JP6905828B2 - Conductive substrate, laminated conductive substrate, 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 manufacturing a conductive substrate, and a method for manufacturing a laminated conductive substrate.

Capacitive touch panels convert information about the position of nearby objects on the panel surface into electrical signals by detecting changes in capacitance caused by objects close to the panel surface. Since the conductive substrate used for the capacitive touch panel is installed on the surface of the display, it is required that the wiring material of the conductive substrate has low reflectance and is difficult to see.

Therefore, as the wiring material used for the capacitive touch panel, a material having low reflectance and difficult to see 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, the screen size of displays equipped with touch panels has been increasing, and in response to this, the area of conductive substrates such as transparent conductive films for touch panels is also required to be increased. However, ITO has a high electric resistance value and causes signal deterioration, so that there is a problem that it is not suitable for a large panel.

Therefore, for example, as disclosed in Patent Documents 2 and 3, it is considered to use a metal foil such as copper instead of the ITO film. However, for example, when copper is used for the metal layer, since copper has a metallic luster, there is a problem that the visibility of the display is lowered due to reflection.

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

Japanese Patent Application Laid-Open No. 2003-151358 Japanese Patent Application Laid-Open No. 2011-018194 Japanese Patent Application Laid-Open No. 2013-069261

However, conventionally, all the blackening layers are formed by a dry method, and it takes time to form a blackening layer having a thickness capable of sufficiently suppressing the metallic luster of the metal layer composed of the metal foil. , There was a problem of low productivity.

In view of the above problems of the prior art, it is an object of the present invention to provide a conductive substrate having a small electric resistance value, capable of suppressing light reflection, and capable of being manufactured with high productivity.

In order to solve the above problems, in one aspect of the present invention,
With a transparent base material
An adhesion layer which is an oxygen-containing Ni—Cr alloy layer formed on at least one surface of the transparent substrate, and a metal layer formed on the adhesion layer.
Provided is a conductive substrate having a blackening layer containing nickel and zinc formed on the metal layer by a wet method.

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

Sectional drawing of the conductive substrate which concerns on embodiment of this invention. Sectional drawing of the conductive substrate which concerns on embodiment of this invention. FIG. 6 is a configuration explanatory view of a patterned conductive substrate according to an embodiment of the present invention. FIG. 6 is a configuration explanatory view of a patterned conductive substrate according to an embodiment of the present invention. FIG. 6 is a configuration explanatory view of a laminated conductive substrate provided with mesh-shaped wiring according to an embodiment of the present invention. FIG. 6 is a configuration explanatory view of a laminated conductive substrate provided with mesh-shaped wiring according to an embodiment of the present invention. FIG. 3 is a cross-sectional view of a conductive substrate provided with mesh-shaped wiring according to an embodiment of the present invention. Explanatory drawing of the roll-to-roll sputtering apparatus which concerns on embodiment of this invention. Surface resistance measured on the surface of the blackened layer of the conductive substrate produced in Examples and Comparative Examples. Specular reflectance on the surface of the blackened layer of the conductive substrate produced in Examples and Comparative Examples. Brightness on the surface of the blackened layer of the conductive substrate produced in Examples and Comparative Examples.

Hereinafter, an embodiment of the conductive substrate, the laminated conductive substrate, the method for manufacturing the conductive substrate, and the method for manufacturing the laminated conductive substrate of the present invention will be described.
(Conductive substrate)
The conductive substrate of the present embodiment is a black containing a transparent base material, a metal layer formed on at least one surface of the transparent base material, and nickel and zinc formed on the metal layer by a wet method. It can have a chemical layer.

The conductive substrate in the present embodiment is a substrate having a metal layer and a blackening layer on the surface of a transparent substrate and a substrate in which the metal layer or the like is patterned before patterning the metal layer or the like, that is, Includes a wiring board. Further, since the conductive substrate after patterning the metal layer and the blackening layer includes a region where the transparent substrate is not covered by the metal layer or the like, light can be transmitted, and the conductive substrate is a transparent conductive substrate. ..

Here, first, each member included in the conductive substrate will be described below.

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

As the material of the resin substrate that transmits visible light, for example, resins such as polyamide resin, polyethylene terephthalate resin, polyethylene naphthalate resin, cycloolefin resin, polyimide resin, and polycarbonate resin 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 of the resin substrate that transmits visible light.

The thickness of the transparent base material is not particularly limited, and can be arbitrarily selected according to the strength, capacitance, light transmittance, etc. required when the conductive substrate is used. The thickness of the transparent substrate can be, for example, 10 μm or more and 200 μm or less. In particular, when used in a touch panel application, the thickness of the transparent base material is preferably 20 μm or more and 120 μm or less, and more preferably 20 μm or more and 100 μm or less. When used for a touch panel, for example, especially in an application where it is required to reduce the thickness of the entire display, the thickness of the transparent base material is preferably 20 μm or more and 50 μm or less.

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

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

The transparent base material has a first main plane and a second main plane, and the main plane referred to here refers to a flat surface portion having the largest area among the planes included in the transparent base material. The first main plane and the second main plane mean planes arranged so as to face each other in one transparent base material.

Next, the metal layer will be described.

The material constituting the metal layer is not particularly limited, and a material having an electric conductivity suitable for the intended use can be selected. For example, Cu and Ni, Mo, Ta, Ti, V, Cr, Fe, Mn, Co, W A copper alloy with at least one metal selected from the above, or a material containing copper is preferable. Further, the metal layer may be a copper layer made of copper.

The method for forming the metal layer on the transparent base material is not particularly limited, but it is preferable not to dispose an adhesive between the transparent base material and the metal layer in order not to reduce the light transmittance. That is, the metal layer is preferably formed directly on the upper surface of the transparent base material. When the adhesion layer is arranged between the transparent base material and the metal layer as described later, it is preferably formed directly on the upper surface of the adhesion layer.

Since the metal layer is directly formed on the upper surface of the transparent base material, the metal layer preferably has a metal thin film layer. Further, 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. As a result, the metal layer can be directly formed on the transparent base material without using an adhesive. As the dry plating method, which will be described in detail later, for example, a sputtering method, a vapor deposition method, or the like can be preferably used.

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 an electroplating method, which is a kind of wet plating method, using the metal thin film layer as a feeding layer. It can also be a metal layer to have. 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 base material without using an adhesive in this case as well.

The thickness of the metal layer is not particularly limited, and when the metal layer is used as wiring, it can be arbitrarily selected according to the magnitude of the current supplied to the wiring, the wiring width, and the like. The thickness of the metal layer is preferably 50 nm or more, more preferably 60 nm or more, and further preferably 150 nm or more so that a sufficient current can be supplied. The upper limit of the thickness of the metal layer is not particularly limited, but when the metal layer becomes thick, side etching occurs because etching takes time when etching is performed to form a wiring pattern, and the resist is peeled off during etching. It is easy to cause problems such as etching. Therefore, the thickness of the metal layer is preferably 8 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less.

When the metal layer has the metal thin film layer and the metal plating layer as described above, the total of the thickness of the metal thin film layer and the thickness of the metal plating layer is preferably in the above range.

Whether the metal layer is composed of a metal thin film layer or a metal thin film layer and a metal plating layer, the thickness of the metal thin film layer is not particularly limited, but is, for example, 50 nm. It is preferably 5 nm or more and 500 nm or less.

The metal layer can be used as wiring, for example, by patterning it into a desired wiring pattern as described later. Since the metal layer can have a lower electric resistance value than ITO which has been conventionally used as a transparent conductive film, the electric resistance value of the conductive substrate can be reduced by providing the metal layer.

Next, the blackening 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 zinc.

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

The method for forming the blackened layer may be a wet method and is not particularly limited. For example, a method of newly forming and laminating a blackened layer on a metal layer by a wet plating method can be mentioned. As the wet plating method in this case, for example, an electroplating method can be preferably used.

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

The ratio of nickel to nickel and zinc contained in the blackening layer here indicates the ratio of nickel when the total amount of nickel and zinc contained in the blackening layer is 100 wt%. , The balance is the proportion of zinc. Therefore, when the above range is shown by the weight ratio of nickel: zinc 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 to 40 wt% or more, it is possible to suppress color unevenness on the surface of the blackened layer. 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. It is preferable because it can enhance the aesthetic appearance.

Further, since the blackening layer contains nickel and zinc, the color can suppress the reflection of light by the metal layer regardless of the ratio, but the proportion of nickel in the nickel and zinc contained in the blackening layer is When it is 99 wt% or less, it is particularly preferable because the reflection of light by the metal layer can be suppressed.

In particular, the proportion of nickel in the nickel and zinc contained in the blackening layer is more preferably 70 wt% or more and 99 wt% or less, and further preferably 75 wt% or more and 99 wt% or less in terms of weight ratio.

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

The thickness of the blackening layer is not particularly limited, and can be arbitrarily selected depending on the degree of reflectance required for the conductive substrate and the like. The thickness of the blackened layer is preferably 5 nm or more, and more preferably 15 nm or more so that the reflection of light on the surface of the metal layer can be sufficiently suppressed.

The upper limit of the thickness of the blackened layer is not particularly limited, but the thickness of the blackened layer is preferably 1 μm or less in consideration of the productivity when forming the wiring pattern. In particular, it is more preferably 500 nm or less from the viewpoint of increasing productivity.

Further, the conductive substrate may be provided with any layer other than the above-mentioned transparent base material, metal layer and blackening layer. For example, an adhesion layer can be provided.

An example of the structure of the adhesion layer will be described.

As described above, the metal layer can be formed on the transparent base material, but when the metal layer is directly formed on the transparent base material, the adhesion between the transparent base material and the metal layer may not be sufficient. .. Therefore, when the metal layer is formed directly on the upper surface of the transparent base material, the metal layer may be peeled off from the transparent base material during the manufacturing process or during use.

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

By arranging the adhesion layer between the transparent base material and the metal layer, the adhesion between the transparent base material and the metal layer can be enhanced, and the peeling of the metal layer from the transparent base material can be suppressed.

In addition, the adhesion layer can also function as a blackening layer. Therefore, it is 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, and the adhesion to the transparent base material and the metal layer, the required degree of suppression of light reflection on the surface of the metal layer, and the use of a conductive substrate are used. It can be arbitrarily selected according to the degree of stability with respect to the environment (for example, humidity and temperature).

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

The adhesion layer may also contain a metal alloy containing at least two or more metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. Also in this case, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be further contained. At this time, the Cu—Ti—Fe alloy is a metal alloy containing at least two or more metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. Alternatively, Cu—Ni—Fe alloys, Ni—Cu alloys, Ni—Zn alloys, Ni—Ti alloys, Ni—W alloys, Ni—Cr alloys, and Ni—Cu—Cr alloys 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 and the like can be preferably used. When the adhesion layer is formed by the dry method, it is more preferable to use the 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 be added to the adhesion layer, and in this case, the 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 are included in the atmosphere when the adhesion layer is formed. By adding a gas containing the element of, it can be added to the adhesion layer. For example, carbon monoxide gas and / or carbon dioxide gas when carbon is added to the adhesion layer, oxygen gas when oxygen is added, hydrogen gas and / or water when hydrogen is added, When nitrogen is added, nitrogen gas can be added to the atmosphere at the time of dry plating.

A gas containing one or more elements selected from carbon, oxygen, hydrogen, and nitrogen is preferably added to the inert gas to be an atmospheric gas for dry plating. The inert gas is not particularly limited, but for example, argon can be preferably used.

By forming the adhesion layer by the dry plating method as described above, the adhesion between the transparent base material and the adhesion layer can be improved. Further, since the adhesion layer can contain, for example, a metal as a main component, the adhesion to the metal layer is also high. Therefore, by arranging the adhesion layer between the transparent base material and the metal layer, peeling of the metal layer can be suppressed.

The thickness of the adhesion layer is not particularly limited, but is preferably 3 nm or more and 50 nm or less, more preferably 3 nm or more and 35 nm or less, and further preferably 3 nm or more and 33 nm or less.

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

The upper limit of the thickness of the adhesion layer is not particularly limited, but even if it is made thicker than necessary, the time required for film formation and the time required for etching when forming wiring will increase, resulting in an increase in cost. I will invite you. Therefore, the thickness of the adhesion layer is preferably 50 nm or less, more preferably 35 nm or less, and further preferably 33 nm or less as described above.

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

As described above, the conductive substrate of the present embodiment includes a transparent base material, a metal layer, and a blackening layer, and the metal layer and the blackening layer are laminated in this order on the transparent base material. Can be.

A specific configuration example will be described below with reference to FIGS. 1A and 1B. 1A and 1B show an example of a cross-sectional view of the conductive substrate of the present embodiment on a plane parallel to the stacking 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 layer by layer on the first main plane 11a side of the transparent substrate 11. Can be done. Further, as in the conductive substrate 10B shown in FIG. 1B, the metal layers 12A and 12B and the blackening layer are formed on the first main plane 11a side and the second main plane 11b side of the transparent base material 11, respectively. 13A and 13B can be laminated layer by layer in that order.

The conductive substrate of this embodiment can be used for various purposes such as a touch panel. When used for various purposes, it is preferable that the metal layer and the blackening layer contained in the conductive substrate of the present embodiment are patterned. The metal layer and the blackening layer can be patterned according to a desired wiring pattern, for example, and it is preferable that the metal layer and the blackening layer are patterned in the same shape.

In the conductive substrate of this embodiment, the blackening layer 13 (13A, 13B) is arranged on the upper surface of the metal layer 12 (12A, 12B) as described above. Therefore, it is possible to suppress the reflection of light from the upper surface side of the metal layer 12 (12A, 12B).

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

When patterning the metal layer and the blackening layer, the adhesion layer can also be patterned according to a desired wiring pattern, for example, and the adhesion layer, the metal layer, and the blackening layer are patterned into the same shape. Is preferable.

The degree of light reflection of the conductive substrate of the present embodiment is not particularly limited, but for example, the reflectance (normal reflectance) of light having a wavelength of 400 nm or more and 700 nm or less 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 visibility of the display is hardly deteriorated, which is preferable.

The reflectance can be measured by irradiating the blackening layer 13 (13A, 13B) with light.

Specifically, for example, when the metal layer 12 and the blackening layer 13 are laminated in this order on the first main plane 11a side of the transparent base material 11 as shown in FIG. 1A, the blackening layer 13 is black so as to irradiate light. Light can be irradiated from the surface 13a side of the chemical layer 13 for measurement. In the measurement, light having a wavelength of 400 nm or more and 700 nm or less is irradiated to the blackening layer 13 of the conductive substrate as described above at intervals of, for example, 1 nm, and the average value of the measured values is taken as the reflectance of the conductive substrate. be able to.

Further, with respect to the surface of the blackening layer 13 (13A, 13B) of the conductive substrate of the present embodiment, it is preferable that the numerical value of the brightness (L ^{* ) in the L *} a ^* b ^{* color system is small.} This is because the blackening layer 13 (13A, 13B) and the metal layer 12 (12A, 12B) become less noticeable as the value of the lightness (L ^{*) becomes smaller, and the brightness of the surface of the blackening layer 13 (13A, 13B) becomes less noticeable.} (L ^* ) is preferably 60 or less.

Since the conductive substrate of the present embodiment is provided with the metal layer as described above, the surface resistance of the conductive substrate can be reduced. The surface resistance is preferably less than 0.2 Ω / □, more preferably less than 0.15 Ω / □, and even more preferably less than 0.06 Ω / □. The method for measuring the surface resistance is not particularly limited, but for example, it can be measured by the four-probe method, and it is preferable to perform the measurement so that the probe comes into contact with the blackened layer of the conductive substrate.

Although the conductive substrate of the present embodiment has been described so far, it is also possible to obtain a laminated conductive substrate in which a plurality of conductive substrates of the present embodiment are laminated. When laminating the conductive substrates, it is preferable that the metal layer and the blackening layer contained in the conductive substrate are patterned as described above. Further, when the adhesion layer is provided, it is preferable that the adhesion layer is also patterned.

In particular, when used in a touch panel application, it is preferable that the conductive substrate or the laminated conductive substrate is provided with mesh-shaped wiring as described later.

Here, taking as an example a case where two conductive substrates are laminated to form a laminated conductive substrate having mesh-shaped wiring, a metal layer formed on the conductive substrate before lamination and a pattern of the metal layer are used. A configuration example of the shape will be described with reference to FIGS. 2A and 2B. The patterned metal layer functions as wiring, but the adhesion layer and / or the blackened layer can also form a part of the wiring depending on the electric resistance value.

In FIG. 2A, of the two conductive substrates constituting the laminated conductive substrate provided with the mesh-like wiring, the conductive substrate 20 is placed on the upper surface side of one of the conductive substrates, that is, the main transparent substrate 11. It is a figure seen from the direction perpendicular to a plane. Further, FIG. 2B shows a cross-sectional view taken along the line AA'of FIG. 2A.

As shown in FIGS. 2A and 2B, in the conductive substrate 20, the patterned metal layer 22 and the blackening layer 23 on the transparent substrate 11 have the same shape. For example, the patterned blackening layer 23 has a plurality of linear patterns (blackening layer patterns 23A to 23G) shown in FIG. 2A, and the plurality of linear patterns are parallel to the Y axis in the drawing. Moreover, they can be arranged apart from each other in the X-axis direction in the figure. At this time, when the transparent base material 11 has a rectangular shape as shown in FIG. 2A, the blackening layer patterns (blackening layer patterns 23A to 23G) are arranged so as to be parallel to one side of the transparent base material 11. It is preferable to be done.

As described above, the patterned metal layer 22 is also patterned in the same manner as the patterned blackening layer 23, has a plurality of linear patterns (metal layer patterns), and has a plurality of such patterns. Can be placed parallel to each other and separated from each other. Further, when an adhesive layer (not shown) is provided, the same pattern can be applied to the adhesive layer. Therefore, the first main plane 11a of the transparent base material 11 is exposed between the patterns.

The pattern forming method of the patterned metal layer 22 and the blackening layer 23 shown in FIGS. 2A and 2B is not particularly limited. For example, in the conductive substrate shown in FIG. 1A, after forming the blackening layer 13, a mask having a shape corresponding to the pattern formed on the surface 13a of the blackening layer 13 is arranged and etched to form a pattern. .. The etching solution to be used is not particularly limited, and can be arbitrarily selected depending on the material constituting the layer to be etched. For example, the etching solution can be changed for each layer, and the metal layer, the blackening layer, and in some cases, the adhesion layer can be further etched with the same etching solution at the same time.

Then, the laminated conductive substrate can be formed by laminating two conductive substrates in which the metal layer and the blackening layer are patterned. The laminated conductive substrate will be described with reference to FIGS. 3A and 3B. FIG. 3A shows a view of the laminated conductive substrate 30 from the upper surface side, that is, the upper surface side along the laminating direction of the two conductive substrates, and FIG. 3B is a line BB'of FIG. 3A. The cross-sectional view of is shown.

The laminated conductive substrate 30 is obtained by laminating the conductive substrate 201 and the conductive substrate 202 as shown in FIG. 3B. Both the conductive substrates 201 and 202 have a patterned metal layer 221 (222) and a blackening layer 231 (232) on the first main plane 111a (112a) of the transparent substrate 111 (112). Are laminated. The patterned metal layers 221 (222) and the blackening layer 231 (232) of the conductive substrates 201 and 202 are all patterned so as to have a plurality of linear patterns similar to the conductive substrate 20 described above. It has been transformed.

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

The second main plane 111b of the transparent base material 111 of one conductive substrate 201 and the second main plane 111b of the transparent base material 112 of the other conductive substrate 202 are turned upside down. It may be laminated so that it faces the main plane 112b. In this case, the arrangement is the same as in FIG. 4, which will be described later.

When laminating two conductive substrates, as shown in FIGS. 3A and 3B, the patterned metal layer 221 of one conductive substrate 201 and the patterned metal layer of the other conductive substrate 202. The 222 and the two can be laminated so as to intersect with each other. Specifically, for example, in FIGS. 3A and 3B, the patterned metal layer 221 of one of the conductive substrates 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.

Since FIG. 3A is a view taken along the stacking direction of the laminated conductive substrates 30 as described above, the patterned blackening layers 231 and 232 arranged at the uppermost portions of the conductive substrates 201 and 202 are shown. Is shown. Since the patterned metal layers 221 and 222 have the same pattern as the patterned blackening layers 231 and 232, the patterned metal layers 221 and 222 also have the same pattern as the patterned blackening layers 231 and 232. Similarly, it becomes a mesh. Further, when the adhesion layer is provided, the patterned adhesion layer can also have a mesh shape similar to that of the patterned blackening layers 231 and 232.

The method of adhering the two laminated conductive substrates is not particularly limited, and for example, they can be adhered 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 30 having mesh-shaped wiring is obtained. be able to.

Although FIGS. 3A and 3B show an example in which linear wiring is combined to form a mesh-shaped wiring (wiring pattern), the wiring pattern is not limited to the above-mentioned form. The wiring can have any shape. For example, the shape of the wiring forming the mesh-like wiring pattern so as not to generate moire (interference fringes) with the image on the display can be made into various shapes such as a jaggedly bent line (zigzag straight line).

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

In this case, a plurality of metal layers 12A and blackening layers 13A laminated on the first main plane 11a side of the transparent base material 11 are arranged in the Y-axis direction in FIG. 1B, that is, parallel to the direction perpendicular to the paper surface. Pattern into a linear pattern. Further, the metal layer 12B and the blackening layer 13B laminated on the second main plane 11b side of the transparent base material 11 are patterned into a plurality of linear patterns parallel to the X-axis direction in FIG. 1B. Patterning can be performed, for example, by etching as described above. As a result, as shown in FIG. 4, the patterned metal layer 42A formed on the first main plane 11a side of the transparent base material 11 and the second main plane 11b side with the transparent base material 11 sandwiched therein. The formed patterned metal layer 42B and the conductive substrate 40 provided with mesh-like wiring can be obtained. In this case, similarly patterned blackening layers 43A and 43B are arranged on the upper surfaces of the patterned metal layers 42A and 42B.

According to the (laminated) conductive substrate described above, the patterned metal layer has a patterned blackening layer arranged on the upper surface thereof. Therefore, it is possible to suppress the reflection of light on the surface of the patterned metal layer. Further, since the metal layer is arranged, the electric resistance value can be reduced. Further, as described above, since the blackened layer is formed by the wet method, it can be produced with high productivity.
(Manufacturing method of conductive substrate, manufacturing method of laminated conductive substrate)
Next, a configuration example of the method for manufacturing the conductive substrate of the present embodiment and the method for manufacturing the laminated conductive substrate will be described.

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

The method for manufacturing the conductive substrate and the method for manufacturing the laminated conductive substrate of the present embodiment will be described below, but the same configurations as those for the above-mentioned conductive substrate and laminated conductive substrate are described except for the points described below. Therefore, the description thereof will be omitted.

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

Then, as described above, the metal layer preferably has a metal thin film layer. Further, the metal layer may have a metal thin film layer and a metal plating layer. Therefore, the metal layer forming step can include, for example, a step of forming a metal thin film layer by a dry plating method. Further, the metal layer forming step includes a step of forming a metal thin film layer by a dry plating method and 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 feeding layer. May have.

The dry plating method used in the step of forming the metal thin film layer is not particularly limited, and for example, a vapor deposition method, a sputtering method, an ion plating method, or the like can be used. The vacuum vapor deposition method can be preferably used as the vapor deposition method. 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 can be easily controlled.

When the metal thin film layer is formed by a sputtering method, it can be preferably formed by using, for example, a roll-to-roll sputtering apparatus.

A method of forming the metal thin film layer will be described by taking the case where the roll-to-roll sputtering apparatus 50 is used 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 its components.

Although the shape of the housing 51 is shown as a rectangular parallelepiped shape in FIG. 5, the shape of the housing 51 is not particularly limited, and an arbitrary shape is used depending on the device to be housed inside, the installation location, the pressure resistance performance, and the like. Can be. For example, the shape of the housing 51 may be a cylindrical shape.

However, in order to remove residual gas that is not related to film formation at the start of film formation, it is preferable that the pressure ^{inside the housing 51 can be reduced to 10 -3 Pa or less, and more preferably 10 -4} Pa or less. It is not necessary that the entire inside of the housing 51 can be depressurized to the above pressure, and it is also possible to configure the housing 51 so that only the lower region in the figure in which the can roll 53 described later is arranged can be depressurized to the above pressure. ..

Inside the housing 51, unwinding rolls 52, can rolls 53, sputtering cathodes 54a to 54d, front feed rolls 55a, rear feed rolls 55b, tension rolls 56a, 56b, which supply a base material for forming a metal thin film layer, The take-up roll 57 can be arranged. In addition to the above rolls, guide rolls 58a to 58h, a heater 61, and the like can be optionally 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 servomotor. The unwinding roll 52 and the winding roll 57 can be configured so that the tension balance of the base material on which the metal thin film layer is formed is maintained by torque control by a powder clutch or the like.

The configuration of the can roll 53 is also not particularly limited, but for example, the surface thereof is finished with hard chrome plating, and a refrigerant or a hot medium supplied from the outside of the housing 51 circulates inside the can roll 53 to adjust the temperature to a substantially constant temperature. It is preferable that it is configured so that it can be used.

It is preferable that the tension rolls 56a and 56b have, for example, a surface finished with hard chrome plating and provided with a tension sensor.

Further, it is preferable that the surfaces of the front feed roll 55a, the rear feed roll 55b, and the guide rolls 58a to 58h are finished with hard chrome plating.

It is preferable that the sputtering cathodes 54a to 54d are arranged so as to face the canroll 53 in a magnetron cathode type. The size of the sputtering cathodes 54a to 54d is not particularly limited, but the width direction of the base material for forming the metal thin film layer of the sputtering cathodes 54a to 54d may be wider than the width of the base material for forming the metal thin film layer. preferable.

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

When the metal thin film layer is formed by using the roll-to-roll sputtering apparatus 50, a predetermined target is attached to the sputtering cathodes 54a to 54d, and the base material for forming the metal thin film layer is set on the unwinding roll 52. The inside of the device is evacuated by the vacuum pumps 60a and 60b. After that, the sputtering gas is introduced into the housing 51 by the gas supply means 59. At this time, the flow rate of the sputtering gas and the opening degree of the pressure adjusting valve provided between the vacuum pump 60b and the housing 51 are adjusted to keep the inside of the apparatus at, for example, 0.13 Pa or more and 13 Pa or less. It is preferable to carry out a membrane.

The gas supply means 59 may have a cylinder (not shown) for each gas type of the sputtering gas to be supplied, for example. Then, for example, a mass flow controller (MFC), a valve, or the like is provided between the cylinder and the housing 51 for each gas type as shown in the figure, and the flow rate of the supplied sputtering gas can be adjusted.

Further, for example, vacuum gauges 62a and 62b are installed in the housing 51, and the degree of vacuum in the housing 51 when the inside of the housing 51 is evacuated or when a sputtering gas is supplied into the housing 51. Can be configured to adjust.

In this state, while transporting 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, electric power is supplied from a DC power source for sputtering connected to the sputtering cathodes 54a to 54d to perform sputtering discharge. As a result, a desired metal thin film layer can be continuously formed on the base material.

Next, the process of forming the 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 of the electroplating treatment are not particularly limited, and various conditions according to the conventional method may be adopted. For example, a metal plating layer can be formed by supplying a base material having a metal thin film layer formed to a plating tank containing a metal plating solution and controlling the current density and the transport speed of the base material.

Next, the process of forming the blackened layer will be described.

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

Further, when the blackened layer is formed by the dry method as in the conventional method, for example, after the metal plating layer is formed by the wet method, the film-deposited body is taken out from the film-forming apparatus of the wet method to form the film-deposited body. It was necessary to dry it and then set it in a dry method device, which reduced productivity. On the other hand, in the method for manufacturing the conductive substrate of the present embodiment, since the blackened layer is also formed by the wet method, the metal plating layer and the blackened layer can be continuously formed by the wet method apparatus, and particularly for production. You can improve your sex.

The method for forming the blackened layer may be a wet method and is not particularly limited. For example, a method of newly forming and laminating a blackened layer on a metal layer by a wet plating method can be mentioned. As the wet plating method in this case, for example, an electroplating method can be preferably used.

Further, as a specific method for forming the blackened layer by a wet method, there is a method of forming a blackened layer by an electroplating method using a plating solution containing nickel and zinc. The type of plating solution used at this time is not particularly limited, and for example, a black nickel plating solution containing nickel and zinc can be preferably used. A preliminary test is conducted in advance on the relationship between the composition of the plating solution and the composition of the blackened layer to be formed, and the composition of the plating solution is selected so that the blackened layer having the desired composition can be obtained. preferable.

Further, any process can be further carried out. For example, when the adhesive layer is formed between the transparent base material and the metal layer, the adhesive layer forming step of forming the adhesive layer on the surface forming the metal layer of the transparent base material can be carried out. When the adhesion layer forming step is carried out, the metal layer forming step can be carried out after the adhesion layer forming step, and the base material for forming the metal thin film layer described in the metal layer forming step is transparent in this step. It becomes a base material in which an adhesion layer is formed on the base material.

The adhesion layer can be formed on, for example, in FIG. 1A, on the first main plane 11a, which is one main plane of the transparent base material 11. Further, 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 base material 11. When the adhesion layer is formed on both the first main plane 11a and the second main plane 11b of the transparent base material 11, the adhesion layer may be formed on both main planes at the same time. Further, the adhesion layer may be formed on one of the main planes and then on the other main plane.

The material constituting the adhesion layer is not particularly limited, and the adhesion with the transparent base material 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 the materials that can be suitably used as the material forming the adhesion layer have already been described, the description thereof will be omitted here.

The method for forming the adhesion layer is not particularly limited, but for example, as described above, the film can be formed by the dry plating method. As the dry plating method, for example, a sputtering method, an ion plating method, a vapor deposition method and the like can be preferably used. 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, the 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 are included in the atmosphere when the adhesion layer is formed. By adding a gas containing the element of, it can be added to the adhesion layer. For example, carbon monoxide gas and / or carbon dioxide gas when carbon is added to the adhesion layer, oxygen gas when oxygen is added, hydrogen gas and / or water when hydrogen is added, When nitrogen is added, nitrogen gas can be added to the atmosphere at the time of dry plating.

A gas containing one or more elements selected from carbon, oxygen, hydrogen, and nitrogen is preferably added to the inert gas to be an atmospheric gas for dry plating. The inert gas is not particularly limited, but for example, argon can be preferably used.

When the adhesion layer is formed by the sputtering method, a target containing a metal species constituting the adhesion layer can be used as the target. When the adhesion layer contains an alloy, a target may be used for each metal type contained in the adhesion layer, and an alloy may be formed on the surface of the film-deposited body such as a transparent base material. It is also possible to use an alloyed target.

The adhesion layer can be suitably formed by 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 will be omitted here.

When the adhesion layer is formed by 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 substrate for forming the adhesion layer, for example, a transparent substrate is attached. Set on the unwinding roll 52. Then, the inside of the device, for example, the inside of the housing 51 is evacuated by the vacuum pumps 60a and 60b. After that, a sputtering gas such as argon gas is introduced into the housing 51 by the gas supply means 59. At this time, the flow rate of the sputtering gas and the opening degree of the pressure adjusting valve provided between the vacuum pump 60b and the housing 51 are adjusted to keep the inside of the apparatus at, for example, 0.13 Pa or more and 13 Pa or less. It is preferable to carry out a membrane.

In this state, while transporting 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 the DC power source for sputtering connected to the sputtering cathodes 54a to 54d to discharge the sputtering. conduct. As a result, a desired adhesion layer can be continuously formed on the base material.

By forming the adhesion layer by the dry plating method as described above, the adhesion between the transparent base material and the adhesion layer can be improved. Further, since the adhesion layer can contain, for example, a metal as a main component, the adhesion to the metal layer is also high. Therefore, by arranging the adhesion layer between the transparent base material and the metal layer, peeling of the metal layer can be suppressed.

The thickness of the adhesion layer is not particularly limited, but is preferably 3 nm or more and 50 nm or less, more preferably 3 nm or more and 35 nm or less, and further preferably 3 nm or more and 33 nm or less.

The conductive substrate obtained by the method for manufacturing a conductive substrate of the present embodiment can be used for various purposes such as a touch panel. When used for various purposes, it is preferable that the metal layer and the blackening layer contained in the conductive substrate of the present embodiment are patterned. When the adhesion layer is provided, 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 according to, for example, a desired wiring pattern, and the metal layer and the blackening layer, and in some cases the adhesion layer, can be patterned into the same shape. It is preferable that it is.

Therefore, the method for manufacturing a conductive substrate of the present embodiment can include a patterning step of patterning 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 carried out by any procedure. For example, in the case of the conductive substrate 10A in which the metal layer 12 and the blackening layer 13 are laminated on the transparent base material 11 as shown in FIG. 1A, a mask placement step of first arranging a mask having a desired pattern on the blackening layer 13. Can be carried out. Next, an etching step of supplying the etching solution to the upper surface of the blackening layer 13, that is, the surface side on which the mask is arranged can be performed.

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

The pattern formed in the etching process is not particularly limited. For example, the metal layer and the blackening layer can be patterned so as 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 blackening layer 23 can be patterned so as to be parallel to each other and separated from each other. ..

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 laminated on the first main plane 11a and the second main plane 11b of the transparent base material 11 is also patterned. The process can be carried out. In this case, for example, a mask arranging step of arranging a mask having a desired pattern on the blackening layers 13A and 13B can be performed. Next, an etching step of supplying the etching solution to the upper surfaces of the blackening layers 13A and 13B, that is, the surface side on which the mask is arranged can be performed.

In the etching step, for example, a plurality of metal layers 12A and blackening layers 13A laminated on the first main plane 11a side of the transparent base material 11 are parallel to the Y-axis direction in FIG. 1B, that is, the direction perpendicular to the paper surface. It can be patterned into a linear pattern. Further, the metal layer 12B and the blackening layer 13B laminated on the second main plane 11b side of the transparent base material 11 can be patterned into a plurality of linear patterns parallel to the X-axis direction in FIG. 1B. As a result, as shown in FIG. 4, the patterned metal layer 42A formed on the first main plane 11a side of the transparent base material 11 and the second main plane 11b side with the transparent base material 11 sandwiched therein. The formed patterned metal layer 42B and the conductive substrate can be provided with mesh-like wiring.

Then, it is also possible to manufacture a laminated conductive substrate in which a plurality of the conductive substrates described above are laminated. The method for manufacturing a laminated conductive substrate can include a laminating step of laminating a plurality of conductive substrates obtained by the above-described method for manufacturing a conductive substrate.

In the laminating step, for example, a plurality of patterned conductive substrates shown in FIGS. 2A and 2B can be laminated. Specifically, as shown in FIGS. 3A and 3B, the first main plane 111a of the transparent base material 111 of one conductive substrate 201 and the second of the transparent base material 112 of the other conductive substrate 202. It can be carried out by laminating so as to face the main plane 112b of the above.

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

The second main plane 111b of the transparent base material 111 of one conductive substrate 201 and the second main plane 111b of the transparent base material 112 of the other conductive substrate 202 are turned upside down. It may be laminated so that it faces the main plane 112b.

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

3A and 3B show an example in which a metal layer patterned in a linear shape is combined to form a mesh-like wiring (wiring pattern), but the present invention is not limited to this form. 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 forming the mesh-like wiring pattern so as not to generate moire (interference fringes) with the image on the display can be made into various shapes such as a jaggedly bent line (zigzag straight line). As described above, the patterned metal layer functions as wiring, but the adhesion layer and / or the blackened layer can also form a part of the wiring depending on the electric resistance value.

According to the conductive substrate manufacturing method of the present embodiment and the conductive substrate and the laminated conductive substrate obtained by the laminated conductive substrate manufacturing method, the electric resistance value can be reduced because the metal layer is provided. Further, since the blackening layer is arranged on the metal layer, the reflection of light can be suppressed. Further, since the blackened layer can be formed by a wet method, it can be produced 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, an evaluation method of the obtained conductive substrate will be described.
(Composition of blackening layer)
The composition analysis of the blackened layer formed on the surface of the obtained conductive substrate was performed using EPMA (Electron Probe MicroAnalyzer Nippon Electronics Co., Ltd. Model: JXA-8900R). From the measurement results, the weight% of Ni and Zn was calculated when the sum of the weights of Ni and Zn contained in the blackened layer was 100.

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

(Appearance evaluation)
The surface of the blackened layer was visually observed and the appearance was evaluated. In the evaluation, if the color of the surface of the blackened layer is uniform and there is no unevenness, 〇, if any unevenness is seen, △, if unevenness is seen over the entire surface of the blackened layer, It was evaluated as ×.

(Specular reflectance)
The measurement was carried out by installing a reflectance measurement unit on an ultraviolet-visible spectrophotometer (model: UV-2600 manufactured by Shimadzu Corporation).

The surface of the blackened layer of the conductive substrate produced in the following Examples and Comparative Examples is specularly reflected by irradiating the surface of the blackened layer of the conductive substrate with an incident angle of 5 ° and a light receiving angle of 5 ° and light having a wavelength of 400 nm or more and 700 nm or less at wavelength intervals of 1 nm. The rate was measured, and the average value was taken as the specular reflectance of the conductive substrate.

In the following examples and comparative examples, except that the cross section of the surface parallel to the stacking direction of each layer of the conductive substrate further forms an adhesion layer between the transparent base material 11 and the metal layer 12. A conductive substrate having the same configuration as that of FIG. 1A is manufactured. Therefore, the specular reflectance was measured by irradiating the surface 13a of the blackening layer 13 with light. Further, in the case of the following brightness, the surface 13a is similarly irradiated with light for measurement.
(brightness)
On the surface of the blackened layer of the conductive substrate produced in the following examples and comparative examples, light having a wavelength of 400 nm or more and 700 nm or less is emitted at intervals of 1 nm by an ultraviolet-visible spectrophotometer (model: UV-2600 manufactured by Shimadzu Corporation). The brightness was measured by irradiation.

(Sample preparation conditions)
As an example and a comparative example, a conductive substrate was produced under the conditions described below, and evaluation was performed by the above-mentioned evaluation method.
[Example 1]
(Adhesion layer forming process)
A transparent base material 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.

Regarding the transparent base material made of polyethylene terephthalate resin used as the transparent base material, the total light transmittance was evaluated by the method specified in JIS K 7361-1 and found to be 97%.

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

The film forming conditions of the adhesion layer will be described.

A target of Ni-17 wt% Cr alloy was 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. to heat the transparent base material, and the water contained in the transparent base material was removed.

Subsequently, after exhausting the inside of the housing 51 to 1 × 10 ^-3 Pa, argon gas and oxygen gas were introduced, and the pressure inside the housing 51 was adjusted to 1.3 Pa. At this time, the supply amounts of argon gas and oxygen gas were adjusted so that the atmosphere inside the housing 51 was 30% oxygen by volume and the balance was argon.

Then, while transporting the 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 to perform sputtering discharge, and a desired adhesion layer is continuously formed on the transparent base material. Membrane. By this operation, a 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 carried out.

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

A metal thin film layer was formed on the close contact layer by the 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, and the base material is a transparent group in the adhesion layer forming step. A material having an adhesion layer formed on the material was used.

The conditions for forming the metal thin film layer were the same as in the adhesion layer forming step except for the following two points and the point where the target was changed as described above.

After exhausting the inside of the housing 51 to 1 × 10 ^-3 Pa, argon gas was introduced and the pressure inside the housing 51 was adjusted to 1.3 Pa.

A point in which a copper thin film layer, which is a metal thin film layer, is formed so as to have a film thickness of 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 a thickness of 2.0 μm by an electroplating method.
(Blackening layer forming process)
Using a black nickel bath black nickel GT solution (manufactured by JCU Co., Ltd.), which is a black nickel plating solution prepared with a weight ratio of Ni in the plating solution to Zn at 94: 6, was applied to the surface of the metal layer by electroplating. The blackened layer was formed so as to have a thickness of 0.4 μm.

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

The composition, surface resistance, appearance, specular reflectance, and brightness of the blackened layer described above were evaluated for the obtained conductive substrate. The results are shown in Table 1.

It should be noted that the Ni and Zn in the blackened layer calculated from the values analyzed by EPMA as described above for the blackened layer prepared by the one described as "blackened layer composition (Ni: Zn)" in Table 1. Shows the weight ratio. The description of "plating solution composition (Ni: Zn) at the time of forming the blackened layer" indicates the weight ratio of Ni and Zn in the plating solution at the time of producing the blackened layer.

Further, in this example, and in the following examples and comparative examples, a graph of the measured values for surface resistance is shown in FIG. 6, and a graph of the measured values for specular reflectance is shown in FIG. 7. Brightness. FIG. 8 shows a graph of the measured values of the above.

For the conductive substrate obtained in this experimental example, an etching step was carried out after carrying out a mask arranging step of forming a mask corresponding to the pattern formed on the surface of the blackened layer. By etching the adhesion layer, the metal layer, and the blackening layer with an etching solution (aqueous cupric chloride solution) in the etching step, the adhesion layer, the metal layer, and the blackening layer are as shown in FIGS. 2A and 2B. A conductive substrate patterned in a plurality of linear patterns was obtained. Although the examples in which the adhesion layer is not arranged are shown in FIGS. 2A and 2B, in this embodiment, the metal layer and the adhesion layer patterned in the same shape as the blackening layer are transparent base materials 11. Will be arranged between the metal layer 22 and the metal layer 22.

Further, another conductive substrate in which the adhesion layer, the metal layer, and the blackening layer were patterned in the same shape as in the above case was produced by the same procedure as the method described so far.

Then, the two prepared conductive substrates were laminated as shown in FIGS. 3A and 3B, and both conductive substrates were fixed with an adhesive to prepare a laminated conductive substrate. Although an example in which the adhesion layer is not provided is also shown in FIGS. 3A and 3B, in this embodiment, between the transparent base material 111 and the metal layer 221 and between the transparent base material 112 and the metal layer 222. An adhesion layer patterned in the same shape as the metal layer 221 and the metal layer 222 is arranged between the two.
[Example 2]
In the blackening layer forming step, a black nickel bath black nickel GT solution (manufactured by JCU Co., Ltd.), which is a black nickel plating solution prepared so that the weight ratio of Ni in the plating solution to Zn is 88:12, is used. A conductive substrate was produced in the same manner as in Example 1 except for the above-mentioned points.

The composition, surface resistance, appearance, specular reflectance, and brightness of the blackened layer described above were evaluated for the obtained conductive substrate. The results are shown in Table 1.

Further, on the obtained conductive substrate, the adhesion layer, the metal layer, and the blackening layer were patterned in the same manner as in the case of Example 1. 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, the two conductive substrates were laminated and fixed in the same manner as in the case of Example 1 to prepare a laminated conductive substrate.
[Example 3]
In the blackening layer forming step, a black nickel bath black nickel GT solution (manufactured by JCU Co., Ltd.), which is a black nickel plating solution prepared so that the weight ratio of Ni in the plating solution to Zn is 44:56, is used. A conductive substrate was produced in the same manner as in Example 1 except for the above-mentioned points.

The composition, surface resistance, appearance, specular reflectance, and brightness of the blackened layer described above were evaluated for the obtained conductive substrate. The results are shown in Table 1.

Further, on the obtained conductive substrate, the adhesion layer, the metal layer, and the blackening layer were patterned in the same manner as in the case of Example 1. 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, the two conductive substrates were laminated and fixed in the same manner as in the case of Example 1 to prepare a laminated conductive substrate.
[Comparative Example 1]
The same as in Example 1 except that a nickel plating solution (manufactured by JCU Co., Ltd.) prepared so that the weight ratio of Ni in the plating solution to Zn in the plating solution is 100: 0 was used in the blackening layer forming step. To prepare a conductive substrate.

The composition, surface resistance, appearance, specular reflectance, and brightness of the blackened layer described above were evaluated for the obtained conductive substrate. The results are shown in Table 1.

Further, on the obtained conductive substrate, the adhesion layer, the metal layer, and the blackening layer were patterned in the same manner as in the case of Example 1. 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, the two conductive substrates were laminated and fixed in the same manner as in the case of Example 1 to prepare a laminated conductive substrate.
[Comparative Example 2]
In the blackening layer forming step, the same as in Example 1 except that a zinc plating solution (manufactured by JCU Co., Ltd.) prepared so that the weight ratio of Ni in the plating solution to Zn is 0: 100 was used. To prepare a conductive substrate.

The composition, surface resistance, appearance, specular reflectance, and brightness of the blackened layer described above were evaluated for the obtained conductive substrate. The results are shown in Table 1.

Further, on the obtained conductive substrate, the adhesion layer, the metal layer, and the blackening layer were patterned in the same manner as in the case of Example 1. 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, the two conductive substrates were laminated and fixed in the same manner as in the case of Example 1 to prepare a laminated conductive substrate.

表１、及び図６〜図８に示した結果から、ニッケルと亜鉛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（正反射率）が３５％以下、表面抵抗が０．０６Ω／□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の導電性基板は、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または△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 reflectance of the conductive substrates of Examples 1 to 3 having the blackening layer containing nickel and zinc (reflectance on the surface of the blackening layer ( It was confirmed that the specular reflectance) was 35% or less, the surface resistance was less than 0.06Ω / □, and the brightness (L ^* ) was 60 or less. From these results, it was confirmed that the conductive substrates of Examples 1 to 3 were obtained with a small electric resistance value while suppressing reflection on the surface of the metal layer. Further, since the brightness is also 60 or less, when the adhesion layer, the metal layer, and the blackening layer are patterned, the laminated body of the patterned adhesion layer, the metal layer, and the blackening layer becomes inconspicuous. Was also confirmed. Further, the appearance evaluation of the conductive substrates of Examples 1 to 3 was 〇 or Δ, and it was confirmed that the color unevenness on the surface of the blackened layer could be sufficiently suppressed.

On the other hand, the reflectances of the conductive substrates of Comparative Example 1 in which the blackening layer does not contain zinc and Comparative Example 2 in which the blackening layer does not contain nickel are 35.20% and 66.50%, respectively. It was confirmed that it was high and the reflection on the surface of the metal layer could not be sufficiently suppressed. Further, in particular, in Comparative Example 2, the appearance evaluation was ×, and it was confirmed that the color unevenness on the surface of the blackened layer became severe.

Further, also in the case of using the laminated conductive substrate of Examples 1 to 3, the reflection of light on the surface of the metal layer can be suppressed, and the laminated body of the adhesion layer, the metal layer, and the blackening layer becomes inconspicuous. I was able to confirm that.

From the above results, the conductive substrate provided with the metal layer and the blackening layer containing nickel and zinc 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. In addition, it was confirmed that the blackened layer can be formed by the wet method, so that the product can be produced with high productivity.

The conductive substrate, the laminated conductive substrate, the method for manufacturing the conductive substrate, and the method for manufacturing the laminated conductive substrate have been described above in the embodiments and examples, but the present invention has been described in the above-described embodiments and examples. Not limited. Various modifications and changes are possible within the scope of the gist of the present invention described in the claims.

This application claims priority based on Japanese Patent Application No. 2014-135123 filed with the Japan Patent Office on June 30, 2014, and the entire contents of Japanese Patent Application No. 2014-135123 are included in this international application. Invite.

10A, 10B, 20, 201, 202, 40 Conductive substrate 11, 111, 112 Transparent substrate 12, 12A, 12B, 22, 222, 222, 42A, 42B Metal layer 13, 13A, 13B, 23, 231, 232 , 43A, 43B Blackened layer 30 Laminated conductive substrate

Claims (7)

With a transparent base material
An adhesion layer which is an oxygen-containing Ni—Cr alloy layer formed on at least one surface of the transparent substrate, and a metal layer formed on the adhesion layer.
A conductive substrate having a blackening layer containing nickel and zinc formed on the metal layer by a wet method. The conductive substrate according to claim 1, wherein the proportion of nickel in the nickel and zinc contained in the blackening layer is 40 wt% or more and 99 wt% or less in terms of weight ratio. The conductive substrate according to claim 1 or 2, wherein the adhesion layer, the metal layer, and the blackening layer are patterned. A laminated conductive substrate in which a plurality of conductive substrates according to any one of claims 1 to 3 are laminated. An adhesion layer forming step of forming an adhesion layer, which is a Ni—Cr alloy layer containing oxygen, on at least one surface of the transparent base material.
A metal layer forming step of forming a metal layer on the close contact layer, and
A method for producing a conductive substrate, comprising a blackening layer forming step of forming a blackening layer containing nickel and zinc on the metal layer by a wet method. The method for manufacturing a conductive substrate according to claim 5, further comprising a patterning step of patterning the adhesion layer, the metal layer, and the blackening layer. A method for manufacturing a laminated conductive substrate, which comprises a laminating step of laminating a plurality of conductive substrates obtained by the method for producing a conductive substrate according to claim 5 or 6.

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