TWI713591B - Laminate substrate, conductive substrate, manufacturing method of multilayer substrate, manufacturing method of conductive substrate - Google Patents

Abstract

Provided is a laminated body substrate including a transparent base material and a laminated body formed on at least one surface side of the transparent base material. This laminate has: a low-reflectivity alloy layer containing copper and nickel; and a copper layer. The ratio of the copper contained in the low-reflectivity alloy layer to the nickel in the nickel is 30% by mass or more and 85% by mass or less.

Description

Laminate substrate, conductive substrate, manufacturing method of multilayer substrate, and manufacturing method of conductive substrate

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

As described in Patent Document 1, in the prior art, a transparent conductive film for touch panels in which an ITO (indium oxide-tin) film is formed on the surface of a transparent substrate such as a transparent polymer film is used as a transparent conductive film.

However, in recent years, displays equipped with touch panels are becoming larger screens. Correspondingly, conductive substrates such as transparent conductive films for touch panels are also being required to have larger areas. However, due to the high resistance value of ITO, there is a problem that it cannot cope with the larger area of the conductive substrate.

For this reason, for example, as described in Patent Documents 2 and 3, studies have been conducted to replace ITO wiring with wiring such as copper. However, for example, in the case of using copper in wiring, since copper has metallic luster, there is a problem that the visibility of the display decreases due to reflection.

Therefore, a conductive substrate in which a blackened layer made of black material is formed on the surface of the wiring parallel to the surface of the transparent substrate together with wiring such as copper has been studied.

【Advanced Technical Literature】 〔Patent Literature〕

[Patent Document 1] Japanese Patent Application Publication No. 2003-151358

[Patent Document 2] Japanese Patent Application Publication No. 2011-018194

[Patent Document 3] JP 2013-069261 A

However, a conductive substrate with copper wiring on a transparent substrate is a method of forming a copper wiring by etching the copper layer into a desired wiring pattern after obtaining a laminate substrate with a copper layer formed on the surface of the transparent substrate. obtain. In addition, a conductive substrate with a blackened layer and copper wiring on a transparent substrate is obtained by combining the blackened layer and the copper layer on the surface of the transparent substrate. The layer is etched into the desired wiring pattern to obtain the wiring pattern.

By etching the blackened layer and the copper layer, for example, as shown in FIG. 1A, a patterned blackened layer 2 and a copper wiring obtained by patterning the copper layer can be formed on the transparent substrate 1 3 conductive substrate. In this case, the patterned width of the black layer 2 of copper wiring width W _A and W _B 3 is preferably of substantially the same.

However, there is a problem that the reactivity of the copper layer and the blackened layer to the etching solution is very different. That is, if it is desired to simultaneously etch the copper layer and the blackened layer, there is a problem that neither layer can be etched into the desired shape as shown in FIG. 1A.

For example, in the case where the etching speed of the blackened layer is very slow compared with the copper layer, as shown in FIG. 1B, the side surface of the copper wiring 3 as the patterned copper layer will be etched, resulting in so-called undercut . Therefore, the cross-sectional shape of the metal wiring 3 is likely to become a wider trapezoid shape at the lower part. If the metal wiring 3 is etched to ensure electrical insulation between the metal wirings 3, there is a problem that the wiring pitch width is too wide.

Moreover, when the etching speed of the blackened layer is faster than that of the copper layer, as shown in FIG. 1C, the width (bottom width) W _{A of} the patterned blackened layer 2 becomes smaller than that of the copper wiring In the state of width W _B of 3, the so-called undercut may occur. Such undercutting occurred after the comparison with a predetermined copper wiring width of 3 W _B, and the transparent substrate 1 as adhesion i.e. the adhesion width of the patterned black layer width W _A of the bottom 2, as the case becomes If the ratio of the bonding width is lower than necessary, there is a problem that sufficient wiring bonding strength cannot be obtained.

Moreover, if the copper layer and the blackened layer are not etched at the same time, but separate steps are used to perform the etching of the copper layer and the blackened layer, there is a problem that the number of steps increases.

In view of the above-mentioned problems of the prior art, an object of the present invention is to provide a laminate substrate having a copper layer and a low-reflectivity alloy layer that can be etched simultaneously.

In order to solve the above-mentioned problems, the present invention provides a laminate substrate comprising: a transparent substrate and a laminate formed on at least one surface side of the transparent substrate; the laminate has: low reflectance containing copper and nickel In the alloy layer and the copper layer, the ratio of the copper contained in the low-reflectivity alloy layer to the nickel in the nickel is 30% by mass or more and 85% by mass or less.

According to the present invention, it is possible to provide a laminate substrate provided with a copper layer and a low-reflectivity alloy layer that can be simultaneously etched.

10A, 10B, 20A, 20B‧‧‧Laminate substrate

11‧‧‧Transparent substrate

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 layer

321A, 321B, 322A, 322B‧‧‧Low reflectivity alloy wiring layer

[FIG. 1A] An explanatory diagram of the case where the copper layer and the blackened layer are simultaneously etched in the conventional conductive substrate.

[Fig. 1B] An explanatory diagram of the case where the copper layer and the blackened layer are simultaneously etched on the conventional conductive substrate.

[FIG. 1C] An explanatory diagram of the case where the copper layer and the blackened layer are simultaneously etched in the conventional conductive substrate.

[FIG. 2A] A cross-sectional view of a laminate substrate according to an embodiment of the present invention.

[FIG. 2B] A cross-sectional view of a laminate substrate according to an embodiment of the present invention.

[FIG. 3A] A cross-sectional view of a laminate substrate according to an embodiment of the present invention.

[FIG. 3B] A cross-sectional view of a laminate substrate according to an embodiment of the present invention.

[FIG. 4] A plan view of a conductive substrate with mesh wiring according to an embodiment of the present invention.

[Figure 5] A cross-sectional view along the line A-A' in Figure 4.

[Figure 6] An explanatory diagram of a roll-to-roll sputtering device.

Hereinafter, one embodiment of the multilayer substrate, the conductive substrate, the manufacturing method of the multilayer substrate, and the manufacturing method of the conductive substrate of the present invention will be described.

(Laminate substrate and conductive substrate)

The laminate substrate of the present embodiment may include a transparent substrate and a laminate formed on at least one surface side of the transparent substrate. In addition, the laminate has a low-reflectivity alloy layer containing copper and nickel, and a copper layer. The ratio of copper contained in the low-reflectivity alloy layer and nickel in nickel may be 30% by mass or more and 85% by mass or less.

It should be noted that the laminate substrate of this embodiment refers to the surface of the transparent substrate A substrate with a copper layer or a low-reflectivity alloy layer before patterning. In addition, the conductive substrate refers to a wiring substrate having a copper wiring layer or a low-reflectivity alloy wiring layer patterned into a wiring shape on the surface of a transparent substrate.

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

The transparent substrate is not particularly limited, and it is preferable to use a polymer film or a glass substrate that can penetrate visible light.

As a polymer film that can penetrate visible light, for example, a polyamide (PA)-based film, a polyethylene terephthalate (PET)-based film, and polyethylene naphthalate (PEN) are preferably used. Resin films such as films, cycloolefin films, polyimide (PI) films, and polycarbonate (PC) films.

The thickness of the transparent substrate is not particularly limited, and when it is used as a conductive substrate, it can be arbitrarily selected according to the required intensity or light transmittance. The thickness of the transparent substrate may be, for example, 10 μm or more and 250 μm or less. Especially in the case of use for a touch panel, it is preferably 20 μm or more and 200 μm or less, and preferably 20 μm or more and 120 μm or less. In the case of use for a touch panel, for example, particularly in applications where the overall thickness of the display needs to be reduced, the thickness of the transparent substrate is preferably 20 μm or more and 100 μm or less.

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

First, the copper layer will be described.

The copper layer is not particularly limited, but in order not to reduce the light transmittance, it is preferable that no adhesive is disposed between the copper layer and the transparent substrate or between the copper layer and the low-reflectivity alloy layer. That is, the copper layer It is preferably formed directly on the upper surface of other members.

In order to directly form a copper layer on the upper surface of other components, a dry plating method such as sputtering, ion plating, or evaporation may be used to form a copper thin film layer, and the copper thin film layer can be used as the copper layer.

Moreover, in the case of making the copper layer thick, 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, after a copper thin film layer is formed by a dry plating method on a transparent substrate or a low-reflectivity alloy layer, the copper thin film layer can be used as a power supply layer, and a wet plating method can be used to form the copper plating layer. In this case, the copper layer has a copper thin film layer and a copper plating layer.

As mentioned above, by using only the dry plating method or a combination of dry plating and wet plating to form the copper layer, the copper layer can be directly formed on the transparent substrate or the low-reflectivity alloy layer without using an adhesive. Therefore, it is better.

The thickness of the copper layer is not particularly limited, and when the copper layer is used as wiring, it can be arbitrarily selected according to the resistance value of the wiring or the wiring width. In particular, in order to allow sufficient electrical flow, the thickness of the copper layer is preferably 50 nm or more, preferably 60 nm or more, and more preferably 150 nm or more. The upper limit of the thickness of the copper layer is not particularly limited. However, if the copper layer becomes thicker, the time required for the etching when etching to form wiring becomes longer, so side etching may occur and light during etching is likely to occur. Problems such as resistance to peeling. For this reason, the thickness of the copper layer is preferably 5000 nm or less, preferably 3000 nm or less. In addition, when the copper layer has a copper thin film layer and a copper plating layer as mentioned above, the sum of the thickness of a copper thin film layer and the thickness of a copper plating layer is preferably in the said range.

Next, the low-reflectivity alloy layer will be described.

Since the copper layer has metallic luster, if only the copper layer is etched on a transparent substrate to form a copper wiring layer as wiring, as mentioned above, copper will reflect light, for example, when used as a touch panel In the case of using a wiring board, the visibility of the display will decrease. Therefore, a study on the provision of a blackened layer was conducted. However, due to the insufficient reactivity of the blackened layer with respect to the etching solution, it is difficult to simultaneously etch the copper layer and the blackened layer into a desired shape.

In contrast, the low-reflectivity alloy layer disposed on the laminate substrate of the present embodiment has copper and nickel. Therefore, the reactivity of the low-reflectivity alloy layer disposed on the laminate substrate of the present embodiment to the etching solution is almost the same as the reactivity of the copper layer to the etching solution, and the etching performance is also better. Therefore, in the laminate substrate of this embodiment, the copper layer and the low-reflectivity alloy layer containing copper and nickel can be simultaneously etched.

Hereinafter, the point that the low-reflectivity alloy layer disposed on the laminate substrate of the present embodiment can be etched simultaneously with the copper layer will be described.

The inventors of the present invention first studied the method of forming a copper oxide layer that oxidizes a part of the copper layer, which is a blackening layer that can suppress light reflection on the surface of the copper layer, and found that a part of the copper layer When it is oxidized to use it as a blackened layer, the blackened layer may contain an indefinite proportion of copper oxide or unoxidized copper.

When simultaneously etching the copper layer and the blackened layer of the laminate substrate provided with the copper layer and the blackened layer, as the etching solution, for example, an etching solution capable of etching the copper layer can be preferably used. In addition, according to the research of the inventor of the present invention, it is known that when the blackened layer contains copper oxide in an indefinite proportion, it is relatively easy to dissolve into an etching solution that can etch the copper layer.

In this way, when the blackened layer contains an indefinite proportion of copper oxide that is easily dissolved in the etching solution, the blackened layer is more reactive to the etching solution. Compared with the copper layer, the etching speed of the blackened layer is greater improve. Therefore, when the copper layer and the blackened layer are simultaneously etched, the blackened layer is prone to undercut.

Therefore, in the laminate substrate of this embodiment, in order to suppress undercutting, the blackening layer may be a low-reflectivity alloy layer that does not use oxygen and contains a nickel component that is not easily dissolved by an etching solution in addition to copper. In this way, by making the low-reflectivity alloy layer of the laminate substrate of the present embodiment not use oxygen and contain copper and nickel, its reactivity to the etching solution can be the same as that of the copper layer, so that the low-reflectivity alloy layer can be treated simultaneously And the copper layer is etched. It should be noted that since oxygen is not used in the low-reflectivity alloy layer, it does not contain oxygen, but it cannot be ruled out that it contains a very small amount as an inevitable component.

The ratio of copper contained in the low reflectivity alloy layer to nickel contained in nickel is not particularly limited, however, the ratio of copper contained in the low reflectivity alloy layer to nickel contained in nickel is preferably 30% by mass or more and 85% by mass or less. It should be noted that the nickel ratio refers to the ratio when the total content of copper and nickel in the low-reflectivity alloy layer is 100% by mass as described above.

The reason is that when the ratio of copper and nickel in the low-reflectivity alloy layer is less than 30% by mass, the average value of the specular reflectance of light with a wavelength of 400nm or more and 700nm or less cannot be set to 55 %the following.

On the other hand, if the ratio of the copper contained in the low-reflectivity alloy layer to the nickel in the nickel exceeds 85% by mass, nickel will be excessive and it is difficult to etch the low-reflectivity alloy layer. That is, the dissolution rate of the low-reflectivity alloy layer to the etching solution is slower than that of the copper layer, and it cannot be a low-reflectivity alloy layer that can be etched simultaneously with the copper layer. In addition, as described later, the low-reflectivity alloy layer can be formed by, for example, sputtering. However, if the ratio of nickel exceeds 85% by mass, magnetron sputtering cannot be performed.

In addition, in the laminate substrate, as described later, a low-reflectivity alloy layer and a copper layer can be laminated on a transparent substrate. According to this, by patterning the low-reflectivity alloy layer and the copper layer, A conductive substrate can be formed. If the ratio of the copper contained in the low-reflectivity alloy layer to the nickel in the nickel exceeds 85% by mass, when the low-reflectivity alloy layer or the copper layer is etched to form an opening, the removal process by etching is insufficient, and there is It can be observed that the surface of the transparent substrate turns yellow. Therefore, as described above, the ratio of copper contained in the low-reflectivity alloy layer to nickel in nickel is preferably 85% by mass or less.

The low-reflectivity alloy layer may contain copper and nickel as metals. It should be noted here that although the metal contained in the low-reflectivity alloy layer may only consist of copper and nickel, it is not limited to copper and nickel. For example, in the low-reflectivity alloy layer, as a metal, there may be inevitable impurities less than 1% by mass.

In addition, the low-reflectivity alloy layer only needs to contain copper and nickel, and the state in which each component is contained is not particularly limited.

The copper wiring layer and the low-reflectivity alloy wiring layer of the conductive substrate obtained from the laminated substrate of this embodiment can maintain the characteristics of the copper layer and the low-reflectivity alloy layer of the laminated substrate of this embodiment, respectively.

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

When the low-reflectivity alloy layer is formed by sputtering, for example, a copper-nickel alloy target may be used, and the film may be formed while supplying an inert gas used as a sputtering gas into the cavity.

In the case of using a copper-nickel alloy target during sputtering, the ratio of copper contained in the copper-nickel alloy to nickel in nickel is preferably 30% by mass or more and 85% by mass or less. According to this, The ratio of the copper and nickel in the formed low-reflectivity alloy layer to the ratio of the copper-nickel alloy in the copper-nickel alloy target used when forming the low-reflectivity alloy layer The ratio of nickel in copper and nickel is the same.

It should be noted that the inert gas used in the formation of the low-reflectivity alloy layer is not particularly limited. For example, argon gas or xenon gas is preferably used, and argon gas is preferably used.

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

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

As mentioned above, the low-reflectivity alloy layer can function as a layer that suppresses light reflection on the surface of the copper layer. However, when the thickness of the low-reflectivity alloy layer is thin, it cannot sufficiently suppress the light reflection of the copper layer. The situation. In this regard, by making the thickness of the low-reflectivity alloy layer 10 nm or more, the light reflection on the surface of the copper layer can be reliably suppressed.

The upper limit of the thickness of the low-reflectivity alloy layer is not particularly limited. However, if it is thicker than necessary, the time required for film formation or the time required for etching during wiring formation becomes longer, leading to increased costs. For this reason, the thickness of the low-reflectivity alloy layer is preferably 70 nm or less, and preferably 50 nm or less.

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

As described above, the laminate substrate of this embodiment may have a transparent base material, and a laminate having a copper layer and a low-reflectivity alloy layer. At this time, the arrangement order of the copper layer and the low-reflectivity alloy layer on the transparent substrate or the number of layers in the laminate is not particularly limited. That is, for example, the The copper layer and the low-reflectivity alloy layer are laminated in an arbitrary order on at least one side of the substrate. In addition, a plurality of copper layers and/or low-reflectivity alloy layers may be formed in the laminate.

However, when arranging the copper layer and the low-reflectivity alloy layer in the laminate, in order to suppress the light reflection on the surface of the copper layer, it is better to arrange the low-reflectivity alloy on the surface of the copper layer where the light reflection is particularly suppressed. Floor.

In particular, it is preferable to have a laminated structure in which a low-reflectivity alloy layer is formed on the surface of the copper layer. Specifically, for example, it is preferable that the laminated body has a first low-reflectivity alloy layer and a second low-reflectivity alloy layer as the low-reflectivity alloy layer. The copper layer is arranged between the first low-reflectivity alloy layer and the second low-reflectivity alloy layer.

Regarding specific configuration examples, the following description will be given with reference to FIGS. 2A, 2B, 3A, and 3B. 2A, FIG. 2B, FIG. 3A, and FIG. 3B show examples of cross-sectional views of a surface parallel to the laminate direction of the transparent base material, the copper layer, and the low-reflectivity alloy layer of the laminate substrate of the present embodiment.

For example, in the laminated substrate 10A shown in FIG. 2A, the copper layer 12 and the low-reflectivity alloy layer 13 can be laminated in order on one surface 11a side of the transparent base material 11. In addition, as shown in FIG. 2B for the laminate substrate 10B, the copper layers 12A, 12B and the low-reflectivity alloy layer 13A may be successively formed on one surface 11a side and the other surface (the other surface) 11b side of the transparent substrate 11, respectively. , 13B each layer of accumulation. It should be noted that the stacking sequence of the copper layer 12 (12A, 12B) and the low-reflectivity alloy layer 13 (13A, 13B) is not limited to the example of FIG. 2A and FIG. 2B, and it can also start from the transparent substrate 11 side in order. The low-reflectivity alloy layer 13 (13A, 13B) and the copper layer 12 (12A, 12B) are stacked.

Also, as described above, for example, it may also be provided on one side of the transparent substrate 11. The structure of multiple low-reflectivity alloy layers. For example, in the laminate substrate 20A shown in FIG. 3A, the first low-reflectivity alloy layer 131, the copper layer 12, and the second low-reflectivity alloy layer 132 can be laminated on one surface 11a of the transparent substrate 11 in this order.

In this way, the low-reflectivity alloy layer has a first low-reflectivity alloy layer 131 and a second low-reflectivity alloy layer 132, and the copper layer 12 is arranged on the first low-reflectivity alloy layer 131 and the second low-reflectivity alloy layer According to this, the reflection of light incident from the upper surface side and the lower surface side of the copper layer 12 can be suppressed more reliably.

In this case, it may be a structure in which a copper layer, a first low-reflectivity alloy layer, and a second low-reflectivity alloy layer are laminated on both surfaces of the transparent substrate 11. Specifically, the laminate substrate 20B shown in FIG. 3B can be sequentially provided with the first low-reflectivity alloy layers 131A, 131B, and copper on one surface 11a side and the other surface (the other surface) 11b of the transparent substrate 11, respectively. The layers 12A, 12B, and the second low-reflectivity alloy layer 132A, 132B are stacked.

It should be noted that both the first low-reflectivity alloy layer 131 (131A, 131B) and the second low-reflectivity alloy layer 132 (132A, 132B) can be low-reflectivity alloy layers containing copper and nickel, and can be Manufactured in the same manufacturing method.

In addition, in the configuration examples of Figs. 2B and 3B in which a copper layer and a low-reflectivity alloy layer are laminated on both surfaces of the transparent substrate, although the layers are laminated on the transparent substrate 11 An example of a symmetrical arrangement with the transparent substrate 11 as the symmetry plane is not limited to this form. For example, in FIG. 3B, the structure on one surface 11a side of the transparent substrate 11 may be formed in the same way as the structure of FIG. 2B in which the copper layer 12A and the low-reflectivity alloy layer 13A are sequentially laminated, and another One surface (the other surface) 11b side is formed in a form in which the first low-reflectivity alloy layer 131B, the copper layer 12B, and the second low-reflectivity alloy layer 132B are laminated in this order. Thus, the transparent substrate 11 The layers stacked on top and bottom can also have an asymmetric structure.

The degree of light reflection of the laminate substrate of this embodiment is not particularly limited. For example, the average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, preferably 40% or less, and more Preferably, it is 30% or less. The reason is that when the average value of the specular reflectance of light having 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 touch panels , It can also especially suppress the decrease of the visibility of the display.

The regular reflectance of the laminate substrate can be measured by irradiating light to the low reflectance alloy layer. That is, the measurement can be performed by irradiating light from the side of the low-reflectivity alloy layer among the copper layer and the low-reflectivity alloy layer contained in the laminate substrate. Specifically, for example, as shown in FIG. 2A, when a copper layer 12 and a low-reflectivity alloy layer 13 are sequentially laminated on one surface 11a of the transparent substrate 11, the low-reflectivity alloy layer 13 can be The light irradiation method is to irradiate the surface A of the low-reflectivity alloy layer 13 with light, and the measurement can be performed accordingly. In addition, in the case where the arrangement order of the copper layer 12 and the low-reflectivity alloy layer 13 in FIG. 2A is exchanged, and the low-reflectivity alloy layer 13 and the copper layer 12 are sequentially laminated on one surface 11a side of the transparent substrate 11 By irradiating the low-reflectivity alloy layer 13 with light, the low-reflectivity alloy layer can be irradiated with light from the surface 11b side of the transparent substrate 11, so that the regular reflectance can be measured.

In addition, the average value of the specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less refers to the average value of the measurement results when the wavelength is changed within the range of 400 nm or more and 700 nm or less. During the measurement, there is no particular limitation on the variation range of the wavelength. For example, it is preferable to change the wavelength every 10 nm and measure the light in the above-mentioned wavelength range, and it is preferable to change the wavelength every 1 nm and measure the light in the above-mentioned wavelength range. Determination.

It should be noted that, as described later, a laminate substrate can be a conductive substrate by forming thin metal wires by wiring processing based on etching the copper layer and the low-reflectivity alloy layer. At this time, the light specular reflectance of the conductive substrate refers to the specular reflectance of the surface of the light incident side of the low-reflectivity alloy layer arranged on the outermost surface with the transparent substrate removed.

Therefore, if it is a conductive substrate that has been etched, it is preferable that the average value of the measurement results of the portion where the copper layer and the low-reflectivity alloy layer remain is within the above range.

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

The conductive substrate of the present embodiment may include a transparent base material and thin metal wires formed on at least one surface side of the transparent base material. In addition, the thin metal wire is a laminate with a low-reflectivity alloy wiring layer containing copper and nickel and a copper wiring layer, and the ratio of copper contained in the low-reflectivity alloy wiring layer to nickel in nickel can be 30% by mass Above and 85% by mass or less.

The conductive substrate of the present embodiment can be obtained, for example, by performing wiring processing on a laminate substrate as described above. Furthermore, in the conductive substrate of the present embodiment, since the copper wiring layer and the low-reflectivity alloy wiring layer are provided on the transparent base material, light reflection by the copper wiring layer can be suppressed. Therefore, by providing a low-reflectivity alloy wiring layer, for example, when used in a touch panel, the display can have good visibility.

The conductive substrate of this embodiment can be suitably used as a conductive substrate for touch panels, for example. In this case, the conductive substrate may have a structure having a wiring pattern formed by providing openings in the copper layer and the low-reflectivity alloy layer of the laminate substrate. Preferably, it has a structure with a mesh wiring pattern.

The conductive substrate on which the wiring pattern with openings is formed can be obtained by etching the copper layer and the low-reflectivity alloy layer of the laminate substrate described so far. also, For example, it may be a conductive substrate having a mesh wiring pattern based on two layers of thin metal wires. A specific configuration example is shown in FIG. 4. FIG. 4 shows a view when the conductive substrate 30 provided with a mesh wiring pattern is viewed from the upper surface side in the direction of the laminate of the copper wiring layer and the low-reflectivity alloy wiring layer. The conductive substrate 30 shown in FIG. 4 has a transparent substrate 11, a plurality of copper wiring layers 31B parallel to the X-axis direction in the figure, and copper wiring layers 31A parallel to the Y-axis direction in the figure. It should be noted that the copper wiring layers 31A, 31B can be formed by etching the above-mentioned laminate substrate, and the copper wiring layers 31A, 31B are also formed on the upper surface and/or the lower surface, which are not shown in the figure. Low reflectivity alloy wiring layer. In addition, the low-reflectivity alloy wiring layer is etched to have approximately the same shape as the copper wiring layers 31A and 31B.

The arrangement of the transparent substrate 11 and the copper wiring layers 31A, 31B is not particularly limited. The configuration example of the arrangement of the transparent substrate 11 and the copper wiring layer is shown in FIG. 5. Fig. 5 is a sectional view taken along the line A-A' of Fig. 4;

For example, as shown in FIG. 5, copper wiring layers 31A and 31B may be arranged on the upper and lower surfaces of the transparent substrate 11, respectively. It should be noted that in the case of the conductive substrate shown in FIG. 5, a first etched to have approximately the same shape as the copper wiring layers 31A, 31B is arranged on the transparent substrate 11 side of the copper wiring layers 31A, 31B. Low-reflectivity alloy wiring layers 321A and 321B. In addition, second low-reflectivity alloy wiring layers 322A, 322B are also arranged on the surface of the copper wiring layers 31A, 31B on the side opposite to the transparent base material 11.

Therefore, in the conductive substrate shown in FIG. 5, the thin metal wires have first low-reflectivity alloy wiring layers 321A, 321B and second low-reflectivity alloy wiring layers 322A, 322B as low-reflectivity alloy wiring layers, and, The copper wiring layers 31A, 31B are arranged between the first low-reflectivity alloy wiring layers 321A, 321B and the second low-reflectivity alloy wiring layers 322A, 322B.

It should be noted that although an example in which the first low-reflectivity alloy wiring layer and the second low-reflectivity alloy wiring layer are provided is shown here, it is not limited to this form. For example, only one of the first low-reflectivity alloy wiring layer and the second low-reflectivity alloy wiring layer may be provided.

The conductive substrate with mesh wiring shown in FIG. 4 can be, for example, as shown in FIG. 2B and FIG. 3B, based on the provision of copper layers 12A, 12B and low-reflectivity alloy layers 13A, 13B on both sides of the transparent substrate 11 (131A, 132A, 131B, and 132B) laminated substrates are formed.

It should be noted that, for example, the conductive substrate including the first low-reflectivity alloy wiring layer and the second low-reflectivity alloy wiring layer shown in FIG. 5 can be formed from the laminate substrate shown in FIG. 3B.

Hereinafter, a case where the laminate substrate of FIG. 3B is used is used as an example for description.

First, the copper layer 12A, the first low-reflectivity alloy layer 131A, and the second low-reflectivity alloy layer 132A on one surface 11a side of the transparent substrate 11 are etched so that a plurality of them are parallel to the Y-axis direction in FIG. 3B The linear patterns are arranged at predetermined intervals along the X-axis direction. It should be noted that the Y-axis direction in FIG. 3B refers to the direction perpendicular to the paper surface. In addition, the X-axis direction in FIG. 3B refers to a direction parallel to the width direction of each layer.

Next, the copper layer 12B, the first low-reflectivity alloy layer 131B, and the second low-reflectivity alloy layer 132B on the other side 11b of the transparent substrate 11 are etched so as to be parallel to the X-axis direction in FIG. 3B. The linear patterns are arranged at a predetermined interval along the Y-axis direction.

Through the above operations, the conductive substrate with mesh wiring shown in FIGS. 4 and 5 can be formed. It should be noted that it is also possible to etch both surfaces of the transparent substrate 11 at the same time. That is, the etching of the copper layers 12A, 12B, the first low-reflectivity alloy layers 131A, 131B, and the second low-reflectivity alloy layers 132A, 132B may be performed simultaneously.

The conductive substrate with mesh wiring shown in FIG. 4 can also be formed using two laminate substrates shown in FIG. 2A or FIG. 3A. If the case of using the conductive substrate of FIG. 3A is used as an example for description, the two conductive substrates shown in FIG. 3A can be firstly subjected to the copper layer 12, the first low-reflectivity alloy layer 131, and the second low-reflectivity alloy layer. The alloy layer 132 is etched so that a plurality of linear patterns parallel to the X-axis direction are arranged at predetermined intervals along the Y-axis direction. Next, the two conductive substrates are bonded together in such a way that the linear patterns formed on each conductive substrate by the above-mentioned etching process are arranged to cross each other, thereby obtaining a conductive substrate with meshed wiring. . The bonding surface when bonding two conductive substrates is not particularly limited here.

For example, for two conductive substrates, the unlaminated copper layer 12 and other surfaces 11b of the transparent substrate 11 in FIG. 3A can be attached to each other to obtain the structure shown in FIG. 5.

It should be noted that the width of the thin metal wires or the distance between the thin metal wires of the conductive substrate with mesh wiring shown in FIG. 4 is not particularly limited. For example, it can be selected according to the required resistance value of the thin metal wires. .

However, in order to provide sufficient adhesion between the transparent substrate and the thin metal wires, it is preferable to select the width of the thin metal wires.

The conductive substrate of this embodiment has a wiring pattern formed by performing wiring processing on the above-mentioned laminate substrate and providing openings in the copper layer and the low-reflectivity alloy layer of the laminate substrate. For this reason, openings for exposing the transparent base material are provided between the thin metal wires contained in the wiring pattern.

In addition, the average value of the light transmittance of the opening having a wavelength of 400 nm or more and 700 nm or less has a better reduction rate than the average value of the light transmittance of the transparent substrate having a wavelength of 400 nm or more and 700 nm or less. It is 3.0% or less.

The reason is that the average value of the transmittance of light with a wavelength of 400nm or more and 700nm or less in the above-mentioned opening and the average of the transmittance of light with a wavelength of 400nm or more and 700nm or less of the transparent substrate used for the laminate substrate If the reduction rate from the value exceeds 3.0%, the color may change to yellow when the transparent substrate is visually observed. In addition, if the reduction rate exceeds 3.0%, the etching speed of the low-reflectivity alloy layer when the low-reflectivity alloy layer and the copper layer are etched will also become slow, and the low-reflectivity alloy layer and the copper layer cannot be etched at the same time. For this reason, as described above, the ratio of copper and nickel contained in the low-reflectivity alloy layer is preferably 85% by mass or less.

It should be noted that in the case of using a blackened layer containing non-stoichiometric oxides of nickel and copper in place of the low-reflectivity alloy layer, the content ratio of nickel and copper or its oxidation state will cause the etching performance to decrease. If it exceeds 3.0%, it may turn to yellow when the transparent substrate is visually observed. In this way, a laminate substrate having a blackened layer using a non-stoichiometric oxide requires control of the sputtering environment during the formation of the blackened layer, so it is difficult to optimize the manufacturing conditions.

On the other hand, in the laminate substrate of this embodiment, since the low-reflectivity alloy layer is used for the blackening layer, only the composition of nickel and copper needs to be controlled. Therefore, it is possible to easily optimize the manufacturing conditions. Jiahua.

In addition, the degree of light reflection of the conductive substrate of this embodiment is not particularly limited. For example, the average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, preferably 40% or less, and further Preferably it is 30% or less. The reason is that when the average value of the specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less is 55% or less, for example, even when it is used as a conductive substrate for a touch panel, the display can be particularly visually recognized Sex drop Low to suppress.

Regarding the conductive substrate having mesh wiring composed of two layers of wiring in the present embodiment described so far, it can be preferably used as a conductive substrate for a touch panel of a projection type capacitance method, for example.

(Manufacturing method of laminated substrate and manufacturing method of conductive substrate)

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

The manufacturing method of the laminated body substrate of this embodiment can have the following steps.

The transparent substrate preparation step of preparing the transparent substrate.

A layered body forming step of forming a layered body on at least one side of the transparent substrate.

In addition, the step of forming the laminate may include the following steps.

The copper layer forming step is to form the copper layer by means of depositing a copper layer of copper.

The low-reflectivity alloy layer forming step includes forming a low-reflectivity alloy layer by depositing a low-reflectivity alloy layer containing copper-nickel low-reflectivity alloy layer.

In addition, the step of forming the low-reflectivity alloy layer is preferably carried out under a reduced pressure environment. In addition, the ratio of copper contained in the low-reflectivity alloy layer to nickel in nickel is preferably 30% by mass or more and 85% by mass or less.

Hereinafter, the manufacturing method of the laminate substrate of the present embodiment will be described, but except for the points described below, since it can have the same configuration as the above-mentioned laminate substrate, the description is omitted.

As described above, in the laminate substrate of the present embodiment, the order of the laminate when the copper layer and the low-reflectivity alloy layer are arranged on the transparent base material is not particularly limited. In addition, the copper layer and the low-reflectivity alloy layer may be formed as plural layers, respectively. For this reason, the above-mentioned copper layer formation steps and low reflection The execution order or the number of executions of the emissivity alloy layer forming step is not particularly limited, and it can be carried out any number of times at any timing according to the structure of the laminate substrate to be formed.

The step of preparing a transparent substrate is, for example, a step of preparing a transparent substrate composed of a polymer film or a glass substrate that can penetrate visible light, and the specific operation is not particularly limited. For example, it can be cut into any size according to the requirements of the subsequent steps. It should be noted that since the preferred polymer film capable of transmitting visible light has been described, the description is omitted here.

Next, the step of forming the laminate will be described. The layered body forming step is a step of forming a layered body on at least one surface side of the transparent substrate, and has a copper layer forming step and a low-reflectivity alloy forming step. For this reason, the steps are described below.

First, the copper layer forming step will be described.

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

In the copper layer forming step, a dry plating method is preferably used to form the copper thin film layer. Furthermore, in the case of making the copper layer thicker, it is preferable to form the copper thin film layer by dry plating, and then form the copper plating layer by wet plating.

To this end, the copper layer forming step may include, for example, a step of forming a copper thin film layer by a dry plating method. In addition, the copper layer forming step may include a step of forming a copper thin film layer by a dry plating method and a step of using the copper thin film layer as a power supply layer and forming a copper plating layer by a wet plating method.

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 mentioned above, by using only the dry plating method or a combination of the dry plating method and the wet plating method to form the copper layer, it is possible to form a copper layer on a transparent substrate or a low-reflectivity alloy layer without bonding It is preferable to form the copper layer directly on the chemical ground.

The dry plating method is not particularly limited, and in a reduced pressure environment, a sputtering method, an ion plating method, an evaporation method, or the like can be preferably used.

In particular, as the dry plating method used when forming the copper thin film layer, since the sputtering method can be used to easily control the thickness, the sputtering method is preferably used. That is, in this case, as a means for forming a copper layer by depositing copper in the copper layer forming step, a sputtering film forming means (sputtering film forming method) can be preferably used.

The copper thin film layer can preferably be formed into a film using, for example, a roll-to-roll sputtering device 60 shown in FIG. 6. Hereinafter, a case where a roll-to-roll sputtering device is used is taken as an example to describe the steps of forming the copper film layer.

FIG. 6 shows an example of the configuration of the roll-to-roll sputtering device 60. The roll-to-roll sputtering device 60 has a frame 61 in which basically all its constituent parts can be stored. The shape of the frame body 61 shown in FIG. 6 is a rectangular parallelepiped shape. However, the shape of the frame body 61 is not particularly limited, and can be designed into any shape according to its internal storage device, installation location, pressure resistance, etc. For example, the shape of the frame 61 may be a cylindrical shape. However, in order to remove residual gas that has nothing to do with film formation at the beginning of film formation, the inside of the frame 61 is preferably reduced to 1 Pa or less, preferably 10 ^-3 Pa or less, and more preferably reduced Press to 10 ^-4 Pa. It should be noted that it is not necessary to decompress all the inside of the frame 61 to the above-mentioned pressure, and it may be configured such that only the lower side of the can roll 63 in the figure is arranged for sputtering. The area is depressurized to the above pressure.

The frame 61 can be equipped with an unwinding roller 62, a film forming roller 63, sputtering electrodes 64a~64d, a feed-forward roller 65a, a post-feed roller 65b, and a tension roller 66a for supplying the substrate for forming the copper film layer. , 66b and take-up roller 67. In addition, it is used in the transportation of the substrate for the film formation of the copper thin film layer In addition to the above-mentioned rollers, guide rollers 68a to 68h, heater 69, etc. can be arbitrarily provided on the route.

The unwinding roller 62, the film forming roller 63, the feed forward roller 65a, and the winding roller 67 can be powered by a servo motor. The unwinding roller 62 and the winding roller 67 can maintain the tension balance of the base material of the film-forming copper film layer by torque control based on a powder clutch or the like.

The structure of the film forming roller 63 is not particularly limited, but it is preferably configured such that, for example, a hard chromium plating process is performed on the surface thereof, and the refrigerant or warming medium supplied from the outside of the frame 61 is treated inside it. Cycle to adjust the temperature to a certain temperature.

The tension rollers 66a and 66b are preferably subjected to a hard chromium plating treatment on the surface thereof, and have tension sensors, for example. In addition, the surfaces of the forward feed roller 65a, the rear feed roller 65b, or the guide rollers 68a to 68h are also preferably treated with hard chromium plating.

The sputtering cathodes 64 a to 64 d are preferably magnetron cathodes, and are arranged opposite to the film forming roller 63. The size of the sputtering electrodes 64a to 64d is not particularly limited. However, the size of the substrate width direction of the deposited copper film layer of the sputtering electrodes 64a to 64d is preferably larger than the substrate width of the opposing deposited copper film layer.

After the base material of the film-forming copper film layer is transported to the roll-to-roll sputtering device 60 as a roll-to-roll vacuum film forming device, the copper film can be formed by sputtering electrodes 64a~64d facing the filming roll 63 Layer of film formation.

Next, the procedure of forming a copper thin film layer using the roll-to-roll sputtering apparatus 60 is demonstrated.

First, the copper target is placed on the sputtering electrodes 64a~64d, and the inside of the frame 61 is evacuated by vacuum pumps 70a, 70B. The unwinding roller 62 in the frame 61 is placed on the The base material of the copper film layer.

Next, an inert gas such as argon or other sputtering gas is introduced into the housing 61 by the gas supply means 71. It should be noted that the configuration of the gas supply means 71 is not particularly limited, and a gas storage tank not shown in the figure may be provided. In addition, it can also be configured that mass flow controllers (MFC) 711a, 711b and valves 712a, 712b are provided between the gas storage tank and the frame 61 according to the gas type to supply each gas to the frame 61 The supply volume is controlled. Figure 6 shows an example of setting two sets of mass flow controllers and valves. However, the number of settings is not particularly limited, and the number to be set can be selected according to the type of gas used.

Furthermore, when the gas supply means 71 is used to supply the sputtering gas into the frame 61, it is preferable to adjust the flow rate of the sputtering gas and the opening of the pressure regulating valve 72 provided between the vacuum pump 70B and the frame 61. The inside of the device is maintained at a pressure of, for example, 0.13 Pa or more and 1.3 Pa or less, and film formation is performed under these conditions.

In this state, while the unwinding roller 62 is used to transport the substrate at a speed of 1 m or more and 20 m or less per minute, the sputtering DC power supply connected to the sputtering electrodes 64a to 64d can be sputtered by applying power. Plating discharge. Accordingly, the desired copper thin film layer can be continuously formed on the substrate.

It should be noted that the roll-to-roll sputtering device 60 may also be equipped with various components other than the above as required. For example, pressure gauges 73a, 73b or exhaust valves 74a, 74b for measuring the pressure in the frame 61 can be provided.

In addition, as described above, the copper layer (copper plating layer) may be formed by wet plating after the dry plating.

In the case of forming a copper-plated layer by a wet plating method, the copper thin film layer formed by the above-mentioned dry plating method can be used as the power supply layer. In this case, as the copper layer formation step For the film forming means of the copper layer of the deposited copper in the step, the electroplating film forming means can be preferably used.

The conditions of the step of using the copper thin film layer as the power supply layer and forming the copper-plated layer by wet plating, that is, the conditions of the electroplating treatment, are not particularly limited, and various conditions in conventional methods can be used. For example, the copper plating layer can be formed by supplying the substrate on which the copper thin film layer is formed to a plating tank filled with a copper plating solution, and controlling the current density or the transport speed of the substrate.

Next, the step of forming the low-reflectivity alloy layer will be described.

As mentioned above, the low-reflectivity alloy forming step is to form the low-reflectivity alloy layer by forming a low-reflectivity alloy layer containing copper and nickel on at least one surface side of the transparent substrate. The film forming step. The method for forming a low-reflectivity alloy layer by depositing a low-reflectivity alloy layer containing copper and nickel in the forming step of the low-reflectivity alloy layer is not particularly limited, but it is preferable to use, for example, a sputtering method under a reduced pressure environment. , Namely sputtering film forming method.

The low-reflectivity alloy layer may preferably be formed by using, for example, a roll-to-roll sputtering device 60 as shown in FIG. 6. Since the structure of the roll-to-roll sputtering device has been described above, its description is omitted here.

A configuration example of the step of forming a low-reflectivity alloy layer using the roll-to-roll sputtering device 60 will be described.

First, the copper-nickel alloy target is placed on the sputtering electrodes 64a to 64d, and the frame 61 is evacuated by vacuum pumps 70a, 70b. In the frame 61, the unwinding roller 62 is placed The base material for film formation of the low-reflectivity alloy layer. After that, an inert gas, for example, a sputtering gas composed of argon gas, is introduced into the housing 61 by the gas supply means 71. At this time, it is preferable to adjust the flow rate of the sputtering gas and the opening degree of the pressure regulating valve 72 provided between the vacuum pump 70b and the frame 61 so that the pressure in the frame 61 is maintained at 0.13 Pa or more, for example. And 13Pa Below, film formation is performed under these conditions.

In this state, while conveying the base material from the unwinding roller 62 at a speed of, for example, 0.5 m or more and 10 m or less per minute, power is applied from the sputtering DC power supply connected to the sputtering electrodes 64a to 64d. Sputtering discharge. Accordingly, the desired low-reflectivity alloy layer can be continuously formed on the substrate.

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

The laminated substrate obtained by the method of manufacturing the laminated substrate of the present embodiment is the same as the above-mentioned laminated substrate, and the thickness of the copper layer is preferably 50 nm or more, preferably 60 nm or more, and more preferably 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, and preferably 3000 nm or less. It should be noted that when the copper layer has a copper thin film layer and a copper plating layer as described above, the total thickness of the copper thin film layer and the copper plating layer thickness is preferably within the above range.

In addition, the thickness of the low-reflectivity alloy layer is not particularly limited. For example, it is preferably 10 nm or more, and preferably 15 nm or more. The upper limit of the thickness of the low-reflectivity alloy layer is not particularly limited, but it is preferably 70 nm or less, and preferably 50 nm or less.

In addition, for the laminated substrate obtained by the method of manufacturing the laminated substrate of this embodiment, the average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, preferably 40% Below, it is more preferably 30% or less.

A conductive substrate can be formed using the laminate substrate obtained by the method of manufacturing the laminate substrate of this embodiment, and the conductive substrate is formed with a wiring pattern having openings in the copper layer and the low-reflectivity alloy layer. The conductive substrate preferably has a structure that can be provided with mesh wiring.

The manufacturing method of the conductive substrate of this embodiment may have an etching step of etching the copper layer and the low-reflectivity alloy layer of the multilayer substrate obtained by the above-mentioned manufacturing method of the multilayer substrate to form a wiring pattern with thin metal wires , The thin metal wire is a laminate with a copper wiring layer and a low-reflectivity alloy wiring layer. Furthermore, by this etching step, openings can also be formed in the copper layer and the low-reflectivity alloy layer.

In the etching step, for example, first, a photoresist 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 laminated substrate 10A shown in FIG. 2A, a photoresist can be formed on the exposed surface A of the low reflectivity alloy layer 13 on the laminated substrate 10A. It should be noted that the formation method of the photoresist having the opening corresponding to the portion to be removed by etching is not particularly limited, but for example, it can be formed by photolithography.

Next, by supplying an etching solution from above the photoresist, the copper layer 12 and the low-reflectivity alloy layer 13 can be etched.

It should be noted that when the copper layer and the low-reflectivity alloy layer are arranged on both sides of the transparent base material 11 as shown in FIG. 2B, a predetermined shape can be formed on the surface A and the surface B of the laminate substrate. The photoresist of the opening part can simultaneously etch the copper layer and the low-reflectivity alloy layer formed on both sides of the transparent substrate 11. In addition, the copper layer and the low-reflectivity alloy layer formed on both sides of the transparent substrate 11 can be etched on one side. That is, for example, after the copper layer 12A and the low-reflectivity alloy layer 13A are etched, the copper layer 12B and the low-reflectivity alloy layer 13B may be etched.

The low-reflectivity alloy layer formed by the manufacturing method of the laminate substrate of the present embodiment shows the same reactivity to the etching solution as the copper layer. For this reason, in the etching step The etching solution used is not particularly limited, and it is preferable to use the etching solution commonly used in etching copper layers.

As the etching solution used in the etching step, for example, an aqueous solution containing one selected from sulfuric acid, hydrogen peroxide water, hydrochloric acid, copper dichloride, and ferric chloride, or an aqueous solution containing one selected from the above sulfuric acid can be preferably used. A mixture of more than two kinds of aqueous solutions. The content of each component in the etching solution is not particularly limited here.

The etching solution can be used at room temperature, but in order to improve the reactivity, it is better to heat it, for example, it can be heated to 40°C or more and 50°C or less.

Regarding the specific form of the mesh wiring obtained by the above-mentioned etching step, it is the same as the above, and its description is omitted here.

In addition, after two laminate substrates having a copper layer and a low-reflectivity alloy layer on one surface side of the transparent substrate 11 as shown in FIGS. 2A and 3A are provided to the etching step to form a conductive substrate, In the case where two conductive substrates are bonded to form a conductive substrate with mesh wiring, a conductive substrate bonding step may also be provided. At this time, the bonding method of the two conductive substrates is not particularly limited. For example, an optical adhesive (OCA) or the like can be used for bonding.

It should be noted that, for the conductive substrate obtained by the method of manufacturing the conductive substrate of this embodiment, the average value of the specular reflectance of light having a wavelength of 400 nm or more and 700 nm or less is preferably 55% or less, preferably It is 40% or less, more preferably 30% or less.

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

The above description of the laminate substrate, conductive substrate, and laminate substrate of this embodiment The manufacturing method and the manufacturing method of the conductive substrate are described. According to the laminate substrate or the laminate substrate obtained by the method of manufacturing the laminate substrate, the copper layer and the low-reflectivity alloy wiring layer show approximately the same reactivity with respect to the etching solution. For this reason, it is possible to provide a laminate substrate having a copper layer and a low-reflectivity alloy layer that can be etched at the same time. In addition, since the copper layer and the low-reflectivity alloy layer can be etched at the same time, the copper wiring layer and the low-reflectivity alloy wiring layer of a desired shape can be easily formed.

In addition, by providing a low-reflectivity alloy wiring layer, the light reflection of the copper wiring layer can be suppressed. For example, when it is used as a conductive substrate for a touch panel, the decrease in visibility can be suppressed. For this reason, by providing a low-reflectivity alloy wiring layer, a conductive substrate with good visibility can be obtained.

[Example]

Hereinafter, the present invention will be described in more detail based on the embodiments and comparative examples of the present invention, but the present invention is not limited to these embodiments.

(Evaluation method)

(1) Regular reflectance

The regular reflectance was measured for the laminate substrates produced in the following examples and comparative examples.

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

In each embodiment, a laminate substrate with the structure of FIG. 3A was produced, and the reflectance was measured by using the exposed surface C of the second low-reflectivity alloy layer 132 of FIG. 3A at an incident angle of 5° 、When the light receiving angle is 5°, the irradiation wavelength is 400nm or more and 700nm or less The light of the scope below is implemented. It should be noted that during the measurement, the wavelength of the light irradiated on the laminate substrate is changed in a range of 1 nm within the wavelength range of 400nm or more and 700nm or less, and the regular reflectance of the light of each wavelength is measured. The average value of the measurement results was taken as the average value of the regular reflectance of the laminate substrate.

(2) Reduction rate of the total light transmittance of the opening

The total light transmittance was measured for the openings between the thin metal wires of the conductive substrates exposing the transparent substrates of the conductive substrates produced in the respective examples and comparative examples.

The measurement is performed by installing an integrating sphere accessory device on the ultraviolet visible spectrophotometer when measuring the specular reflectance. In the measurement, the wavelength of the irradiated light is changed in the range of 400nm or more and 700nm or less in the range of 1nm, and the transmittance of the light of each wavelength is measured, and then the average of the measurement results is used as the conductivity The average value of the total light transmittance of the opening of the flexible substrate.

In addition, the average value of the total light transmittance was measured in the same way for the transparent base material used when the laminate substrate was produced in advance.

Next, the reduction rate of the average value of the total light transmittance of the openings of the conductive substrates produced in each of the examples and comparative examples and the average value of the total light transmittance of the transparent substrate (the following and Table 1 is also described as "the reduction rate of the total light transmittance of the opening") for calculation.

(Production conditions of samples)

As an example and a comparative example, a laminate substrate and a conductive substrate were produced under the conditions described below, and they were evaluated by the above-mentioned evaluation method.

[Example 1]

A laminate substrate having the structure shown in FIG. 3A is produced.

First, a transparent substrate preparation step is implemented.

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

Next, a layered body forming step is implemented.

As the layered body forming step, a first low-reflectivity alloy layer forming step, a copper layer forming step, and a second low-reflectivity alloy layer forming step were performed. This will be specifically described below.

First, the first low-reflectivity alloy layer forming step is performed.

The prepared transparent substrate is placed in the roll-to-roll sputtering device 60 shown in FIG. 6. In addition, an alloy target of copper -30 mass% Ni (manufactured by Sumitomo Metal Mining Co., Ltd.) was placed on the sputtering electrodes 64a to 64d.

Next, the heater 69 of the roll-to-roll sputtering device 60 is heated to 100° C. to heat the transparent substrate to remove the moisture contained in the substrate.

Next, after evacuating the inside of the frame 61 to 1×10 ^-4 Pa with vacuum pumps 70a and 70b, the argon gas is fed into the frame 61 by the gas supply means 71 at a flow rate of 240 sccm. Import. Next, while transporting the transparent substrate by the unwinding roller 62 at a speed of 2m per minute, power is applied from the sputtering DC power supply connected to the sputtering electrodes 64a to 64d to perform sputtering discharge. The expected first low-reflectivity alloy layer is continuously formed on the upper surface. By this operation, the first low-reflectivity alloy layer 131 with a thickness of 20 nm was formed on the transparent substrate.

Next, a copper layer formation step is implemented.

In the copper layer forming step, replace the target placed on the magnetron sputtering electrode with A copper target (manufactured by Sumitomo Metal Mining Co., Ltd.), except that a copper layer with a thickness of 200 nm was formed on the first low-reflectivity alloy layer in the same manner as the first low-reflectivity alloy layer.

It should be noted that, as the substrate for forming the copper layer, a substrate in which the first low-reflectivity alloy layer was formed on the transparent substrate in the first low-reflectivity alloy layer forming step was used.

Next, a second low-reflectivity alloy layer forming step is performed.

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

The average value of the specular reflectance of light with a wavelength of 400nm or more and 700nm or less of the fabricated laminate substrate was measured using the above steps, and the average value of the specular reflectance of light with a wavelength of 400nm or more and 700nm or less is 55%.

Furthermore, after measuring the specular reflectance of the obtained laminate substrate, an etching step was performed to produce a conductive substrate.

In the etching step, first, a photoresist having an opening corresponding to the portion to be removed by etching is formed on the surface C of FIG. 3A of the produced laminate substrate. Next, it was immersed in an etching solution composed of 10% by weight of ferric chloride, 10% by weight of hydrochloric acid, and the remainder of water for 1 minute to produce a conductive substrate.

After that, the total light transmittance of the opening was measured for the produced conductive substrate.

The evaluation results are shown in Table 1.

[Example 2~Example 6]

Except for the composition change of the sputtering target used when forming the first and second low-reflectivity alloy layers Except for the values shown in Table 1, a laminate substrate was produced in the same manner as in Example 1, and evaluated.

Moreover, based on the produced laminate substrate, a conductive substrate was produced in the same manner as in Example 1, and evaluated.

The results are shown in Table 1.

[Comparative Example 1~Comparative Example 3]

In Comparative Example 1, a laminate was produced in the same manner as in Example 1, except that the composition of the sputtering target used in forming the first and second low-reflectivity alloy layers was changed to the values shown in Table 1. Substrate and evaluate it.

In addition, in Comparative Examples 2 and 3, the first and second blackened layers were formed instead of the first and second low-reflectivity alloy layers. Regarding the film formation of the first and second blackened layers, except that the composition of the sputtering target used in the film formation was changed to the values shown in Table 1, and the argon gas was also supplied when the blackened layer was formed. Except for oxygen, film formation was carried out in the same manner as the low-reflectivity alloy layer of Example 1. In addition, the parts other than the blackened layer were the same as in Example 1, and a laminate substrate was produced accordingly.

It should be noted that in Comparative Examples 2 and 3, the oxygen supply amount shown in Table 1 was used for the oxygen supply when the low-reflectivity alloy layer was formed.

Based on the laminate substrates produced in Comparative Examples 1 to 3, conductive substrates were produced in the same manner as in Example 1, and evaluated.

The results are shown in Table 1.

From the results shown in Table 1, it can be seen that in Examples 1 to 6, the reduction rate of the total light transmittance of the opening is 3.0% or less. That is, the copper layer and the first and second low-reflectivity alloy layers can be simultaneously etched.

The reason is that the ratio of copper and nickel contained in the sputtering target material used when forming the first and second low-reflectivity alloy layers is 30% by mass or more and 85% by mass or less. The low-reflectivity alloy layer after the film also has the same composition. That is, it can be considered that the reactivity of the low-reflectivity alloy layer to the etching solution is the same as that of the copper layer.

In contrast, in Comparative Example 1, the ratio of copper and nickel contained in the sputtering target used in the formation of the low-reflectivity alloy layer is less than 30% by mass, so the ratio after film formation is low The reflectivity alloy layer also has the same composition. Therefore, the regular reflectance exceeds 55%.

In addition, in Comparative Example 2, the reduction rate of the total light transmittance of the opening exceeded 3.0%, and it was confirmed that the etching rate of the blackened layer was slower than that of the copper layer, so the total light transmitted through the opening The reduction rate of the rate becomes 3.5%, and the yellow color can be confirmed visually.

In Comparative Example 3, the undercut was confirmed, and it was also 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 and the blackened layer that could be etched at the same time could not be formed.

As mentioned above, the multilayer substrate, the conductive substrate, the manufacturing method of the multilayer substrate, and the manufacturing method of the conductive substrate have been described with reference to the embodiments and examples, but the present invention is not limited to the above embodiments and examples. Various modifications and changes can be made within the scope of the gist of the present invention described in the scope of the patent application.

This application claims priority based on Japanese Patent Application No. 2015-189936 filed to the Japan Patent Office on September 28, 2015, and the entire content of Japanese Patent Application No. 2015-189936 is cited in this international application.

10A‧‧‧Laminate substrate

11‧‧‧Transparent substrate

11a‧‧‧One side

11b‧‧‧The other side

12‧‧‧Copper layer

13‧‧‧Low reflectivity alloy layer

A‧‧‧surface

X, Y‧‧‧X axis, Y axis

Claims (11)

A laminated body substrate comprising: a transparent substrate and a laminated body directly formed on at least one surface side of the transparent substrate; the laminated body is composed of a low-reflectivity alloy layer containing copper and nickel and a copper layer, the The ratio of the copper contained in the low-reflectivity alloy layer to the nickel in the nickel is 30% by mass or more and 85% by mass or less. For example, the laminated body substrate of the first item of the patent application, wherein the laminated body has a first low-reflectivity alloy layer and a second low-reflectivity alloy layer as the low-reflectivity alloy layer, and the copper layer is arranged on the first low-reflectivity alloy layer. Between the reflectance alloy layer and the second low reflectance alloy layer. For example, the laminated substrate of item 1 or 2 in the scope of patent application, wherein the average value of the specular reflectance of light with a wavelength of 400nm or more and 700nm or less is 55% or less. A conductive substrate comprising: a transparent base material and a thin metal wire formed directly on at least one surface side of the transparent base material, the thin metal wire being made of a low-reflectivity alloy wiring layer containing copper and nickel and a copper wiring layer In the laminate formed, the ratio of the copper contained in the low-reflectivity alloy wiring layer and the nickel in the nickel is 30% by mass or more and 85% by mass or less. For example, the conductive substrate of item 4 of the scope of patent application, wherein the thin metal wire has a first low-reflectivity alloy wiring layer and a second low-reflectivity alloy wiring layer as the low-reflectivity alloy wiring layer, and the copper wiring layer is disposed on Between the first low-reflectivity alloy wiring layer and the second low-reflectivity alloy wiring layer. For example, the conductive substrate of item 4 or 5 of the scope of patent application, wherein an opening portion exposing the transparent substrate is provided between the thin metal wires, and the wavelength of the opening portion is greater than 400nm and less than 700nm. The reduction rate of the average value compared to the average value of the transmittance of light having a wavelength of 400 nm or more and 700 nm or less of the transparent substrate is 3.0% or less. A method for manufacturing a laminate substrate, which has the following steps: a transparent substrate preparation step for preparing a transparent substrate, a laminate formation step for directly forming a laminate on at least one side of the transparent substrate, the laminate formation step It includes the following steps: a copper layer forming step, which forms a copper layer by depositing a copper layer of copper, and a low reflectivity alloy layer forming step, which is formed by depositing a low reflectivity alloy layer containing copper and nickel Means for forming a low-reflectivity alloy layer to form a low-reflectivity alloy layer; the laminate is composed of the low-reflectivity alloy layer and the copper layer, and the low-reflectivity alloy layer forming step is carried out under a reduced pressure environment. The ratio of the copper contained in the alloy layer to the nickel in the nickel is 30% by mass or more and 85% by mass or less. For example, the manufacturing method of laminated substrate of item 7 of the scope of patent application, in which, The method for forming the low-reflectivity alloy layer is a sputtering method. For example, the manufacturing method of the laminated substrate of the 7th or 8th patent application, wherein the thickness of the low-reflectivity alloy layer is 10nm or more. A method of manufacturing a conductive substrate, which has the following steps: the copper layer and the low reflectivity of a multilayer substrate obtained by the method of manufacturing a multilayer substrate of any one of the 7th to 9th patents The alloy layer is etched to form an etching step of a wiring pattern with thin metal wires, the thin metal wires being a laminate with a copper wiring layer and a low-reflectivity alloy wiring layer; and the etching step is performed on the copper layer and the low reflection The rate alloy layer forms an opening. For example, the method for manufacturing a conductive substrate in the scope of the patent application, wherein the obtained conductive substrate has an average value of the specular reflectance of light with a wavelength of 400 nm or more and 700 nm or less of 55% or less.

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