer opposite to a surface opposite to the first blackened layer. In the etching step of the conductive layer, the conductive layer and the second blackened layer are etched by the first etchant.         The method for manufacturing a transparent conductive substrate according to claim 1, wherein the layered body further includes a second black containing nickel and copper on a surface of the conductive layer opposite to a surface opposite to the first blackened layer. Layer, the patterning step further includes a second blackened layer etching step of etching the second blackened layer by the second etchant before the conductive layer etching step.         The method for manufacturing a transparent conductive substrate according to any one of claims 1 to 3, wherein the second etching solution contains one or more selected from ferric chloride and copper chloride.         The method for manufacturing a transparent conductive substrate according to any one of claims 1 to 4, wherein the second etching solution contains hydrochloric acid and water, the concentration of the hydrochloric acid is 10% by mass or more and 37% by mass or less, and the copper ion concentration It is 0.4% by mass or less.         The method for manufacturing a transparent conductive substrate according to any one of claims 1 to 5, wherein the second etching solution contains hydrochloric acid and water, a concentration of the hydrochloric acid is 10% by mass or more and 37% by mass or less, and an iron ion concentration It is 0.2% by mass or less.         The method for manufacturing a transparent conductive substrate according to any one of claims 1 to 6, further comprising: before the patterning step, on the opposite side of a surface of the laminated body opposite to the transparent substrate The surface is a resist disposing step of placing a resist on the exposed surface. The resist disposing step includes: a photoresist layer forming stage of forming a photoresist layer on the exposed surface; and a resist to be formed according to the resist to be formed. The resist pattern is a resist pattern forming stage in which the photosensitive resist layer is exposed to ultraviolet rays and unexposed portions are developed to form a resist pattern.         A transparent conductive substrate comprising: a transparent base material; and a thin metal wire disposed on at least one surface of the transparent base material. The thin metal wire is a first blackened wiring containing nickel and copper laminated in this order from the transparent base material side. Of the first blackened wiring layer protruding from the conductive wiring layer when viewed from a direction perpendicular to one surface of the transparent base material, and a laminate of the conductive wiring layer containing copper. It is 0.5 μm or less.         The transparent conductive substrate according to claim 8, wherein the thin metal wire further has a second blackening containing nickel and copper on a surface of the conductive wiring layer opposite to a surface opposite to the first blackened wiring layer. Wiring layer.         The transparent conductive substrate according to claim 8 or 9, wherein an average value of the reflectance of light having a wavelength of 400 nm or more and 700 nm or less of the first blackened wiring layer is 15% or less.