CN110709805A - Method for manufacturing transparent conductive substrate, and transparent conductive substrate - Google Patents

Abstract

Provided is a method for manufacturing a transparent conductive substrate, comprising: and a patterning step of patterning a laminate of a laminate substrate including a transparent base and the laminate, wherein the laminate sequentially laminates, from the transparent base side, a 1 st black layer containing nickel and copper and a conductive layer containing copper, the first black layer being disposed on at least one surface of the transparent base. Wherein the patterning step includes a conductive layer etching step of etching the conductive layer with a 1 st etching solution capable of dissolving copper; and a 1 st black layer etching step of etching the 1 st black layer by a 2 nd etching solution containing chloride ions and water. The chloride ion concentration of the 2 nd etching solution is 10 mass% or more in terms of hydrochloric acid.

Description

Method for manufacturing transparent conductive substrate, and transparent conductive substrate

Technical Field

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

Background

A capacitive touch screen (touch panel) converts positional information of an object close to a panel surface into an electrical signal by detecting a change in electrostatic capacitance caused by the object close to the panel surface. Since the transparent conductive substrate used for the capacitive touch panel is provided on the surface of the display, the wiring material of the transparent conductive substrate needs to have a low reflectance and be difficult to be visually recognized.

Therefore, as a wiring material used for the capacitive touch panel, a material having a low reflectance and being difficult to be visually recognized 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, displays having touch screens are becoming larger in size, and accordingly, there is also a demand for larger areas of conductive substrates such as transparent conductive films for touch screens. However, ITO has a high resistance value and a long wiring length, which causes deterioration (degradation) of signals, and thus 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 the metal used as the material of the metal wiring has metallic luster, there is a problem that visibility of the display is deteriorated due to reflection.

Therefore, a transparent conductive substrate in which a blackened layer for suppressing light reflection on the surface of a conductive layer is formed on the conductive layer using a metal material on a transparent base material, and then the conductive layer and the blackened layer are patterned has been studied as a transparent conductive substrate in which a blackened layer is formed on the surface of a metal wiring.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese laid-open patent application No. 2003-151358

[ patent document 2] Japanese patent application laid-open No. 2011-Ach 018194

[ patent document 3] Japanese laid-open patent publication No. 2013-069261

Disclosure of Invention

[ problems to be solved by the invention ]

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 which can suppress light reflection particularly on the surface of a conductive layer using a metal material. Specifically, a transparent conductive substrate provided with a laminate in which a 1 st black layer containing nickel and copper, a conductive layer which is a layer using a metal material containing copper, and a 2 nd black layer containing nickel and copper are laminated in this order from the transparent base material side was examined.

In order to pattern a laminate substrate in which a laminate including a black layer and a conductive layer is disposed on a transparent base material to manufacture a transparent conductive substrate having a wiring pattern, a resist (resist) having an opening having a shape corresponding to a portion to be removed by etching is first disposed on a surface of the laminate. Then, an etching solution capable of etching the black layer and the conductive layer at the same time is supplied, thereby etching the laminate including the black layer and the conductive layer. After that, the photo resist was peeled off and removed, thereby producing a transparent conductive substrate having a wiring pattern. As described above, conventionally, from the viewpoint of productivity, the blackened layer and the conductive layer are etched with the same etching liquid.

However, when the blackened layer and the conductive layer are etched with one etching solution, if the blackened layer in contact with the transparent substrate is configured as described above, a portion of the blackened layer 1 is dissolved and left after etching, and thus, there is a problem that residues are easily generated.

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

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, since nickel oxide has low reactivity with an etching solution that can simultaneously etch the blackened layer and the conductive layer, for example, an etching solution such as ferric chloride, it is difficult to pattern the blackened layer into a desired shape because the suppression of reflectance causes a residue of the blackened layer to be more likely to be generated.

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

[ means for solving problems ]

In order to solve the above problem, one aspect of the present invention provides a method for manufacturing a transparent conductive substrate, including:

a patterning step of patterning a laminate substrate comprising a transparent base material and a laminate comprising a nickel/copper 1 th black layer and a copper-containing conductive layer, which are arranged on at least one surface of the transparent base material in this order from the transparent base material side,

the patterning step comprises

A conductive layer etching step of etching the conductive layer with a 1 st etching solution capable of dissolving copper; and

a 1 st black layer etching step of etching the 1 st black layer by a 2 nd etching solution containing chloride ions and water,

wherein the chloride ion concentration of the 2 nd etching solution is 10 mass% or more in terms of hydrochloric acid.

[ Effect of the invention ]

According to an aspect of the present invention, a method for manufacturing a transparent conductive substrate in which a blackened layer can be patterned into a desired shape can be provided.

Drawings

FIG. 1A is an explanatory view of a laminate substrate.

FIG. 1B is an explanatory view of a laminate substrate.

FIG. 2A is an explanatory view of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

FIG. 2B is an explanatory view of a method for manufacturing a transparent conductive substrate according to the embodiment of the present invention.

FIG. 2C is an explanatory view of a method for manufacturing a transparent conductive substrate according to the embodiment of the present invention.

Fig. 2D is an explanatory view of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

FIG. 3A is an explanatory view of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

FIG. 3B is an explanatory view of a method for manufacturing a transparent conductive substrate according to the embodiment of the present invention.

FIG. 3C is an explanatory view of a method for manufacturing a transparent conductive substrate according to the embodiment of the present invention.

Fig. 3D is an explanatory view of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

FIG. 3E is an explanatory view of a method for manufacturing a transparent conductive substrate according to the embodiment of the present invention.

FIG. 4A is an explanatory view of a method for manufacturing a transparent conductive substrate according to an embodiment of the present invention.

FIG. 4B is an explanatory view of a method for manufacturing a transparent conductive substrate according to the embodiment of the present invention.

Fig. 4C is an explanatory view of a method for manufacturing a transparent conductive substrate according to the embodiment of the present invention.

Fig. 4D is an explanatory view of a method for manufacturing a transparent conductive substrate according to the embodiment of the present invention.

FIG. 5 is an explanatory view of a transparent conductive substrate having mesh-like wiring.

FIG. 6A is a sectional view taken along line A-A' of FIG. 5.

FIG. 6B is a sectional view taken along line A-A' of FIG. 5.

FIG. 7A is an explanatory view of a transparent conductive substrate according to an embodiment of the present invention.

FIG. 7B is an explanatory view of a transparent conductive substrate according to an embodiment of the present invention.

FIG. 8 is an electron micrograph of a transparent conductive substrate containing fine metal wires in a lattice shape obtained in Experimental example 4-1.

FIG. 9 is an electron micrograph of a conductive wiring layer portion of the transparent conductive substrate obtained in Experimental example 7-1.

FIG. 10 is an electron micrograph of a conductive wiring layer portion of the transparent conductive substrate obtained in Experimental example 7-6.

Detailed Description

An embodiment of the method for producing a transparent substrate of the present invention will be described below.

The method for producing a transparent conductive substrate according to the present embodiment may include a patterning step of patterning a laminate of a laminate substrate including a transparent base and the laminate, the laminate being formed by laminating a 1 st black layer containing nickel and copper and a conductive layer containing copper in this order from the transparent base side, the first black layer being disposed on at least one surface of the transparent base.

In addition, the patterning step may also have the following steps.

Etching the conductive layer with a 1 st etching solution capable of dissolving copper.

And a 1 st black layer etching step of etching the 1 st black layer by a 2 nd etching solution containing chloride ions and water.

The chloride ion concentration of the 2 nd etching solution is 10 mass% or more in terms of hydrochloric acid.

Here, first, each member included in the laminate substrate used in the method for manufacturing a transparent conductive substrate according to the present embodiment will be described below.

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

As a 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, a cycloolefin resin, a Polyimide (PI) resin, a Polycarbonate (PC) resin, or the like can be preferably used. In particular, as a material of the resin substrate which can transmit visible light, polyamide, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), COP (cycloolefin polymer), polyamide, polycarbonate, or the like is preferably used.

The thickness of the transparent base material is not particularly limited, and may be arbitrarily selected depending on the strength, capacitance, light transmittance, and the like required for the transparent conductive substrate. The thickness of the transparent substrate may be, for example, 10 μm or more and 200 μm or less. Particularly, when the transparent substrate is used 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. When the transparent substrate is used for a touch panel application, for example, when the transparent substrate is used for an application requiring a thin thickness of the entire display, the thickness of the transparent substrate is preferably 20 μm or more and 50 μm or less.

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

The total light transmittance of the transparent substrate can be evaluated by the method defined in JIS K7361-1.

Next, the laminated body will be explained.

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

As described above, the laminate may have a structure in which the 1 st black layer containing nickel and copper and the conductive layer containing copper are sequentially laminated from the transparent base material side. As described later, the laminate may further include a 2 nd blackened layer containing nickel and copper on a surface of the conductive layer opposite to the 1 st blackened layer.

The conductive layer may contain copper (Cu), and the other components are not particularly limited. The resistance value can be arbitrarily selected according to the resistance value required for the transparent conductive substrate. The conductive layer is preferably a copper alloy of Cu and at least 1 or more element selected from the group consisting of Ni (nickel), Mo (molybdenum), Ta (tantalum), Ti (titanium), V (vanadium), Cr (chromium), Fe (iron), Mn (manganese), Co (cobalt), and W (tungsten), or a material containing Cu and at least 1 or more element selected from the group consisting of Cu and W (tungsten). Further, the conductive layer may be a copper layer made of copper.

The method for forming the conductive layer on the transparent substrate is not particularly limited, but it is preferable that an adhesive is not disposed between the conductive layer and the 1 st blackened layer so as not to decrease the transmittance of light. That is, the conductive layer is preferably formed directly on the upper surface of the 1 st blackened layer.

In order to directly form the conductive layer on the upper surface of the 1 st blackened layer, the conductive layer preferably has a conductive thin film layer. In addition, the conductive layer may also have a conductive thin film layer and a conductive plating layer.

For example, a conductive thin film layer may be formed on the 1 st black layer by a dry plating method, and the conductive thin film layer may be used as a conductive layer. Accordingly, a conductive layer can be directly formed on the 1 st blackened layer without using an adhesive. As the dry plating method, for example, a sputtering method, a vapor deposition method, an ion plating method, or the like can be preferably used.

In addition, when the 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 one of wet plating methods, thereby forming the conductive layer having the conductive thin film layer and the conductive plating layer. In this case, the conductive layer can be directly formed on the 1 st black layer without using an adhesive.

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

However, if the conductive layer is thickened, when the conductive layer is etched to pattern the laminate, a time required for etching is long, so that side etching (side etching) is likely to occur, and there is a problem that it is difficult to form a fine line or the like. 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 and sufficiently supplying the current, for example, the thickness of the conductive layer is preferably 50nm or more, preferably 60nm or more, and more preferably 150nm or more.

In the case where 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.

In both cases where the conductive layer is composed of a conductive thin film layer and a conductive plating layer, the thickness of the conductive thin film layer is not particularly limited, but is preferably 50nm or more and 500nm or less, for example.

The conductive layer is patterned into a shape corresponding to the desired wiring pattern, and thus can be a conductive wiring layer as a wiring. The pattern shape of the conductive wiring layer is not particularly limited, and may be a shape corresponding to a wiring pattern required for the transparent conductive substrate.

As for the conductive wiring layer, for example, it can be formed by patterning the conductive layer as described above. For this reason, in the case where 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, in the case where the conductive layer has a conductive thin film layer and a conductive plating layer, the conductive wiring layer may have a patterned conductive thin film layer and a patterned conductive plating layer.

Since the conductive layer can have a lower resistance value than the conventional ITO used as a material of the conductive layer of the transparent conductive substrate, the resistance value of the transparent conductive substrate can be reduced by providing a wiring formed by patterning the conductive layer.

Next, the 1 st blackened layer will be explained.

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

Therefore, in the laminate substrate used in the method for manufacturing a transparent conductive substrate according to the present embodiment, the 1 st black layer may be provided between the conductive layer and the transparent base material in order to improve the adhesion between the transparent base material and the conductive layer and suppress reflection of light incident from the transparent base material side on the surface of the conductive layer.

The 1 st blackened layer may contain nickel and copper, and other components are not particularly limited, but preferably has a color suitable for suppressing light reflection on the surface of the conductive layer in order to suppress light reflection as described above. For this reason, the 1 st blackened layer preferably contains nickel, copper, and nickel oxide. In addition, the 1 st blackened layer may further contain copper oxide. With respect to the nickel oxide and the copper oxide, for example, it may be present as an oxide of a metal on the cutting surface, as is an oxide of a metal containing nickel and copper.

The 1 st blackened layer may be formed of, for example, nickel, copper, nickel oxide, and copper oxide described above. The 1 st blackened layer may further contain an optional component. The optional component may contain, for example, a hydroxide of 1 or more metals selected from nickel and copper.

The method for forming the 1 st blackened layer is not particularly limited, but the film is preferably formed 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 1 st blackened layer is formed by a dry method, it is more preferable to use a sputtering method from the viewpoint of easier control of the film thickness. The 1 st black layer may further contain an oxide such as nickel oxide as described above. For this reason, oxygen may be added to the atmosphere (ambient gas) in the process of forming the 1 st black layer, and in this case, the reactive sputtering method is more preferably used.

By adding oxygen to the atmosphere in the process of forming the 1 st black layer in advance, oxygen can be added to the 1 st black layer to form an oxide.

When the 1 st blackened layer is formed, oxygen is preferably added to an inert gas (inert gas), for example, as an atmosphere in the dry plating. The inert gas is not particularly limited, but for example, argon gas can be preferably used.

By forming the 1 st blackened layer by the dry plating method as described above, the adhesion between the transparent substrate and the 1 st blackened layer can be improved. Further, since the 1 st blackened layer may contain, for example, a metal as a main component, the adhesion to the conductive layer is also high. Therefore, by disposing the 1 st black layer between the transparent base material 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 1 st blackened layer is not particularly limited, but is, for example, preferably 3nm or more and 50nm or less, more preferably 3nm or more and 35nm or less, and still more preferably 3nm or more and 33nm or less.

The thickness of the 1 st blackened layer is preferably 3nm or more, because light reflection on the surface of the conductive layer can be particularly suppressed.

However, if the 1 st black layer is too thick, the time required for film formation and/or the time required for etching when patterning the 1 st black layer becomes long, which leads to an increase in cost. Therefore, the thickness of the 1 st blackened layer is preferably 50nm or less, more preferably 35nm or less, and still more preferably 33nm or less, as described above.

Next, the 2 nd blackened layer will be explained.

The laminate provided in the laminate substrate used in the method for producing a transparent conductive substrate according to the present embodiment may further include a 2 nd blackened layer containing nickel and copper on a surface of the conductive layer opposite to the 1 st blackened layer.

The inclusion of the 2 nd blackened layer is preferable because light reflection from the surface of the conductive layer on which the 1 st blackened layer is not provided can be suppressed.

The 2 nd blackened layer may contain nickel and copper, and other components are not particularly limited, but preferably has a color suitable for suppressing light reflection on the surface of the conductive layer in order to suppress light reflection as described above. For this reason, the 2 nd blackened layer preferably contains nickel, copper, and nickel oxide. In addition, the 2 nd blackened layer may further contain copper oxide. With respect to the nickel oxide and the copper oxide, for example, it may be present as an oxide of a metal on the cutting surface, as is an oxide of a metal containing nickel and copper.

The 2 nd blackened layer may be formed of, for example, nickel, copper, nickel oxide, and copper oxide as described above. The 2 nd blackened layer may contain an optional component. The optional component may contain, for example, a hydroxide of 1 or more metals selected from nickel and copper.

The 1 st blackened layer and the 2 nd blackened layer may have the same composition (composition), but may also have different compositions. As described above, both the 1 st and 2 nd blackened layers may contain nickel and copper. In addition, both the 1 st and 2 nd blackened layers may further contain nickel oxide, copper oxide, 1 or more kinds of hydroxide selected from nickel and copper, and the like. For this reason, the 1 st black layer and the 2 nd black layer may contain the same components, and the content ratio thereof may be the same or different. The components contained in the 1 st blackened layer and the 2 nd blackened layer may be different from each other.

The method for forming the 2 nd blackened layer is not particularly limited, and any method may be selected as long as nickel and copper can be formed. However, the 2 nd black layer is preferably formed directly on the upper surface of another member such as a conductive layer without using an adhesive.

As a method for forming the 2 nd blackened layer, for example, a wet plating method and/or a dry plating method can be used. In the case of the wet plating method, for example, an electroplating method can be used, and in the case of the dry plating method, for example, a sputtering method, an ion plating method, an evaporation method, or the like can be used. In the case of the dry plating method, the sputtering method is preferably used, particularly from the viewpoint of easy control of the film thickness.

As described above, the 2 nd black layer may contain an oxide such as nickel oxide. Therefore, when the 2 nd blackened layer is formed by the dry plating method, oxygen may be added to the atmosphere during film formation, and in this case, the reactive sputtering method may be more preferably used.

Oxygen gas is added to the 2 nd blackened layer in advance to form an oxide by adding oxygen gas to the atmosphere in the case of forming the 2 nd blackened layer by dry plating.

When the 2 nd blackened layer is formed, oxygen is preferably added to an inert gas as an atmosphere in dry plating, for example. The inert gas is not particularly limited, but for example, argon gas can be preferably used.

The thickness of the 2 nd blackened layer is not particularly limited, and may be arbitrarily selected depending on the degree of suppression of light reflection required for the transparent conductive substrate, and the like.

The thickness of the 2 nd blackened layer is, for example, preferably 15nm or more, and more preferably 20nm or more. The thickness of the 2 nd blackened layer is preferably 15nm or more, because light reflection on the surface of the conductive layer can be reliably suppressed.

The upper limit of the thickness of the 2 nd blackened layer is not particularly limited, but if it is too thick, the time required for etching in the patterning step becomes long, which leads to an increase in cost. For this purpose, the thickness of the 2 nd blackened layer is preferably 70nm or less, and more preferably 50nm or less.

Here, the structure of the multilayer substrate will be described with reference to fig. 1A and 1B. Fig. 1A and 1B are schematic cross-sectional views of a plane parallel to the stacking direction of the transparent substrate and the laminate.

As shown in fig. 1A, the laminate substrate 10A may have a transparent base 11 and a laminate 121 disposed on one surface 11A of the transparent base 11. The laminate 121 includes a 1 st black layer 121A and a conductive layer 121B in this order from the transparent substrate 11 side.

As shown in fig. 1B, the laminate substrate 10B may have a transparent base 11 and a laminate 122 disposed on one surface 11a of the transparent base 11. In the case of the laminate substrate 10B shown in fig. 1B, the laminate 122 may have a structure in which a 1 st black layer 122A, a conductive layer 122B, and a 2 nd black layer 122C are laminated in this order from the transparent base material 11 side.

In fig. 1A and 1B, an example in which a laminate is disposed only on one surface 11A of the transparent base material 11 is shown as a laminate substrate, but the present invention is not limited to this embodiment, and a laminate substrate in which a laminate is also disposed on the other surface 11B of the transparent base material 11 may be used. In the case where the laminate is also disposed on the other surface 11b of the transparent base material 11, the laminate disposed vertically with the transparent base material 11 interposed therebetween may be configured to have a symmetrical structure or may be configured to have a different structure. For example, in the laminate substrate 10A shown in fig. 1A, a laminate having a structure in which the 1 st black layer 122A, the conductive layer 122B, and the 2 nd black layer 122C are laminated in this order from the transparent base material 11 side, similarly to the laminate 122 shown in fig. 1B, may be disposed on the other surface 11B.

Next, the steps of the method for manufacturing a transparent conductive substrate according to the present embodiment and a configuration example thereof will be described with reference to the drawings. In the attached drawings, the same components are denoted by the same reference numerals, and a part of the description is omitted.

The method for manufacturing a transparent conductive substrate according to the present embodiment may include a patterning step of patterning a laminate substrate including a transparent base material and a laminate layer disposed on at least one surface of the transparent base material, the laminate substrate including the transparent base material and the laminate layer.

Fig. 2A to 2D show an example in which a patterning step is performed using the laminate substrate 10A shown in fig. 1A. Fig. 2A to 2D are schematic cross-sectional views of the surface of the laminate substrate 10A parallel to the stacking direction of the transparent base material 11 and the laminate 121.

In the case of performing the patterning step of the method for manufacturing a transparent conductive substrate according to the present embodiment, the photoresist pattern 21 may be disposed in advance on the surface 121b opposite to the surface 121a facing the transparent base material 11 among the surfaces of the laminate 121 of the laminate substrate 10A. 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 stacked body 121.

In addition, the patterning step may have a conductive layer etching step of etching the conductive layer by a 1 st etching solution capable of dissolving copper.

By performing the conductive layer etching step, as shown in fig. 2B, the conductive layer 121B of the stacked body 121 can be patterned to become the conductive wiring layer 22 as wiring. At this time, since the 1 st blackened layer 121A is not substantially etched, it can maintain the same shape as before the conductive layer etching step as shown in fig. 2B.

The etching solution 1 is not particularly limited as long as it is an etching solution that can dissolve copper, but for example, an aqueous solution containing 1 kind selected from sulfuric acid, hydrogen peroxide water, hydrochloric acid, copper chloride, and ferric chloride, or a mixed aqueous solution containing 2 or more kinds selected from the above sulfuric acid and the like can be used more preferably. The content of each component in the etching solution is not particularly limited. However, it is preferable that the concentration of each component in the 1 st etching solution is adjusted so that the conductive layer can be selectively etched.

The etching solution can be used at room temperature, but can be used after heating it in order to improve the reactivity, for example, after heating it to 30 ℃ or more and 50 ℃ or less.

Next, a 1 st black layer etching step of etching the 1 st black layer by a 2 nd etching solution containing chloride ions and water may be performed.

By performing the 1 st blackened layer etching step, as shown in fig. 2C, the 1 st blackened layer 121A of the laminate 121 remaining without being patterned after the conductive layer etching step can be patterned, thereby making it possible to form the 1 st blackened wiring layer 23 which is a patterned 1 st blackened layer.

In addition, in the 1 st blackened layer etching step, by using the 2 nd etching solution containing chloride ions and water, the 1 st blackened layer containing nickel and copper can be patterned in a manner of suppressing the occurrence of residues and forming a desired shape, and the occurrence of side etching of the conductive wiring layer 22 can be suppressed.

The second etching solution 2 is not particularly limited in concentration of each component, other components, and the like, as long as it contains chloride ions and water as described above. However, in order to sufficiently improve the reactivity with respect to the 1 st blackened layer, the concentration of chloride ions in the 2 nd etching solution is preferably 10% by mass or more in terms of hydrochloric acid. The concentration of chloride ions in terms of hydrochloric acid is calculated assuming that all chloride ions contained in the 2 nd etching solution are contained in the state of hydrochloric acid (HCl).

The 2 nd etching solution preferably contains hydrochloric acid and water. When the 2 nd etching solution contains hydrochloric acid and water, the concentration of hydrochloric acid is not particularly limited, but is preferably 10 mass% or more and 37 mass% or less.

This is because the reactivity with the 1 st blackened layer can be sufficiently improved by setting the concentration of hydrochloric acid to 10 mass% or more. The concentration of hydrochloric acid that can be easily obtained is about 37 mass% or less, and from the viewpoint of cost and the like, 37 mass% or less is preferable.

The 2 nd etching solution may further contain, for example, 1 or more selected from ferric chloride and cupric chloride.

However, if the concentration of iron ions and/or copper ions in the 2 nd etching solution is too high, there is a possibility that the conductive layer and/or the conductive wiring layer formed by patterning the conductive layer may be corroded. For this reason, the concentration of iron ions in the 2 nd etching solution is preferably 0.2 mass% or less. The concentration of copper ions in the etching solution 2 is preferably 0.4 mass% or less. The 2 nd etching solution may be configured not to contain iron ions and/or copper ions, and therefore the iron ion concentration may be 0 or more. The copper ion concentration may be 0 or more.

As is clear from the above, the 2 nd etching solution contains hydrochloric acid and water, and the hydrochloric acid concentration may be 10 mass% or more and 37 mass% or less, and the iron ion concentration may be 0.2 mass% or less.

The 2 nd etching solution contains, for example, hydrochloric acid and water, and the hydrochloric acid concentration may be 10 mass% or more and 37 mass% or less, and the copper ion concentration may be 0.4 mass% or less.

After the patterning step, as shown in fig. 2D, the resist pattern 21 is peeled and removed, whereby a transparent conductive substrate having a conductive wiring layer 22 in which the conductive layer and the blackened layer are patterned and a 1 st blackened wiring layer 23 which is a patterned 1 st blackened layer can be obtained.

The method of peeling and removing the resist pattern 21 may be any method depending on the type of resist used, but for example, the resist pattern may be removed by immersing the resist pattern in an aqueous sodium hydroxide solution to swell and peel the resist pattern.

Between the conductive layer etching step and the 1 st black layer etching step in the patterning step, after the 1 st black layer etching step, and the like, for example, the laminate substrate subjected to the patterning treatment may be cleaned (water washing) or the like. In this way, by performing cleaning after each step of the patterning step, it is possible to prevent the etching solution adhering to the laminate substrate from being carried into the subsequent step. After the resist pattern is stripped, cleaning, drying, etc. may be performed as necessary. In the case of another configuration example of the patterning step described later, similarly, the laminate substrate subjected to the patterning treatment may be cleaned or the like between the steps and/or after the steps.

The laminate substrate used in the method for manufacturing a transparent conductive substrate according to the present embodiment may further include a 2 nd black layer as described above. A configuration example of the method for manufacturing a transparent conductive substrate according to the present embodiment in this case will be described below with reference to fig. 3A to 3E.

As described with reference to fig. 1B, the laminate 122 of the laminate substrate 10B may further include a 2 nd blackening layer 122C containing nickel and copper on the surface of the conductive layer 122B opposite to the surface opposite to the 1 st blackening layer 122A.

In this case, as shown in fig. 3A, the photoresist pattern 31 may be disposed in advance on a surface 122B opposite to a surface 122a facing the transparent base material 11 among the surfaces of the laminate 122 of the laminate substrate 10B. 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 stacked body 122.

In addition, in the patterning step, as shown in fig. 3B, before the conductive layer etching step, a 2 nd black layer etching step of etching the 2 nd black layer 122C by a 2 nd etching solution may be further provided.

Since the description of the etching solution 2 has already been given, the description thereof will be omitted here.

By performing the 2 nd blackened layer etching step, as shown in fig. 3B, the 2 nd blackened layer 122C of the laminated body 122 can be patterned to be the 2 nd blackened wiring layer 32 which is a patterned 2 nd blackened layer. Since the conductive layer 122B is not substantially etched by the 2 nd etching solution, it can maintain substantially the same shape as that before the 2 nd black layer etching step, as shown in fig. 3B.

Thereafter, similarly to the case of the above configuration example, a conductive layer etching step of etching the conductive layer 122B with a 1 st etching solution capable of dissolving copper may be performed. Accordingly, as shown in fig. 3C, the conductive layer 122B may be patterned as the conductive wiring layer 33.

Next, a 1 st black layer etching step of etching the 1 st black layer 122A with a 2 nd etching solution containing chloride ions and water may be performed. Accordingly, as shown in fig. 3D, the 1 st blackened wiring layer 34, which is a patterned 1 st blackened layer, can be formed.

Since the description has already been made with respect to the conductive layer etching step and the 1 st blackening layer etching step, the description thereof is omitted here.

After the patterning step, as shown in fig. 3E, by peeling and removing the resist pattern 31, a transparent conductive substrate having the 2 nd blackened wiring layer 32, the conductive wiring layer 33, and the 1 st blackened wiring layer 34 patterned by the 2 nd blackened layer 122C, the conductive layer 122B, and the 1 st blackened layer 122A can be obtained.

Next, another configuration example of the method for manufacturing a transparent conductive substrate according to the present embodiment in the case where the laminate of the laminate substrate used in the method for manufacturing a transparent conductive substrate according to the present embodiment further includes a 2 nd blackened layer containing nickel and copper on the surface of the conductive layer opposite to the surface facing the 1 st blackened layer will be described with reference to fig. 4A to 4D.

In this case, as shown in fig. 4A, the photoresist pattern 41 may be disposed in advance on a surface 122B opposite to a surface 122a facing the transparent base 11 among the surfaces of the laminate 122 of the laminate substrate 10B. The photoresist pattern 41 may have an opening portion 41A having a shape corresponding to a portion to be removed in the patterning step of the stacked body 122.

In addition, in the conductive layer etching step of the patterning step, as shown in fig. 4B, the conductive layer 122B and the 2 nd blackened layer 122C may be etched using the 1 st etching liquid.

The 1 st etching solution can etch the conductive layer 122B as described above, and has low reactivity with the 2 nd blackened layer 122C. However, since the 2 nd blackened layer 122C is disposed on the conductive layer 122B, the 2 nd blackened layer 122C can be etched similarly by etching the conductive layer 122B.

For this reason, by performing the conductive layer etching step, the 2 nd blackened wiring layer 42 and the conductive wiring layer 43 can be formed.

Since the description of the etching solution 1 has already been given, the description thereof will be omitted here.

Thereafter, similarly to the case of the above configuration example, a 1 st black layer etching step of etching the 1 st black layer 122A with a 2 nd etching solution containing chloride ions and water may be performed. Accordingly, as shown in fig. 4C, the 1 st blackened wiring layer 44 can be formed.

Since the 1 st black layer etching step has already been described, the description thereof will be omitted here.

After the patterning step, as shown in fig. 4D, by peeling and removing the resist pattern 41, a transparent conductive substrate having the 2 nd blackened wiring layer 42, the conductive wiring layer 43, and the 1 st blackened wiring layer 44 patterned by the 2 nd blackened layer 122C, the conductive layer 122B, and the 1 st blackened layer 122A can be obtained.

Although the patterning step has been performed using the laminate substrate in which the laminate is disposed on only one surface of the transparent base material 11, the present invention is not limited to this embodiment. For example, the patterning step may be performed using a laminate substrate in which a laminate is disposed on one surface of a transparent base material and the other surface located on the opposite side of the one surface. The patterning step may be performed simultaneously with or separately from the laminate disposed on one surface and the laminate disposed on the other surface.

The pattern formed in the patterning step of the transparent conductive substrate of the present embodiment is not particularly limited, and may be arbitrarily selected according to the application and the like. For example, when used for touch panel applications, a transparent conductive substrate having mesh-like (lattice-like) wiring may be required. For this purpose, the conductive layer may be patterned into a lattice-like conductive wiring layer, for example. In addition, since the purpose of providing the 1 st and 2 nd black layers is to suppress light reflection on the surface of the conductive layer, it is preferable to pattern these layers so that the cross-sectional shape of the surface parallel to the surface of the transparent base on which the laminate is disposed is the same as the shape of the conductive wiring layer.

An example of the structure of a transparent conductive substrate having mesh-like wiring will be described. The transparent conductive substrate having the mesh-like wiring can be obtained by 1 transparent conductive substrate, but the transparent conductive substrate having the mesh-like wiring can also be obtained by combining 2 transparent conductive substrates.

Fig. 5 is a plan view of a transparent conductive substrate having mesh-like wiring, and fig. 6A and 6B are structural examples of cross-sectional views taken along line a-a' of fig. 5. The plan view is a view seen from above in a direction perpendicular to the surface of the transparent substrate 11 on which the laminate is disposed. Note that, although the 1 st blackened wiring layer and the 2 nd blackened wiring layer are not illustrated in fig. 5, the cross-sectional shape of the surface of the 1 st blackened wiring layer and the 2 nd blackened wiring layer parallel to the surface of the transparent substrate 11 on which the conductive wiring layer 51A and the like are disposed may have the same shape as the adjacent conductive wiring layers 51A and 51B.

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

As shown in fig. 6A, the conductive wiring layer 51A may be disposed on one surface 11A of the transparent base material 11, and the conductive wiring layer 51B may be disposed on the other surface 11B. In this case, as shown in fig. 6A, the 1 st blackened wiring layers 52A, 52B may be disposed on the transparent substrate 11 side of the conductive wiring layers 51A, 51B. Further, the 2 nd blackened wiring layers 53A and 53B may be arranged on the surfaces of the conductive wiring layers 51A and 51B on the side opposite to the transparent base material 11 side. Note that the 2 nd blackened wiring layers 53A and 53B may not be provided.

The transparent conductive substrate having the structure shown in fig. 5 and 6A can be manufactured, for example, by the following steps. First, the laminate was patterned by the above-described patterning step so as to have a plurality of linear patterns parallel to each other, for 2 laminate substrates each having a laminate disposed on one surface of a transparent base material. Next, the direction was adjusted so that the plurality of linear lines of the 2 transparent conductive substrates were in a grid pattern, and the other surfaces of the transparent substrates on which the laminate was not disposed were bonded to each other, whereby the production was possible. In this case, the transparent substrate 11 in fig. 6A is configured by bonding 2 transparent substrates.

In addition, the transparent conductive substrate having the structure shown in fig. 5 and 6A can be manufactured by the following steps. First, 1 laminate substrate in which a laminate is disposed on one surface of a transparent base material and the other surface opposite to the one surface is prepared. Then, the laminate disposed on both surfaces of the transparent base material is patterned by a patterning step so that the conductive wiring layer as the wiring of the laminate has the same configuration as that of fig. 5 and 6A.

As shown in fig. 5 and 6B, the conductive wiring layer 51A may be disposed on the transparent substrate 11A, and the conductive wiring layer 51B may be disposed between the transparent substrate 11A and the transparent substrate 11B. In this case, the 1 st blackened wiring layers 52A, 52B may be disposed on the transparent substrates 11A, 11B side of the conductive wiring layers 51A, 51B. Further, the 2 nd blackened wiring layers 53A and 53B may be arranged on the surfaces of the conductive wiring layers 51A and 51B on the opposite side to the transparent base materials 11A and 11B. In this case, the 2 nd blackened wiring layers 53A and 53B may not be provided.

The transparent conductive substrate having the structure shown in fig. 5 and 6B can be manufactured, for example, by the following steps. First, the laminate was patterned by the above-described patterning step so as to have a plurality of linear patterns parallel to each other, for 2 laminate substrates each having a laminate disposed on one surface of a transparent base material. Then, the direction is adjusted so that the plurality of linear lines of the 2 transparent conductive substrates are in a grid pattern, and the other surface of the transparent base material of one transparent conductive substrate on which the laminate is not disposed and the exposed surface of the patterned laminate of the other transparent conductive substrate are bonded to each other, whereby the production can be performed.

In fig. 5, 6A, and 6B, an example of forming a mesh-like wiring (wiring pattern) by combining conductive wiring layers, which are linear-shaped wirings, is shown, but the present invention is not limited to this form, and the wiring constituting the wiring pattern may have any shape. For example, the conductive wiring layer constituting the mesh-like wiring pattern may be designed in various shapes such as a zigzag line (zigzag line) so as not to generate interference fringes (moir) with an image of a display.

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

For example, before the patterning step, a resist disposing step of disposing a resist on an exposed surface opposite to the surface of the laminate opposite to the transparent substrate may be further provided.

The photoresist disposing step may further have the following steps.

A photosensitive resist layer forming step of forming a photosensitive resist layer on the exposed surface.

And a resist pattern forming step of exposing the photosensitive resist layer to ultraviolet rays according to a resist pattern to be formed and developing an unexposed portion to form the resist pattern.

In the photoresist arrangement step, the photoresist patterns 21, 31, 41 shown in fig. 2A, 3A, 4A may be formed.

To describe with reference to fig. 2A, first, a photosensitive resist layer may be formed on a surface 121b of the laminate 121 opposite to the surface 121a facing the transparent substrate 11. The method of forming the photosensitive resist layer depends on the type of resist used, but examples thereof include a method of coating the surface 121b of the laminate 121 on which the resist is to be disposed, a method of attaching by a lamination (plating) method, and the like.

Next, ultraviolet exposure is performed using a mask or the like in accordance with a resist pattern to be formed, and then, for example, by developing and removing an unexposed portion, the resist pattern can be formed.

The method of developing the photosensitive resist layer is not particularly limited, and a method of immersing the photosensitive resist layer in a developer such as an aqueous sodium carbonate solution may be mentioned.

The method for manufacturing a transparent conductive substrate according to the present embodiment may include a laminate substrate manufacturing step, for example.

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

A 1 st blackened layer forming step of forming a 1 st blackened layer on at least one surface of the transparent substrate.

And a conductive layer forming step of forming a conductive layer on the 1 st blackened layer.

Further, a 2 nd blackening layer forming step of forming a 2 nd blackening layer on the conductive layer may be further provided as necessary.

Since the description has already been given for the example of the specific method for forming the 1 st black layer, the conductive layer, and the 2 nd black layer, the description thereof will be omitted here.

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

According to the method for manufacturing a transparent conductive substrate of the present embodiment described above, the 1 st black layer and the conductive layer in contact with the transparent base material are etched using different etching solutions, whereby the generation of the residue of the 1 st black layer on the transparent base material can be suppressed. Further, the conductive layer can be suppressed from being undercut to be large.

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

[ transparent conductive substrate ]

Next, a description will be given of a configuration example of the transparent conductive substrate of the present embodiment.

The transparent conductive substrate of the present embodiment can be manufactured by the above-described method for manufacturing a transparent conductive substrate, for example. For this reason, a part of the description of the matters already described is omitted.

The 1 st blackened wiring layer, the conductive wiring layer, and the 2 nd blackened wiring layer, which will be described below, can be formed by patterning the 1 st blackened layer, the conductive layer, and the 2 nd blackened layer, respectively, as described above. Therefore, the 1 st blackened wiring layer, the conductive wiring layer, and the 2 nd blackened wiring layer may have the same configurations as the 1 st blackened layer, the conductive layer, and the 2 nd blackened layer described in the method for manufacturing the transparent conductive substrate, respectively, except that patterning is performed.

The transparent conductive substrate of the present embodiment may have a transparent base material and a fine metal wire disposed on at least one surface of the transparent base material.

The thin metal wire may be a laminate in which a 1 st blackened wiring layer containing nickel and copper and a conductive wiring layer containing copper are laminated in this order from the transparent base material side.

Further, the 1 st blackened wiring layer which is protruded (protrude) from the conductive wiring layer may have a protrusion width of 0.5 μm or less when viewed in a direction perpendicular to the one surface of the transparent substrate.

Here, first, the transparent conductive substrate of the present embodiment will be described with reference to fig. 7A and 7B. Fig. 7A is a schematic cross-sectional view of the transparent base material of the transparent conductive substrate according to the present embodiment and a plane parallel to the stacking direction of the fine metal wires.

As shown in fig. 7A, the transparent conductive substrate 70 of the present embodiment may have a structure in which a thin metal wire 71 having a 1 st blackened wiring layer 712 and a conductive wiring layer 711 is disposed on at least one surface 11a of a transparent base material 11.

Here, fig. 7B shows an enlarged view of a region B surrounded by dotted lines (broken lines) when the transparent conductive substrate 70 shown in fig. 7A is viewed in a direction perpendicular to the one surface 11a of the transparent base material 11, that is, when the transparent conductive substrate is viewed along a block arrow a in the figure.

In the method for manufacturing a transparent conductive substrate, the patterning of the 1 st blackened layer or the like is performed as described above, whereby the thin metal wire 71 in which the patterned 1 st blackened wiring layer 712 and the conductive wiring layer 711 are laminated on the transparent base material 11 can be obtained. However, in the process of patterning the 1 st blackened layer and the like, a part of the 1 st blackened layer may be dissolved and left, and the 1 st blackened wiring layer 712 may protrude from the conductive wiring layer 711. For this reason, in the transparent conductive substrate of the present embodiment, the 1 st blackened wiring layer 712 preferably has an extension width L of 0.5 μm or less.

The protrusion width L of the 1 st blackened wiring layer 712 is preferably 0, so the protrusion width L of the 1 st blackened wiring layer 712 may be 0 or more.

The method of setting the protrusion width L of the 1 st blackened wiring layer 712 within the above range is not particularly limited, but may be set within the above range by using the above-described method of manufacturing a transparent conductive substrate, for example.

Fig. 7A and 7B show an example in which the thin metal wires are formed of the 1 st blackened wiring layer 712 and the conductive wiring layer 711, but the present invention is not limited to this embodiment. For example, the fine metal wire may further have a 2 nd blackened wiring layer containing nickel and copper on the surface of the conductive wiring layer 711 opposite to the surface facing the 1 st blackened wiring layer 712.

Fig. 7A shows an example in which the thin metal wires are disposed only on one surface 11a of the transparent base material 11, but the present invention is not limited to this embodiment. As described with reference to fig. 6A and the like, the thin metal wires may be disposed on the other surface 11b of the transparent substrate 11. In this case, the layers included in the thin metal wires disposed on the first surface 11a and the thin metal wires disposed on the second surface 11b of the transparent substrate 11 may have different structures. For example, a thin metal wire having a 1 st blackened wiring layer and a conductive wiring layer may be disposed on one surface 11a, and a thin metal wire having a 1 st blackened wiring layer, a conductive wiring layer, and a 2 nd blackened wiring layer may be disposed on the other surface 11 b. However, in any of the thin metal wires, the protrusion width of the 1 st blackened wiring layer included preferably satisfies the above range.

In the case where the thin metal wire is disposed on the other surface, the measurement can be performed by observing the protrusion width of the 1 st blackened wiring layer protruding from the conductive wiring layer from the thin metal wire on the other surface side so that the protrusion can be confirmed. Since the transparent substrate generally has one surface parallel to the other surface, when the protrusion width of the 1 st blackened wiring layer on the other surface side is measured, it can be said that observation in the direction perpendicular to the one surface of the transparent substrate is performed in the direction perpendicular to the other surface of the transparent substrate. In the case where the thin metal wires are disposed on both the one surface and the other surface of the transparent base material, the projecting width of the 1 st blackened wiring layer is a projecting width projecting from the conductive wiring layer located on the same side as the 1 st blackened layer, that is, the adjacent conductive wiring layer.

Further, for example, as described with reference to fig. 5, 6A, and 6B, a transparent conductive substrate having mesh-like wiring lines can also be obtained by combining a plurality of conductive wiring layers.

In the 1 st blackened wiring layer, the cross-sectional shape of the surface parallel to the surface of the transparent base material on which the fine metal wires are provided is preferably the same shape as the conductive wiring layer. Therefore, when a conductive substrate having mesh-like wiring is obtained by combining conductive wiring layers, it is also preferable that the 1 st blackened wiring layer included in the transparent conductive substrate is formed in a mesh-like shape by combination. The same applies to the 2 nd blackened wiring layer, in the case where the 2 nd blackened wiring layer is provided on both surfaces of the transparent base material.

In the transparent conductive substrate of the present embodiment, by providing the 1 st blackened wiring layer on the surface of the conductive wiring layer, the adhesion between the transparent base material and the conductive wiring layer can be improved, and the reflection on the surface of the conductive wiring layer on the 1 st blackened wiring layer side can be suppressed. The degree of light reflection on the surface of the 1 st blackened wiring layer is not particularly limited, but for example, the average value of the reflectance of light having a wavelength of 400nm or more and 700nm or less in the 1 st blackened wiring layer is preferably 15% or less.

The average value of the reflectance of light having a wavelength of 400nm or more and 700nm or less in the 1 st blackened wiring layer is preferably close to the average value of the reflectance of light of the transparent base material. Therefore, the lower limit of the average value of the reflectance of light having a wavelength of 400nm or more and 700nm or less in the 1 st blackened wiring layer can be selected depending on the transparent substrate used, and is not particularly limited. For example, when a polyethylene terephthalate resin or the like is used as the transparent base material, the average value of the reflectance of light having a wavelength of 400nm or more and 700nm or less is about 6%. Even if the average value of the reflectance of light having a wavelength of 400nm or more and 700nm or less in the 1 st blackened wiring layer is 0, the difference from the average value of the reflectance of light of a transparent substrate such as polyethylene terephthalate resin can be as small as about 6%. Therefore, the average value of the reflectance of light having a wavelength of 400nm or more and 700nm or less in the 1 st blackened wiring layer may be 0 or more, for example.

The measurement of the light reflectance of the 1 st blackened wiring layer can be performed by irradiating the 1 st blackened wiring layer of the transparent conductive substrate with light. Specifically, for example, as in the case of the transparent conductive substrate 70 shown in fig. 7A, when the 1 st blackened wiring layer 712 and the conductive wiring layer 711 are sequentially stacked on the one surface 11a of the transparent base material 11, the measurement can be performed by irradiating the surface 712a of the 1 st blackened wiring layer 712 with light through the transparent base material 11 in order to irradiate the 1 st blackened wiring layer 712 with light. In the measurement, light having a wavelength of 400nm or more and 700nm or less may be irradiated to the surface 712a of the 1 st blackened wiring layer 712 of the transparent conductive substrate at intervals of, for example, 1nm as described above, and the average value of the measured values may be defined as the average value of the reflectance of light having a wavelength of 400nm or more and 700nm or less of the 1 st blackened wiring.

The 1 st blackened wiring layer is a layer in which the 1 st blackened layer is patterned as described above. Therefore, the average value of the reflectance of light having a wavelength of 400nm or more and 700nm or less may be measured and calculated in advance for the 1 st blackened layer, and the value may be set as the average value of the reflectance of light having a wavelength of 400nm or more and 700nm or less in the 1 st blackened wiring layer.

[ examples ] A method for producing a compound

The following examples and comparative examples are given for illustrative purposes, but the present invention is not limited to these examples.

[ Experimental example 1]

Transparent conductive substrates were produced as experimental examples 1-1 to 1-30. Experimental examples 1-4E

Examples 1 to 18 are examples, and examples 1 to 3 and examples 1 to 19 to 1 to 30 are comparative examples.

First, a laminate substrate was prepared, which was used in the patterning step and in which a 1 st black layer, a conductive layer, and a 2 nd black layer were sequentially laminated on one surface of a transparent base material, which was a polyethylene terephthalate resin (PET) film having a thickness of 50 μm. The total light transmittance of the transparent substrate was evaluated according to the method defined in JIS K7361-1, and the result was 93%. In the other experimental examples below, the same transparent base material was used.

The 1 st blackened layer has a thickness of 0.03 μm and contains nickel, copper, nickel oxide, and 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 an electroplating method. The following was also constructed in the same manner in other experimental examples.

The 2 nd blackened layer had a thickness of 0.05 μm and contained nickel, copper, nickel oxide, and copper oxide.

Both the 1 st and 2 nd black layers were formed by a reactive sputtering method using an atmosphere in which oxygen was added to argon gas. The film formation was similarly performed in the following other experimental examples.

There were prepared 3 different kinds of laminate substrates in which the same laminate substrate had the same composition (composition) for the 1 st black layer and the 2 nd black layer, and the reflectance of the 1 st black layer surface was between 12% and 16%.

The light reflectance of the surface of the 1 st blackened layer was measured by providing a reflectance measuring unit on an ultraviolet-visible spectrophotometer (model UV-2550, manufactured by Shimadzu corporation).

Light having a wavelength of 400nm or more and 700nm or less was irradiated onto the surface of the 1 st blackened layer through the transparent base material of the produced laminate substrate at an incident angle of 5 ° and a light receiving angle of 5 ° at intervals of 1nm, and the normal reflectance was measured, and the average value thereof was used as the reflectance. The reflectance was measured in the same manner in the other experimental examples below. Hereinafter, the average value of the reflectance of light having a wavelength of 400nm or more and 700nm or less on the 1 st blackened layer surface will be simply referred to as "reflectance of the 1 st blackened layer surface". In addition, the table may be simply referred to as "reflectance".

Table 1 shows the content ratio of metallic nickel, nickel oxide, or nickel hydroxide in the nickel components contained in the 1 st blackened layer and the 2 nd blackened layer when the light reflectance of the 1 st blackened layer surface is 12% to 16%. The values of the reflectances shown in table 1, which are 12% and 16%, are calculated from the results of XPS (X-ray photoelectron spectroscopy) analysis in which the reflectance is 14%, taking into account the oxygen supply amounts at the time of film formation of the 1 st blackened layer and the 2 nd blackened layer.

In table 1, for example, the case where the reflectance is 12% means that, in the 1 st black layer and the 2 nd black layer, in the nickel component, 50.5 mass% of metallic nickel, 49.5 mass% of nickel oxide, and nickel hydroxide may be present.

[ Table 1]

After the prepared laminate substrate is cut into an arbitrary size, a resist arrangement step is performed. Specifically, a photosensitive resist (product name: AQ-1F 59, manufactured by Asahi Kasei corporation) was applied to the surface of the 2 nd blackened layer by a lamination method to form a photosensitive resist layer (photosensitive resist layer forming step). Then, the photosensitive resist layer is exposed to ultraviolet rays, and the unexposed portion is developed, thereby forming a resist pattern of a grid pattern (resist pattern forming step). In the resist pattern, the interval between adjacent lines was 0.1mm, and the line width (resist width) was 13 μm.

The following patterning steps were performed on the laminate substrate having the resist pattern formed on the surface of the 2 nd black layer. The laminated substrate was also cleaned between the steps.

As the 1 st etching solution, an iron chloride solution having a concentration of 25 mass% and a temperature of 30 ℃. Next, the prepared laminate substrate was immersed in the 1 st etching solution for 10 seconds, thereby etching the conductive layer and the 2 nd black layer (conductive layer etching step).

Then, as the 2 nd etching solution, a hydrochloric acid aqueous solution having a concentration of 5 to 37 mass%, a nitric acid aqueous solution having a concentration of 10 to 35 mass%, or a sulfuric acid aqueous solution having a concentration of 10 to 30 mass%, shown in table 2, was prepared for each experimental example. The No. 2 etching solution was used at room temperature (25 ℃ C.). The etching solution 2 had a copper ion concentration and an iron ion concentration of 0.

Next, the laminate substrate after the conductive layer etching step was completed was immersed in the 2 nd etching solution of each experimental example, and the time until the 1 st blackened layer was dissolved, no residue was left on the film, and the film was visually transparent was measured. The evaluation results are shown in Table 2.

[ Table 2]

From the results shown in table 2, it was confirmed that the 1 st blackened layer can be etched in a time shorter than (less than) 180 seconds by using, as the 2 nd etching solution, a hydrochloric acid aqueous solution containing chloride ions and water and having a chloride ion concentration of 10 mass% or more in terms of hydrochloric acid. That is, it was confirmed that the 1 st black layer, the conductive layer, and the 2 nd black layer can be patterned into desired shapes while suppressing the occurrence of residues of the 1 st black layer on the transparent substrate.

It was confirmed that, when the obtained transparent conductive substrate was observed by SEM (scanning electron microscope, model JSM-6360 LV, manufactured by Nippon electronics Co., Ltd.), the protrusion width of the 1 st blackened wiring layer from the conductive wiring layer was 0.5 μm or less in any of experimental examples 1-4 to 1-18.

On the other hand, when an aqueous solution of nitric acid and/or sulfuric acid containing no chloride ion was used as the 2 nd etching solution, it was confirmed that the 1 st blackened layer could not be completely etched even for more than 180 seconds, and a residue of the 1 st blackened layer appeared on the transparent substrate.

[ Experimental example 2]

As experimental examples 2-1 to 2-6, transparent conductive substrates were produced, and the influence of the copper ion concentration in the etching solution 2 was examined. Experimental example 2-1 to Experimental example 2-6 are examples.

First, a laminate substrate was prepared, which was used in the patterning step and in which a 1 st black layer, a conductive layer, and a 2 nd black layer were sequentially laminated on one surface of a transparent base material, which was a polyethylene terephthalate resin (PET) film having a thickness of 50 μm.

The 1 st blackened layer has a thickness of 0.03 μm and contains nickel, copper, nickel oxide, and copper oxide.

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

The 2 nd blackened layer had a thickness of 0.05 μm and contained nickel, copper, nickel oxide, and copper oxide.

A laminate substrate was prepared in which the 1 st blackened layer and the 2 nd blackened layer had the same composition (components) and the reflectivity of the 1 st blackened layer surface was 14%. The composition (components) of the 1 st and 2 nd black layers was the same as that in the case of experimental examples 1 to 5.

After the prepared laminate substrate is cut into an arbitrary size, a resist arrangement step is performed. Specifically, a photosensitive resist (product name: AQ-1F 59, manufactured by Asahi Kasei corporation) was laminated on the surface of the 2 nd black layer to form a photosensitive resist layer (photosensitive resist layer forming step). Then, the photosensitive resist layer is exposed to ultraviolet rays and the unexposed portion is developed, thereby forming a resist pattern of a grid pattern (resist pattern forming step). In the resist pattern, the interval between adjacent lines was 0.1mm, and the line width (resist width) was 13 μm.

The following patterning steps were performed on the laminate substrate having the resist pattern formed on the surface of the 2 nd black layer. The laminate substrate was also cleaned between the steps.

As the No. 2 etching solution, a hydrochloric acid aqueous solution having a hydrochloric acid concentration of 25% by mass and a temperature of room temperature (25 ℃ C.) was prepared. In the preparation of the 2 nd etching solution, each experimental example was adjusted by adding copper chloride to hydrochloric acid having the above concentration so that the copper ion concentration in the 2 nd etching solution became the value shown in table 3. The 2 nd etching solution used in this experimental example had an iron ion concentration of 0.

Next, the laminate substrate was immersed in the 2 nd etching solution for 30 seconds, thereby etching the 2 nd blackened layer (2 nd blackened layer etching step).

Thereafter, as the 1 st etching solution, an iron chloride solution having a concentration of 25 mass% and a temperature of 30 ℃ was prepared. Then, the laminate substrate after the 2 nd black layer etching step was immersed in the 1 st etching solution for 10 seconds, whereby the conductive layer was etched (conductive layer etching step).

Next, the 1 st blackened layer was etched using the 2 nd etching solution used in the etching of the 2 nd blackened layer in each experimental example (1 st blackened layer etching step).

Thereafter, the substrate was immersed in an aqueous solution of sodium hydroxide having a concentration of 5% by mass and a temperature of 40 ℃ for 60 seconds to swell and peel off the resist pattern and then removed, followed by cleaning and drying, thereby obtaining a transparent conductive substrate.

In any of the experimental examples, no residue of the 1 st 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 or not the conductive wiring layer was corroded was confirmed by visual observation. The evaluation results are shown in Table 3.

In table 3, when the wiring is normally formed, the evaluation is a, and when a part of the wiring is visible, the evaluation is B.

[ Table 3]

In any of experimental examples 2-1 to 2-6, it was confirmed that the 1 st black layer, the conductive layer, and the 2 nd black layer could be patterned into desired shapes. However, from the results shown in table 3, it was also confirmed that a part of the conductive wiring layer, which was the wiring obtained under the condition that the copper ion concentration in the 2 nd etching solution was about 0.5 mass%, was slightly thinned. From the above results, it was confirmed that the copper ion concentration in the 2 nd etching solution is preferably less than 0.5 mass%, and more preferably 0.4 mass% or less.

In addition, it was confirmed that the protrusion width of the 1 st blackened wiring layer from the conductive wiring layer was 0.5 μm or less in any of experimental example 2-1 to experimental example 2-6 by observing the obtained transparent conductive substrate with SEM.

[ Experimental example 3]

Transparent conductive substrates were produced as experimental examples 3-1 to 3-7, and the influence of the iron ion concentration in the etching solution 2 was examined. Experimental example 3-1 to Experimental example 3-7 are examples.

First, a laminate substrate was prepared in which a 1 st black layer, a conductive layer, and a 2 nd black layer were laminated in this order on one surface of a transparent base material, which was a polyethylene terephthalate resin (PET) film having a thickness of 50 μm, for use in the patterning step.

The 1 st blackened layer has a thickness of 0.03 μm and contains nickel, copper, nickel oxide, and copper oxide.

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

The 2 nd blackened layer had a thickness of 0.05 μm and contained nickel, copper, nickel oxide, and copper oxide.

A laminate substrate was prepared in which the 1 st blackened layer and the 2 nd blackened layer had the same composition (composition) and the reflectivity of the 1 st blackened layer surface was 14%. The composition (components) of the 1 st and 2 nd black layers was the same as that in the case of experimental examples 1 to 5.

After the prepared laminate substrate is cut into an arbitrary size, a resist arrangement step is performed. Specifically, a photosensitive resist (product name: AQ-1F 59, manufactured by Asahi Kasei corporation) was laminated on the surface of the 2 nd black layer to form a photosensitive resist layer (photosensitive resist layer forming step). Next, the photosensitive resist layer is exposed to ultraviolet light and the unexposed portion is developed, thereby forming a resist pattern of a grid pattern (resist pattern forming step). In the resist pattern, the interval between adjacent lines was 0.1mm, and the line width (resist width) was 13 μm.

The following patterning steps were performed on the laminate substrate having the resist pattern formed on the surface of the 2 nd black layer. The cleaning of the laminate substrate was also performed between the steps.

As the No. 2 etching solution, a hydrochloric acid aqueous solution having a hydrochloric acid concentration of 25% by mass and a temperature of room temperature (25 ℃ C.) was prepared. In the preparation of the 2 nd etching solution, ferric chloride was added to hydrochloric acid having the above concentration, and the concentration of iron ions in the 2 nd etching solution was adjusted to the value shown in table 4 in the range of 0 to 0.3 mass% in each experimental example. The copper ion concentration of the etching solution 2 used in this experimental example was 0.

Next, the laminate substrate was immersed in the 2 nd etching solution for 30 seconds, thereby etching the 2 nd blackened layer (2 nd blackened layer etching step).

Thereafter, as the 1 st etching solution, an iron chloride solution having a concentration of 25 mass% and a temperature of 30 ℃ was prepared. Then, the laminate substrate after the 2 nd black layer etching step was immersed in the 1 st etching solution for 10 seconds, thereby etching the conductive layer (conductive layer etching step).

Next, the 1 st blackened layer was etched using the 2 nd etching solution used in the etching of the 2 nd blackened layer in each experimental example (1 st blackened layer etching step).

Thereafter, the substrate was immersed in an aqueous solution of sodium hydroxide having a concentration of 5% by mass and a temperature of 40 ℃ for 60 seconds to swell and peel off the resist pattern and then removed, followed by cleaning and drying, thereby obtaining a transparent conductive substrate.

In any of the experimental examples, no residue of the 1 st 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 or not the conductive wiring layer was corroded was confirmed by visual observation. The evaluation results are shown in Table 4.

In table 4, when the wiring is normally formed, the evaluation is a, and when a part of the wiring is thinned, the evaluation is B.

[ Table 4]

It was confirmed that in any of experimental examples 3-1 to 3-7, the 1 st black layer, the conductive layer, and the 2 nd black layer were patterned into desired shapes. However, from the results shown in table 4, it was also confirmed that a part of the conductive wiring layer, which was obtained under the condition that the iron ion concentration in the 2 nd etching solution was about 0.30 mass%, was slightly thinned. From the above results, it was confirmed that the concentration of iron ions in the 2 nd etching solution is preferably less than 0.30 mass%, and more preferably 0.20 mass% or less.

In addition, it was confirmed that the protrusion width of the 1 st blackened wiring layer from the conductive wiring layer was 0.5 μm or less in any of experimental example 3-1 to experimental example 3-7 by observing the obtained transparent conductive substrate with SEM.

[ Experimental example 4]

As experimental example 4-1 and experimental example 4-2, transparent conductive substrates were manufactured. Experimental example 4-1 and Experimental example 4-2 are examples.

First, a laminate substrate was prepared in which a 1 st black layer, a conductive layer, and a 2 nd black layer were laminated in this order on one surface of a transparent base material, which was a polyethylene terephthalate resin (PET) film having a thickness of 50 μm, for use in the patterning step.

The 1 st blackened layer has a thickness of 0.03 μm and contains nickel, copper, nickel oxide, and copper oxide.

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

The 2 nd blackened layer had a thickness of 0.05 μm and contained nickel, copper, nickel oxide, and copper oxide.

A laminate substrate was prepared in which the 1 st blackened layer and the 2 nd blackened layer had the same composition (components) and the reflectivity of the 1 st blackened layer surface was 14%. The composition (components) of the 1 st and 2 nd black layers was the same as that in the case of experimental examples 1 to 5.

Thereafter, a photoresist placement step is performed. Specifically, a photosensitive resist (product name: AQ-1F 59, manufactured by Asahi Kasei corporation) was laminated on the surface of the 2 nd black layer to form a photosensitive resist layer (photosensitive resist layer forming step).

Next, the photosensitive resist layer is subjected to ultraviolet exposure through a glass mask having a predetermined pattern. The glass mask used in this case was one in which the photoresist width after development was 13 μm and a lattice pattern with a side length of 100 μm was formed.

Thereafter, the unexposed portion was developed by immersion in a 1 mass% and 30 ℃ aqueous solution of sodium carbonate for 60 seconds, thereby forming a resist pattern (resist pattern forming step).

The following patterning steps were performed on the laminate substrate having the resist pattern formed on the surface of the 2 nd black layer. In the patterning step, cleaning of the laminate substrate was also performed between the steps.

As the 1 st etching solution, an iron chloride solution having a concentration of 25 mass% and a temperature of 30 ℃. Then, the prepared laminate substrate was immersed in the 1 st etching solution for 10 seconds, whereby the conductive layer and the 2 nd black layer were etched (conductive layer etching step).

Next, as the No. 2 etching solution, hydrochloric acid aqueous solutions having concentrations of 20 mass% (Experimental example 4-1) or 30 mass% (Experimental example 4-2) shown in Table 5 were prepared for the respective experimental examples. The No. 2 etching solution was used at room temperature (25 ℃ C.). In any of the 2 nd etching solutions, the copper ion concentration and the iron ion concentration were 0.

Thereafter, the laminate substrate after the conductive layer etching step was immersed in the 2 nd etching solution of each experimental example for 45 seconds (experimental example 4-1) or 20 seconds (experimental example 4-2), and thereby the 1 st black layer was etched (1 st black layer etching step).

Next, the substrate was immersed in an aqueous solution of sodium hydroxide having a concentration of 5 mass% and a temperature of 40 ℃ for 60 seconds to swell and peel off the resist pattern and then removed, followed by cleaning and drying, thereby obtaining a transparent conductive substrate.

The obtained transparent conductive substrate was observed for the presence or absence of the residue of the 1 st blackened layer using an optical microscope. Further, observation of the wiring shape (conductive wiring layer shape) and measurement of the wiring width (conductive wiring layer width) were also carried out by an electron microscope.

The wiring width was measured for 4 arbitrarily selected wirings, and the average value thereof was taken as the wiring width of the transparent conductive substrate.

The evaluation results are shown in Table 5. Fig. 8 shows an electron micrograph of the transparent conductive substrate including the fine metal wires in a lattice (mesh) shape obtained in experimental example 4-1.

[ Table 5]

From the results shown in table 5, it was confirmed that in both of experimental example 4-1 and experimental example 4-2, the residue of the 1 st blackening layer was not present, and the mesh wiring was etched satisfactorily without peeling and/or chipping. That is, it was confirmed that the blackening layer and the conductive layer can be patterned into desired shapes.

In addition, it was confirmed that the protrusion width of the 1 st blackened wiring layer from the conductive wiring layer was 0.5 μm or less in any of experimental example 4-1 and experimental example 4-2 by observing the obtained transparent conductive substrate with SEM.

[ Experimental example 5]

As experimental example 5-1 and experimental example 5-2, transparent conductive substrates were manufactured. 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 mass% and a temperature of 35 ℃ was prepared as a 1 st etching solution, and the prepared laminate substrate was immersed in the 1 st etching solution for 45 seconds, thereby etching the conductive layer and the 2 nd black layer.

In the 1 st black layer etching step, as the 2 nd etching solution, hydrochloric acid aqueous solutions having hydrochloric acid concentrations of 20 mass% (experimental example 5-1) or 30 mass% (experimental example 5-2) shown in table 6 were prepared for the respective experimental examples, and the immersion time was set to 20 seconds (experimental example 5-1) or 10 seconds (experimental example 5-2).

In the same manner as in experimental example 4 except for the above two points, the transparent conductive substrate was produced and evaluated. The results are shown in Table 6.

The No. 2 etching solution was used at room temperature (25 ℃ C.). In any of the 2 nd etching solutions, the copper ion concentration and the iron ion concentration were 0.

[ Table 6]

From the results shown in table 6, it was confirmed that in both of experimental example 5-1 and experimental example 5-2, the residue of the 1 st blackening layer was not present, and the mesh wiring was etched satisfactorily without peeling and/or chipping. That is, it was confirmed that the blackening layer and the conductive layer can be patterned into desired shapes.

In addition, it was confirmed that, in both of experimental example 5-1 and experimental example 5-2, the protrusion width of the 1 st blackened wiring layer from the conductive wiring layer was 0.5 μm or less by observing the obtained transparent conductive substrate with SEM.

[ Experimental example 6]

A transparent conductive substrate was produced. Experimental example 6 is an example.

First, a laminate substrate in which a resist pattern was formed on the surface of the 2 nd black layer was prepared in the same manner as in the case of experimental example 4. Next, the following patterning step was performed on this laminate substrate.

As the 2 nd etching solution, a hydrochloric acid aqueous solution having a concentration of 20 mass% was prepared. The No. 2 etching solution was used at room temperature (25 ℃ C.). The etching solution of the 2 nd etching solution had both a copper ion concentration and an iron ion concentration of 0. Thereafter, the prepared laminate substrate was immersed in the 2 nd etching solution for 45 seconds, thereby etching the 2 nd black layer (2 nd black layer etching step). After the 2 nd black layer etching step, cleaning is performed.

As the 1 st etching solution, an iron chloride solution having a concentration of 25 mass% and a temperature of 30 ℃. Next, the laminate substrate subjected to the 2 nd black layer etching step was immersed in the 1 st etching solution for 10 seconds, thereby etching the conductive layer (conductive layer etching step). After the conductive layer etching step, cleaning is performed.

Thereafter, the laminate substrate subjected to the conductive layer etching step was immersed in the 2 nd etching solution for 45 seconds, thereby etching the 1 st black layer (1 st black layer etching step). After the 1 st black layer etching step, cleaning was performed.

Next, the substrate was immersed in an aqueous solution of sodium hydroxide having a concentration of 5 mass% and a temperature of 40 ℃ for 60 seconds to swell and peel off the resist pattern and then removed, followed by cleaning and drying, thereby obtaining a transparent conductive 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.

[ Table 7]

From the results shown in table 7, it was confirmed that in the present experimental example, the residue of the 1 st blackened layer was not present, and the mesh wiring was etched satisfactorily without peeling and/or chipping. That is, it was confirmed that the blackening layer and the conductive layer can be patterned into desired shapes.

In addition, it was confirmed that, in experimental example 6, the protrusion width of the 1 st blackened wiring layer from the conductive wiring layer was 0.5 μm or less by observing the obtained transparent conductive substrate with SEM.

[ Experimental example 7]

Transparent conductive substrates were produced as experimental examples 7-1 to 7-6. Experimental example 7-1 to 7-3 are examples, and Experimental example 7-4 to 7-6 are comparative examples.

First, a laminate substrate in which a 1 st blackened layer, a conductive layer, and a 2 nd blackened layer were laminated in this order on one surface of a transparent base material, which is a polyethylene terephthalate resin (PET) film having a thickness of 50 μm, was prepared in the same manner as in example 1, except that the film thickness of the 1 st blackened layer and the film thickness of the 2 nd blackened layer, and the reflectance of the surface of the 1 st blackened layer were adjusted to desired values.

The 1 st blackened layer has a thickness of 0.02 μm and contains nickel, copper, nickel oxide, and 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 an electroplating method.

The 2 nd blackened layer had a thickness of 0.02 μm and contained nickel, copper, nickel oxide, and copper oxide.

Both the 1 st and 2 nd black layers were formed by a reactive sputtering method using an atmosphere in which oxygen gas was added to argon gas.

3 different kinds of laminate substrates were prepared in which the same laminate substrate had the same composition (composition) for the 1 st black layer and the 2 nd black layer, and the reflectance of the 1 st black layer surface was 10%, 14%, and 20%. As shown in table 8, the laminate substrate having a reflectivity of 10% at the surface of the 1 st blackened layer was used in experimental example 7-1 and experimental example 7-4, the laminate substrate having a reflectivity of 14% at the surface of the 1 st blackened layer was used in experimental example 7-2 and experimental example 7-5, and the laminate substrate having a reflectivity of 20% at the surface of the 1 st blackened layer was used in experimental example 7-3 and experimental example 7-6.

In each of the experimental examples, in order to make the reflectance of the 1 st blackened layer surface the above value, the film formation conditions, specifically, the voltage and atmosphere applied to the nickel-copper alloy palladium were adjusted and the film formation was performed according to a test performed in advance.

The reflectance of the 1 st blackened layer surface is an average value of the reflectance of light having a wavelength of 400nm or more and 700nm or less on the 1 st blackened layer surface as described above.

After the prepared laminate substrate is cut into an arbitrary size, a resist arrangement step is performed. Specifically, a dry film resist (product name: ATP-053, manufactured by Asahi Kasei corporation) was laminated on the surface of the 2 nd blackened layer to form a photosensitive resist layer (photosensitive resist layer forming step). Next, the photosensitive resist layer is exposed to ultraviolet rays, and the unexposed portion is developed, thereby forming a resist pattern having a plurality of linear shapes parallel to each other (resist pattern forming step). In the resist pattern, the interval between adjacent lines was 0.1mm, and the line width (resist width) was 16 μm.

The following patterning steps were performed on the laminate substrate having the resist pattern formed on the surface of the 2 nd black layer. The laminated substrate is cleaned between the steps.

In each of experimental example 7-1 to 7-3, the patterning step was performed under the following conditions.

As the 1 st etching solution, an iron chloride solution having a concentration of 25 mass% and a temperature of 30 ℃. Next, the prepared laminate substrate was immersed in the 1 st etching solution for 10 seconds, thereby etching the conductive layer and the 2 nd black layer (conductive layer etching step).

Then, as the 2 nd etching solution, a hydrochloric acid aqueous solution having a concentration of 25 mass% and a temperature of 30 ℃ was prepared. Then, the prepared laminate substrate was immersed in the 2 nd etching solution for 20 seconds, thereby etching the 1 st black layer (1 st black layer etching step). The etching solution of the 2 nd etching solution had both a copper ion concentration and an iron ion concentration of 0.

In each of experimental examples 7-4 to 7-6, the patterning step was performed under the following conditions.

As the 1 st etching solution, an iron chloride solution having a concentration of 25 mass% and a temperature of 30 ℃. Next, the prepared laminate substrate was immersed in the 1 st etching solution for 50 seconds, thereby etching the 1 st black layer, the conductive layer, and the 2 nd black layer.

In examples 7-4 to 7-6, the etching by the No. 2 etching solution was not performed.

After the patterning step described above was performed in each experimental example, the substrate was immersed in an aqueous sodium hydroxide solution having a concentration of 5 mass% and a temperature of 40 ℃ for 60 seconds to swell and peel off the resist pattern and then removed, followed by cleaning and drying, thereby obtaining a transparent conductive substrate.

With respect to the obtained transparent conductive substrate, the maximum value of the protrusion width L of the 1 st blackened wiring layer protruding from the conductive wiring layer was evaluated using SEM.

The evaluation results are shown in Table 8. Further, fig. 9 and 10 show SEM images of the peripheries of the conductive wiring layers of experimental example 7-1 and experimental example 7-6, respectively.

[ Table 8]

It was confirmed that in examples 7-1 to 7-3, the residue of the 1 st blackened layer was not present, and the conductive wiring layer was etched satisfactorily without peeling and/or chipping. As shown in table 7, it was also confirmed that the 1 st blackened wiring layer had a projecting width L of 0.5 μm or less in the transparent conductive substrates obtained in experimental example 7-1 to experimental example 7-3. 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 2 nd blackened wiring layer 92 were substantially observed, and the protrusion from the 1 st blackened wiring layer of the conductive wiring layer covered with the 2 nd blackened wiring layer 92 was not observed.

On the other hand, it was confirmed that the 1 st blackened layer was not etched and remained on the entire surface in experimental examples 7-4 and 7-5. In addition, it was also confirmed that in experimental example 7-6, since the average reflectance of the 1 st blackened layer was high, the reactivity with respect to the etching solution was high and a part of the blackened layer was removed as compared with experimental examples 7-4 and 7-5. However, as shown in fig. 10, it was also confirmed that the 1 st blackened wiring layer 103 was protruded from the conductive wiring layer covered with the 2 nd blackened wiring layer 102 disposed on the transparent substrate 101, and the maximum value of the protrusion width L of the 1 st blackened wiring layer was 0.9 μm.

The method for manufacturing the transparent conductive substrate and the transparent conductive substrate have been described above by way of the embodiments and examples, but the present invention is not limited to the embodiments and examples. Various modifications and changes can be made within the scope of the invention described in the claims.

The application claims the priority of the special application 2017 plus 105836 number applied to the native patent hall on 29 th in 2017 and the special application 2017 plus 143963 applied to the native patent hall on 25 th in 7 th in 2017, and the contents of the special application 2017 plus 105836 number and the special application 2017 plus 143963 number are all cited in the international application.

[ description of symbols ]

10A, 10B laminate substrate

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

121. 122 laminated body

121A, 122A No. 1 blackened layer

121B, 122B conductive layer

122C No. 2 blackened layer

71 metallic thin wire

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

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

32. 42, 53A, 53B, 92, 102 No. 2 blackened wiring layer

70 transparent conductive substrate

L1 st blackened wiring layer protrusion width

Claims (10)

1. A method for manufacturing a transparent conductive substrate includes:

a patterning step of patterning a laminate of a laminate substrate including a transparent base and the laminate, the laminate having a 1 st black layer containing nickel and copper and a conductive layer containing copper, which are arranged on at least one surface of the transparent base, and laminated in this order from the transparent base side,

wherein the patterning step has

A conductive layer etching step of etching the conductive layer with a 1 st etching solution capable of dissolving copper; and

a 1 st black layer etching step of etching the 1 st black layer by a 2 nd etching solution containing chloride ions and water,

the chloride ion concentration of the 2 nd etching solution is 10 mass% or more in terms of hydrochloric acid.

2. The method for manufacturing a transparent conductive substrate according to claim 1,

the laminate further has a 2 nd blackened layer containing nickel and copper on a surface of the conductive layer opposite to the 1 st blackened layer,

in the conductive layer etching step, the conductive layer and the 2 nd blackened layer are etched by the 1 st etching solution.

3. The method for manufacturing a transparent conductive substrate according to claim 1,

the laminate further has a 2 nd blackened layer containing nickel and copper on a surface of the conductive layer opposite to the 1 st blackened layer,

the patterning step further includes a 2 nd blackened layer etching step of etching the 2 nd blackened layer with the 2 nd etching liquid before the conductive layer etching step.

4. The method for manufacturing a transparent conductive substrate according to any one of claims 1 to 3,

the 2 nd etching solution contains 1 or more selected from ferric chloride and cupric chloride.

5. The method for manufacturing a transparent conductive substrate according to any one of claims 1 to 4,

the 2 nd etching solution contains hydrochloric acid and water,

the concentration of hydrochloric acid is 10 to 37 mass%,

the copper ion concentration is 0.4 mass% or less.

6. The method for manufacturing a transparent conductive substrate according to any one of claims 1 to 5,

the 2 nd etching solution contains hydrochloric acid and water,

the concentration of hydrochloric acid is 10 to 37 mass%,

the iron ion concentration is 0.2 mass% or less.

7. The method for manufacturing a transparent conductive substrate according to any one of claims 1 to 6,

before the patterning step, the method also comprises

A resist disposing step of disposing a resist on an exposed surface opposite to a surface of the laminate opposite to the transparent base material,

the photoresist disposing step has

A photosensitive resist layer forming step of forming a photosensitive resist layer on the exposed surface; and

and a resist pattern forming step of exposing the photosensitive resist layer to ultraviolet rays according to a resist pattern to be formed and developing an unexposed portion to form the resist pattern.

8. A transparent conductive substrate comprises:

a transparent substrate; and

a fine metal wire disposed on at least one surface of the transparent base material,

wherein the thin metal wire is a laminate in which a 1 st blackened wiring layer containing nickel and copper and a conductive wiring layer containing copper are laminated in this order from the transparent base material side,

the 1 st blackened wiring layer protruding from the conductive wiring layer has a protruding width of 0.5 [ mu ] m or less when viewed in a direction perpendicular to the one surface of the transparent substrate.

9. The transparent conductive substrate according to claim 8,

the fine metal wire further has a 2 nd blackened wiring layer containing nickel and copper on a surface of the conductive wiring layer opposite to the 1 st blackened wiring layer.

10. The transparent conductive substrate according to claim 8 or 9,

the average value of the reflectance of light having a wavelength of 400nm to 700nm in the 1 st blackened wiring layer is 15% or less.

Images