JP2015151592A - Etching solution for metal layer laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an etching solution for a metal layer laminate, with which a blackened layer and a wiring layer can be simultaneously etched into a desired pattern.SOLUTION: An etching solution for a metal layer laminate is to be used for etching a metal layer laminate formed on at least one surface of a substrate. The metal layer laminate includes: a blackened layer containing at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu, and at least one element selected from carbon, oxygen, and nitrogen; and a wiring layer containing copper or a copper alloy of Cu and at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, and W. The etching solution for a metal layer laminate contains a permanganate by 0.5 wt.% or more and 10 wt.% or less and hydrochloric acid by 0.1 wt.% or more and 5 wt.% or less.

Description

  The present invention relates to an etching solution for a metal layer laminate.

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

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

  For this reason, for example, as disclosed in Patent Documents 2 and 3, the use of a metal foil such as copper instead of the ITO film has been studied. However, for example, when copper is used for the wiring layer, since copper has a metallic luster, there is a problem that the visibility of the display decreases due to reflection.

  Therefore, a conductive substrate in which a blackening layer made of a black material is formed together with a wiring layer made of a metal foil such as copper has been studied.

  In order to form a wiring pattern on a conductive substrate including a wiring layer and a blackened layer in this manner, after forming the wiring layer and the blackened layer, the wiring layer and the blackened layer are etched to obtain a desired pattern. It is necessary to form a pattern.

  However, the blackened layer could not be etched with the ferric chloride salt used as an etchant when etching the wiring layer. Further, when a Ni—W alloy, for example, is used as the blackening layer, the wiring layer could not be etched with cerium ammonium nitrate used as an etching solution for the blackening layer.

  For this reason, it is necessary to carry out the blackening layer etching step separately from the wiring layer etching step, which increases the number of steps. In addition, when each layer is etched, there is a case where undissolved residue is generated and etching cannot be performed in a desired shape.

JP 2003-151358 A JP 2011-018194 A JP 2013-0669261 A

  In view of the above-described problems of the prior art, an object of the present invention is to provide an etching solution for a metal layer laminate that can simultaneously etch a blackened layer and a wiring layer into a desired shape.

In order to solve the above problems, the present invention
An etching solution for a metal layer laminate that etches a metal layer laminate formed on at least one surface side of a substrate,
The metal layer laminate is
A blackening layer containing at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu and one or more elements selected from carbon, oxygen, and nitrogen. When,
A copper alloy of Cu and at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, and W, or a wiring layer containing copper,
The metal layer laminate etching solution includes a metal layer laminate etch comprising 0.5 wt% to 10 wt% permanganate and 0.1 wt% to 5 wt% hydrochloric acid. Provide liquid.

  ADVANTAGE OF THE INVENTION According to this invention, the etching liquid for metal layer laminated bodies which can etch a blackening layer and a wiring layer to a desired shape simultaneously can be provided.

Sectional drawing of an electroconductive board | substrate. Sectional drawing of an electroconductive board | substrate. The top view of the electroconductive board | substrate provided with the mesh-shaped wiring. Sectional drawing in the AA 'line of FIG. Explanatory drawing of the roll-to-roll sputtering apparatus which concerns on embodiment of this invention.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and the following embodiments are not departed from the scope of the present invention. Various modifications and substitutions can be made.
(Etching solution for metal laminate)
Hereinafter, an embodiment of the etching solution for metal layer laminate of the present invention will be described.

  The etching solution for metal layer laminates of this embodiment relates to an etching solution for metal layer laminates that etches a metal layer laminate formed on at least one surface side of a substrate.

  The metal layer laminate to which the etching solution for metal layer laminate of the present embodiment can be applied can have a blackened layer and a wiring layer. The blackening layer includes at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu, and one or more elements selected from carbon, oxygen, and nitrogen, Can be included. The wiring layer can contain Cu and a copper alloy of at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, and W, or copper.

  And the etching liquid for metal layer laminated bodies can contain 0.5 weight% or more and 10 weight% or less permanganate, and 0.1 weight% or more and 5 weight% or less hydrochloric acid.

  Here, first, a configuration example of a metal layer laminate to which the etching solution for a metal layer laminate of the present embodiment can be applied will be described.

  The metal layer laminate can be formed on at least one surface side of the substrate as described above.

  Here, it does not specifically limit as a base material which forms a metal layer laminated body, For example, an insulator film, a glass substrate, a ceramic substrate etc. can be used preferably. In particular, when a conductive substrate having a metal layer laminate formed on a base material is used for applications such as a touch panel, the base material is preferably an insulating film that transmits visible light or a glass substrate.

  As the insulator film that transmits visible light, for example, a polyamide film, a polyethylene terephthalate film, a polyethylene naphthalate film, a resin film such as a cycloolefin film, and the like can be preferably used.

  It does not specifically limit about the thickness of a base material, According to the intensity | strength etc. which are requested | required, it can select arbitrarily. The thickness of the substrate can be, for example, 20 μm or more and 200 μm or less. In particular, when a conductive substrate having a metal layer laminate formed on a substrate is used for a touch panel, the thickness of the substrate is preferably 40 μm or more and 120 μm or less.

  Next, the blackened layer will be described.

  Since a wiring layer to be described later has a metallic luster, the wiring layer reflects light only by forming a wiring obtained by etching the wiring layer on a base material, for example. For this reason, for example, when a wiring layer is formed on a transparent substrate and used for a touch panel, there is a problem that the visibility of the display is lowered. Therefore, by forming the blackened layer, it is possible to suppress the reflection of light on the surface of the wiring layer.

  The blackening layer is not particularly limited, but as described above, at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu, and carbon. And one or more elements selected from oxygen and nitrogen.

  The blackening layer is selected from a metal alloy containing at least two metals selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu, and carbon, oxygen, and nitrogen. It can also contain more than seed elements. At this time, as a metal alloy containing at least two kinds of metals selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu, Ni—Cu alloy, Ni—Ti alloy, Ni A -W alloy can be preferably used.

  Although the formation method of a blackening layer is not specifically limited, For example, dry plating methods, such as sputtering method, an ion plating method, a vapor deposition method, can be used preferably. In particular, the sputtering method (reactive sputtering method) is more preferably used because the film thickness can be easily controlled.

  When the blackened layer is formed by reactive sputtering, a target containing a metal species constituting the blackened layer can be used as the target. When the blackened layer contains an alloy, a target may be used for each metal species contained in the blackened layer, and the alloy may be formed on the surface of the film-deposited body such as a substrate, and is included in the blackened layer in advance. It is also possible to use a target obtained by alloying a metal.

  In addition, one or more elements selected from carbon, oxygen, and nitrogen contained in the blackened layer should be added to the blackened layer by adding them to the atmosphere when forming the blackened layer. Can do. For example, when adding carbon to the blackening layer, carbon monoxide gas or carbon dioxide gas, when adding nitrogen, nitrogen gas is added, when adding oxygen, oxygen gas is used for sputtering. It can be added to the atmosphere. One or more elements selected from carbon, oxygen, and nitrogen can be added to the blackening layer by adding these gases to the inert gas when forming the blackening layer. Argon can be preferably used as the inert gas.

  Although the thickness of a blackening layer is not specifically limited, For example, it is preferable that it is 20 nm or more, and it is more preferable that it is 30 nm or more. The blackening layer is black as described above and functions as a blackening layer that suppresses reflection of light by the wiring layer. However, when the blackening layer is thin, sufficient blackness is obtained. In some cases, reflection of light by the wiring layer cannot be sufficiently suppressed. On the other hand, it is preferable to set the thickness of the blackened layer in the above range because the reflection of the wiring layer can be more reliably suppressed.

  The upper limit of the thickness of the blackening layer is not particularly limited, but even if it is thicker than necessary, the time required for film formation and the time required for etching when forming the wiring are increased, resulting in an increase in cost. Will be invited. For this reason, the thickness of the blackened layer is preferably 60 nm or less, and more preferably 50 nm or less.

  Although it does not specifically limit about a wiring layer, It contains Cu, the copper alloy of at least 1 or more types of metal chosen from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, and W, or copper. Is preferred.

  It is preferable not to arrange an adhesive between the wiring layer and the base material or between the wiring layer and the blackening layer. That is, the wiring layer is preferably formed directly on the upper surface of another member.

  In order to directly form the wiring layer on the upper surface of another member, it is preferable to form the wiring layer by using a dry plating method such as a sputtering method, an ion plating method, or a vapor deposition method.

  In the case where the wiring layer is made thicker and the material is applicable to the wet plating method, it is preferable to form the film using the wet plating method after the dry plating. That is, for example, a copper alloy thin film layer or a copper thin film layer is formed on a base material or a blackened layer by a dry plating method, and the copper alloy thin film layer or the copper thin film layer is used as a power feeding layer by a wet plating method. A copper alloy plating layer or a copper plating layer can be formed.

  As described above, it is preferable because the wiring layer can be formed directly on the base material or the blackening layer without using an adhesive by forming the wiring layer only by the dry plating method or by combining the dry plating method and the wet plating method. .

  The thickness of the wiring layer is not particularly limited, and when the wiring layer is used as a wiring, it can be arbitrarily selected according to the magnitude of the current supplied to the wiring, the wiring width, and the like. In particular, the wiring layer preferably has a thickness of 100 nm or more, and more preferably 200 nm or more so that sufficient current can be supplied. The upper limit value of the thickness of the wiring layer is not particularly limited. However, when the wiring layer becomes thick, side etching occurs because etching takes time when performing etching to form the wiring, and the resist peels off during the etching. Etc. are likely to occur. For this reason, the thickness of the wiring layer is preferably 2000 nm or less. When the wiring layer has a copper alloy thin film layer or a copper thin film layer and a copper alloy plating layer or a copper plating layer as described above, the copper alloy thin film layer or the copper thin film layer The total of the thickness and the copper alloy plating layer or the thickness of the copper plating layer is preferably in the above range.

  Next, the example of arrangement | positioning of each layer of a metal layer laminated body is demonstrated.

  As described above, the metal layer laminate that can suitably use the etching solution of the present embodiment is formed on at least one surface of the substrate, and includes a blackened layer and a wiring layer. The order of lamination when the blackening layer and the wiring layer are arranged on the substrate is not particularly limited. Further, a plurality of blackening layers and wiring layers can be formed. In order to suppress the reflection of light on the surface of the wiring layer, it is preferable that a blackening layer is disposed on the surface of the wiring layer on which it is particularly desired to suppress the reflection of light. In particular, it is more preferable to have a laminated structure in which the blackened layer is formed on the surface of the wiring layer. For this reason, for example, when the substrate is a transparent substrate, the wiring layer has a structure sandwiched between the blackened layers. More preferably.

  A specific configuration example will be described below with reference to FIGS. 1 and 2 are parallel to the stacking direction of the base material, the blackening layer, and the wiring layer of the conductive substrate in which the metal layer laminate that can suitably use the etching solution of the present embodiment is stacked on the base material. An example of a cross-sectional view on a rough surface is shown. Hereinafter, a member in which a metal layer laminate is laminated on a base material is also referred to as a conductive substrate.

  For example, as shown in FIG. 1A, a structure in which a wiring layer 12 and a blackening layer 13 are laminated on a base material 11 in order from one surface (front surface) 11a side of the base material 11 is formed. It can be set as 10 A of conductive substrates which have the metal layer laminated body which has.

  Further, like the conductive substrate 10B shown in FIG. 1B, the wiring layers 12A and 12B are respectively formed on the one surface 11a side of the base 11 and the other surface (the other surface) 11b side. The blackening layers 13A and 13B can be stacked one by one in that order. The order in which the wiring layers 12 (12A, 12B) and the blackening layers 13 (13A, 13B) are stacked is not limited to the example of FIGS. 1 (a) and 1 (b). 1A and 1B, the order of the wiring layer 12 and the blackened layer 13 is switched, for example, the blackened layer 13 and the wiring are sequentially formed from one surface (front surface) 11a side of the substrate 11. It is also possible to arrange a metal layer laminate having a structure in which the layer 12 is laminated.

  In addition, for example, a configuration in which a plurality of blackening layers are provided on one surface side of the substrate 11 may be employed. For example, like the conductive substrate 20A shown in FIG. 2A, the first blackened layer 131, the wiring layer 12, and the second blackened layer 132 are formed on the one surface 11a side of the base material 11. , Can be stacked in that order.

  Also in this case, the wiring layer, the first blackened layer, and the second blackened layer can be laminated on both surfaces of the base material 11. Specifically, like the conductive substrate 20B shown in FIG. 2B, the first black is formed on one surface 11a side of the base material 11 and on the other surface (the other surface) 11b side. The layering layers 131A and 131B, the wiring layers 12A and 12B, and the second blackening layers 132A and 132B can be stacked in that order.

  In FIGS. 1B and 2B, when a wiring layer and a blackening layer are laminated on both surfaces of the base material 11, the base material 11 is laminated on the top and bottom of the base material 11 with the symmetrical surface. Although the example which arrange | positioned so that the layer which became symmetrical may be shown, it is not limited to the form which concerns. For example, in FIG. 2B, the configuration on the one surface 11a side of the substrate 11 is formed by laminating the wiring layer 12 and the blackening layer 13 in that order, similarly to the configuration of FIG. The layers laminated on the top and bottom of the base material 11 may be asymmetrical.

  Further, the number of blackening layers and wiring layers is not limited to the above example, and a plurality of layers can be arranged.

  The conductive substrate provided with the metal layer laminate on the substrate described so far can be preferably used as a conductive substrate for a touch panel, for example. In this case, the conductive substrate can be configured to have mesh-like wiring.

  The conductive substrate provided with the mesh-like wiring can be obtained by etching the wiring layer and the blackening layer of the conductive substrate described so far. And the etching liquid of this embodiment can be preferably used in the case of an etching.

  The etching solution for metal layer laminate of the present embodiment preferably contains 0.5 wt% or more and 10 wt% or less permanganate and 0.1 wt% or more and 5 wt% or less hydrochloric acid. . In particular, the etching solution for a metal layer laminate of the present embodiment contains 0.5 wt% or more and 5 wt% or less permanganate and 0.1 wt% or more and 3 wt% or less hydrochloric acid. More preferably, 0.5 to 3% by weight of permanganate and 0.1 to 1% by weight of hydrochloric acid.

  Permanganate is mainly effective for etching the blackened layer, and when it is contained in an amount of 0.5% by weight or more, it exhibits sufficient reactivity with the blackened layer. Since the blackened layer can be dissolved over time, side etching can be suppressed.

  In addition, hydrochloric acid is mainly effective for etching the wiring layer, and when it is contained in an amount of 0.1% by weight or more, it exhibits sufficient reactivity with the wiring layer. Since the layer can be dissolved, side etching can be suppressed.

  After the blackened layer and the wiring layer are formed on the base material, as described above, the blackened layer and the wiring layer are etched so as to form, for example, a mesh-like wiring. In particular, in recent years, it may be required to form a wiring having a wiring width of 10 μm or less, particularly 5 μm or less as a wiring board. And it is preferable that it is an etching liquid which can etch, without destroying a wiring shape, when patterning these wiring by an etching.

  When patterning wiring with such a narrow wiring width, for example, the blackened layer or wiring layer formed on the substrate is dissolved over about 10 seconds rather than instantaneously dissolving the blackened layer or wiring layer. It is preferable to do. In the etching liquid of this embodiment, by containing permanganate and hydrochloric acid in the above-mentioned range, it becomes possible to dissolve the blackened layer and the wiring over an appropriate time.

  For this reason, by containing permanganate and hydrochloric acid in the above-mentioned predetermined ratio, it can be preferably used as an etching solution for simultaneously etching the wiring layer and the blackened layer. Moreover, since the difference in the reactivity of the etching solution with respect to the wiring layer and the blackening layer can be sufficiently suppressed, a wiring pattern having a desired shape can be easily formed.

  The permanganate contained in the etching solution is not particularly limited, and for example, potassium permanganate and alkali metal permanganate such as sodium permanganate can be preferably used. In particular, as permanganate, potassium permanganate or sodium permanganate can be preferably used because of its sufficiently high reactivity with the blackening layer.

  Components other than the permanganate and hydrochloric acid in the etching solution for a metal layer laminate of the present embodiment are not particularly limited, and for example, the remainder can be water.

  About the etching liquid of this embodiment, permanganate and hydrochloric acid should just be contained in the above-mentioned range, respectively, and the addition amount ratio of permanganate and hydrochloric acid is not specifically limited. . However, in order to more reliably form the blackened layer and the wiring layer in a desired shape, the permanganate and the hydrochloric acid are used so that the time required for the etching solution to dissolve the blackened layer and the wiring layer is approximately the same. It is preferable that the ratio of the added amount to be adjusted. Specifically, for example, the dissolution time required to dissolve one of the blackening layer and the wiring layer is preferably within 3 times the dissolution time required to dissolve the other layer. It is more preferable that it is within the range. Since the dissolution time for the blackened layer and the wiring layer can be adjusted by adding the ratio of permanganate and hydrochloric acid, the blackening layer formed on the substrate to be etched in advance, the thickness of the wiring layer, etc. Accordingly, it is preferable to adjust the amount ratio of permanganate and hydrochloric acid. For example, when etching a conductive substrate having a thick wiring layer, the content of hydrochloric acid in the etching solution is preferably adjusted within the above range.

  When etching the blackened layer and the wiring layer formed on the substrate, the method of supplying the etching solution to the blackened layer and the wiring layer is not particularly limited, and can be supplied by any method. However, a method of spraying an etching solution onto the surface of the conductive substrate by a shower or a method of immersing the conductive substrate in the etching solution can be preferably used so that the etching process can be uniformly performed on a region to be etched.

  Next, a configuration example in the case where the above-described conductive substrate is etched using the metal layer laminate etching solution of the present embodiment to form a conductive substrate provided with mesh-like wiring will be described.

  A specific configuration example is shown in FIG. FIG. 3 shows a view of the conductive substrate 30 having mesh-like wiring as viewed from the upper surface side in the stacking direction of the wiring layer and the blackening layer. The conductive substrate 30 shown in FIG. 3 includes a base material 11, a plurality of wirings 31A parallel to the X-axis direction in the drawing, and wirings 31B parallel to the Y-axis direction. The wirings 31A and 31B are formed by etching a wiring layer, and a blackening layer (not shown) is formed on the upper surface and / or the lower surface of the wirings 31A and 31B. The blackened layer is etched in the same shape as the wirings 31A and 31B.

  The arrangement of the base material 11 and the wirings 31A and 31B is not particularly limited. An example of the arrangement of the base material 11 and the wiring is shown in FIGS. 4A and 4B correspond to cross-sectional views taken along line AA ′ of FIG.

  First, as illustrated in FIG. 4A, wirings 31 </ b> A and 31 </ b> B may be disposed on the upper and lower surfaces of the base material 11, respectively. In this case, blackening layers 32A and 32B etched in the same shape as the wiring are disposed on the upper surfaces of the wirings 31A and 31B.

  Further, as shown in FIG. 4B, a set of base materials 11 is used, wirings 31A and 31B are arranged on the upper and lower surfaces with one base material 11 being sandwiched, and one wiring 31B is a base material. 11 may be arranged. Also in this case, blackened layers 32A and 32B etched in the same shape as the wiring are disposed on the upper surfaces of the wirings 31A and 31B. As described above, the arrangement of the blackened layer and the wiring layer is not limited. For this reason, in any of FIGS. 4A and 4B, the arrangement of the blackening layers 32A and 32B and the wirings 31A and 31B can be reversed upside down. For example, a plurality of blackening layers can be provided.

  However, it is preferable that the blackening layer is disposed on the surface of the wiring layer surface where light reflection is particularly desired to be suppressed. Therefore, in the conductive substrate shown in FIG. 4B, for example, when the base material 11 is a transparent base material and it is necessary to suppress the reflection of light from the lower surface side in the figure, the blackening layer It is preferable to reverse the position of 32B and the position of the wiring 31B. Further, in addition to the blackening layer 32B, a blackening layer may be further provided between the wiring 31B and the substrate 11.

  The conductive substrate having the mesh-like wiring shown in FIG. 3 and FIG. 4A includes, for example, wiring layers 12A and 12B on both surfaces of the base material 11 as shown in FIG. 1B and FIG. It can form from the electroconductive board | substrate provided with the blackening layers 13A and 13B (131A, 132A, 131B, 132B).

  A case where the conductive substrate of FIG. 1B is used as an example will be described. First, the wiring layer 12A and the blackened layer 13A on the one surface 11a side of the base 11 are shown as X in FIG. Etching is performed so that a plurality of linear patterns parallel to the axial direction are arranged at predetermined intervals. The X-axis direction in FIG. 1 (b) means a direction parallel to the width direction of each layer in FIG. 1 (b).

  A plurality of linear patterns parallel to the Y-axis direction in FIG. 1B are arranged at predetermined intervals on the wiring layer 12B and the blackening layer 13B on the other surface 11b side of the substrate 11. Etching is performed as follows. In addition, the Y-axis direction in FIG.1 (b) means the direction perpendicular | vertical to a paper surface.

  Through the above operation, the conductive substrate having the mesh-like wiring shown in FIGS. 3 and 4A can be formed. Note that the etching of both surfaces of the substrate 11 can be performed simultaneously. That is, the wiring layers 12A and 12B and the blackening layers 13A and 13B may be etched simultaneously.

  The conductive substrate having the mesh-like wiring shown in FIG. 3 can also be formed by using two conductive substrates shown in FIG. 1 (a) or FIG. 2 (a). A case where the conductive substrate of FIG. 1A is used will be described as an example. For the two conductive substrates shown in FIG. 1A, the wiring layer 12 and the blackened layer 13 are parallel to the X-axis direction, respectively. Etching is performed so that a plurality of linear patterns are arranged at predetermined intervals. Then, the conductive substrate having mesh-like wiring is obtained by bonding the two conductive substrates so that the linear patterns formed on the respective conductive substrates intersect with each other by the etching process. be able to. The surface to be bonded when the two conductive substrates are bonded is not particularly limited. The surface A in FIG. 1A in which the wiring layer 12 and the like are stacked as shown in FIG. The surface 11b in FIG. 1A on which the layer 12 and the like are not stacked may be bonded.

  The blackening layer is preferably disposed on the surface of the wiring layer surface where light reflection is particularly desired to be suppressed. For this reason, in the conductive substrate shown in FIG. 4B, when the base material 11 is a transparent base material and it is necessary to suppress the reflection of light from the lower surface side in the figure, the position of the blackened layer 32B. It is preferable to reverse the position of the wiring 31B. Further, in addition to the blackening layer 32B, a blackening layer may be further provided between the wiring 31B and the substrate 11.

  Further, for example, the surfaces 11b in FIG. 1A where the wiring layer 12 or the like of the substrate 11 is not laminated may be bonded together so that the cross section has the structure shown in FIG. 4A.

  Note that the width of the wiring and the distance between the wirings in the conductive substrate having the mesh-like wiring shown in FIGS. 3 and 4 are not particularly limited, and are selected according to, for example, the amount of current flowing through the wiring. can do.

  Thus, a conductive substrate having a mesh-like wiring composed of two layers of wiring can be preferably used as a conductive substrate for a projected capacitive touch panel, for example.

According to the etching solution of this embodiment, the blackened layer and the wiring layer can be etched into a desired shape at the same time. Therefore, the number of etching processes can be reduced, and a conductive substrate, for example, a conductive substrate having the mesh-like wiring described above can be manufactured with high productivity. Further, since the blackening layer and the wiring layer can be easily etched into a desired shape, the yield rate of the conductive substrate can be improved.
(Method for producing conductive substrate)
Next, an embodiment of a method for producing a conductive substrate of the present invention will be described.

  The manufacturing method of the conductive substrate of this embodiment can have the following processes.

  A base material preparation step for preparing a base material.

  At least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu and one or more selected from carbon, oxygen, and nitrogen on at least one surface side of the substrate A blackening layer forming step of forming a blackening layer containing the element.

  A copper alloy or at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, and W, or a wiring containing copper on at least one surface side of the substrate A wiring layer forming step for forming a layer.

  An etching process for etching the blackened layer and the wiring layer.

  In the etching process, an etching solution for a metal layer laminate containing 0.5 wt% or more and 10 wt% or less permanganate and 0.1 wt% or more and 5 wt% or less hydrochloric acid is used. Thus, the wiring layer and the blackened layer can be etched simultaneously.

  Although the manufacturing method of the electroconductive board | substrate of this embodiment is demonstrated below, it shall be the above-mentioned structure regarding the electroconductive board | substrate demonstrated together with the etching liquid for the above-mentioned metal laminated body except the point demonstrated below. The explanation is omitted.

  As described above, in the conductive substrate obtained in the method for manufacturing a conductive substrate according to the present embodiment, the order of stacking when the blackening layer and the wiring layer are arranged on the base material is particularly limited. is not. Further, a plurality of blackening layers and wiring layers can be formed. For this reason, the order in which the blackening layer forming step and the wiring layer forming step are performed and the number of times to perform are not particularly limited, and any number of times according to the structure of the conductive substrate to be formed, Can be implemented at the timing.

  Each step will be described below.

  The base material preparation step of preparing the base material is a step of preparing a base material composed of, for example, an insulator film, a glass substrate, a ceramic substrate, or the like. As described above, when the conductive substrate is used for applications such as a touch panel, the base material is preferably an insulating film that transmits visible light or a glass substrate. The specific operation in the substrate preparation step is not particularly limited. For example, in order to use for each process in a latter process, it can cut | disconnect etc. to arbitrary sizes as needed.

  Next, the blackening layer forming process will be described.

  As a film formation method of the blackened layer in the blackened layer forming step, for example, a dry plating method such as a sputtering method, an ion plating method or a vapor deposition method can be preferably used. In particular, the sputtering method is more preferable because the film thickness can be easily controlled.

  The blackening layer can be suitably formed using, for example, a roll-to-roll sputtering apparatus.

  The blackening layer forming process will be described by taking a roll-to-roll sputtering apparatus as an example.

  FIG. 5 shows a configuration example of the roll-to-roll sputtering apparatus 50.

  The roll-to-roll sputtering apparatus 50 includes a housing 51 that houses most of the components.

  In FIG. 5, the shape of the housing 51 is shown as a rectangular parallelepiped shape, but the shape of the housing 51 is not particularly limited, and may be any shape depending on the device accommodated therein, the installation location, the pressure resistance performance, and the like. It can be. For example, the shape of the housing 51 can be a cylindrical shape.

However, in order to remove residual gas not related to film formation at the start of film formation, it is preferable that the inside of the casing 51 can be depressurized to 10 ⁻³ Pa or less, and more preferably 10 ⁻⁴ Pa or less. Note that it is not necessary that the entire interior of the casing 51 can be reduced to the above pressure, and it can be configured such that only the lower region in the figure in which a can roll 53 (to be described later) where sputtering is performed can be reduced to the above pressure. .

  In the housing 51, an unwinding roll 52, a can roll 53, sputtering cathodes 54a to 54d, a front feed roll 55a, a rear feed roll 55b, tension rolls 56a and 56b, which supply a substrate for forming a blackened layer, A winding roll 57 can be arranged. In addition to the above rolls, guide rolls 58a to 58h, a heater 61, and the like can be arbitrarily provided on the transport path of the base material on which the blackening layer is formed.

  The unwinding roll 52, the can roll 53, the front feed roll 55a, and the winding roll 57 can be provided with power by a servo motor. The unwinding roll 52 and the winding roll 57 are configured so that the tension balance of the substrate on which the blackened layer is formed is maintained by torque control using a powder clutch or the like.

  The configuration of the can roll 53 is not particularly limited. For example, the surface of the can roll 53 is finished with hard chrome plating, and a coolant and a heating medium supplied from the outside of the casing 51 are circulated inside the can roll 53 so as to be adjusted to a substantially constant temperature. It is preferable to be configured to be able to.

  For example, the tension rolls 56a and 56b are preferably finished with hard chrome plating and provided with a tension sensor.

  Further, the front feed roll 55a, the rear feed roll 55b, and the guide rolls 58a to 58h are preferably finished with hard chrome plating.

  The sputtering cathodes 54 a to 54 d are preferably magnetron cathode types and arranged to face the can roll 53. The size of the sputtering cathodes 54a to 54d is not particularly limited, but the width direction dimension of the substrate on which the blackening layer of the sputtering cathodes 54a to 54d is formed may be wider than the width of the substrate on which the blackening layer is formed. preferable.

  The base material on which the blackening layer is formed is transported through a roll-to-roll sputtering apparatus 50, which is a roll-to-roll vacuum film forming apparatus, and blackened by the sputtering cathodes 54a to 54d facing the can roll 53. A layer is deposited.

  When a blackened layer is formed using the roll-to-roll sputtering apparatus 50, a target including a metal constituting the blackened layer is attached to the sputtering cathodes 54a to 54d.

  When the blackening layer contains an alloy, an alloy target can be used by previously synthesizing the alloy. However, a metal target contained in the alloy is placed on the sputtering cathodes 54a to 54d, and a substrate or the like is formed. An alloy can also be formed on the surface of the film body.

  And the inside of the apparatus which set the base material which forms a blackening layer in the unwinding roll 52 is evacuated by the vacuum pumps 60a and 60b. Thereafter, a sputtering gas containing argon and a gas corresponding to any one of carbon, oxygen, and nitrogen added to the blackening layer is introduced into the casing 51 by the gas supply means 59. At this time, the flow rate of the sputtering gas and the opening of the pressure adjusting valve provided between the vacuum pump 60b and the casing 51 are adjusted to maintain the inside of the apparatus at, for example, 0.13 Pa or more and 13 Pa or less. It is preferred to carry out the membrane.

  In this state, while discharging the substrate from the unwinding roll 52 at a speed of about 0.5 m to 10 m per minute, for example, power is supplied from the sputtering DC power source connected to the sputtering cathodes 54 a to 54 d to perform the sputtering discharge. I do. Thereby, a desired blackening layer can be continuously formed on the substrate.

  Next, the wiring layer forming process will be described.

  As described above, the wiring layer is preferably formed using a dry plating method. In addition, when the wiring layer is a material to which a wet plating method can be applied and the film thickness is increased, the wet plating method is preferably used after the dry plating method is performed.

  For this reason, the wiring layer forming step can include a step of forming a copper alloy thin film layer or a copper thin film layer by a dry plating method. Also, a step of forming a copper alloy thin film layer or a copper thin film layer by a dry plating method and a copper alloy plating layer or a copper by a wet plating method using the copper alloy thin film layer or the copper thin film layer as a power feeding layer And a step of forming a plating layer.

  Although it does not specifically limit as a dry-type plating method, For example, sputtering method, an ion plating method, a vapor deposition method etc. can be used preferably. In particular, the sputtering method is more preferable because the film thickness can be easily controlled.

  The wiring layer can also be suitably formed using, for example, the roll-to-roll sputtering apparatus 50 described above. Since the roll-to-roll sputtering apparatus 50 has already been described, the description thereof is omitted here.

  When the wiring layer is formed using the roll-to-roll sputtering apparatus 50, the target is mounted on the sputtering cathodes 54a to 54d, and the inside of the apparatus in which the substrate for forming the wiring layer is set on the unwinding roll 52 is vacuumed. The pumps 60a and 60b are evacuated. Thereafter, a sputtering gas such as argon is introduced into the casing 51 by the gas supply means 59. At this time, by adjusting the flow rate of the sputtering gas and the opening of the pressure adjusting valve provided between the vacuum pump 60b and the casing 51, the inside of the casing 51 is set to 0.13 Pa or more and 1.3 Pa or less, for example. It is preferable to hold and perform film formation.

  In this state, while discharging the base material from the unwinding roll 52 at a speed of, for example, about 1 m to 20 m per minute, power is supplied from the DC power source for sputtering connected to the sputtering cathodes 54 a to 54 d to perform the sputtering discharge. Thereby, a desired wiring layer can be continuously formed on the substrate.

  When the wiring layer includes a copper alloy, a copper alloy target can be used by previously synthesizing the copper alloy. However, a metal target included in the copper alloy is disposed on the sputtering cathodes 54a to 54d, and a base material or the like. A copper alloy can also be formed on the surface of the film formation body.

  When a copper alloy plating layer or a copper plating layer is further formed by a wet plating method after the dry plating method, the film forming conditions, that is, the conditions of the electroplating treatment are not particularly limited, and are ordinary methods. The various conditions may be adopted. For example, by supplying a copper alloy thin film layer or a base material on which a copper thin film layer is formed to a plating tank containing a plating solution, and controlling the current density and the transport speed of the base material, A copper plating layer can be formed.

  As described above, the blackening layer forming step and the wiring layer forming step can be repeatedly performed in any number of times and in order. Then, after a predetermined number of blackening layers and wiring layers are formed, an etching process can be performed to obtain a mesh-like wiring board.

  In the etching step, for example, first, a resist having an opening corresponding to a portion to be removed by etching is formed on the outermost surface of the conductive substrate. In the case of the conductive substrate shown in FIG. 1A, a resist can be formed on the exposed surface A of the blackening layer 13 disposed on the conductive substrate. Note that a method for forming a resist having an opening corresponding to a portion to be removed by etching is not particularly limited. For example, the resist can be formed by a photolithography method.

  Next, the wiring layer 12 and the blackened layer 13 can be etched by supplying an etching solution from the upper surface of the resist.

  The metal layer laminate etching solution used at this time preferably contains 0.5 wt% or more and 10 wt% or less permanganate and 0.1 wt% or more and 5 wt% or less hydrochloric acid. In particular, the etching solution for a metal layer laminate preferably contains 0.5 wt% or more and 5 wt% or less permanganate and 0.1 wt% or more and 3 wt% or less hydrochloric acid, Preferably, 0.5 wt% or more and 3 wt% or less of permanganate and 0.1 wt% or more and 1 wt% or less of hydrochloric acid are contained.

  Further, it is preferable that the etching solution has a dissolution time required to dissolve one of the blackening layer and the wiring layer within three times the dissolution time required to dissolve the other layer. For this reason, it is preferable to adjust the addition amount ratio between the permanganate contained in the etching solution and hydrochloric acid within the above range.

  In addition, although it does not specifically limit as permanganate, For example, potassium permanganate and sodium permanganate can be used conveniently.

  Although the etching solution can be used at room temperature, it is preferably heated to increase the reactivity. For example, it is preferably heated to 30 ° C. or higher and 50 ° C. or lower.

  When etching the blackened layer and the wiring layer formed on the substrate, the method of supplying the etching solution to the blackened layer and the wiring layer is not particularly limited, and can be supplied by any method. However, a method of spraying an etching solution onto the surface of the conductive substrate by a shower or a method of immersing the conductive substrate in the etching solution can be preferably used so that the etching process can be uniformly performed on a region to be etched.

  Although the pattern formed in this etching process is not specifically limited, For example, it can etch so that it may respond | correspond to the conductive substrate provided with the above-mentioned mesh-like wiring.

  In addition, as described above, two conductive substrates having a wiring layer and a blackening layer are bonded to one side of the base 11 shown in FIGS. 1A and 2A to form a mesh. In the case of using a conductive substrate provided with the wiring, a step of bonding the conductive substrate can be further provided. At this time, a method for bonding the two conductive substrates is not particularly limited, and the bonding can be performed using, for example, an adhesive.

  According to the manufacturing method of the conductive substrate of this embodiment described above, the etching solution for metal layer laminate that can simultaneously etch the blackening layer and the wiring layer in the etching process is used. For this reason, the number of processes of the etching process can be reduced and productivity can be increased. Furthermore, since the blackening layer and the wiring layer can be easily etched into a desired shape, the yield rate of the conductive substrate can be improved.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited to these Examples.
[Example 1]
After producing a conductive substrate in which the film 1 and the film 2 were laminated in that order on one surface of the base material in the following procedure, a dissolution test of the film 1 and the film 2 of the conductive substrate was performed with an etching solution.
(Base material preparation process)
First, a transparent substrate made of polyethylene terephthalate resin (PET) having a width of 500 mm and a thickness of 100 μm was set in the roll-to-roll sputtering apparatus 50 shown in FIG.
(Film forming step of film 1)
As film 1, a blackened layer was formed on one surface of the substrate. As the blackening layer, a Ni-17 wt% W alloy layer containing nitrogen was formed.

  A Ni-17 wt% W alloy target was connected to the sputtering cathodes 54a to 54d of the roll-to-roll sputtering apparatus 50 shown in FIG. 5, and a blackened layer was formed by the following procedure.

  The heater 61 of the roll-to-roll sputtering apparatus 50 was heated to 60 ° C., the transparent base material was heated, and water contained in the base material was removed.

Subsequently, after the inside of the casing 51 was evacuated to 1 × 10 ⁻³ Pa, argon gas and nitrogen gas were introduced, and the pressure in the casing 51 was adjusted to 1.3 Pa. At this time, the supply amounts of argon gas and nitrogen gas were adjusted so that the atmosphere in the casing 51 was 30% nitrogen by volume and the remainder was argon.

And while conveying a transparent base material from the unwinding roll 52, electric power is supplied from the DC power source for sputtering connected to the sputtering cathodes 54a to 54d, and sputtering discharge is performed, and a desired blackening layer is continuously formed on the base material. Filmed. By this operation, a blackened layer was formed on the transparent substrate so as to have a thickness of 30 nm.
(Film forming process of film 2)
A wiring layer was formed on the film 1 formed in the film 1 forming process as the film 2. A copper layer was formed as the wiring layer.

  The wiring layer is formed by connecting a copper target to the sputtering cathodes 54a to 54d of the roll-to-roll sputtering apparatus 50 shown in FIG. What formed the film | membrane 1 on the material was used.

  The conditions for forming the film 2 were the same as those for the film 1 except that the following two points were changed.

A point in which the inside of the casing 51 is evacuated to 1 × 10 ⁻³ Pa, and then argon gas is introduced to adjust the pressure in the casing 51 to 1.3 Pa.

The copper layer which is a wiring layer was formed to a film thickness of 500 nm.
(Dissolution test)
About the electroconductive board | substrate which laminated | stacked the film 1 and the film | membrane 2 on the surface of the base material in the order by the above-mentioned procedure, the dissolution test was implemented with the following procedures.

  The dissolution test was carried out using an etching solution having a temperature of 40 ° C. containing 1% by weight of potassium permanganate and 1% by weight of hydrochloric acid, and the balance being ion-exchanged water.

  And the electrolysis board | substrate was immersed in etching liquid, and the melt | dissolution time required to melt | dissolve the film | membrane 1 and the film | membrane 2 was measured.

Table 1 shows the film forming conditions of the conductive substrate, the composition of the etching solution in the dissolution test, and the results of the dissolution test.
[Examples 2 to 5, Comparative Examples 1 to 8]
About Examples 2-5 and Comparative Examples 1-8, the etching liquid used in a dissolution test contains potassium permanganate and hydrochloric acid at the concentrations shown in Table 1, and the remainder is ion-exchanged water. A conductive substrate was prepared and a dissolution test was conducted in the same manner as in Example 1 except that the liquid was changed.

  In Comparative Examples 3 and 5, even when the conductive substrate was immersed in the etching solution, dissolution of the wiring layer did not occur and there was no prospect of dissolution, so the dissolution test was interrupted.

  In Comparative Examples 4 and 6, since the wiring layer was dissolved at the moment when the conductive substrate was immersed in the etching solution, the conductive substrate was taken out of the etching solution at that time, and the dissolution test was interrupted.

The results are shown in Table 1.
[Example 6]
Film 1 and film 2 were replaced with the case of Example 1, film 1 was a copper layer as a wiring layer, and film 2 was a Ni-17 wt% W alloy layer containing nitrogen as a blackening layer.

  The copper layer as film 1 was formed under the same conditions as when film 2 of Example 1 was formed.

  Further, the Ni-17 wt% W alloy layer containing nitrogen as the film 2 was formed under the same conditions as when the film 1 of Example 1 was formed.

  The dissolution test was carried out in the same manner as in Example 1.

The results are shown in Table 1.
[Example 7]
In Example 7, a conductive substrate was prepared and a dissolution test was performed in the same manner as in Example 1 except that the following two points were changed.

  The etching solution used in the dissolution test was changed to an etching solution containing potassium permanganate and hydrochloric acid at the concentrations shown in Table 1 and the balance being ion-exchanged water.

  The film thickness of the film 2 is 1000 nm.

  The results are shown in Table 1.

実施例１〜７いずれの場合でも溶解試験の結果、黒化層及び配線層を溶解できることを確認できた。また、いずれか一方の層が瞬時に溶解したり、いずれか一方の層の溶解時間が他方の層の溶解時間に比べて著しく遅くなることもなかった。

As a result of the dissolution test in any of Examples 1 to 7, it was confirmed that the blackened layer and the wiring layer could be dissolved. In addition, either one of the layers did not dissolve instantaneously, and the dissolution time of either one of the layers did not become significantly slower than the dissolution time of the other layer.

  Furthermore, in each of Examples 1 to 7, the dissolution time required to dissolve any one of the blackening layer and the wiring layer is within 3 times the dissolution time required to dissolve the other layer. It was confirmed that In this way, by using an etching solution in which the dissolution time of the blackened layer and the dissolution time of the wiring layer are not significantly different, the blackened layer and the wiring layer are more reliably destroyed without breaking the shape. The wiring layer can be simultaneously etched into a desired shape.

  Further, as is clear from the comparison between Example 1 and Example 6, it was confirmed that etching can be performed regardless of the order of lamination of the blackened layer and the wiring layer.

  On the other hand, in Comparative Examples 1 and 2 in which potassium permanganate was not added to the etching solution, only the wiring layer was dissolved, and the blackened layer could not be dissolved. In Comparative Examples 3 and 5 in which hydrochloric acid was not added to the etching solution, only the blackened layer was dissolved, and the wiring layer could not be dissolved. For this reason, it was confirmed that the blackened layer and the wiring layer cannot be etched simultaneously with these etching solutions.

  In Comparative Examples 4 and 6 having a high hydrochloric acid concentration of 10% by weight, only the wiring layer was dissolved at the moment when the conductive substrate was immersed in the etching solution. For this reason, it has been confirmed that it is difficult to etch the blackened layer and the wiring layer into a desired shape simultaneously with these etching solutions.

  Further, in Comparative Examples 7 and 8 where the concentration of potassium permanganate was as high as 15% by weight, it was confirmed that the blackened layer was dissolved in a very short time. For this reason, it has been confirmed that it is difficult to etch the blackened layer and the wiring layer into a desired shape at the same time with these etching solutions.

10A, 10B, 20A, 20B, 30 Conductive substrate 11 Base material 12, 12A, 12B Wiring layer 13, 13A, 13B, 131, 132, 131A, 131B, 132A, 132B, 32A, 32B Blackening layer 31A, 31B Wiring layer

Claims (5)

An etching solution for a metal layer laminate that etches a metal layer laminate formed on at least one surface side of a substrate,
The metal layer laminate is
A blackening layer containing at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, W, and Cu and one or more elements selected from carbon, oxygen, and nitrogen. When,
A copper alloy of Cu and at least one metal selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Co, and W, or a wiring layer containing copper,
The metal layer laminate etching solution includes a metal layer laminate etch comprising 0.5 wt% to 10 wt% permanganate and 0.1 wt% to 5 wt% hydrochloric acid. liquid.   The etching solution for metal layer laminate according to claim 1, wherein the permanganate is potassium permanganate.   The etching solution for a metal layer laminate according to claim 1 or 2, wherein the metal layer laminate has a structure in which the blackening layer and the wiring layer are laminated in order from the surface side of the substrate.   The etching solution for a metal layer laminate according to claim 1 or 2, wherein the metal layer laminate has a structure in which the wiring layer and the blackening layer are laminated in order from the surface side of the base material. The dissolution time required to dissolve any one of the blackening layer and the wiring layer is as follows:
The etching solution for a metal layer laminate according to any one of claims 1 to 4, wherein the etching time is within 3 times the dissolution time required to dissolve the other layer.

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