JP6447185B2 - Method for manufacturing conductive substrate, method for manufacturing laminated conductive substrate - Google Patents

Description

  The present invention relates to a conductive substrate, a laminated conductive substrate, a method for producing a conductive substrate, and a method for producing a laminated conductive substrate.

  The capacitive touch panel converts information on the position of an adjacent object on the panel surface into an electrical signal by detecting a change in electrostatic capacitance caused by the object adjacent to the panel surface. Since the conductive substrate used for the capacitive touch panel is installed on the surface of the display, the wiring material of the conductive substrate is required to have low reflectance and be difficult to be visually recognized.

  Therefore, as a wiring material used for the capacitive touch panel, a material having low reflectivity and not easily visible is used, and the 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 tin oxide) film is formed as a transparent conductive film on a polymer film.

  In recent years, display screens equipped with a touch panel have 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 and causes signal deterioration, there is a problem that ITO is not suitable for a large panel.

  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 metal layer, since copper has a metallic luster, there is a problem in that the visibility of the display is lowered due to reflection.

  Therefore, a conductive substrate in which a blackened layer made of a black material is formed on the upper and lower surfaces of a metal layer together with a metal layer made of a metal foil such as copper has been studied.

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

  Conventionally, however, all blackening layers are formed by a dry method, and it takes time to form a blackening layer that can sufficiently suppress the metallic luster of a metal layer composed of metal foil, and productivity There was a problem of low.

In view of the above-described problems of the related art, an object of one aspect of the present invention is to provide a method for manufacturing a conductive substrate that has a small electrical resistance value, can suppress light reflection, and can be manufactured with high productivity.

In order to solve the above problems, in one aspect of the present invention,
A metal layer forming step of forming a metal layer on at least one surface of the transparent substrate ;
A blackening layer forming step of forming a blackening layer containing nickel and sulfur on the metal layer by a wet method,
Provided is a method for manufacturing a conductive substrate in which the proportion of nickel in nickel and sulfur contained in the blackening layer is 40 wt% or more and 99 wt% or less by weight .

According to one aspect of the present invention, it is possible to provide a method for manufacturing a conductive substrate that has a small electrical resistance value, can suppress reflection of light, and can be manufactured with high productivity.

Sectional drawing of the electroconductive board | substrate which concerns on embodiment of this invention. The structure explanatory view of the patterned conductive substrate concerning the embodiment of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Structure explanatory drawing of the laminated conductive board provided with the mesh-shaped wiring which concerns on embodiment of this invention. Sectional drawing of the electroconductive board | substrate provided with the mesh-shaped wiring which concerns on embodiment of this invention. Explanatory drawing of a roll-to-roll sputtering apparatus. The surface resistance measured on the surface of the blackened layer of the conductive substrate prepared in Examples and Comparative Examples. The regular reflectance in the blackening layer surface of the electroconductive board | substrate produced in the Example and the comparative example. Lightness on the surface of the blackened layer of the conductive substrates prepared in Examples and Comparative Examples.

Hereinafter, an embodiment of a conductive substrate, a laminated conductive substrate, a method for producing a conductive substrate, and a method for producing a laminated conductive substrate according to the present invention will be described.
(Conductive substrate)
The conductive substrate of the present embodiment includes a transparent base material, a metal layer formed on at least one surface of the transparent base material, and a black containing nickel and sulfur formed on the metal layer by a wet method. And a stratified layer.

  The conductive substrate in this embodiment is a conductive substrate having a metal layer or a blackened layer before patterning on the surface of the transparent substrate, and a patterned copper layer on the surface of the transparent substrate. A conductive substrate having a blackened layer, that is, a wiring substrate is included. Moreover, since the conductive substrate after patterning the metal layer and the blackening layer includes a region where the transparent base material is not covered with the metal layer or the like, it can transmit light, and becomes a transparent conductive substrate. Yes.

  First, each member included in the conductive substrate of this embodiment will be described below.

  It does not specifically limit as a transparent base material, The resin substrate (resin film) which permeate | transmits visible light, a glass substrate etc. can be used preferably.

  As a material for the resin substrate that transmits visible light, for example, a polyamide resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, a cycloolefin resin, a polyimide resin, a polycarbonate resin, or the like can be preferably used. In particular, PET (polyethylene terephthalate), COP (cycloolefin polymer), PEN (polyethylene naphthalate), polyimide, polycarbonate, and the like can be more preferably used as the material for the resin substrate that transmits visible light.

  It does not specifically limit about the thickness of a transparent base material, It can select arbitrarily according to the intensity | strength, electrostatic capacitance, light transmittance, etc. which are required when it is set as an electroconductive board | substrate. The thickness of the transparent substrate can be, for example, 10 μm or more and 200 μm or less. In particular, when used for touch panel applications, the thickness of the transparent substrate is preferably 20 μm or more and 120 μm or less, and more preferably 20 μm or more and 100 μm or less. In the case of use for touch panel applications, for example, particularly in applications where it is required to reduce the thickness of the entire display, the thickness of the transparent substrate is preferably 20 μm or more and 50 μm or less.

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

  In addition, the total light transmittance of a transparent base material can be evaluated by the method prescribed | regulated to JISK7361-1.

  The transparent substrate can have a first main plane and a second main plane. The main plane here refers to the plane portion having the largest area among the planes included in the transparent substrate. And a 1st main plane and a 2nd main plane mean the surface arrange | positioned facing in one transparent base material.

  Next, the metal layer will be described.

  Although the material which comprises a metal layer is not specifically limited, The material which has the electrical conductivity according to the application can be selected, For example, the material which comprises a metal layer is Cu, Ni, Mo, Ta, Ti, V, Cr , Fe, Mn, Co, and W, it is preferable to include a copper alloy with at least one or more metals selected from W, or copper. The metal layer can be a copper layer made of copper.

  The method for forming the metal layer on the transparent substrate is not particularly limited, but it is preferable not to place an adhesive between the transparent substrate and the metal layer in order not to reduce the light transmittance. That is, the metal layer is preferably formed directly on at least one surface of the transparent substrate. In addition, when arrange | positioning an adhesion layer between a transparent base material and a metal layer as mentioned later, it is preferable that the metal layer is directly formed on the upper surface of the adhesion layer.

  In order to directly form the metal layer on the upper surface of the transparent substrate, the metal layer preferably has a metal thin film layer. Moreover, the metal layer may have a metal thin film layer and a metal plating layer.

  For example, a metal thin film layer can be formed on a transparent substrate by a dry plating method, and the metal thin film layer can be used as a metal layer. Thereby, a metal layer can be directly formed on the transparent substrate without using an adhesive. The dry plating method will be described in detail later. For example, a sputtering method, a vapor deposition method, an ion plating method, or the like can be preferably used.

  In addition, when increasing the thickness of the metal layer, the metal thin film layer and the metal plating layer are formed by forming the metal plating layer by electroplating, which is a kind of wet plating method, using the metal thin film layer as a power feeding layer. It can also be a metal layer. Since the metal layer has the metal thin film layer and the metal plating layer, the metal layer can be directly formed on the transparent substrate without using an adhesive.

  The thickness of the metal layer is not particularly limited, and when the metal 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.

  However, when the metal layer becomes thick, it takes time to perform etching to form a wiring pattern, so that side etching is likely to occur, and it may be difficult to form fine lines. For this reason, the thickness of the metal layer is preferably 5 μm or less, and more preferably 3 μm or less.

  In particular, from the viewpoint of reducing the resistance value of the conductive substrate and supplying a sufficient current, for example, the metal layer preferably has a thickness of 50 nm or more, more preferably 60 nm or more, and 150 nm. More preferably, it is the above.

  In addition, when a metal layer has a metal thin film layer and a metal plating layer as mentioned above, it is preferable that the sum total of the thickness of a metal thin film layer and the thickness of a metal plating layer is the said range.

  The thickness of the metal thin film layer is not particularly limited in either case where the metal layer is constituted by the metal thin film layer or in the case of being constituted by the metal thin film layer and the metal plating layer. The thickness is preferably 500 nm or more.

  As described later, the metal layer can be used as a wiring by patterning it into a wiring pattern of a desired shape, for example. And since a metal layer can make an electrical resistance value lower than ITO conventionally used as a transparent conductive film, the electrical resistance value of an electroconductive board | substrate can be made small by providing a metal layer.

  Next, the blackened layer will be described.

  The blackening layer can be formed on the upper surface of the metal layer.

  The blackened layer can be formed by a wet method and can contain nickel and sulfur.

  As described above, in the conventional conductive substrate, all blackening layers are also formed by the dry plating method. On the other hand, in the conductive substrate of the present embodiment, the blackened layer can be formed in a shorter time than the dry plating method by forming the blackened layer by a wet method, thereby improving productivity. it can. Further, by providing the blackening layer, it is possible to suppress reflection of light on the upper surface of the metal layer.

  The method for forming the blackened layer is not particularly limited as long as it is a wet method, and examples thereof include a method of newly forming and laminating a blackened layer on the metal layer by a wet plating method. As the wet plating method in this case, for example, an electroless plating method can be suitably used.

  The ratio of nickel and sulfur contained in the blackened layer is not particularly limited, but the proportion of nickel in the nickel and sulfur contained in the blackened layer is 40 wt% or more and 99 wt% or less by weight. It is preferable.

  In addition, the ratio for which nickel occupies the nickel and sulfur contained in the blackened layer here indicates the ratio of nickel when the total amount of nickel and sulfur contained in the blackened layer is 100 wt%. The balance is the sulfur ratio. For this reason, when the above-mentioned range is expressed by the weight ratio of nickel: sulfur in the blackened layer, it means that it is preferably 40:60 or more and 99: 1 or less.

  By setting the proportion of nickel in the blackened layer and sulfur contained in the blackened layer to 40 wt% or more, color unevenness on the blackened layer surface can be suppressed. By suppressing color unevenness on the surface of the blackened layer, for example, when a conductive substrate in which the metal layer and the blackened layer are patterned is used, the wiring portion in which the metal layer and the blackened layer are patterned becomes less noticeable. This is preferable because it can enhance aesthetics.

  In addition, the blackened layer contains nickel and sulfur, so that the reflection of light by the metal layer can be suppressed regardless of the ratio, but the nickel occupies the proportion of nickel and sulfur contained in the blackened layer. In the case of 99 wt% or less, reflection of light by the metal layer can be particularly suppressed, which is preferable.

  In particular, of the nickel and sulfur contained in the blackened layer, the proportion of nickel is more preferably 70 wt% or more and 99 wt% or less, and further preferably 75 wt% or more and 99 wt% or less.

  The blackening layer can contain any component other than nickel and sulfur, and the composition thereof is not particularly limited, but nickel and sulfur are preferably the main components, and are composed of nickel and sulfur. More preferably. In addition, that nickel and sulfur are the main components means that nickel and sulfur are contained more than 50 wt% in the blackened layer. Even when the blackened layer is composed of nickel and sulfur, it does not exclude the inclusion of impurity components and inevitable components.When the blackened layer is formed by a wet plating method, nickel and sulfur are not excluded. In addition to sulfur, a component derived from the plating solution may be contained in the blackened layer.

  In addition, the conductive substrate can be provided with an arbitrary layer other than the above-described transparent base material, metal layer, and blackening layer. For example, an adhesion layer can be provided.

  A configuration example of the adhesion layer will be described.

  As described above, the metal layer can be formed on the transparent substrate, but when the metal layer is directly formed on the transparent substrate, the adhesion between the transparent substrate and the metal layer may not be sufficient. . For this reason, when a metal layer is directly formed on the upper surface of the transparent substrate, the metal layer may be peeled off from the transparent substrate during the production process or use.

  Therefore, in the conductive substrate of the present embodiment, an adhesion layer can be disposed on the transparent substrate in order to improve the adhesion between the transparent substrate and the metal layer.

  By disposing the adhesion layer between the transparent substrate and the metal layer, the adhesion between the transparent substrate and the metal layer can be improved, and the metal layer can be prevented from peeling from the transparent substrate.

  Further, the adhesion layer can function as a blackening layer. For this reason, it becomes possible to suppress the reflection of the light of the metal layer by the light from the lower surface side of the metal layer, that is, the transparent base material side.

  The material constituting the adhesion layer is not particularly limited, the adhesion strength with the transparent base material and the metal layer, the degree of suppression of light reflection on the surface of the required metal layer, and the use of a conductive substrate It can be arbitrarily selected according to the degree of stability to the environment (for example, humidity and temperature).

  The adhesion layer preferably contains at least one metal selected from, for example, Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. The adhesion layer may further contain one or more elements selected from carbon, oxygen, hydrogen, and nitrogen.

  The adhesion layer can include a metal alloy including at least two kinds of metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. Also in this case, the adhesion layer can further include one or more elements selected from carbon, oxygen, hydrogen, and nitrogen. At this time, as a metal alloy containing at least two kinds of metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn, a Cu—Ti—Fe alloy is used. Alternatively, a Cu—Ni—Fe alloy, Ni—Cu alloy, Ni—Zn alloy, Ni—Ti alloy, Ni—W alloy, Ni—Cr alloy, Ni—Cu—Cr alloy and the like can be preferably used.

  The method for forming the adhesion layer is not particularly limited, but it is preferable to form the film by a dry plating method. As the dry plating method, for example, a sputtering method, an ion plating method, a vapor deposition method, or the like can be preferably used. In the case where the adhesion layer is formed by a dry method, it is more preferable to use a sputtering method because the film thickness can be easily controlled. Note that, as described above, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the adhesion layer, and in this case, a reactive sputtering method can be more preferably used.

  When the adhesion layer contains one or more elements selected from carbon, oxygen, hydrogen, and nitrogen, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen in the atmosphere when forming the adhesion layer Can be added to the adhesion layer. For example, carbon is added to the adhesion layer when carbon monoxide gas and / or carbon dioxide gas is added, nitrogen gas is added when nitrogen is added, oxygen gas is added when oxygen is added, and hydrogen is added. In some cases, hydrogen gas and / or water can be added to the atmosphere during dry plating.

  A gas containing one or more elements selected from carbon, oxygen, hydrogen, and nitrogen is preferably added to an inert gas and used as an atmosphere gas during dry plating. Although it does not specifically limit as an inert gas, For example, argon can be used preferably.

  By forming the adhesion layer by dry plating as described above, the adhesion between the transparent substrate and the adhesion layer can be enhanced. And since an adhesion layer can contain a metal as a main component, for example, its adhesiveness with a metal layer is also high. For this reason, peeling of a metal layer can be suppressed by arrange | positioning an adhesion layer between a transparent base material and a metal layer.

  The thickness of the adhesion layer is not particularly limited, but is preferably 3 nm to 50 nm, for example, more preferably 3 nm to 35 nm, and still more preferably 3 nm to 33 nm.

  When the adhesion layer also functions as a blackening layer, that is, when light reflection on the metal layer is suppressed, the thickness of the adhesion layer is preferably 3 nm or more as described above.

  The upper limit value of the thickness of the adhesion 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 adhesion layer is preferably 50 nm or less as described above, more preferably 35 nm or less, and further preferably 33 nm or less.

  Next, a configuration example of the conductive substrate will be described.

  As described above, the conductive substrate of this embodiment includes a transparent base material, a metal layer, and a blackened layer. For example, a metal layer and a blackened layer are laminated in that order on the transparent base material. It can be configured.

  A specific configuration example will be described below with reference to FIG. FIG. 1 shows an example of a cross-sectional view of the conductive substrate of the present embodiment on a plane parallel to the lamination direction of the transparent base material, the metal layer, and the blackening layer.

  For example, as in the conductive substrate 10A shown in FIG. 1A, the metal layer 12 and the blackening layer 13 are laminated in that order on the first main plane 11a side of the transparent base material 11 one by one. It can be. Moreover, like the electroconductive board | substrate 10B shown in FIG.1 (B), metal layer 12A, 12B on the 1st main plane 11a side of the transparent base material 11, and the 2nd main plane 11b side, respectively, The blackening layers 13A and 13B can be stacked one by one in that order.

  The conductive substrate of the present embodiment can be used for various applications such as a touch panel. And when using for various uses, it is preferable that the metal layer and blackening layer which are contained in the electroconductive board | substrate of this embodiment are patterned. The metal layer and the blackened layer can be patterned in accordance with a desired wiring pattern, for example, and the metal layer and the blackened layer are preferably patterned in the same shape.

  In the conductive substrate of this embodiment, as described above, the blackening layer 13 (13A, 13B) can be disposed on the upper surface of the metal layer 12 (12A, 12B). For this reason, reflection of the light from the upper surface side of the metal layer 12 (12A, 12B) can be suppressed.

  Further, as described above, for example, an adhesion layer (not shown) can be provided between the transparent substrate 11 and the metal layer 12. In the case of the conductive substrate 10B shown in FIG. 1B, an adhesion layer may be provided between the transparent base material 11 and the metal layer 12A and / or between the transparent base material 11 and the metal layer 12B. it can. By providing the adhesion layer, the adhesion between the transparent substrate 11 and the metal layer 12 (12A, 12B) can be improved, and the metal layer 12 (12A, 12B) is particularly prevented from peeling from the transparent substrate 11. can do. In addition, it is preferable to provide an adhesion layer because the reflection of light can be suppressed even on the surface of the metal layer 12 (12A, 12B) where the blackening layer is not provided.

  When the metal layer and the blackened layer are patterned, the adhesive layer can also be patterned in accordance with, for example, a desired wiring pattern, and the adhesive layer, the metal layer, and the blackened layer are patterned in the same shape. It is preferable.

  The degree of light reflection of the conductive substrate of the present embodiment is not particularly limited. For example, the reflectance (regular reflectance) of light having a wavelength of 400 nm to 700 nm is preferably 35% or less, More preferably, it is 30% or less. When the reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 35% or less, for example, even when used as a conductive substrate for a touch panel, the display visibility is hardly deteriorated, which is preferable.

  The light reflectance of the conductive substrate can be measured by irradiating the blackened layer 13 (13A, 13B) with light.

  Specifically, for example, when the metal layer 12 and the blackened layer 13 are laminated in this order on the first main plane 11a side of the transparent substrate 11 as shown in FIG. It can be measured by irradiating the surface 13a of the blackened layer 13 with light. Then, the wavelength is changed at a predetermined interval within the wavelength range of 400 nm to 700 nm, the reflectance is measured for the light of each wavelength, and the average value is the reflectance of the light having the wavelength of 400 nm to 700 nm of the conductive substrate. It can be. In the measurement, the light in the above wavelength range can be measured by changing the wavelength, for example, at a wavelength of 1 nm.

Further, regarding the surface of the blackening layer 13 (13A, 13B) of the conductive substrate of the present embodiment, it is preferable that the value of lightness (L ^* ) in the L ^* a ^* b ^* color system is small. This is because the blackened layer 13 (13A, 13B) and the metal layer 12 (12A, 12B) become less conspicuous as the value of the lightness (L ^* ) decreases, and the lightness of the surface of the blackened layer 13 (13A, 13B). (L ^* ) is preferably 60 or less.

  And since the metal layer is provided in the conductive substrate of this embodiment as mentioned above, the surface resistance of a conductive substrate can be made small. The surface resistance is preferably less than 0.2Ω / □, more preferably less than 0.15Ω / □, and even more preferably less than 0.06Ω / □. The method for measuring the surface resistance is not particularly limited. For example, the surface resistance can be measured by a four-probe method, and the measurement is preferably performed such that the probe contacts the blackened layer of the conductive substrate.

  Although the conductive substrate of this embodiment has been described so far, a laminated conductive substrate in which a plurality of conductive substrates of this embodiment are stacked may be used. When laminating a conductive substrate, it is preferable that the metal layer and the blackened layer included in the conductive substrate are patterned as described above. Moreover, when providing an adhesion layer, it is preferable that the adhesion layer is also patterned.

  In particular, when used for touch panel applications, the conductive substrate or the laminated conductive substrate preferably includes a mesh-like wiring as described later.

  Here, taking as an example the case of forming a laminated conductive substrate having mesh-like wiring by laminating two conductive substrates, the metal layer formed on the conductive substrate before lamination, and the pattern of the metal layer A configuration example of the shape will be described with reference to FIG. Although the patterned metal layer functions as a wiring, the adhesion layer and / or the blackened layer can also constitute a part of the wiring depending on the electric resistance value.

  FIG. 2A shows the conductive substrate 20 on the upper surface side, that is, the transparent base material of one of the two conductive substrates constituting the laminated conductive substrate having mesh-like wiring. It is the figure seen from the direction perpendicular | vertical to 11 main planes. FIG. 2B is a cross-sectional view taken along line AA ′ in FIG.

  2A and 2B, in the conductive substrate 20, the patterned metal layer 22 and the blackened layer 23 on the first main plane 11a of the transparent base material 11 are the same. Can have a shape. For example, the patterned blackened layer 23 has a plurality of linear patterns (blackened layer patterns 23A to 23G) shown in FIG. 2A. Parallel to each other and spaced apart from each other in the X-axis direction in the figure. At this time, when the transparent substrate 11 has a quadrangular shape as shown in FIG. 2 (A), the pattern of the blackened layer (blackened layer patterns 23A to 23G) so as to be parallel to one side of the transparent substrate 11. ) Is preferably arranged.

  As described above, the patterned metal layer 22 is also patterned in the same manner as the patterned blackened layer 23, and has a plurality of linear patterns (metal layer patterns). The patterns can be spaced apart from each other in parallel. Moreover, when providing the adhesion layer which is not shown in figure, it can be set as the same pattern also about an adhesion layer. For this reason, the 1st main plane 11a of the transparent base material 11 will be exposed between patterns.

  The pattern forming method of the patterned metal layer 22 and the blackened layer 23 shown in FIGS. 2A and 2B is not particularly limited. For example, after forming the blackened layer 23, a pattern can be formed by placing a mask having a shape corresponding to the pattern to be formed on the blackened layer 23 and etching it. The etching solution to be used is not particularly limited, and can be arbitrarily selected according to the material constituting the layer to be etched. For example, the etching solution can be changed for each layer, and the metal layer and the blackening layer, and in some cases, the adhesion layer can be etched simultaneously with the same etching solution.

  And a laminated conductive substrate can be formed by laminating | stacking two conductive substrates in which the metal layer and the blackening layer were patterned. A laminated conductive substrate will be described with reference to FIG. FIG. 3A shows a view of the laminated conductive substrate 30 as viewed from the upper surface side, that is, the upper surface side along the lamination direction of the two conductive substrates, and FIG. Sectional drawing in the BB 'line of (A) is shown.

  The laminated conductive substrate 30 is obtained by laminating a conductive substrate 201 and a conductive substrate 202 as shown in FIG. The conductive substrates 201 and 202 are both patterned metal layer 221 (222) and blackened layer 231 (232) on the first main plane 111a (112a) of the transparent base 111 (112). Are stacked. The patterned metal layers 221 (222) and the blackened layer 231 (232) of the conductive substrates 201 and 202 are both patterned so as to have a plurality of linear patterns as in the conductive substrate 20 described above. It has become.

  The first main plane 111a of the transparent base 111 of one conductive substrate 201 and the second main plane 112b of the transparent base 112 of the other conductive substrate 202 are laminated so as to face each other. .

  Note that one conductive substrate 201 is turned upside down, and the second main plane 111b of the transparent base 111 of the one conductive substrate 201 and the second main plane 111b of the other conductive substrate 202 are second. You may laminate | stack so that the main plane 112b may oppose. In this case, the arrangement is the same as in FIG.

  When two conductive substrates are stacked, as shown in FIGS. 3A and 3B, the patterned metal layer 221 of one conductive substrate 201 and the other conductive substrate 202 are stacked. It can be laminated so that the patterned metal layer 222 intersects. Specifically, for example, in FIG. 3A, the patterned metal layer 221 of one conductive substrate 201 can be arranged so that the length direction of the pattern is parallel to the X-axis direction in the drawing. The patterned metal layer 222 of the other conductive substrate 202 can be arranged so that the length direction of the pattern is parallel to the Y-axis direction in the drawing.

  Note that FIG. 3A is a view seen along the stacking direction of the stacked conductive substrate 30 as described above, and therefore, a patterned blackened layer disposed on the top of each conductive substrate 201, 202. 231 and 232 are shown. Since the patterned metal layers 221 and 222 have the same pattern as the patterned black layers 231 and 232, the patterned metal layers 221 and 222 are also patterned black layers 231 and 232. Similarly, it becomes a mesh shape. When the adhesion layer is provided, the patterned adhesion layer can also have a mesh shape similar to the patterned blackening layers 231 and 232.

  The method for adhering two laminated conductive substrates is not particularly limited. For example, the conductive substrates can be bonded and fixed with an adhesive or the like.

  As described above, by laminating one conductive substrate 201 and the other conductive substrate 202, as shown in FIG. 3A, a laminated conductive substrate provided with mesh-like wiring. 30.

  3A and 3B show an example in which a mesh-like wiring (wiring pattern) is formed by combining linear wiring, but the present invention is not limited to such a form. The wiring constituting the pattern can have any shape. For example, the shape of the wiring constituting the mesh-like wiring pattern can be changed to various shapes such as jagged lines (zigzag straight lines) so that moire (interference fringes) does not occur between the images on the display.

  Here, an example in which a laminated conductive substrate having a mesh-like wiring is formed by laminating two conductive substrates has been described, but a (laminated) conductive substrate having a mesh-like wiring is used. The method is not limited to such a form. For example, from the conductive substrate 10B shown in FIG. 1B in which the metal layers 12A and 12B and the blackening layers 13A and 13B are stacked on the first main plane 11a and the second main plane 11b of the transparent substrate 11. A conductive substrate provided with mesh-like wiring can be formed.

  In this case, the metal layer 12A and the blackening layer 13A laminated on the first main plane 11a side of the transparent substrate 11 are parallel to the Y-axis direction in FIG. 1B, that is, the direction perpendicular to the paper surface. Pattern into a plurality of linear patterns. Further, the metal layer 12B and the blackening layer 13B laminated on the second main plane 11b side of the transparent substrate 11 are patterned into a plurality of linear patterns parallel to the X-axis direction in FIG. To do. Patterning can be performed, for example, by etching as described above. As a result, as shown in FIG. 4, the patterned metal layer 42 </ b> A formed on the first main plane 11 a side of the transparent base material and the second main plane 11 b side across the transparent base material 11. With the formed patterned metal layer 42B, a conductive substrate having mesh-like wiring can be obtained.

  As shown in FIG. 4, blackened layers 43A and 43B patterned in the same shape as the metal layer 42A (42B) are formed on the patterned metal layer 42A and the patterned metal layer 42B. Will be placed.

  Up to this point, an example of a conductive substrate in which a metal layer patterned on at least one surface of a transparent base material and a blackened layer patterned in the same shape is laminated (laminated) has been described. It is not limited. A conductive substrate in which a blackened layer is disposed not only on the upper surface of the patterned metal layer but also on the side surface can be provided.

  For example, first, after forming a metal layer on at least one surface of the transparent substrate, the metal layer can be patterned into a desired shape before forming the blackened layer. As described above, an adhesion layer can be formed between the transparent substrate and the metal layer. When the adhesion layer is formed, the adhesion layer is also patterned when the metal layer is patterned. be able to. And after patterning a metal layer etc., a blackening layer can be formed so that the surface of the patterned metal layer may be covered.

  When the blackened layer is formed after patterning the metal layer or the like, for example, when the metal layer is patterned into a linear shape in the same manner as shown in FIGS. 2A and 2B, FIG. A blackened layer can be formed on the upper surface of the patterned metal layer 22 as in the case of. At the same time, a blackened layer can also be formed on the side surface of the patterned metal layer 22, that is, on the surface of the patterned metal layer 22 that is perpendicular to the transparent substrate 11.

  Thus, for example, in the conductive substrate 20 shown in FIGS. 2A and 2B, the conductive substrate 20 is patterned by forming a blackened layer on the side surface of the patterned metal layer 22. In addition, reflection of light on the side surface of the metal layer 22 can be suppressed. For this reason, when it uses for uses, such as a touch panel, it becomes possible to improve the visibility of a display especially.

  The conductive substrate in which the blackened layer is also formed on the side surface of the patterned metal layer 22 of the conductive substrate 20 shown in FIGS. 2A and 2B has been described as an example. In the conductive substrate 40, a blackened layer can be similarly disposed on the side surfaces of the patterned metal layers 42A and 42B. Further, in the laminated conductive substrate 30 shown in FIGS. 3A and 3B, a blackened layer can also be disposed on the side surfaces of the similarly patterned metal layers 221 and 222.

According to the (laminated) conductive substrate described above, the patterned metal layer has the patterned blackened layer disposed on the upper surface thereof. For this reason, reflection of light on the surface of the patterned metal layer can be suppressed. Moreover, since the metal layer is disposed, the electrical resistance value can be reduced. Furthermore, since the blackened layer is formed by a wet method as described above, it can be manufactured with high productivity.
(Method for producing conductive substrate, method for producing laminated conductive substrate)
Next, the structural example of the manufacturing method of the conductive substrate of this embodiment and the manufacturing method of a laminated conductive substrate is demonstrated.

The manufacturing method of the conductive substrate of this embodiment can have the following processes.
A metal layer forming step of forming a metal layer on at least one surface of the transparent substrate.
A blackening layer forming step of forming a blackening layer containing nickel and sulfur on the metal layer by a wet method.

  Although the manufacturing method of the electroconductive board | substrate of this embodiment and the manufacturing method of a laminated electroconductive board | substrate are demonstrated below, except the point demonstrated below, the structure similar to the case of the above-mentioned electroconductive board | substrate and a laminated electroconductive board | substrate is demonstrated. Therefore, a part of the description of the overlapping parts is omitted.

  The transparent base material used for the metal layer forming step can be prepared in advance. Although the kind of transparent base material to be used is not particularly limited, a resin substrate (resin film) that transmits visible light, a glass substrate, or the like can be preferably used as described above. The transparent base material can be cut into an arbitrary size in advance if necessary.

  And as above-mentioned, it is preferable that a metal layer has a metal thin film layer. The metal layer can also have a metal thin film layer and a metal plating layer. For this reason, a metal layer formation process can have a process of forming a metal thin film layer, for example by a dry-type plating method. The metal layer forming step includes a step of forming a metal thin film layer by a dry plating method, a step of forming a metal plating layer by an electroplating method which is a kind of wet plating method, using the metal thin film layer as a power feeding layer, You may have.

  The dry plating method used in the step of forming the metal thin film layer is not particularly limited, and for example, an evaporation method, a sputtering method, an ion plating method, or the like can be used. In addition, as a vapor deposition method, a vacuum vapor deposition method can be used preferably. As the dry plating method used in the step of forming the metal thin film layer, it is more preferable to use the sputtering method because the film thickness is particularly easy to control.

  When forming a metal thin film layer by sputtering, it can be suitably formed using, for example, a roll-to-roll sputtering apparatus.

  A method for forming a metal thin film layer will be described by taking as an example the case where the roll-to-roll sputtering apparatus 50 is used.

  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 base material for forming a metal thin film 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 metal thin film 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 can be configured such that the tension balance of the substrate on which the metal thin film 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.

  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 base material on which the metal thin film layer of the sputtering cathodes 54a to 54d is formed may be wider than the width of the base material on which the metal thin film layer is formed. preferable.

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

  When forming a metal thin film layer using the roll-to-roll sputtering apparatus 50, a predetermined target is mounted on the sputtering cathodes 54 a to 54 d, and a base material for forming the metal thin film layer is set on the unwinding roll 52. The inside of the apparatus is evacuated by vacuum pumps 60a and 60b. Thereafter, sputtering gas 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 base material from the unwinding roll 52 at a speed of, for example, 1 m or more and 20 m or less per minute, power is supplied from a sputtering DC power source connected to the sputtering cathodes 54a to 54d to perform sputtering discharge. Thereby, a desired metal thin film layer can be continuously formed on the substrate.

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

  Next, the blackening layer forming process will be described.

  In the blackened layer forming step, the blackened layer can be formed by a wet method. By forming the blackening layer by a wet method, the conductive substrate can be manufactured with high productivity as compared with the case where the blackening layer is formed only by a conventional dry method.

  Further, when the blackening layer is formed by a dry method as in the conventional case, for example, when a metal plating layer is formed by a wet method, after the metal plating layer is formed, the deposition target is removed from the wet method film forming apparatus. Since it was necessary to take out and dry a to-be-film-formed body, it was necessary to set it to the apparatus of a dry process, and productivity fell. On the other hand, in the manufacturing method of the conductive substrate of this embodiment, since the blackened layer is also formed by a wet method, the metal plated layer and the blackened layer are formed even when the metal plated layer is formed by a wet method apparatus. Can be formed continuously, and productivity can be particularly improved.

  The method for forming the blackened layer is not particularly limited as long as it is a wet method, and examples thereof include a method of newly forming and laminating a blackened layer on the metal layer by a wet plating method. In this case, for example, an electroless plating method can be preferably used as the wet plating method.

  Moreover, as a specific method for forming the blackened layer by a wet method, a method for forming the blackened layer by an electroplating method using a plating solution containing nickel and sulfur can be given. The kind of the plating solution used in this case is not particularly limited, and for example, a plating solution containing nickel and sulfur can be preferably used. In addition, it is possible to conduct a preliminary test on the relationship between the composition of the plating solution and the composition of the blackened layer to be formed in advance and select the composition of the plating solution so that a blackened layer having a desired composition can be obtained. preferable.

  Furthermore, an arbitrary process can be performed. For example, when forming an adhesion layer between a transparent substrate and a metal layer, an adhesion layer forming step of forming an adhesion layer on the surface of the transparent substrate on which the metal layer is formed can be performed. When carrying out the adhesion layer forming step, the metal layer forming step can be carried out after the adhesion layer forming step, and is transparent in this step with the substrate on which the metal thin film layer described in the metal layer forming step is formed. The base material has an adhesion layer formed on the base material.

  For example, in FIG. 1A, the adhesion layer can be formed on the first main plane 11 a that is one main plane of the transparent substrate 11. In the case of the conductive substrate 10B shown in FIG. 1B, an adhesion layer can be formed on both the first main plane 11a and the second main plane 11b of the transparent substrate 11. In the case where an adhesion layer is formed on both the first main plane 11a and the second main plane 11b of the transparent substrate 11, the adhesion layer may be formed simultaneously on both main planes. In addition, after the adhesion layer is formed on one of the main planes, the adhesion layer may be formed on the other main plane.

  The material constituting the adhesion layer is not particularly limited, the adhesion strength with the transparent substrate and the metal layer, the degree of suppression of light reflection on the surface of the metal layer, and the environment in which the conductive substrate is used ( For example, it can be arbitrarily selected according to the degree of stability with respect to humidity and temperature. Since materials that can be suitably used as the material constituting the adhesion layer have already been described, description thereof is omitted here.

  The method for forming the adhesion layer is not particularly limited. For example, as described above, the adhesion layer can be 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. In the case where the adhesion layer is formed by a dry method, it is more preferable to use a sputtering method because the film thickness can be easily controlled.

  As described above, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen can also be added to the adhesion layer, and in this case, a reactive sputtering method can be more preferably used.

  In the case where the adhesion layer contains one or more elements selected from carbon, oxygen, hydrogen, and nitrogen, one or more selected from carbon, oxygen, hydrogen, and nitrogen in the atmosphere when forming the adhesion layer By adding a gas containing these elements, it can be added to the adhesion layer. For example, when adding carbon to the adhesion layer, carbon monoxide gas and / or carbon dioxide gas, when adding oxygen, oxygen gas, when adding hydrogen, hydrogen gas and / or water, In the case of adding nitrogen, nitrogen gas can be added to the atmosphere when dry plating is performed.

  A gas containing one or more elements selected from carbon, oxygen, hydrogen, and nitrogen is preferably added to an inert gas and used as an atmosphere gas during dry plating. Although it does not specifically limit as an inert gas, For example, argon can be used preferably.

  When the adhesion layer is formed by a reactive sputtering method, a target containing a metal species that constitutes the adhesion layer can be used as the target. When the adhesion layer contains an alloy, a target may be used for each metal species contained in the adhesion layer, and the alloy may be formed on the surface of the film-formed body such as a transparent substrate. An alloyed target can also be used.

  The adhesion layer can be suitably formed using, for example, the roll-to-roll sputtering apparatus 50 shown in FIG.

  Since the configuration of the roll-to-roll sputtering apparatus has already been described, the description thereof is omitted here.

  When forming the adhesion layer using the roll-to-roll sputtering apparatus 50, a metal target constituting the adhesion layer is attached to the sputtering cathodes 54a to 54d, and a base material for forming the adhesion layer, for example, a transparent base material is used. Set on the unwinding roll 52. Then, the inside of the apparatus, for example, the inside of the casing 51 is evacuated by the vacuum pumps 60a and 60b. After that, sputtering gas such as argon gas 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 base material from the unwinding roll 52 at a speed of, for example, 0.5 m or more and 10 m or less per minute, power is supplied from a sputtering DC power source connected to the sputtering cathodes 54a to 54d to cause sputtering discharge. Do. Thereby, a desired adhesion layer can be continuously formed on the substrate.

  By forming the adhesion layer by dry plating as described above, the adhesion between the transparent substrate and the adhesion layer can be enhanced. And since an adhesion layer can contain a metal as a main component, for example, its adhesiveness with a metal layer is also high. For this reason, peeling of a metal layer can be suppressed by arrange | positioning an adhesion layer between a transparent base material and a metal layer.

  The thickness of the adhesion layer is not particularly limited, but is preferably 3 nm to 50 nm, for example, more preferably 3 nm to 35 nm, and still more preferably 3 nm to 33 nm.

  The conductive substrate obtained by the method for manufacturing a conductive substrate of the present embodiment can be used for various applications such as a touch panel. And when using for various uses, it is preferable that the metal layer and blackening layer which are contained in the electroconductive board | substrate of this embodiment are patterned. In addition, when providing an adhesion layer, it is preferable that the adhesion layer is also patterned. The metal layer and the blackening layer, and in some cases, the adhesion layer can be patterned, for example, in accordance with a desired wiring pattern. The metal layer and the blackening layer, and in some cases, the adhesion layer can be patterned in the same shape. It is preferable that

  For this reason, the manufacturing method of the electroconductive board | substrate of this embodiment can have the patterning process which patterns a metal layer and a blackening layer. When the adhesion layer is formed, the patterning step can be a step of patterning the adhesion layer, the metal layer, and the blackening layer.

  The specific procedure of the patterning step is not particularly limited, and can be performed by an arbitrary procedure. For example, in the case of the conductive substrate 10A in which the metal layer 12 and the blackened layer 13 are laminated on the transparent base material 11 as shown in FIG. 1A, a mask having a desired pattern is first arranged on the blackened layer 13. A mask placement step can be performed. Next, an etching step of supplying an etching solution to the upper surface of the blackening layer 13, that is, the surface side where the mask is disposed can be performed.

  The etching solution used in the etching step is not particularly limited, and can be arbitrarily selected according to the material constituting the layer to be etched. For example, the etching solution can be changed for each layer, and the metal layer and the blackening layer, and in some cases, the adhesion layer can be etched simultaneously with the same etching solution.

  The pattern formed in the etching process is not particularly limited. For example, the metal layer and the blackened layer can be patterned to form a plurality of linear patterns. When patterning into a plurality of linear patterns, as shown in FIGS. 2A and 2B, the patterned metal layer 22 and the blackened layer 23 are parallel to each other and spaced apart from each other. Pattern.

  Further, as shown in FIG. 1B, the conductive substrate 10B in which the metal layers 12A and 12B and the blackening layers 13A and 13B are stacked on the first main plane 11a and the second main plane 11b of the transparent substrate 11 is also used. A patterning process for patterning can be performed. In this case, for example, a mask placement step of placing a mask having a desired pattern on the blackening layers 13A and 13B can be performed. Next, an etching step of supplying an etching solution to the upper surfaces of the blackening layers 13A and 13B, that is, the surface side where the mask is disposed can be performed.

  In the etching step, for example, the metal layer 12A and the blackening layer 13A stacked on the first main plane 11a side of the transparent substrate 11 are parallel to the Y-axis direction in FIG. 1B, that is, the direction perpendicular to the paper surface. Can be patterned into a plurality of linear patterns. Further, the metal layer 12B and the blackened layer 13B laminated on the second main plane 11b side of the transparent substrate 11 can be patterned into a plurality of linear patterns parallel to the X-axis direction in FIG. As a result, as shown in FIG. 4, the patterned metal layer 42 </ b> A formed on the first main plane 11 a side of the transparent base material and the second main plane 11 b side across the transparent base material 11. With the formed patterned metal layer 42B, a conductive substrate having mesh-like wiring can be obtained.

  As described above, the patterning step can be performed after the metal layer forming step and before the blackening layer forming step. In this case, the metal layer is patterned in the patterning step. When the adhesion layer is formed, the adhesion layer and the metal layer are patterned.

  When the patterning step is performed before the blackening layer forming step, a mask having a desired pattern is placed on the metal layer in the mask placement step described above. In the etching process, an etching solution is supplied to the upper surface of the metal layer, that is, the surface side where the mask is disposed.

  The shape of the metal layer or the like to be patterned in the patterning step is not particularly limited, but can be patterned into an arbitrary shape such as a linear shape as described above. Then, by performing the blackened layer forming step after the patterning step, the blackened layer can be formed also on the side surface of the patterned metal layer, and the reflection of light on the surface of the metal layer is particularly suppressed. it can.

  And the laminated conductive substrate which laminated | stacked several conductive substrates demonstrated so far can also be manufactured. The method for producing a laminated conductive substrate can include a lamination step of laminating a plurality of conductive substrates obtained by the above-described method for producing a conductive substrate.

  In the stacking step, for example, a plurality of patterned conductive substrates shown in FIGS. 2A and 2B can be stacked. Specifically, as shown in FIGS. 3A and 3B, the first main plane 111a of the transparent base 111 of one conductive substrate 201 and the transparent of the other conductive substrate 202 are transparent. It can be implemented by laminating so that the second main plane 112b of the substrate 112 faces.

  After lamination, the two conductive substrates 201 and 202 can be fixed with an adhesive or the like, for example.

  Note that one conductive substrate 201 is turned upside down, and the second main plane 111b of the transparent base 111 of the one conductive substrate 201 and the second main plane 111b of the other conductive substrate 202 are second. You may laminate | stack so that the main plane 112b may oppose.

  In the case of a laminated conductive substrate provided with a mesh-like wiring, in the lamination step, as shown in FIGS. 3A and 3B, a pattern formed in advance on one conductive substrate 201 is formed. The metal layer 221 and the patterned metal layer 222 formed in advance on the other conductive substrate 202 can be stacked so as to intersect each other.

3A and 3B show an example in which a mesh-like wiring (wiring pattern) is formed by combining metal layers patterned in a linear shape, but the present invention is not limited to such a form. Absent. The wiring constituting the wiring pattern, that is, the shape of the patterned metal layer can be any shape. For example, the shape of the wiring constituting the mesh-like wiring pattern can be changed to various shapes such as jagged lines (zigzag straight lines) so that moire (interference fringes) does not occur between the images on the display. As described above, the patterned metal layer functions as a wiring, but the adhesion layer and / or the blackened layer can also constitute a part of the wiring depending on the electric resistance value.
According to the conductive substrate and the laminated conductive substrate obtained by the conductive substrate manufacturing method and the laminated conductive substrate manufacturing method of the present embodiment described above, the electric resistance value can be reduced because the metal layer is provided. Moreover, since the blackening layer is arrange | positioned on the metal layer, reflection of light can be suppressed. Furthermore, since the blackened layer can be formed by a wet method, it can be manufactured with high productivity.

Specific examples and comparative examples will be described below, but the present invention is not limited to these examples.
(Evaluation method)
First, a method for evaluating the obtained conductive substrate will be described.
(Composition of blackened layer)
Composition analysis of the blackened layer formed on the surface of the obtained conductive substrate was performed using EPMA (Electron Probe MicroAnalyzer JEOL Ltd., model: JXA-8900R). From the measurement results, the weight percent of Ni and S was calculated when the sum of the weights of Ni and S (sulfur) contained in the blackened layer was taken as 100.

(Surface resistance)
The surface resistance of the conductive substrates produced in the following examples and comparative examples was measured using a low resistivity meter (model number: Lorester EP MCP-T360, manufactured by Dia Instruments Co., Ltd.). The measurement was performed by the 4-probe method, and the measurement was performed such that the probe was in contact with the blackened layer.

(Appearance evaluation)
The surface of the blackened layer was visually confirmed and the appearance was evaluated. In the evaluation, when the surface color of the blackened layer is uniform and there is no unevenness, ◯, when even a little unevenness is seen, Δ, when unevenness is seen over the entire surface of the blackened layer X was evaluated.

(Regular reflectance)
The measurement was performed by installing a reflectance measurement unit in an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV-2600).

The surface of the blackened layer of the conductive substrate prepared in the following examples and comparative examples is irradiated with light having a wavelength of 400 nm or more and 700 nm or less at intervals of 1 nm at an incident angle of 5 ° and a light receiving angle of 5 °. The regular reflectance of each light was measured, and the average value of the measurement results was taken as the regular reflectance of the conductive substrate.
(brightness)
About the blackening layer surface of the electroconductive board | substrate produced by the following example and the comparative example, light with a wavelength of 400 nm or more and 700 nm or less is wavelength 1 nm intervals with an ultraviolet visible spectrophotometer (Shimadzu Corporation model: UV-2600). The brightness was measured by irradiation.
(Sample preparation conditions)
As examples and comparative examples, conductive substrates were produced under the conditions described below and evaluated by the above-described evaluation method.
[Example 1]
(Adhesion layer forming process)
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. In addition, about the transparent base material made from the polyethylene terephthalate resin used as a transparent base material, when the total light transmittance was evaluated by the method prescribed | regulated to JISK7361-1, it was 97%.

  Then, an adhesion layer was formed on one main plane of the transparent substrate by the roll-to-roll sputtering apparatus 50. A Ni—Cr alloy layer containing oxygen was formed as the adhesion layer.

  The conditions for forming the adhesion layer will be described.

  Ni-17 wt% Cr alloy targets were connected to the sputtering cathodes 54a to 54d of the roll-to-roll sputtering apparatus 50 shown in FIG.

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

Subsequently, after the inside of the casing 51 was evacuated to 1 × 10 ⁻³ Pa, argon gas and oxygen gas were introduced to adjust the pressure in the casing 51 to 1.3 Pa. At this time, the supply amounts of argon gas and oxygen gas were adjusted so that the atmosphere in the casing 51 was 30% oxygen by volume and the balance 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, sputtering discharge is performed, and a desired adhesion layer is continuously formed on the transparent base material. Filmed. With this operation, an adhesion layer was formed on one main plane of the transparent substrate so as to have a thickness of 20 nm.
(Metal layer forming process)
In the metal layer forming step, a metal thin film layer forming step and a metal plating layer forming step were performed.

  First, the metal thin film layer forming step will be described.

  A metal thin film layer was formed on the adhesion layer using a roll-to-roll sputtering apparatus 50. A copper thin film layer was formed as the metal thin film layer.

  In the metal thin film layer forming step, a copper target is connected to the sputtering cathodes 54a to 54d of the roll-to-roll sputtering apparatus 50 shown in FIG. 5 to form a film. A material having an adhesion layer formed on a material was used.

  The metal thin film layer was formed in the same manner as the adhesion layer forming step except that the following two points and the target were changed as described above.

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 point which formed the copper thin film layer which is a metal thin film layer so that film thickness might be set to 150 nm.

Next, in the metal plating layer forming step, a copper plating layer was formed as the metal plating layer. A copper plating layer was formed to have a thickness of 2.0 μm by electroplating.
(Blackening layer forming process)
Using a plating solution prepared by setting the weight ratio of Ni and S in the plating solution to 90:10, a blackened layer was formed on the surface of the metal layer to a thickness of 0.4 μm by electroplating. .

  As a result, a blackening layer is formed on the upper surface of the metal layer, that is, the surface opposite to the surface of the metal layer facing the adhesion layer, and the adhesion layer, the metal layer, and the blackening layer are arranged in that order on the transparent substrate. As a result, a conductive substrate laminated in the above was obtained.

  About the obtained electroconductive board | substrate, the composition of the above-mentioned blackening layer, surface resistance, an external appearance, a regular reflectance, and the brightness were evaluated. The results are shown in Table 1.

  It should be noted that the blackening layer produced by what is described as “blackening layer composition (Ni: S)” in Table 1 was calculated from the values analyzed by EPMA as described above. The weight ratio is shown. And what has been described as "plating solution composition (Ni: S) at the time of blackening layer formation" has shown the weight ratio of Ni and Zn in the plating solution at the time of producing a blackening layer.

  In addition, FIG. 6 shows a graph of measured values for surface resistance in this example, and the following examples and comparative examples, and FIG. 7 shows a graph of measured values for regular reflectance. FIG. 8 shows graphs of the measured values for.

  About the electroconductive board | substrate obtained by the present Example, the etching process was implemented after implementing the mask arrangement | positioning process which forms the mask corresponding to the pattern formed in the blackening layer surface. By etching the adhesion layer, the metal layer, and the blackening layer with an etching solution (cupric chloride aqueous solution) in the etching step, the adhesion layer, the metal layer, and the blackening layer are shown in FIGS. A conductive substrate patterned into a plurality of linear patterns as shown was obtained. 2A and 2B show an example in which the adhesion layer is not arranged, but in this embodiment, the adhesion layer patterned in the same shape as the metal layer and the blackening layer. Is disposed between the transparent substrate 11 and the metal layer 12.

  In addition, another conductive substrate in which the adhesion layer, the metal layer, and the blackening layer were patterned in the same shape as described above was manufactured by the same procedure as described above.

Then, the two produced conductive substrates were laminated as shown in FIGS. 3A and 3B, and both the conductive substrates were fixed with an adhesive to produce a laminated conductive substrate. 3A and 3B also show examples in which the adhesion layer is not provided. In this embodiment, the transparent substrate 111 and the metal layer 221 and the transparent substrate are used. An adhesion layer patterned in the same shape as the metal layer 221 and the metal layer 222 is disposed between the metal layer 222 and the metal layer 222.
[Example 2]
In the blackening layer forming step, a conductive substrate was produced in the same manner as in Example 1 except that the plating solution prepared so that the weight ratio of Ni and S in the plating solution was 85:15 was used. .

  About the obtained electroconductive board | substrate, the composition of the above-mentioned blackening layer, surface resistance, an external appearance, a regular reflectance, and the brightness were evaluated. The results are shown in Table 1 and FIGS.

Moreover, about the obtained electroconductive board | substrate, it carried out similarly to the case of Example 1, and patterned the adhesion layer, the metal layer, and the blackening layer. Further, another conductive substrate in which the adhesion layer, the metal layer, and the blackening layer were patterned in the same manner was produced. Then, two conductive substrates were laminated and fixed in the same manner as in Example 1 to produce a laminated conductive substrate.
[Example 3]
In the blackening layer forming step, a conductive substrate was produced in the same manner as in Example 1 except that a plating solution prepared so that the weight ratio of Ni and S in the plating solution was 48:52 was used. .

  About the obtained electroconductive board | substrate, the composition of the above-mentioned blackening layer, surface resistance, an external appearance, a regular reflectance, and the brightness were evaluated. The results are shown in Table 1 and FIGS.

Moreover, about the obtained electroconductive board | substrate, it carried out similarly to the case of Example 1, and patterned the adhesion layer, the metal layer, and the blackening layer. Further, another conductive substrate in which the adhesion layer, the metal layer, and the blackening layer were patterned in the same manner was produced. Then, two conductive substrates were laminated and fixed in the same manner as in Example 1 to produce a laminated conductive substrate.
[Comparative Example 1]
In the blackening layer forming step, the same procedure as in Example 1 was performed except that a nickel plating solution (manufactured by JCU Co., Ltd.) prepared so that the weight ratio between Ni and S in the plating solution was 100: 0 was used. Thus, a conductive substrate was produced.

  About the obtained electroconductive board | substrate, the composition of the above-mentioned blackening layer, surface resistance, an external appearance, a regular reflectance, and the brightness were evaluated. The results are shown in Table 1 and FIGS.

Moreover, about the obtained electroconductive board | substrate, it carried out similarly to the case of Example 1, and patterned the adhesion layer, the metal layer, and the blackening layer. Further, another conductive substrate in which the adhesion layer, the metal layer, and the blackening layer were patterned in the same manner was produced. Then, two conductive substrates were laminated and fixed in the same manner as in Example 1 to produce a laminated conductive substrate.
[Comparative Example 2]
In the blackening layer forming step, the same procedure as in Example 1 was performed except that a sulfur plating solution (manufactured by JCU Co., Ltd.) prepared so that the weight ratio of Ni and S in the plating solution was 0: 100 was used. Thus, a conductive substrate was produced.

  About the obtained electroconductive board | substrate, the composition of the above-mentioned blackening layer, surface resistance, an external appearance, a regular reflectance, and the brightness were evaluated. The results are shown in Table 1 and FIGS.

  Moreover, about the obtained electroconductive board | substrate, it carried out similarly to the case of Example 1, and patterned the adhesion layer, the metal layer, and the blackening layer. Further, another conductive substrate in which the adhesion layer, the metal layer, and the blackening layer were patterned in the same manner was produced. Then, two conductive substrates were laminated and fixed in the same manner as in Example 1 to produce a laminated conductive substrate.

表１、及び図６〜図８に示した結果から、ニッケルと硫黄とを含有する黒化層を有する実施例１〜実施例３の導電性基板については、黒化層表面での反射率が３５％以下、表面抵抗が０．２Ω／□未満、明度（Ｌ^＊）が６０以下となっていることを確認できた。これらの結果から、実施例１〜実施例３では、金属層表面での反射を抑制しつつも、電気抵抗値が小さい導電性基板が得られていることを確認できた。また、明度も６０以下になっていることから、密着層、金属層、及び黒化層をパターン化した場合に、パターン化した密着層、金属層、及び黒化層の積層体が目立たなくなることも確認できた。さらに、実施例１〜実施例３の導電性基板については外観評価が〇であり、黒化層表面での色ムラも十分に抑制できていることを確認できた。

From the results shown in Table 1 and FIGS. 6 to 8, the conductive substrate of Examples 1 to 3 having a blackening layer containing nickel and sulfur has a reflectance on the surface of the blackening layer. It was confirmed that the surface resistance was 35% or less, the surface resistance was less than 0.2Ω / □, and the lightness (L ^* ) was 60 or less. From these results, in Examples 1 to 3, it was confirmed that a conductive substrate having a small electric resistance value was obtained while suppressing reflection on the surface of the metal layer. In addition, since the brightness is 60 or less, when the adhesion layer, the metal layer, and the blackening layer are patterned, the laminated body of the patterned adhesion layer, metal layer, and blackening layer becomes inconspicuous. Was also confirmed. Furthermore, about the electroconductive board | substrate of Example 1- Example 3, external appearance evaluation is (circle) and it has confirmed that the color nonuniformity on the blackening layer surface was fully suppressed.

  In contrast, for the conductive substrates of Comparative Example 1 in which the blackened layer does not contain sulfur and Comparative Example 2 in which the blackened layer does not contain nickel, the regular reflectances are 35.10% and 60.50%, respectively. It was confirmed that reflection on the surface of the metal layer could not be sufficiently suppressed. In particular, in Comparative Example 2, the external appearance evaluation was x, and it was confirmed that the color unevenness on the surface of the blackened layer was tight.

  Moreover, also about the laminated electroconductive board | substrate produced in Example 1- Example 3, the reflection of the light in the metal layer surface can be suppressed, and the laminated body of an adhesion layer, a metal layer, and a blackening layer becomes inconspicuous. I was able to confirm.

  From the above results, the conductive substrate provided with the metal layer and the blackened layer containing nickel and sulfur formed by the wet method on the transparent substrate has a small electric resistance value and reflects light. It was confirmed that it could be sufficiently suppressed. Moreover, since the blackening layer can be formed by a wet method, it has been confirmed that it can be produced with high productivity.

10A, 10B, 20, 201, 202, 40 Conductive substrate 11, 111, 112 Transparent base material 12, 12A, 12B, 22, 221, 222, 42A, 42B Metal layers 13, 13A, 13B, 23, 231, 232 , 43A, 43B Blackening layer 30 Multilayer conductive substrate

Claims (3)

A metal layer forming step of forming a metal layer on at least one surface of the transparent substrate;
By a wet method on the metal layer, it possesses the blackening layer forming step of forming a blackened layer containing nickel and sulfur, and
The manufacturing method of the electroconductive board | substrate which is 40 wt% or more and 99 wt% or less in the weight ratio among nickel and sulfur contained in the said blackening layer . The method for manufacturing a conductive substrate according to claim 1 , further comprising a patterning step of patterning the metal layer and the blackened layer. Method for producing a laminated conductive substrate having Claim 1 or 2 laminating step of laminating a plurality a conductive substrate obtained by the method for producing a conductive substrate according to.

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