JP6531596B2 - Laminate substrate, conductive substrate, method of producing laminate substrate, method of producing conductive substrate - Google Patents

Description

  The present invention relates to a laminate substrate, a conductive substrate, a method of manufacturing a laminate substrate, and a method of manufacturing a conductive substrate.

  As disclosed in Patent Document 1, a transparent conductive film for a touch panel in which an ITO (indium tin oxide) film is formed as a transparent conductive film on the surface of a transparent base material such as a transparent polymer film is conventionally used It is done.

  By the way, in recent years, the screen size of a display provided with a touch panel has been increased, and correspondingly, the area of a conductive substrate such as a transparent conductive film for a touch panel is also required to be increased. However, since ITO has a high electric resistance value, there is a problem that it can not cope with the increase in the area of the conductive substrate.

  For this reason, using wiring of copper etc. instead of wiring of ITO as disclosed by patent document 2, 3 is examined, for example. However, for example, when copper is used for the wiring, since copper has a metallic luster, there is a problem that the visibility of the display is lowered by reflection.

  Therefore, a conductive substrate in which a blackening layer formed of a black material is formed on a surface parallel to the surface of the transparent base material of the wiring as well as the wiring such as copper is studied.

Unexamined-Japanese-Patent No. 2003-151358 JP, 2011-018194, A JP, 2013-069261, A

  By the way, after obtaining a laminate substrate in which a copper layer is formed on the surface of a transparent base material, a conductive substrate provided with copper wiring on a transparent base material is etched to obtain a desired wiring pattern. It can be obtained by forming a copper wiring. In addition, the conductive substrate having the blackening layer and the copper wiring on the transparent base material is obtained as a desired wiring after obtaining a laminate substrate in which the blackening layer and the copper layer are sequentially laminated on the surface of the transparent base material. It is obtained by forming a wiring by etching the blackening layer and the copper layer so as to form a pattern.

By etching the blackening layer and the copper layer, for example, as shown in FIG. 1A, the blackening layer 2 patterned on the transparent substrate 1 and the copper wiring 3 patterned on the copper layer And the conductive substrate may be stacked. In this case, the width W _A of the blackening layer 2 patterned into, it is preferable that the width W _B of the copper wiring 3 substantially the same.

  However, there is a problem that the reactivity to the etching solution is largely different between the copper layer and the blackened layer. That is, when the copper layer and the blackening layer are to be etched at the same time, there is a problem that any layer can not be etched to the intended shape as shown in FIG.

  For example, when the etching rate of the blackening layer is much lower than that of the copper layer, as shown in FIG. 1 (b), the copper wiring 3 which is a patterned copper layer is etched on its side surface , So-called side etching occurs. For this reason, the cross-sectional shape of the copper wiring 3 tends to be a trapezoidal shape with a skirt spread, and if etching is performed until the electrical insulation between the copper wiring 3 is secured, the wiring pitch width becomes too wide.

In comparison with the copper layer, if the etch rate of the blackening layer is faster significantly, the Figure 1 patterned blackening layer 2 having a width as shown in (c) (bottom width) W _A copper wire 3 There may be a case where a so-called undercut occurs, which is smaller than the width W _{B of} . Such undercuts occur, and depending on the degree, the bottom width W _{A of the} patterned blackened layer 2 which is the adhesion width to the transparent substrate 1 with respect to the predetermined width W _B of the copper wiring 3 When the ratio of the adhesion width is reduced more than necessary, there is a problem that sufficient wiring adhesion strength can not be obtained.

  In addition, when the copper layer and the blackened layer are not etched simultaneously and the etching of the copper layer and the etching of the blackened layer are performed in separate steps, there is a problem that the number of steps increases.

  SUMMARY OF THE INVENTION In view of the above-described problems of the prior art, an object of the present invention is to provide a laminate substrate provided with a copper layer which can be etched at the same time and a low reflectance alloy layer.

In order to solve the above problems, the present invention is
A transparent substrate,
And a laminate directly formed on at least one surface side of the transparent substrate,
The laminate is
A low reflectivity alloy layer containing copper and nickel;
It consists of a copper layer,
The laminate substrate is provided, wherein the proportion of the nickel in the copper and the nickel contained in the low reflectance alloy layer is 30% by mass or more and 85% by mass or less.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body board | substrate provided with the copper layer which can perform an etching process simultaneously, and a low-reflectance alloy layer can be provided.

Explanatory drawing at the time of etching a copper layer and a blackening layer simultaneously in the conventional conductive substrate. BRIEF DESCRIPTION OF THE DRAWINGS Sectional drawing of the laminated body board | substrate which concerns on embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS Sectional drawing of the laminated body board | substrate which concerns on embodiment of this invention. The top view of the conductive substrate provided with the mesh-like wiring concerning the embodiment of the present invention. Sectional drawing in the AA 'line | wire of FIG. Explanatory drawing of a roll-to-roll sputtering apparatus.

Hereinafter, an embodiment of a laminate substrate, a conductive substrate, a method of manufacturing a laminate substrate, and a method of manufacturing a conductive substrate according to the present invention will be described.
(Laminated substrate, conductive substrate)
The laminate substrate of the present embodiment can include a transparent substrate and a laminate formed on at least one surface side of the transparent substrate. Then, the laminate includes a low reflectance alloy layer containing copper and nickel, and a copper layer, and the proportion of nickel in copper and nickel contained in the low reflectance alloy layer is 30% by mass More than 85 mass% can be carried out.

  In addition, the laminated body board | substrate in this embodiment is a board | substrate which has a copper layer and low reflectance alloy layer before patterning on the surface of a transparent base material. Moreover, a conductive substrate is a wiring board which has the copper wiring layer and low reflectance alloy wiring layer which were patterned and made the shape of wiring on the surface of a transparent base material.

  Here, first, each member included in the laminate substrate of the present embodiment will be described below.

  The transparent substrate is not particularly limited, and a polymer film which transmits visible light, a glass substrate or the like can be preferably used.

  As a polymer film which transmits visible light, resin films, such as a polyamide system film, a polyethylene terephthalate system film, a polyethylene naphthalate system film, a cycloolefin system film, a polyimide system film, a polycarbonate system film, can be used preferably, for example.

  The thickness of the transparent substrate is not particularly limited, and can be arbitrarily selected in accordance with the strength, the light transmittance, and the like required for the conductive substrate. The thickness of the transparent substrate can be, for example, 10 μm or more and 250 μm or less. In particular, when used for touch panel applications, it is preferably 20 μm or more and 200 μm or less, and more preferably 20 μm or more and 120 μm or less. When used for touch panel applications, for example, in applications where it is required to reduce the thickness of the entire display, the thickness of the transparent substrate is preferably 20 μm to 100 μm.

  Next, the laminate will be described. The laminate is formed on at least one surface side of the transparent substrate, and can have a low reflectance alloy layer and a copper layer.

  Here, the copper layer will be described first.

  The copper layer is also not particularly limited, but it is preferable not to dispose an adhesive between the copper layer and the transparent substrate or between the copper layer and the low reflectance alloy layer, in order not to reduce the light transmittance. . That is, the copper layer is preferably formed directly on the top surface of the other member.

  In order to form a copper layer directly on the upper surface of another member, a copper thin film layer may be formed using a dry plating method such as sputtering, ion plating or evaporation to make the copper thin film layer a copper layer. it can.

  When the copper layer is made thicker, it is preferable to use the wet plating method after forming the copper thin film layer by the dry plating method. That is, for example, a copper thin film layer can be formed by a dry plating method on a transparent base material or a low reflectance alloy layer, and a copper plating layer can be formed by a wet plating method using the copper thin film layer as a power feeding layer. In this case, the copper layer has a copper thin film layer and a copper plating layer.

  As described above, the copper layer is formed directly on the transparent substrate or the low reflectance alloy layer by forming the copper layer by only the dry plating method or a combination of the dry plating method and the wet plating method, without using an adhesive. It is preferable because it can be done.

  The thickness of the copper layer is not particularly limited, and when the copper layer is used as a wire, it can be arbitrarily selected according to the electric resistance value of the wire, the wire width, and the like. In particular, the thickness of the copper layer is preferably 50 nm or more, more preferably 60 nm or more, and still more preferably 150 nm or more so that electricity flows sufficiently. Although the upper limit of the thickness of the copper layer is not particularly limited, when the copper layer is thick, side etching occurs because etching takes time to form the wiring, and the resist is peeled off in the middle of the etching. And the like. Therefore, the thickness of the copper layer is preferably 5000 nm or less, more preferably 3000 nm or less. In addition, when a copper layer has a copper thin film layer and a copper plating layer as mentioned above, it is preferable that the sum total of the thickness of a copper thin film layer and the thickness of a copper plating layer is the said range.

  Next, the low reflectance alloy layer will be described.

  Since the copper layer has metallic luster, the copper reflects light as described above only by etching the copper layer on the transparent substrate to form a copper wiring layer which is a wiring, for example, as a wiring substrate for touch panel When used, there is a problem that the visibility of the display is reduced. Then, although the method of providing a blackening layer has been examined, there are cases where the blackening layer does not have sufficient reactivity to the etching solution, and the copper layer and the blackening layer are simultaneously etched to a desired shape. It was difficult.

  On the other hand, the low reflectance alloy layer disposed on the laminate substrate of the present embodiment contains copper and nickel. For this reason, the reactivity of the low reflectance alloy layer disposed on the laminate substrate of the present embodiment to the etching solution is substantially the same as that of the copper layer to the etching solution, and the etching property is also good. Therefore, in the laminate substrate of the present embodiment, the copper layer and the low reflectance alloy layer containing copper and nickel can be etched simultaneously.

  The point which the low reflectance alloy layer arrange | positioned to the laminated body board | substrate of this embodiment can etch simultaneously with a copper layer is demonstrated below.

  The inventors of the present invention initially studied a method of forming a copper oxide layer obtained by oxidizing a part of a copper layer as a blackening layer capable of suppressing light reflection on the surface of the copper layer. And when oxidizing a part of copper layer and setting it as a blackening layer, it discovered that the black oxide layer concerned might contain copper oxide of non-stoichiometrics and copper which is not oxidized.

  When simultaneously etching the copper layer of the laminate substrate provided with the copper layer and the blackening layer, and the blackening layer, an etching solution capable of etching, for example, a copper layer can be suitably used as the etching solution. Then, according to the study of the inventors of the present invention, when the blackening layer contains a non-stoichiometric copper oxide, the copper layer is easily eluted in an etching solution capable of etching.

  As described above, when the blackening layer contains a non-stoichiometric copper oxide which is easily eluted to the etching solution, the blackening layer has high reactivity to the etching solution, and compared with the copper layer, The etch rate is significantly faster. Therefore, when the copper layer and the blackening layer were etched simultaneously, the blackening layer was likely to be an undercut.

  Therefore, in the laminate substrate of the present embodiment, in order to suppress undercut, the blackened layer does not use oxygen, and in addition to copper, has a low reflectance that contains a nickel component that is difficult to dissolve in the etching solution. It can be an alloy layer. Thus, the low reflectance alloy layer of the laminate substrate of the present embodiment contains copper and nickel without using oxygen, thereby making the reactivity to the etching solution equal to that of the copper layer. It is possible to simultaneously etch the low reflectivity alloy layer and the copper layer.

  The proportion of nickel in copper and nickel contained in the low reflectance alloy layer is not particularly limited, but the proportion of nickel in copper and nickel contained in the blackened layer is 30% by mass or more and 85% by mass It is preferable that it is the following. In addition, the ratio of nickel has shown the ratio at the time of making the sum total of content of copper in a blackening layer, and nickel into 100 mass% as mentioned above.

  This is because if the proportion of nickel in copper and nickel contained in the low reflectance alloy layer is less than 30% by mass, the average specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less can not be 55% or less It is.

  On the other hand, if the proportion of nickel exceeds 85% by mass with respect to copper and nickel contained in the low reflectance alloy layer, nickel is excessive and etching of the low reflectance alloy layer becomes difficult. That is, the dissolution rate of the low reflectance alloy layer in the etching solution is lower than that of the copper layer, and it can not be a low reflectance alloy layer which can be etched simultaneously with the copper layer. Also, as described later, the low reflectance alloy layer can be formed, for example, by sputtering, but if the proportion of nickel exceeds 85 mass%, magnetron sputtering film formation may become impossible.

  Furthermore, in the laminate substrate, as described later, a low reflectance alloy layer and a copper layer can be stacked on a transparent base material, and by patterning the low reflectance alloy layer and the copper layer, conductivity is achieved. It can be a substrate. And when the ratio of nickel exceeds 85 mass% among copper and nickel contained in a low reflectance alloy layer, when etching a low reflectance alloy layer or a copper layer and forming an opening, removal by etching In some cases, the surface of the transparent substrate may appear to turn yellow. For this reason, it is preferable that the ratio of nickel is 85 mass% or less among copper and nickel contained in a low reflectance alloy layer as mentioned above.

  The low reflectivity alloy layer can contain copper and nickel as metal species, and the metal species contained in the low reflectivity alloy layer can be composed of only copper and nickel, but is limited to copper and nickel only It is not something to be done. For example, in the low reflectance alloy layer, 1% by mass or less of unavoidable impurities may be further present as a metal species.

  In addition, the low reflectance alloy layer may contain copper and nickel, and there is no particular limitation on the state in which each component is contained.

  The copper wiring layer and the low reflectance alloy wiring layer of the conductive substrate obtained from the laminate substrate of the present embodiment maintain the characteristics of the copper layer and the low reflectance alloy layer of the laminate substrate of the present embodiment, respectively. Ru.

  The method for forming the low reflectance alloy layer disposed on the conductive substrate of the present embodiment is not particularly limited. The low reflectance alloy layer is preferably formed, for example, by a dry film formation method such as a sputtering method.

  When the low reflectance alloy layer is formed by sputtering, the film can be formed using, for example, a copper-nickel alloy target and supplying an inert gas used as a sputtering gas into the chamber.

  When a target of copper-nickel alloy is used at the time of sputtering, it is preferable that the ratio of nickel is 30 mass% or more and 85 mass% or less among copper and nickel contained in copper-nickel alloy. This is the ratio of nickel of copper and nickel contained in the low reflectivity alloy layer to be deposited, and copper-nickel of the target of the copper-nickel alloy used in depositing the low reflectivity alloy layer This is because the ratio of nickel to copper and nickel contained in the alloy is the same.

  The inert gas for forming the low reflectance alloy layer is not particularly limited, and, for example, argon gas or xenon gas can be used, but argon gas can be suitably used.

  The thickness of the low reflectance alloy layer formed in the laminate substrate of the present embodiment is not particularly limited, and may be arbitrarily selected according to the degree of suppression of light reflection on the surface of the copper layer, for example. it can.

  The lower limit of the thickness of the low reflectance alloy layer is, for example, preferably 10 nm or more, and more preferably 15 nm or more. The upper limit value is, for example, preferably 70 nm or less, more preferably 50 nm or less.

  The low reflectance alloy layer functions as a layer that suppresses the reflection of light on the surface of the copper layer as described above, but when the thickness of the low reflectance alloy layer is thin, the reflection of light by the copper layer is sufficiently suppressed It may not be possible. On the other hand, by setting the thickness of the low reflectance alloy layer to 10 nm or more, the reflection of light on the surface of the copper layer can be more reliably suppressed.

  The upper limit of the thickness of the low reflectance alloy 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 a wiring become longer, and the cost Will cause a rise in Therefore, the thickness of the low reflectance alloy layer is preferably 70 nm or less, and more preferably 50 nm or less.

  Next, a configuration example of the laminate substrate of the present embodiment will be described.

  As described above, the laminate substrate of the present embodiment can have a transparent substrate and a laminate having a copper layer and a low reflectance alloy layer. Under the present circumstances, the order which arrange | positions the copper layer and low-reflectance alloy layer in a laminated body on a transparent base material, and the number of the layers in particular are not limited. That is, for example, the copper layer and the low reflectance alloy layer can be laminated in any order in any order on at least one surface side of the transparent substrate. Also, multiple copper layers and / or low reflectivity alloy layers can be formed in the laminate.

  However, when arranging the copper layer and the low reflectance alloy layer in the laminated body, low reflection on the surface of the copper layer on which light reflection is particularly desired to be suppressed in order to suppress light reflection on the copper layer surface. Preferably, a rate alloy layer is disposed.

  In particular, it is more preferable that the low reflectance alloy layer has a laminated structure formed on the surface of the copper layer. Specifically, for example, the laminate is a low reflectance alloy layer, a first low reflectance alloy layer and It is preferable to have two layers of the second low reflectance alloy layer, and the copper layer be disposed between the first low reflectance alloy layer and the second low reflectance alloy layer.

  A specific configuration example will be described below with reference to FIGS. 2 and 3. FIG. 2 and FIG. 3 show examples of cross-sectional views in a plane parallel to the laminating direction of the transparent base, the copper layer, and the low reflectance alloy layer of the laminate substrate of the present embodiment.

  For example, as in the laminate substrate 10A shown in FIG. 2A, the copper layer 12 and the low reflectance alloy layer 13 are sequentially laminated one by one on the one surface 11a side of the transparent base material 11 Can. Further, as in the laminate substrate 10B shown in FIG. 2 (b), copper layers 12A and 12B are formed on one surface 11a side of the transparent substrate 11 and the other surface (the other surface) 11b side, respectively. And the low reflectance alloy layers 13A and 13B can be stacked one by one in that order. The order in which the copper layers 12 (12A and 12B) and the low reflectance alloy layers 13 (13A and 13B) are stacked is not limited to the examples shown in FIGS. From the side, the low reflectance alloy layers 13 (13A, 13B) and the copper layers 12 (12A, 12B) can be stacked in this order.

  In addition, as described above, for example, a plurality of low reflectance alloy layers may be provided on one surface side of the transparent substrate 11. For example, as in the laminate substrate 20A shown in FIG. 3A, the first low reflectance alloy layer 131, the copper layer 12, and the second low reflection are provided on the side 11a of the transparent substrate 11. The rate alloy layer 132 can be stacked in that order.

  Thus, as the low reflectance alloy layer, the first low reflectance alloy layer 131 and the second low reflectance alloy layer 132 are provided, and the copper layer 12 is used as the first low reflectance alloy layer 131; It becomes possible to suppress more reliably reflection of the light which injects from the upper surface side of the copper layer 12, and a lower surface side by arrange | positioning with the low reflectance alloy layer 132 of (1).

  Also in this case, a copper layer, a first low reflectance alloy layer, and a second low reflectance alloy layer can be laminated on both surfaces of the transparent substrate 11. Specifically, as in the laminate substrate 20B shown in FIG. 3B, the first surface 11a of the transparent substrate 11 and the other surface (the other surface) 11b are first The low reflectance alloy layers 131A and 131B, the copper layers 12A and 12B, and the second low reflectance alloy layers 132A and 132B can be stacked in this order.

  The first low reflectance alloy layer 131 (131A, 131B) and the second low reflectance alloy layer 132 (132A, 132B) both contain copper and nickel. It can be manufactured by the same manufacturing method.

  In the configuration examples of FIG. 2 (b) and FIG. 3 (b), in which the copper layer and the low reflectance alloy layer are laminated on both sides of the transparent substrate, the transparent substrate 11 is a symmetrical plane and the transparent substrate 11 is used. Although the example arrange | positioned so that the layer laminated | stacked on the upper and lower sides may become symmetrical was shown, it is not limited to the form which concerns. For example, in FIG. 3 (b), the copper layer 12A and the low reflectance alloy layer 13A are laminated in that order on the side of the transparent substrate 11 in the same manner as the configuration of FIG. 2 (b). The other surface (the other surface) 11b is formed by stacking the first low reflectance alloy layer 131B, the copper layer 12B, and the second low reflectance alloy layer 132B in this order. The layers stacked on the upper and lower sides of the transparent substrate 11 may be asymmetric.

  The degree of reflection of light of the laminate substrate of the present embodiment is not particularly limited. For example, the average specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, and 40% or less Is more preferably 30% or less. This is because, when the average regular reflectance of light with a wavelength of 400 nm or more and 700 nm or less is 55% or less, for example, even when the laminate substrate of this embodiment is used as a conductive substrate for a touch panel, It is because it can suppress especially.

  The measurement of the regular reflectance of the laminate substrate can be performed by irradiating light to the low reflectance alloy layer. That is, measurement can be performed by irradiating light from the low reflectance alloy layer side among the copper layer and the low reflectance alloy layer contained in the laminate substrate. Specifically, for example, when the copper layer 12 and the low reflectance alloy layer 13 are sequentially stacked on one surface 11 a of the transparent base 11 as shown in FIG. 2A, the low reflectance alloy layer 13 can be irradiated with light. Thus, the surface A of the low reflectance alloy layer 13 can be irradiated with light and measured. Further, the arrangement of the copper layer 12 and the low reflectance alloy layer 13 is changed in the case of FIG. 2A, and the low reflectance alloy layer 13 and the copper layer 12 are laminated in this order on one surface 11 a of the transparent substrate 11. In this case, the regular reflectance can be measured by irradiating the low reflectance alloy layer with light from the side of the surface 11 b of the transparent substrate 11 so that the low reflectance alloy layer 13 can be irradiated with light.

  Moreover, the average of the regular reflectance of light with a wavelength of 400 nm or more and 700 nm or less means an average value of measurement results when the wavelength is changed in a range of 400 nm or more and 700 nm or less. Although the width of changing the wavelength is not particularly limited in the measurement, for example, it is preferable to change the wavelength every 10 nm to measure the light in the above wavelength range, and change the wavelength every 1 nm to be the above wavelength range. It is more preferred to make measurements on light.

  As described later, the laminate substrate can be processed as a conductive substrate by forming a fine metal wire by wiring processing of the copper layer and the low reflectance alloy layer by etching. The regular reflectance of light in the conductive substrate means the regular reflectance on the surface on the light incident side of the low reflectance alloy layer disposed on the outermost surface when the transparent base material is removed.

  For this reason, in the case of the conductive substrate after the etching process, it is preferable that the measurement value in the portion in which the copper layer and the low reflectance alloy layer remain is within the above range.

  Next, the conductive substrate of the present embodiment will be described.

  The conductive substrate of the present embodiment can include a transparent base and fine metal wires formed on at least one surface side of the transparent base. The metal thin wire is a laminate including a low reflectance alloy wiring layer containing copper and nickel, and a copper wiring layer, and copper and nickel contained in the low reflectance alloy wiring layer, The proportion of nickel can be 30% by mass or more and 85% by mass or less.

  The conductive substrate of the present embodiment can be obtained, for example, by wiring the above-described laminated substrate. And in the conductive substrate of this embodiment, since the copper wiring layer and the low reflectance alloy wiring layer are provided on the transparent base material, it is possible to suppress the reflection of light by the copper wiring layer. Therefore, by providing the low reflectance alloy wiring layer, for example, when used for a touch panel or the like, good visibility of the display can be obtained.

  The conductive substrate of the present embodiment can be preferably used, for example, as a conductive substrate for a touch panel. In this case, the conductive substrate can be configured to have a wiring pattern formed by providing an opening in the copper layer in the above-described laminate substrate and the low reflectance alloy layer. More preferably, a mesh-shaped wiring pattern can be provided.

  The conductive substrate on which the wiring pattern having the opening is formed can be obtained by etching the copper layer and the low reflectance alloy layer of the laminate substrate described above. Then, for example, a conductive substrate having a mesh-like wiring pattern can be formed by two-layer metal thin lines. A specific configuration example is shown in FIG. FIG. 4 is a view of the conductive substrate 30 provided with a mesh-like wiring pattern as viewed from the top side in the stacking direction of the copper wiring layer and the low reflectance alloy wiring layer. The conductive substrate 30 shown in FIG. 4 has a transparent base 11, a plurality of copper wiring layers 31B parallel to the X-axis direction in the drawing, and a copper wiring layer 31A parallel to the Y-axis direction. The copper wiring layers 31A and 31B can be formed by etching the above-described laminate substrate, and a low reflectance alloy wiring layer (not shown) is formed on the upper surface and / or the lower surface of the copper wiring layers 31A and 31B. There is. In addition, the low reflectance alloy wiring layer is etched in substantially the same shape as the copper wiring layers 31A and 31B.

  The arrangement of the transparent substrate 11 and the copper wiring layers 31A and 31B is not particularly limited. A configuration example of the arrangement of the transparent base 11 and the copper wiring layer is shown in FIG. FIG. 5 corresponds to a cross-sectional view taken along line A-A 'of FIG.

  For example, as shown in FIG. 5, copper wiring layers 31A and 31B may be disposed on the upper and lower surfaces of the transparent substrate 11, respectively. In the case of the conductive substrate shown in FIG. 5, the first low reflectivity alloy wiring etched to substantially the same shape as the copper wiring layers 31A and 31B on the transparent base 11 side of the copper wiring layers 31A and 31B. Layers 321A, 321B are disposed. In addition, second low reflectance alloy wiring layers 322A and 322B are disposed on the surfaces of the copper wiring layers 31A and 31B opposite to the transparent substrate 11.

  Therefore, in the conductive substrate shown in FIG. 5, the thin metal wires are formed of the first low reflectivity alloy interconnection layers 321A and 321B and the second low reflectivity alloy interconnection layers 322A and 322B as low reflectivity alloy interconnection layers. The copper wiring layers 31A and 31B are disposed between the first low reflectance alloy wiring layers 321A and 321B and the second low reflectance alloy wiring layers 322A and 322B. .

  Although an example in which the first low reflectance alloy wiring layer and the second low reflectance alloy wiring layer are provided is shown here, the present invention is not limited to such a form. For example, only one of the first low reflectance alloy wiring layer and the second low reflectance alloy wiring layer can be provided.

  The conductive substrate having the mesh-like wiring shown in FIG. 4 has, for example, copper layers 12A and 12B on both sides of the transparent substrate 11 as shown in FIG. 2 (b) and FIG. 3 (b) and a low reflectance alloy layer. 13A and 13B (131A, 132A, 131B, 132B) can be formed from a laminate substrate.

  Note that, for example, the conductive substrate provided with the first low reflectance alloy wiring layer and the second low reflectance alloy wiring layer shown in FIG. 5 is formed from the laminated substrate shown in FIG. be able to.

  Then, the case where it forms using the laminated body board | substrate of FIG.3 (b) is demonstrated to an example.

  First, the copper layer 12A, the first low reflectance alloy layer 131A, and the second low reflectance alloy layer 132A on one surface 11a side of the transparent substrate 11 are parallel to the Y axis direction in FIG. 3B. A plurality of linear patterns are etched so as to be disposed at predetermined intervals along the X-axis direction. Note that the Y-axis direction in FIG. 3 (b) indicates a direction perpendicular to the paper surface. Moreover, the X-axis direction in FIG. 3B means a direction parallel to the width direction of each layer.

  The copper layer 12B on the other surface 11b side of the transparent substrate 11, the first low reflectance alloy layer 131B, and the second low reflectance alloy layer 132B are parallel to the X-axis direction in FIG. 3B. Etching is performed such that a plurality of linear patterns are arranged at predetermined intervals along the Y-axis direction.

  By the above-described operation, the conductive substrate having the mesh-like wiring shown in FIGS. 4 and 5 can be formed. In addition, the etching of both surfaces of the transparent base material 11 can also be performed simultaneously. That is, the etching of the copper layers 12A and 12B, the first low reflectance alloy layers 131A and 131B, and the second low reflectance alloy layers 132A and 132B may be performed simultaneously.

  The conductive substrate having the mesh-like wiring shown in FIG. 4 can also be formed by using two laminate substrates shown in FIG. 2 (a) or FIG. 3 (a). Taking the case of using the conductive substrate of FIG. 3A as an example, the copper layer 12, the first low reflectance alloy layer 131, and the first low reflectance alloy layer 131 are provided for the two conductive substrates shown in FIG. 3A. The second low reflectance alloy layer 132 is etched such that a plurality of linear patterns parallel to the X-axis direction are disposed at predetermined intervals along the Y-axis direction. Then, by aligning two conductive substrates in a direction such that the linear patterns formed on the conductive substrates by the above etching process intersect with each other, a conductive substrate provided with a mesh-like wiring is obtained. be able to. The surface to be bonded when bonding the two conductive substrates is not particularly limited.

  For example, the two conductive substrates can be configured as shown in FIG. 5 by bonding surfaces 11 b of the transparent base 11 in FIG. 3A on which the copper layer 12 and the like are not laminated. .

  The width of the metal fine wires and the distance between the metal fine wires in the conductive substrate having the mesh-like wiring shown in FIG. 4 are not particularly limited, and, for example, according to the electrical resistance value etc. necessary for the metal fine wires. Can be selected.

  However, it is preferable to select the width and the like of the thin metal wire so that the transparent base material and the thin metal wire have sufficient adhesion.

  The conductive substrate of the present embodiment has a wiring pattern formed by wiring the above-described laminated substrate and forming an opening in the copper layer in the laminated substrate and the low reflectance alloy layer. For this reason, the opening part which exposes a transparent base material is provided between the metal fine wire contained in a wiring pattern.

  And the reduction rate from the average of the transmittance of light of wavelength 400 nm or more and 700 nm or less of the transparent base material of the average of the transmittance of light of wavelength 400 nm or more and 700 nm or less of the opening is 3.0% or less Is preferred.

  This is because the rate of decrease of the transmittance of light of wavelengths 400 nm to 700 nm from the average of the transparent substrate to be provided to the laminate substrate from the average of the transmittances of light of wavelengths 400 nm to 700 nm of the opening is 3.0. If it exceeds 10%, the transparent substrate may be seen to turn yellow when visually observed. When the reduction rate exceeds 3.0%, the low reflectance alloy layer and the copper layer can be etched at the same time because the low reflectance alloy layer and the copper layer are etched at a low etching rate. Not because Therefore, as described above, it is preferable to set the ratio of nickel to 85% by mass or less in copper and nickel contained in the low reflectance alloy layer.

  When using a blackened layer containing a chemically nonstoichiometric oxide of nickel and copper instead of the low reflectance alloy layer, the etchability decreases due to the content ratio of nickel and copper and the oxidation state of these. When the rate of decrease exceeds 3.0%, the transparent substrate may be observed to turn yellow when visually observed. As described above, since it is necessary to control the sputtering atmosphere at the time of film formation of the blackened layer, the laminate substrate having the blackened layer using the chemically nonstoichiometric oxide, it is difficult to optimize the manufacturing conditions There is also.

  On the other hand, in the laminate substrate according to the present embodiment, since the low reflectance alloy layer is used for the blackening layer, only the composition of nickel and copper needs to be controlled, so that the manufacturing conditions can be easily optimized.

  Further, the degree of reflection of light of the conductive substrate of the present embodiment is not particularly limited, but for example, the average specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, 40 % Or less is more preferable, and 30% or less is more preferable. This is because when the average specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less is 55% or less, a decrease in the visibility of the display can be particularly suppressed even when used as a conductive substrate for a touch panel.

The conductive substrate having the mesh-like wiring composed of the two-layer wiring of the present embodiment described above can be preferably used, for example, as a conductive substrate for a projected capacitive touch panel.
(Method of manufacturing laminate substrate, method of manufacturing conductive substrate)
Next, a configuration example of a method of manufacturing a laminate substrate of the present embodiment will be described.

The method for manufacturing a laminate substrate of the present embodiment can have the following steps.
Transparent substrate preparation process of preparing a transparent substrate.
A laminate forming step of forming a laminate on at least one surface side of a transparent substrate.
And the said laminated body formation process can include the following steps.
A copper layer forming step of forming a copper layer by copper layer deposition means for depositing copper.
A low reflectance alloy layer forming step of forming a low reflectance alloy layer by low reflectance alloy layer film forming means for depositing a low reflectance alloy layer containing copper and nickel.

  The low reflectance alloy layer forming step is preferably performed in a reduced pressure atmosphere. Moreover, it is preferable that the ratio of nickel is 30 to 85 mass% among copper and nickel contained in a low-reflectance alloy layer.

  Although the manufacturing method of the laminated body board | substrate of this embodiment is demonstrated below, since it can be set as the structure similar to the case of the above-mentioned laminated body board | substrate except the point demonstrated below, it abbreviate | omits description.

  As described above, in the laminate substrate of the present embodiment, the order of lamination when disposing the copper layer and the low reflectance alloy layer on the transparent substrate is not particularly limited. Moreover, a copper layer and a low reflectance alloy layer can also each be formed in multiple layers. Therefore, the order of carrying out the copper layer forming step and the low reflectance alloy layer forming step and the number of times of carrying out the steps are not particularly limited, and any order may be made according to the structure of the laminate substrate to be formed. It can be implemented by the number of times and timing.

  The step of preparing a transparent substrate is, for example, a step of preparing a transparent substrate made of a polymer film that transmits visible light, a glass substrate or the like, and the specific operation is not particularly limited. For example, cutting or the like to an arbitrary size can be performed as needed in order to provide each process or step in the subsequent stage. In addition, about what can be used suitably as a polymeric film which permeate | transmits visible light, since it is stated above, description is abbreviate | omitted here.

  Next, the laminate formation step will be described. The laminate forming step is a step of forming a laminate on at least one surface side of the transparent base material, and includes a copper layer forming step and a low reflectance alloy layer forming step. Therefore, each step will be described below.

  First, the copper layer forming step will be described.

  In the copper layer forming step, the copper layer can be formed by a copper layer forming means for depositing copper on at least one surface side of the transparent substrate.

  In the copper layer forming step, it is preferable to form a copper thin film layer using a dry plating method. Moreover, when making a copper layer thicker, it is preferable to form a copper plating layer further using a wet plating method, after forming a copper thin film layer by a dry plating method.

  For this reason, the copper layer forming step can include, for example, a step of forming a copper thin film layer by a dry plating method. Further, the copper layer forming step may have the step of forming a copper thin film layer by a dry plating method, and the step of forming a copper plating layer by a wet plating method using the copper thin film layer as a feeding layer. .

  Therefore, the above-mentioned copper layer film forming means is not limited to one film forming means, and a plurality of film forming means may be used in combination.

  As described above, the copper layer is formed directly on the transparent substrate or the low reflectance alloy layer by forming the copper layer by only the dry plating method or a combination of the dry plating method and the wet plating method, without using an adhesive. It is preferable because it can be done.

  The dry plating method is not particularly limited, but a sputtering method, an ion plating method, a vapor deposition method and the like can be preferably used under a reduced pressure atmosphere.

  In particular, as the dry plating method used for forming the copper thin film layer, it is more preferable to use the sputtering method because the control of the thickness is easy. That is, in this case, sputtering film forming means (sputtering film forming method) can be preferably used as a copper layer film forming means for depositing copper in the copper layer forming step.

  The copper thin film layer can be suitably formed, for example, using the roll-to-roll sputtering apparatus 60 shown in FIG. The process of forming a copper thin film layer will be described below by taking a roll-to-roll sputtering apparatus as an example.

FIG. 6 shows an example of the configuration of a roll-to-roll sputtering apparatus 60. The roll-to-roll sputtering apparatus 60 comprises a housing 61 housing most of its components. Although the shape of the case 61 is shown as a rectangular parallelepiped in FIG. 6, the shape of the case 61 is not particularly limited, and any shape depending on the device to be accommodated inside, the installation place, the pressure resistance, etc. It can be done. For example, the shape of the housing 61 may be cylindrical. However, in order to remove residual gas not related to film formation at the start of film formation, it is preferable that the pressure in the casing 61 can be reduced to 1 Pa or less, more preferably to 10 ⁻³ Pa or less, and further reduced to 10 ⁻⁴ Pa or less It is further preferred that it is possible. It is not necessary that the pressure inside the casing 61 can be reduced to the above-mentioned pressure, and only the lower region in the drawing where the can roll 63 described later is disposed can perform the pressure reduction. .

  In the housing 61, an unwinding roll 62 for supplying a substrate for forming a copper thin film layer, a can roll 63, sputtering cathodes 64a to 64d, a front feed roll 65a, a rear feed roll 65b, tension rolls 66a, 66b, A winding roll 67 can be arranged. In addition to the above-described rolls, guide rolls 68a to 68h, a heater 69, and the like may be optionally provided on the transport path of the base on which the copper thin film layer is formed.

  The unwinding roll 62, the can roll 63, the front feed roll 65a, and the winding roll 67 can be provided with power by a servomotor. The unwinding roll 62 and the winding roll 67 are configured such that the tension balance of the substrate on which the copper thin film layer is formed is maintained by torque control using a powder clutch or the like.

  The configuration of the can roll 63 is also not particularly limited, but for example, its surface is finished by hard chromium plating, and a refrigerant or a heat medium supplied from the outside of the housing 61 circulates in the inside to adjust to a constant temperature. It is preferable that it is comprised.

  The tension rolls 66a, 66b are preferably finished, for example, by hard chromium plating on the surface and provided with a tension sensor. The surfaces of the front feed roll 65a, the rear feed roll 65b, and the guide rolls 68a to 68h are also preferably finished by hard chromium plating.

  The sputtering cathodes 64a to 64d are preferably arranged to face the can roll 63 in a magnetron cathode type. Although the size of the sputtering cathodes 64a to 64d is not particularly limited, the dimension in the width direction of the substrate on which the copper thin film layers of the sputtering cathodes 64a to 64d are formed is wider than the width of the substrate on which the opposing copper thin film layers are formed Is preferred.

  The substrate on which the copper thin film layer is formed is transported in the roll-to-roll sputtering apparatus 60, which is a roll-to-roll vacuum film forming apparatus, and copper thin films are formed on the sputtering cathodes 64a to 64d facing the can roll 63. A layer is deposited.

  The procedure in the case of forming a copper thin film layer using roll-to-roll sputtering apparatus 60 will be described.

  First, a copper target is attached to the sputtering cathodes 64a to 64d, and the inside of the housing 61 in which the base material for forming the copper thin film layer is set on the unwinding roll 62 is evacuated by vacuum pumps 70a and 70b.

  Thereafter, a sputtering gas such as an inert gas such as argon is introduced into the housing 61 by the gas supply means 71. Although the configuration of the gas supply means 71 is not particularly limited, it may have a gas storage tank (not shown). Further, mass flow controllers (MFCs) 711a and 711b and valves 712a and 712b are provided for each gas type between the gas storage tank and the housing 61 so that the supply amount of each gas into the housing 61 can be controlled. Can be configured. Although FIG. 6 shows an example in which two sets of mass flow controllers and valves are provided, the number of installation is not particularly limited, and the number of installation may be selected according to the number of gas types used.

  Then, when the sputtering gas is supplied into the housing 61 by the gas supply unit 71, the flow rate of the sputtering gas and the opening degree of the pressure adjusting valve 72 provided between the vacuum pump 70 b and the housing 61 are adjusted. It is preferable to carry out film formation while maintaining the inside of the apparatus at, for example, 0.13 Pa or more and 1.3 Pa or less.

  In this state, while the base material is transported from the unwinding roll 62 at a speed of, for example, 1 m or more and 20 m or less, electric power is supplied from the sputtering DC power supply connected to the sputtering cathodes 64 a to 64 d to perform sputtering discharge. Thereby, a desired copper thin film layer can be continuously formed on the base material.

  In addition to the above, various members can be disposed in the roll-to-roll sputtering apparatus 60 as needed. For example, pressure gauges 73a and 73b for measuring the pressure in the housing 61 and vent valves 74a and 74b may be provided.

  Further, as described above, it is possible to further form a copper layer (copper plating layer) using a wet plating method after dry plating.

  When forming a copper plating layer by a wet plating method, the copper thin film layer formed by dry plating as described above can be used as a feeding layer. In this case, an electroplating film forming means can be preferably used as a copper layer film forming means for depositing copper in the copper layer forming step.

  The conditions in the process of forming a copper plating layer by a wet plating method by using a copper thin film layer as a feeding layer, that is, the conditions for electroplating treatment are not particularly limited, and various conditions according to an ordinary method may be adopted. For example, a copper plating layer can be formed by supplying a base on which a copper thin film layer is formed to a plating tank containing a copper plating solution and controlling the current density and the transport speed of the base.

  Next, the low reflectance alloy layer forming step will be described.

  As described above, the low reflectance alloy layer forming step of forming a low reflectance alloy layer containing copper and nickel on at least one surface of the transparent substrate as described above Is a step of depositing a low reflectance alloy layer. Although the low reflectance alloy layer film forming means for depositing the low reflectance alloy layer containing copper and nickel in the low reflectance alloy layer forming step is not particularly limited, for example, sputtering film formation under a reduced pressure atmosphere It is preferable that the method is a sputtering film forming method.

  The low reflectance alloy layer can be suitably formed, for example, using the roll-to-roll sputtering apparatus 60 shown in FIG. The configuration of the roll-to-roll sputtering apparatus has already been described, and thus the description thereof is omitted here.

  A configuration example of a procedure in the case of forming a low reflectance alloy layer using roll-to-roll sputtering apparatus 60 will be described.

  First, a copper-nickel alloy target is mounted on the sputtering cathodes 64a to 64d, and the inside of the housing 61 in which the base material for forming the low reflectance alloy layer is set on the unwinding roll 62 is evacuated by vacuum pumps 70a and 70b. . Thereafter, a sputtering gas composed of an inert gas, for example, argon, is introduced into the housing 61 by the gas supply means 71. At this time, by adjusting the flow rate of the sputtering gas and the opening degree of the pressure adjusting valve 72 provided between the vacuum pump 70 b and the housing 61, the inside of the housing 61 is maintained at 0.13 Pa or more and 13 Pa or less, for example. It is preferable to carry out film formation.

  In this state, power is supplied from the sputtering DC power source connected to the sputtering cathodes 64a to 64d while the base material is transported from the unwinding roll 62 at a speed of, for example, 0.5 m to 10 m per minute to perform sputtering discharge. I do. Thereby, a desired low reflectance alloy layer can be continuously formed on the substrate.

  So far, the respective steps and steps included in the method for manufacturing a laminate substrate of the present embodiment have been described.

  In the laminate substrate obtained by the method for producing a laminate substrate of the present embodiment, the copper layer preferably has a thickness of 50 nm or more, more preferably 60 nm or more, as in the above-described laminate substrate. And 150 nm or more. The upper limit of the thickness of the copper layer is not particularly limited, but the thickness of the copper layer is preferably 5000 nm or less, more preferably 3000 nm or less. In addition, when a copper layer has a copper thin film layer and a copper plating layer as mentioned above, it is preferable that the sum total of the thickness of a copper thin film layer and the thickness of a copper plating layer is the said range.

  The thickness of the low reflectance alloy layer is not particularly limited, but is preferably 10 nm or more, and more preferably 15 nm or more. The upper limit of the thickness of the low reflectance alloy layer is not particularly limited, but is preferably 70 nm or less, and more preferably 50 nm or less.

  Furthermore, in the laminate substrate obtained by the method of producing a laminate substrate of the present embodiment, the average specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, and is 40% or less More preferably, it is more preferably 30% or less.

  It can be set as the conductive substrate by which the wiring pattern which provided the opening part in the copper layer and the low reflectance alloy layer was formed using the laminated substrate obtained by the manufacturing method of the laminated substrate of this embodiment. The conductive substrate can more preferably be configured to have a mesh-like wiring.

  In the method of manufacturing a conductive substrate according to the present embodiment, the copper layer of the laminate substrate obtained by the method of manufacturing a laminate substrate described above and the low reflectance alloy layer are etched to form a copper wiring layer; It is possible to have an etching step of forming a wiring pattern having a metal fine wire, which is a laminate including a reflectance alloy wiring layer. And an opening can be formed in a copper layer and a low reflectance alloy layer by the etching process concerned.

  In the etching step, for example, first, a resist having an opening corresponding to the portion to be removed by etching is formed on the outermost surface of the laminate substrate. For example, in the case of the laminate substrate 10A shown in FIG. 2A, a resist can be formed on the exposed surface A of the low reflectance alloy layer 13 disposed on the laminate substrate 10A. Although a method for forming a resist having an opening corresponding to a portion to be removed by etching is not particularly limited, for example, the resist can be formed by photolithography.

  Subsequently, the copper layer 12 and the low reflectance alloy layer 13 can be etched by supplying an etching solution from the upper surface of the resist.

  When a copper layer and a low reflectance alloy layer are disposed on both sides of the transparent substrate 11 as shown in FIG. 2 (b), openings of predetermined shapes are respectively formed on the surface A and the surface B of the laminate substrate. It is also possible to form a resist and simultaneously etch the copper layer and the low reflectance alloy layer formed on both sides of the transparent substrate 11. In addition, with respect to the copper layer and the low reflectance alloy layer formed on both sides of the transparent substrate 11, it is also possible to perform an etching process on each side. That is, for example, after the copper layer 12A and the low reflectance alloy layer 13A are etched, the copper layer 12B and the low reflectance alloy layer 13B can also be etched.

  The low reflectance alloy layer formed by the method of manufacturing a laminate substrate of the present embodiment exhibits the same reactivity to the etching solution as the copper layer. Therefore, the etchant used in the etching step is not particularly limited, and an etchant generally used for etching a copper layer can be preferably used.

  As an etching solution used in the etching step, for example, an aqueous solution containing one selected from sulfuric acid, hydrogen peroxide water, hydrochloric acid, cupric chloride, and ferric chloride, or two or more types selected from the above sulfuric acid and the like More preferably, a mixed aqueous solution containing The content of each component in the etching solution is not particularly limited.

  The etching solution can be used at room temperature, but is preferably heated to enhance reactivity, for example, preferably heated to 40 ° C. or more and 50 ° C. or less.

  The specific form of the mesh-like wiring obtained by the above-described etching process is as described above, and thus the description thereof is omitted here.

  In addition, two laminate substrates having a copper layer and a low reflectance alloy layer on one side of the transparent substrate 11 shown in FIGS. 2 (a) and 3 (a) are subjected to the etching step to conduct the conductivity. In the case where two conductive substrates are bonded to form a substrate and a conductive substrate having a mesh-like wiring is formed, a step of bonding the conductive substrates can be further provided. Under the present circumstances, the method to bond two conductive substrates together is not specifically limited, For example, it can adhere using optical adhesive agent (OCA) etc.

  In the conductive substrate obtained by the method for producing a conductive substrate according to the present embodiment, the average specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, and is 40% or less More preferably, it is more preferably 30% or less.

  This is because when the average specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less is 55% or less, a decrease in the visibility of the display can be particularly suppressed even when used as a conductive substrate for a touch panel.

  The laminate substrate, the conductive substrate, the method of manufacturing the laminate substrate, and the method of manufacturing the conductive substrate according to the present embodiment have been described above. According to the laminate substrate or the laminate substrate obtained by the method of manufacturing the laminate substrate, the copper layer and the low reflectance alloy layer exhibit substantially the same reactivity to the etching solution. For this reason, it is possible to provide a laminate substrate provided with a copper layer which can be etched simultaneously and a low reflectance alloy layer. Then, since the copper layer and the low reflectance alloy layer can be simultaneously etched, it is possible to easily form a copper wiring layer having a desired shape and a low reflectance alloy wiring layer.

  Further, by providing the low reflectance alloy wiring layer, it is possible to suppress the reflection of light by the copper wiring layer, and, for example, when using a conductive substrate for a touch panel, it is possible to suppress the reduction in visibility. Therefore, by providing the low reflectance alloy wiring layer, a conductive substrate having good visibility can be obtained.

Hereinafter, the present invention will be described in more detail by way of examples of the present invention and comparative examples, but the present invention is not limited by these examples.
(Evaluation method)
(1) Specular reflectance The specular reflectance was measured on the laminate substrates manufactured in the following examples and comparative examples.

  The measurement was performed by installing a reflectance measurement unit in an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV-2550).

Although the laminate substrate having the structure of FIG. 3A was manufactured in each example, the measurement of the reflectance was performed on the surface C exposed to the outside of the second low reflectance alloy layer 132 in FIG. 3A. It implemented by irradiating the light of the range of wavelength 400-700 nm as incident angle 5 degree and light reception angle 5 degrees. In addition, the light irradiated to the laminate substrate is changed in wavelength every 1 nm within the wavelength range of 400 nm to 700 nm, the specular reflectance is measured for the light of each wavelength, and the average of the measurement results is the laminate It was an average of the regular reflectance of the substrate.
(2) The reduction rate of the total light transmittance of the opening The total light transmittance was measured for the openings between the metal thin wires which expose the transparent substrate of the conductive substrate produced in each example and comparative example.

  The measurement was performed by installing an integrating sphere attachment device on the UV-visible spectrophotometer when measuring the regular reflectance. The irradiated light is measured for transmittance for light of each wavelength by changing the wavelength for each 1 nm within a wavelength range of 400 nm to 700 nm, and the average of the measurement results is the total light of the opening of the conductive substrate. It was taken as the average of the transmittance.

  Moreover, about the transparent base material used when manufacturing a laminated body board | substrate previously, the average of the total light transmittance was measured similarly.

And the decreasing rate from the average of the total light transmittance of a transparent base material of the average of the total light transmittance of the opening of the conductive substrate produced by each example and a comparative example was computed.
(Sample preparation conditions)
As an Example and a comparative example, the laminated body board | substrate and the electroconductive substrate were produced on the conditions demonstrated below, and evaluation was performed by the above-mentioned evaluation method.
Example 1
A laminate substrate having the structure shown in FIG. 3 (a) was produced.

  First, a transparent substrate preparation step was performed.

  Specifically, a transparent substrate made of polyethylene terephthalate resin (PET) for optics having a width of 500 mm and a thickness of 100 μm was prepared.

  Next, a laminate formation step was performed.

  As the laminate formation step, the first low reflectance alloy layer formation step, the copper layer formation step, and the second low reflectance alloy layer formation step were performed. The details will be described below.

  First, the first low reflectance alloy layer forming step was performed.

  The prepared transparent substrate was set in the roll-to-roll sputtering apparatus 60 shown in FIG. In addition, a copper-30 mass% Ni alloy target (manufactured by Sumitomo Metal Mining Co., Ltd.) was attached to the sputtering cathodes 64a to 64d.

  Then, the heater 69 of the roll-to-roll sputtering apparatus 60 was heated to 100 ° C., and the transparent substrate was heated to remove the water contained in the substrate.

Subsequently, the inside of the case 61 was evacuated to 1 × 10 ⁻⁴ Pa by the vacuum pumps 70 a and 70 b, and then argon gas was introduced into the case 61 by the gas supply unit 71 such that the flow rate of argon gas was 240 sccm. . Then, while conveying the transparent substrate from the unwinding roll 62 at a speed of 2 m / min, power is supplied from the sputtering DC power source connected to the sputtering cathodes 64a to 64d to perform sputtering discharge, and desired on the substrate The first low reflectance alloy layer was continuously formed. By the operation, the first low reflectance alloy layer 131 was formed to a thickness of 20 nm on the transparent base material.

  Subsequently, a copper layer forming step was performed.

  In the copper layer forming step, the first low reflection is performed in the same manner as the first low reflectance alloy layer except that the target attached to the magnetron sputtering cathode is changed to a copper target (Sumitomo Metal Mining Co., Ltd.). A copper layer was formed to a thickness of 200 nm on the upper surface of the rate alloy layer.

  In addition, as a base material which forms a copper layer, the base material in which the 1st low reflectance alloy layer was formed on the transparent base material was used at the 1st low reflectance alloy layer formation process.

  Then, a second low reflectance alloy layer forming step was performed.

  In the second low reflectance alloy layer forming step, the second low reflectance alloy layer 132 is formed on the upper surface of the copper layer 12 under the same conditions as the first low reflectance alloy layer 131 (see FIG. 3A). ).

  The average specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less of the produced laminate substrate was measured according to the above-mentioned procedure, the average specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less was 55%.

  Moreover, after performing regular reflectance measurement about the obtained laminated body board | substrate, the etching process was performed and the conductive substrate was produced.

  In the etching step, first, a resist having an opening corresponding to the portion to be removed by etching was formed on the surface C in FIG. 3A of the manufactured laminate substrate. Then, it was immersed for 1 minute in an etching solution consisting of 10% by weight of ferric chloride, 10% by weight of hydrochloric acid, and the balance with water to prepare a conductive substrate.

  The total light transmittance of the opening was measured for the produced conductive substrate.

The evaluation results are shown in Table 1.
[Examples 2 to 6]
A laminate substrate was produced in the same manner as in Example 1, except that the composition of the sputtering target used when forming the first and second low reflectance alloy layers was changed as shown in Table 1. I made an evaluation.

  Moreover, it carried out similarly to Example 1 from the produced laminated body board | substrate, produced the conductive substrate, and evaluated.

The results are shown in Table 1.
[Comparative Example 1 to Comparative Example 3]
In Comparative Example 1, a laminate was prepared in the same manner as Example 1, except that the composition of the sputtering target used when forming the first and second low reflectance alloy layers was changed as shown in Table 1. The substrate was prepared and evaluated.

  In Comparative Examples 2 and 3, the first and second blackening layers were formed instead of the first and second low reflectance alloy layers. In the first and second blackened layers, the composition of the sputtering target used in forming the film was changed as shown in Table 1, and oxygen was added to the argon gas in forming the blackened layer. The film was formed in the same manner as the case of the low reflectance alloy layer of Example 1 except for the point. Further, a laminate substrate was produced in the same manner as in Example 1 except for the blackening layer.

  In Comparative Examples 2 and 3, oxygen was supplied such that the oxygen supply amount shown in Table 1 was obtained when forming the low reflectance alloy layer.

  A conductive substrate was produced from the laminate substrate produced in Comparative Example 1 to Comparative Example 3 in the same manner as in Example 1 and evaluated.

  The results are shown in Table 1.

表１に示した結果によると、実施例１〜実施例６については、開口部の全光線透過率の減少率が３．０％以下となった。すなわち、銅層と、第１、第２の低反射率合金層を同時にエッチングすることができた。

According to the results shown in Table 1, in Examples 1 to 6, the reduction rate of the total light transmittance at the opening was 3.0% or less. That is, the copper layer and the first and second low reflectance alloy layers could be etched simultaneously.

  The ratio of nickel is 30% by mass or more and 85% by mass or less of copper and nickel contained in the sputtering target used when forming the first and second low reflectance alloy layers. It is considered that the same composition was also used in the blackened layer. That is, it is considered that the reactivity of the low reflectance alloy layer to the etching solution can be made equal to that of the copper layer.

  On the other hand, in Comparative Example 1, the proportion of nickel is less than 30% by mass of copper and nickel contained in the sputtering target used when forming the low reflectance alloy layer, and the low reflection film formed The same composition was obtained also in the rate alloy layer. For this reason, the regular reflectance has exceeded 55%.

  In addition, in Comparative Example 2, it can be confirmed that the reduction rate of the total light transmittance of the opening exceeds 3.0% and the etching rate of the blackened layer is slower than that of the copper layer, The total light transmittance decrease rate of the opening was 3.5%, and it was confirmed that the light appeared to be visible visually.

  Undercut was confirmed in Comparative Example 3, and it was confirmed that the etching rate of the blackened layer was faster than that of the copper layer.

  Therefore, in Comparative Examples 2 and 3, it was confirmed that the copper layer which can be etched simultaneously and the blackening layer could not be formed.

10A, 10B, 20A, 20B Laminated substrate 11 Transparent base 12, 12A, 12B Copper layer 13, 13A, 13B, 131, 132, 131A, 131B, 132A, 132B Low reflectivity alloy layer 30 Conductive substrate 31A, 31B Copper wiring layers 321A, 321B, 322A, 322B, 61 low reflectivity alloy wiring layers

Claims (11)

A transparent substrate,
And a laminate directly formed on at least one surface side of the transparent substrate,
The laminate is
A low reflectivity alloy layer containing copper and nickel;
It consists of a copper layer,
The laminated body board | substrate whose ratio of the said nickel is 30 mass% or more and 85 mass% or less among the said copper contained in the said low-reflectance alloy layer, and the said nickel. The laminate includes a first low reflectance alloy layer and a second low reflectance alloy layer as the low reflectance alloy layer,
The laminate substrate according to claim 1, wherein the copper layer is disposed between the first low reflectance alloy layer and the second low reflectance alloy layer.   The laminate substrate according to claim 1 or 2, wherein an average specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 55% or less. A transparent substrate,
And a metal fine wire formed directly on at least one surface side of the transparent substrate,
The thin metal wire is
A low reflectivity alloy wiring layer containing copper and nickel;
A laminate comprising a copper wiring layer,
The conductive substrate whose ratio of the said nickel is 30 mass% or more and 85 mass% or less among the said copper contained in the said low-reflectance alloy wiring layer, and the said nickel. The metal fine wire has a first low reflectance alloy wiring layer and a second low reflectance alloy wiring layer as the low reflectance alloy wiring layer,
The conductive substrate according to claim 4, wherein the copper wiring layer is disposed between the first low reflectance alloy wiring layer and the second low reflectance alloy wiring layer. An opening for exposing the transparent substrate is provided between the thin metal wires,
The rate of decrease of the average of the transmittance of light of wavelengths 400 nm to 700 nm of the opening from the average of the transmittance of light of wavelengths 400 nm to 700 nm of the transparent substrate is 3.0% or less. The conductive substrate according to 4 or 5. A transparent substrate preparation step of preparing a transparent substrate;
And a laminate forming step of directly forming a laminate on at least one surface side of the transparent substrate,
In the laminate forming step,
A copper layer forming step of forming a copper layer by copper layer deposition means for depositing copper;
Copper, and low-reflectivity alloy layer forming step for forming a low reflectivity alloy layer with a low reflectivity alloy layer forming means for depositing a low reflectivity alloy layer containing nickel and consist,
The low reflectance alloy layer forming step is performed under a reduced pressure atmosphere, and the ratio of the nickel in the copper and the nickel contained in the low reflectance alloy layer is 30% by mass to 85% by mass. Method of manufacturing body substrate   The method for manufacturing a laminate substrate according to claim 7, wherein the low reflectance alloy layer film forming means is a sputtering film forming method.   The method for manufacturing a laminate substrate according to claim 7, wherein the low reflectance alloy layer has a thickness of 10 nm or more. The copper layer of the laminate substrate obtained by the method of manufacturing a laminate substrate according to any one of claims 7 to 9 and the low reflectance alloy layer are etched to obtain a copper wiring layer and low reflection. Forming a wiring pattern having metal fine lines, which is a laminate including a rate alloy wiring layer,
The manufacturing method of the conductive substrate which forms an opening in the copper layer and the low reflectance alloy layer by the etching process.   The method for producing a conductive substrate according to claim 10, wherein the average specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less of the obtained conductive substrate is 55% or less.

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