TWI712506B - Laminate substrate, method of manufacturing laminate substrate, conductive substrate, and method of manufacturing conductive substrate - Google Patents

Abstract

The present invention provides a laminate substrate comprising a transparent substrate and a laminate formed on at least one side of the transparent substrate, the laminate having a blackened layer and a copper layer, and the blackened layer contains oxygen, copper and Nickel, the film thickness of the blackened layer is 15 nm or more, and the atomic ratio O/Ni of oxygen atoms to nickel atoms contained in the blackened layer satisfies the following formula (1).

0.1≦O/Ni≦0.8 (1)

Description

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

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

As disclosed in Patent Document 1, the transparent conductive film traditionally used for touch panels is a structure in which an ITO (indium oxide-tin) film is formed as a transparent conductive film on a polymer film.

Here, display screens equipped with touch panels have become larger in recent years, and accordingly, conductive substrates such as transparent conductive films for touch panels have also been required to have larger areas. However, due to the high resistance value of ITO, there is a problem that it cannot cope with the large area of the conductive substrate.

In this regard, for example, Patent Documents 2 and 3 disclose technical research on using thin metal wires formed by processing metal foils such as copper instead of ITO films. However, for example, when copper is used for thin metal wires, since copper has metallic luster, there is a problem that the visibility of the display screen decreases due to reflection.

Therefore, a laminate substrate in which a blackened layer is formed together with a copper layer has been studied. The copper layer is composed of a metal foil such as copper, and the blackened layer is composed of a black material. In order to process the laminate substrate into a conductive substrate with a wiring pattern of thin metal wires, after forming a copper layer and a blackened layer with required optical properties such as reflectance, it is necessary to etch the copper layer and the blackened layer To form the The pattern of hope.

However, there is a problem that the copper layer and the blackened layer have different reactivity to the etching solution. That is, if the copper layer and the blackened layer are simultaneously etched, one of the layers cannot be etched into a desired shape. In addition, if the copper layer etching and the blackening layer etching are performed as separate steps, it will cause the problem of increasing the number of steps.

<Prior 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

In view of the above-mentioned conventional technical problems, an object of the present invention is to provide a laminate substrate having a copper layer and a blackened layer that can be simultaneously etched.

In order to solve the above 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 having: black containing oxygen, copper, and nickel The thickness of the blackened layer is 15nm or more, and the atomic ratio O/Ni of oxygen atoms to nickel atoms contained in the blackened layer satisfies the following formula (1), 0.1≦O/Ni≦0.8 ( 1).

According to the present invention, it is possible to provide a copper layer and a black layer that can be simultaneously etched. Layered laminate substrate.

10A, 10B, 20A, 20B: laminated substrate

11: Transparent substrate

12, 12A, 12B: copper layer

13, 13A, 13B, 131, 132, 131A, 131B, 132A, 132B: blackened layer

30: Conductive substrate

31A, 31B: Copper wiring layer

32A, 32B: Blackened wiring layer

Fig. 1A is a cross-sectional view of a laminate substrate according to an embodiment of the present invention.

Fig. 1B is a cross-sectional view of a laminate substrate according to an embodiment of the present invention.

Fig. 2A is a cross-sectional view of a laminate substrate according to an embodiment of the present invention.

Fig. 2B is a cross-sectional view of the laminate substrate according to the embodiment of the present invention.

Fig. 3 is a plan view of a conductive substrate having a grid-like wiring pattern according to an embodiment of the present invention.

Fig. 4A is a sectional view taken along the line A-A' in Fig. 3;

Fig. 4B is a sectional view taken along the line A-A' in Fig. 3;

Fig. 5 is an explanatory diagram of a roll-to-roll sputtering device.

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

(Laminate substrate, conductive substrate)

The laminate substrate of the present embodiment may include a transparent base material and a laminate formed on at least one surface side of the transparent base material. In addition, the laminate may have a blackened layer and a copper layer, and the blackened layer contains oxygen, copper, and nickel. In addition, the film thickness of the blackened layer is 15 nm or more, and the atomic ratio O/Ni of oxygen atoms to nickel atoms contained in the blackened layer preferably satisfies the following formula (1).

0.1≦O/Ni≦0.8 (1)

Here, the laminate substrate of this embodiment means that the surface of the transparent substrate has a copper layer and black Laminated body of chemical layer, and substrate before etching copper layer etc. The conductive substrate refers to a substrate on which thin metal wires are formed by etching the copper layer and the blackened layer.

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

The transparent substrate is not particularly limited, and an insulator film or a glass substrate that can transmit visible light can be preferably used.

As the insulator film that can penetrate visible light, for example, a polyamide film, a polyethylene terephthalate (PET) film, a polyethylene naphthalate film, a cycloolefin film, and a polyamide film can be preferably used. Resin films such as imide films and polycarbonate films.

The thickness of the transparent substrate is not particularly limited, and can be arbitrarily selected according to the required strength or light transmittance when used for a conductive substrate. The thickness of the transparent substrate may be, for example, 10 μm or more and 250 μm or less. Especially when it is 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, where the thickness of the entire display screen needs to be reduced, the thickness of the transparent substrate is preferably 20 μm or more and 100 μm or less.

Hereinafter, the copper layer will be described.

The copper layer is also not particularly limited, but in order not to lower the light transmittance, it is preferable not to arrange an adhesive between the copper layer and the transparent substrate or between the copper layer and the blackened layer. That is, it is preferable to form the copper layer directly on the other components.

In order to directly form a copper layer on other parts, it is preferable to form the copper layer by a dry plating method such as sputtering, ion plating, or vapor deposition.

In addition, if you want to increase the thickness of the copper layer, it is preferable to use the Use wet plating. That is, for example, a copper thin film layer can be formed by a dry plating method on a transparent substrate or a blackened layer, and the copper thin film layer can be used as a power supply layer, and the copper plating layer can be formed by a wet plating method. In this case, the copper thin film layer and the copper plating layer can constitute the copper layer.

As mentioned above, the copper layer can be formed directly on the transparent substrate or the blackened layer by using only the dry plating method or by combining the dry plating method and the wet plating method. The above method.

The film 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 magnitude of the current supplied to the wiring and the wiring width. In particular, in order to be able to provide sufficient current, the thickness of the copper layer is preferably 80 nm or more, more preferably 100 nm or more, and still more preferably 150 nm or more. There is no particular limitation on the upper limit of the thickness of the copper layer, but when the copper layer is thicker, more etching time is required for etching to form wiring, and side etching is likely to occur, causing problems such as peeling of the protective layer during etching. . Therefore, the film thickness of the copper layer is preferably 5000 nm or less, more preferably 3000 nm, and still more preferably 1200 nm or less. In addition, as described above, when the copper layer has a copper thin film layer and a copper plating layer, the total thickness of the copper thin film layer and the copper plating layer thickness is preferably within the above range.

Next, the blackened layer will be described. In the laminate substrate of this embodiment, the blackened layer may contain oxygen, copper, and nickel.

A thin metal wire that does not have a blackening layer but is formed of a copper layer and is processed by wiring. Because the copper layer of the wiring has a metallic luster, copper reflects light. For example, when it is used as a wiring substrate for a touch panel, it will display The problem of reduced screen visibility. In this regard, study the method of setting the black layer.

In order to suppress light reflection on the surface of the copper layer, and to form a copper layer on a transparent substrate Wiring processing is performed after the blackening layer. The blackening layer is required to have both low reflectivity and etching properties that can simultaneously etch the copper layer and the blackening layer into a desired shape.

The inventors of the present invention, in order to obtain a blackened layer with both low reflectivity and etching properties, studied a blackened layer containing oxygen, copper, and nickel. Among them, it was found that, depending on the ratio of the number of metal atoms to the number of oxygen atoms constituting the blackened layer, the reactivity of the blackened layer to the etching solution, that is, the etching property, is sometimes insufficient.

It was further found that when the film thickness of the blackened layer containing oxygen, copper, and nickel is 15 nm or more, and the atomic ratio of oxygen atoms to nickel atoms (O/Ni) contained in the blackened layer satisfies the following formula (1) , The blackened layer can have both low reflectivity and etchability.

0.1≦O/Ni≦0.8 (1)

For example, it is possible to form a blackened layer containing oxygen, copper, and nickel of the laminate substrate of the present embodiment by dry plating. In addition, when a blackened layer containing oxygen, copper, and nickel is formed in an environment where oxygen is added to an inert gas such as argon using a nickel-copper alloy through a dry plating method, nickel will be preferentially oxidized.

However, when the O/Ni ratio of the above formula (1) is less than 0.1, the oxidation of nickel will be insufficient, and the reflectivity of the Ni-Cu-O film formed as a blackened layer may sometimes increase.

In addition, when the O/Ni ratio of the above formula (1) is greater than 0.8, the oxidation of nickel will be promoted, the Ni-Cu-O film formed as a blackened layer becomes transparent, and the transmittance may increase. Therefore, when the Ni-Cu-O film and the copper layer are laminated, the degree of reflection of the light penetrating the Ni-Cu-O film by the copper layer increases, and as a result, the reflectivity increases. In addition, when the O/Ni ratio of the above formula (1) is greater than 0.8, the etching properties may decrease.

In this regard, as mentioned above, the O/Ni ratio in the blackened layer containing oxygen, copper and nickel is In the case of 0.1 or more and 0.8 or less, the blackened layer can have both low reflectance and etchability, which is preferable. The O/Ni ratio of the blackened layer is particularly preferably 0.2 or more and 0.7 or less.

Here, the state of each atom contained in the blackened layer is not particularly limited. For example, it may contain non-stoichiometric nickel-copper oxide, and part of nickel and copper may also be used as non-constituted oxides (also Including non-stoichiometric oxides) atoms are contained therein.

In addition, the composition of oxygen, nickel, and copper contained in the blackened layer can be found by XPS.

The ratio of copper to nickel in the blackened layer of the laminate substrate of this embodiment is not particularly limited. The ratio of copper in the blackened layer to the total of copper and nickel in the blackened layer is preferably mass ratio Above 20% and below 80%.

The reason is that by making the ratio of copper in the blackened layer to the total of copper and nickel in the blackened layer to be 20% (mass %) or more by mass, the etching properties of the blackened layer can be improved in particular. However, when the ratio of copper in the blackened layer to the total of copper and nickel in the blackened layer exceeds 80% (mass%) by mass, the reflectivity of the blackened layer will increase and it will be used as a conductive substrate for touch panels. In this case, the visibility of the display screen may be reduced, so it is preferably 80% or less.

The ratio of copper in the blackened layer to the total of copper and nickel in the blackened layer is more preferably 30% to 50% in terms of mass ratio.

Here, when a sputtering method is used and a nickel-copper alloy sputtering target is used to form the blackened layer, the ratio of copper to nickel in the blackened layer can be roughly equal to the ratio of copper to nickel in the sputtering target Become equal. Therefore, when the blackened layer is formed by the sputtering method, the ratio of copper to nickel in the blackened layer can be changed by the composition of the sputtering target.

There is no particular limitation on the film forming method of the blackened layer, and it can be performed by any method The film formation can be suitably performed by a dry plating method, for example. In particular, if a sputtering method is used to use a nickel-copper alloy sputtering target, while oxidizing the nickel-copper alloy from the sputtering target, a blackened layer containing oxygen, copper, and nickel can be formed relatively easily. Therefore, the sputtering method is preferably used to form the blackened layer.

When sputtering is used to form the blackened layer of the laminate substrate of the present embodiment, a nickel-copper alloy target can be used, and inert gas and oxygen are supplied into the chamber while sputtering is used to form the film. Here, as the inert gas, for example, argon gas can be used.

In the case of forming a blackened layer by sputtering, a mixed gas of inert gas and oxygen can also be provided into the chamber in advance. In addition, inert gas and oxygen can also be supplied into the chamber separately, and the partial pressure of each gas can be adjusted. In particular, in order to be able to adjust the amount of oxygen supplied to the blackening layer, it is preferable to simultaneously supply inert gas and oxygen into the chamber, and adjust the oxygen partial pressure in the chamber.

As described above, when the inert gas and oxygen are supplied into the chamber while the dry plating method such as sputtering is used to form the blackened layer, there is no limitation on the ratio of the inert gas to oxygen supplied to the chamber. However, when the blackened layer is formed, the number of oxygen molecules (Γ(O ₂ )) incident on the film surface and the number of nickel atoms deposited on the film surface (Γ(Ni)) preferably satisfy the formula (2) . That is, it is preferable to adjust the partial pressure of the inert gas and the partial pressure of oxygen to satisfy the following formula (2).

2≦Γ(O ₂ )/Γ(Ni)≦10 (2)

The reason is that when Γ(O ₂ )/Γ(Ni) is 2 or more, the blackened layer can be sufficiently blackened, and in particular, the reflectivity of the blackened layer of the laminate substrate can be reduced, thereby serving as a conductive substrate It can especially improve the recognition of the display screen.

In addition, when Γ(O ₂ )/Γ(Ni) is 10 or less, excessive oxidation of nickel contained in the blackened layer can be suppressed, thereby preventing the nickel oxide from becoming transparent and causing the problem of increasing the transmittance of the blackened layer. Therefore, in a laminate substrate in which a blackened layer and a copper layer are laminated, the blackened layer suppresses light reflection on the surface of the copper layer, and can reduce the reflectance of the laminate substrate. In addition, in particular, the etching properties of the blackened layer can be improved, so that the copper layer and the blackened layer can be etched at the same time.

Therefore, when forming a blackened layer, as described above, Γ(O ₂ )/Γ(Ni) is preferably 2 or more and 10 or less, more preferably 4 or more and 8 or less.

In addition, not all of the O ₂ molecules incident on the surface of the film to be formed react with Ni atoms, and part of the O ₂ molecules incident on the surface of the film to be formed react with Ni atoms. Therefore, considering the reaction probability of O ₂ molecules and Ni atoms, the relationship between the number of O ₂ molecules injected into the film surface (Γ(O ₂ )) and the number of atoms deposited on the film surface (Γ(Ni)) Preferably, formula (2) is satisfied.

The film-formed surface of the blackened layer refers to the outermost surface part when the blackened layer is formed. When the blackened layer is formed, it means the lower layer of the blackened layer, that is, the surface of the transparent substrate or The surface of the copper layer. In addition, the beginning of the film formation of the blackened layer means the outermost surface of the blackened layer in the film formation.

According to the following formula (3), the number of O ₂ molecules Γ(O ₂ ) injected into the film-forming surface of the blackened layer in the above formula (2) can be obtained.

Γ(O ₂ )=p/(2 π mkT) ^0.5 [piece/(m ² s)] (3)

The parameters in formula (3) are as follows. p: partial pressure of oxygen [Pa], m: mass of oxygen molecules [kg], k: Boltzmann constant (1.38×10 ^-23 [J/K]), T: temperature (K).

The number of nickel atoms (Γ(Ni)) on the surface of the film to be deposited on the blackened layer in the above formula (1) can be calculated based on the mass of nickel deposited per unit area and the film formation time. Specifically, it can be calculated according to the following formula (4).

Γ(Ni)=W‧Na/(M‧A‧t) [piece/(m ² s)] (4)

Among them, W: mass of Ni, Na: Avogajue constant, M: atomic weight of Ni, A: film formation area, t: film formation time.

The thickness of the blackening layer is not particularly limited. For example, it is preferably 15 nm or more, and more preferably 20 nm or more. As mentioned above, the blackened layer is black, which has the effect of suppressing the light reflection of the copper layer. However, when the thickness of the blackened layer is thin, sufficient black cannot be obtained and sometimes the light reflection of the copper layer cannot be sufficiently suppressed. In this regard, setting the thickness of the blackened layer within the above-mentioned range can more reliably suppress reflection of the copper layer, which is preferable.

The upper limit of the thickness of the blackened layer is not particularly limited, but if the thickness exceeds the necessary thickness, the time required for film formation will increase, the time required for etching during wiring formation will increase, and the cost will increase. Therefore, the thickness of the blackened layer is preferably 60 nm or less, more 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 includes a transparent base material, a copper layer, and a blackened layer. Here, there is no particular limitation on the stacking order when the copper layer and the blackened layer are arranged on the transparent substrate. In addition, the copper layer and the blackened layer may be formed in plural layers, respectively. In addition, in order to suppress light reflection on the surface of the copper layer, it is preferable to arrange a blackening layer on the surface of the copper layer on which light reflection is particularly desired to be suppressed. In particular, a multilayer structure in which a blackened layer is formed on the surface of the copper layer is more preferable, that is, a structure in which the copper layer is sandwiched between the blackened layers is more preferable.

A specific example of the structure of the laminate substrate of this embodiment will be described with reference to FIGS. 1A, 1B, 2A, and 2B. 1A, FIG. 1B, FIG. 2A, and FIG. 2B are diagrams illustrating the laminate substrate of this embodiment, and are cross-sectional views of a plane parallel to the laminate direction of the transparent substrate, the copper layer, and the blackened layer.

For example, like the laminated substrate 10A shown in FIG. 1A, a copper layer 12 and a blackened layer 13 may be sequentially laminated on one surface 11 a side of the transparent base material 11. In addition, as shown in FIG. 1B, a laminate substrate 10B can be laminated with copper layers 12A, 12B and blackened layers 13A, 13B on one surface 11a side and the other surface (the other surface) 11b side of the transparent substrate 11, respectively. Each floor. Here, the stacking order of the copper layer 12 (12A, 12B) and the blackened layer 13 (13A, 13B) is not limited to the example shown in FIG. 1A and FIG. 1B, and the blackened layer 13 may be started from the transparent substrate 11 side. (13A, 13B) and copper layer 12 (12A, 12B) are laminated in this order.

The laminate substrate of this embodiment may have a structure in which a plurality of blackened layers are provided on one surface side of the transparent base material 11, for example. For example, like the laminated substrate 20A shown in FIG. 2A, the first blackened layer 131, the copper layer 12, and the second blackened layer 132 may be laminated on one surface 11a of the transparent base material 11 in this order.

In this case, a structure in which a copper layer, a first blackened layer, and a second blackened layer are layered on both areas of the transparent substrate 11 can also be adopted. Specifically, as shown in FIG. 2B, the laminated substrate 20B can be respectively laminated with the first blackened layers 131A, 131B and the copper layer 12A on one surface 11a side and the other surface (the other surface) 11b side of the transparent base material 11. , 12B and the second blackened layers 132A, 132B.

In addition, FIG. 1B and FIG. 2B show that in the case where the two areas of the transparent substrate are layered with copper layers and blackened layers, the transparent substrate 11 is used as the symmetry plane, and the layers laminated on the transparent substrate 11 are symmetrically arranged. Examples, but not limited to this form. For example, in FIG. 2B, the structure of one side 11a of the transparent substrate 11 can also be the same as the structure of FIG. 1A, in which a copper layer 12 and a blackened layer 13 are sequentially laminated on the transparent substrate 11. The lower layer becomes an asymmetric structure.

So far, the laminate substrate of the present embodiment has been described. In the laminate substrate of the present embodiment, since the copper layer and the blackened layer are provided on the transparent substrate, the copper layer The reflection of light.

The degree of light reflection of the laminated substrate of this embodiment is not particularly limited. For example, the average reflectivity (regular reflectance) of the blackened layer of the laminated substrate of this embodiment to light with a wavelength of 400 nm or more and 700 nm or less (normal reflectance) is preferably 40 %the following. In particular, the average reflectivity of the blackened layer of the laminate substrate of the present embodiment to light having a wavelength of 400 nm or more and 700 nm or less is more preferably 30% or less, and still more preferably 20% or less. The reason is that when the average reflectivity of the surface of the blackened layer of the laminate substrate of this embodiment to light having a wavelength of 400 nm or more and 700 nm or less is 40% or less, for example, when it is used as a conductive substrate for touch panels, it is particularly It can suppress the reduction of the display screen's recognition.

By irradiating the blackened layer with light, the reflectance of the blackened layer of the laminate substrate can be measured. That is, the measurement can be performed from the blackened layer side among the copper layer and the blackened layer contained in the laminate substrate.

Specifically, for example, when a copper layer 12 and a blackened layer 13 are sequentially laminated on one surface 11a of the transparent substrate 11 like the laminated substrate 10A shown in FIG. 1A, the blackened layer 13 can be irradiated In the light method, the surface A in the figure can be illuminated and measured.

In addition, the arrangement of the copper layer 12 and the blackened layer 13 in FIG. 1A is changed. When the blackened layer 13 and the copper layer 12 are sequentially laminated on one surface 11a of the transparent substrate 11, the blackened layer 13 In the method of irradiating light, the blackened layer is irradiated with light from the surface 11b side of the transparent substrate 11, so that the reflectance can be measured.

Here, the average of light reflectance refers to the average value of the measurement results of reflectance measurement while changing the wavelength within the range of 400nm to 700nm for the same sample. In the measurement, there is no particular limitation on the range of changing the wavelength. For example, the above In the above-mentioned wavelength range, the wavelength is changed in 10 nm units and the light is measured, and it is more preferable to change the wavelength in 1 nm units in the above-mentioned wavelength range and the light is measured.

As described above, the laminate substrate of the present embodiment may have a structure in which a copper layer and a blackened layer are arranged on a transparent base material. In addition, according to a desired wiring pattern, the copper layer and the blackened layer arranged on the transparent base material are etched to form wires that are thin metal wires, which can be used as a conductive substrate.

Therefore, the conductive substrate of this embodiment can be equipped with a transparent base material and the thin metal wire formed on at least one surface side of a transparent base material. Furthermore, the thin metal wire may be a laminate having a blackened wiring layer and a copper wiring layer, and the blackened wiring layer contains oxygen, copper, and nickel.

In addition, the film thickness of the blackened wiring layer can be 15 nm or more. In addition, the atomic ratio O/Ni of oxygen atoms to nickel atoms contained in the blackened wiring layer preferably satisfies the following formula (1).

0.1≦O/Ni≦0.8 (1)

The conductive substrate of the present embodiment can be preferably used as, for example, a conductive substrate for touch panels. In this case, the conductive substrate may have a structure having, for example, a grid-like wiring pattern.

By etching the copper layer and the blackened layer of the laminate substrate of the present embodiment described above, a conductive substrate having a grid-like wiring pattern can be obtained.

For example, a grid-like wiring pattern can be formed by two layers of thin metal wires. The specific structure is shown in Figure 3. FIG. 3 shows a view of a conductive substrate 30 provided with a grid-like wiring pattern viewed from the upper surface side along the stacking direction of the copper wiring layer and the blackened wiring layer. The conductive substrate 30 shown in FIG. 3 has a transparent base 11, a plurality of copper wiring layers 31A parallel to the Y-axis direction in the figure, and copper wiring layers 31B parallel to the X-axis direction. In addition, copper wiring layers 31A and 31B are formed by etching the copper layer, and a blackened wiring layer (not shown) is formed on the upper and/or lower surfaces of the copper wiring layers 31A and 31B. The blackened wiring layer can be formed by etching the blackened layer, which is etched into the same shape (pattern) 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. Examples of the arrangement structure of the transparent substrate 11 and the copper wiring layer are shown in FIGS. 4A and 4B. 4A and 4B are cross-sectional views taken along the line A-A' in FIG. 3.

First, as shown in FIG. 4A, copper wiring layers 31A and 31B may be arranged on the upper and lower surfaces of the transparent substrate 11, respectively. Here, in the case of the example shown in FIG. 4A, on the upper surface of the copper wiring layer 31A and the lower surface of the copper wiring layer 31B, a blackened wiring layer 32A, which is etched into the same shape as the copper wiring layer 31A, 31B, 32B.

In addition, as shown in FIG. 4B, a set of transparent substrates 11 are used, and copper wiring layers 31A and 31B are arranged on the upper and lower sides of one of the transparent substrates 11, and one copper wiring layer 31B can be arranged on the transparent substrate. Between 11. In this case, the blackened wiring layers 32A, 32B etched into the same shape as the copper wiring layer are also arranged on the copper wiring layers 31A, 31B.

In addition, the arrangement of the blackened wiring layer and the copper wiring layer is not limited. Therefore, in either case of FIGS. 4A and 4B, the arrangement of the blackened wiring layers 32A, 32B and the copper wiring layers 31A, 31B can be turned upside down. In addition, for example, a plurality of blackened wiring layers can be provided.

However, the blackened wiring layer is preferably arranged on the surface of the copper wiring layer where light reflection is particularly required to be suppressed. Therefore, in the conductive substrate shown in FIG. 4B, for example, when it is necessary to suppress light reflection on the lower side in the figure, it is preferable to reverse the positions of the blackened wiring layers 32A, 32B and the positions of the copper wiring layers 31A, 31B. . In addition to the blackened wiring layers 32A and 32B, a blackened wiring layer may be arranged between the copper wiring layers 31A and 31B and the transparent base material 11.

For example, using the copper layer shown in FIG. 1B on both sides of the transparent substrate 11 The laminated substrate of 12A, 12B and the blackened layers 13A, 13B can form a conductive substrate with a grid-like wiring pattern as shown in FIGS. 3 and 4A.

Taking the case of using the laminated substrate of FIG. 1B as an example for description, firstly, the copper layer 12A and the blackened layer 13A on the side of one surface 11a of the transparent substrate 11 are etched to form a line along X in FIG. 1B A plurality of linear patterns arranged in the axial direction at predetermined intervals and parallel to the Y-axis direction in FIG. 1B. Here, the X-axis direction in FIG. 1B indicates a direction parallel to the width direction of each layer in FIG. 1B. In addition, the Y-axis direction in FIG. 1B indicates a direction perpendicular to the paper surface.

Then, the copper layer 12B and the blackened layer 13B on the other surface 11b side of the transparent substrate 11 are etched to form a plurality of linear shapes arranged at predetermined intervals along the Y-axis direction in FIG. 1B and parallel to the X-axis direction pattern.

Through the above operations, it is possible to form a conductive substrate having a grid-like wiring pattern as shown in FIGS. 3 and 4A. Here, it is also possible to simultaneously etch both surfaces of the transparent substrate 11. That is, the copper layers 12A, 12B, and the blackened layers 13A, 13B can be etched simultaneously.

In addition, in FIG. 4A, when a blackened wiring layer is also arranged between the copper wiring layers 31A and 31B and the transparent base material 11, the laminate substrate of FIG. 2B can be used instead of the laminate substrate of FIG. 1B. In this case, the first blackened layers 131A and 131B of the laminate substrate of FIG. 2B can be etched in the same manner as in the above case to produce a conductive substrate.

By using two conductive substrates as shown in FIG. 1A or FIG. 2A, it is also possible to form a conductive substrate with a grid-like wiring pattern as shown in FIG. Taking the case of using the laminate substrate shown in FIG. 1A as an example for description, the copper layer 12 and the blackened layer 13 are respectively etched on two laminate substrates as shown in FIG. 1A to form along the Y axis A plurality of linear patterns whose directions are separated by a predetermined interval and arranged parallel to the X-axis direction. Then, through the above etching process The linear patterns formed on each conductive substrate are arranged in a direction crossing each other, and two conductive substrates are bonded together, so that a conductive substrate with grid-like wiring can be obtained.

There are no particular limitations on the bonding surface when bonding two conductive substrates. For example, by bonding the surfaces such as the unlaminated copper layer 12 of the transparent base material 11, that is, the surface 11b in FIG. 1A, the same structure as the conductive substrate shown in FIG.

In addition, for example, the surface of an etched laminate substrate on which the copper layer 12 is laminated, that is, the surface A in FIG. 1A, and the surface of the unlaminated copper layer 12 of another etched laminate substrate, as shown in the figure The surface 11b in 1A is bonded. In this case, the same structure as the conductive substrate shown in FIG. 4B is formed.

Here, it is preferable that the blackening layer is arranged on the surface of the copper layer where light reflection is particularly required to be suppressed.

Therefore, in the conductive substrate shown in FIG. 4B, when it is necessary to suppress the reflection of light from the lower side in the figure, it is preferable to reverse the positions of the blackened wiring layers 32A, 32B and the positions of the copper wiring layers 31A, 31B Configuration. In this case, when producing a conductive substrate, a laminate substrate in which the copper layer 12 and the blackened layer 13 are arranged upside down in FIG. 1A can be used instead of the laminate substrate 10A shown in FIG. 1A to produce the conductive substrate .

In addition to the blackened wiring layers 32A and 32B, a blackened wiring layer may be provided between the copper wiring layers 31A and 31B and the transparent base material 11. At this time, when producing a conductive substrate, it is possible to produce a conductive substrate by using the laminated substrate 20A shown in FIG. 2A instead of the laminated substrate 10A shown in FIG. 1A.

Here, the width of the thin metal lines or the distance between the thin metal lines in the conductive substrate with a grid-like wiring pattern shown in FIGS. 3, 4A, and 4B is not particularly limited. For example, it can be selected according to the amount of current flowing through the thin metal wire. In consideration of the recognizability when used as a conductive substrate for a touch panel of a display screen, the width of the thin metal wire is preferably 20 μm or less.

。因此，本實施方式之導電性基板之銅配線層及黑化配線層可分別具有與上述積層體基板之銅層及黑化層相同之特性。 As described above, by etching the copper layer and the blackened layer of the laminate substrate according to the desired wiring pattern, the conductive substrate of this embodiment can be produced

. Therefore, the copper wiring layer and the blackened wiring layer of the conductive substrate of this embodiment can each have the same characteristics as the copper layer and the blackened layer of the above-mentioned laminate substrate.

Here, for example, the ratio of copper in the blackened wiring layer to the total of copper and nickel in the blackened wiring layer is preferably 20% or more and 80% or less, and more preferably 30% or more and 50% or less in terms of mass ratio.

In addition, the average reflectivity of the blackened wiring layer to light having a wavelength of 400 nm or more and 700 nm or less is preferably 40% or less, more preferably 30% or less, and still more preferably 20% or less. The reason is that when the average reflectivity of the blackened wiring layer of the conductive substrate of this embodiment to light having a wavelength of 400 nm or more and 700 nm or less is 40% or less, for example, when it is used as a conductive substrate for touch panels, it can be Especially suppress the reduction of the display screen's recognition.

Reflectance refers to the reflectance of the surface of the blackened wiring layer arranged on the outermost surface of the light incident side when the transparent base material in the conductive substrate is removed. Therefore, it is possible to measure the reflectance of the blackened wiring layer of the conductive substrate by light irradiating the blackened wiring layer of the thin metal wires remaining after etching the blackened layer of the laminate substrate.

Regarding the specific measurement method of reflectance, the same method as that of the reflectance of the blackened layer of the laminate substrate can be used for measurement, so the details are omitted.

In addition, for example, the thickness of the copper wiring layer and the blackened wiring layer may have the same characteristics as the copper layer and the blackened layer of the above-mentioned laminated substrate.

In addition, the above-mentioned FIGS. 3, 4A, and 4B show examples of combining thin metal wires in a linear shape to form a grid-like wiring pattern, but it is not limited to this form, and the thin metal wires constituting the wiring pattern may have any shape. For example, the shapes of the thin metal wires constituting the grid-like wiring pattern can be zigzag curved lines (z-shaped straight lines) and other shapes to prevent moiré (interference patterns) from being generated between the surface images of the display screen.

The conductive substrate having a grid-like wiring pattern composed of the above-mentioned two-layer metal thin wires can be preferably used as, for example, a conductive substrate for a touch panel of a projection type capacitance system.

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

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

Here, the above-mentioned multilayer substrate can be manufactured by the manufacturing method of the multilayer substrate of this embodiment, and the above-mentioned conductive substrate can be manufactured by the manufacturing method of the conductive substrate of this embodiment. Therefore, except for the content described below, the same structure as the above-mentioned laminate substrate and conductive substrate can be adopted, and therefore a part of the description is omitted.

The manufacturing method of the laminated body substrate of this embodiment may have a black layer formation step of forming a black layer by dry plating method, such as a sputtering method. In addition, in the blackening layer forming step, when the blackening layer is formed, the number of oxygen molecules (Γ(O ₂ )) injected into the surface of the blackened layer and the number of nickel atoms deposited on the blackened layer (Γ (Ni)) It is preferable to satisfy the following formula (2).

2≦Γ(O ₂ )/Γ(Ni)≦10 (2)

In the step of forming the blackened layer, a blackened layer containing oxygen, copper, and nickel may be formed on at least one side of the transparent substrate. Furthermore, in the blackening layer forming step, the blackening layer forming step can be performed by, for example, a film forming means for depositing non-stoichiometric nickel-copper oxide. About the black layer formation step The film forming means for depositing non-stoichiometric nickel-copper alloy oxides in the step is not particularly limited, and a dry plating method is preferred, and a sputtering film forming means (sputtering method) is particularly preferred.

In the blackened layer forming step of the manufacturing method of the laminated substrate of the present embodiment, when the blackened layer is formed by a dry plating method such as sputtering, a nickel-copper alloy target can be used in the chamber. Provide inert gas and oxygen at the same time for film formation. Here, as the inert gas, for example, argon gas can be used.

In addition, when the inert gas and oxygen are supplied into the chamber while the blackened layer is formed by a dry plating method such as sputtering, there is no limitation on the ratio of the inert gas to oxygen supplied to the chamber. However, when the blackened layer is formed, the number of oxygen molecules (Γ(O ₂ )) incident on the surface of the film and the number of nickel atoms deposited on the surface of the film (Γ(Ni)) preferably satisfy the above formula (2) ).

The reason is that when Γ(O ₂ )/Γ(Ni) is 2 or more, the blackened layer can be sufficiently blackened, so that the reflectance of the blackened layer of the laminate substrate can be reduced, and it is especially useful as a conductive substrate Improve the recognition of the display screen.

In addition, when Γ(O ₂ )/Γ(Ni) is 10 or less, excessive oxidation of the nickel contained in the blackened layer can be suppressed, thereby suppressing the problem of increased penetration of the blackened layer caused by the transparent nickel oxide. Therefore, in a laminated substrate formed by laminating a blackened layer and a copper layer, the blackened layer can suppress light reflection on the surface of the copper layer and reduce the reflectance of the laminated substrate. In addition, the etching properties of the blackened layer can be improved, and the copper layer and the blackened layer can be simultaneously etched more reliably.

Therefore, when forming a blackened layer, as described above, Γ(O ₂ )/Γ(Ni) is preferably 2 or more and 10 or less, more preferably 4 or more and 8 or less.

When the blackened layer is formed by the dry plating method, the roll-to-roll sputtering device 50 shown in FIG. 5 can be used to form the film appropriately, for example. Next, the case of using a roll-to-roll sputtering device As an example, the steps of forming the blackened layer are described.

FIG. 5 shows an example of the configuration of the roll-to-roll sputtering device 50. The roll-to-roll sputtering device 50 has a housing 51 capable of accommodating almost all its constituent parts. The shape of the housing 51 in FIG. 5 is shown as a rectangle, but there is no particular limitation on the shape of the housing 51, and any shape can be adopted according to the device housed inside, the installation position, the pressure resistance, etc. For example, the shape of the housing 51 may be a cylindrical shape. However, in order to eliminate residual gas unrelated to film formation at the beginning of film formation, it is preferable to reduce the pressure inside the housing 51 to 1 Pa or less, more preferably to 10 ^-3 Pa or less, and even more preferably to 10 ^-4 Pa or less . Here, there is no need to depressurize the entire interior of the housing 51 to the above pressure, and it can be used only for sputtering, and the lower region 51a and the region 51b in the figure where the film forming roll 53 described below is arranged is decompressed to the above pressure.

In the housing 51, the unwinding roller 52, the film forming roller 53, the sputtering cathode 54a to 54d, the feed forward roller 55a, the rear feed roller 55b, the tension roller 56a, 56b, take-up roller 57.

In addition, in addition to the above-mentioned rollers, guide rollers 58a to 58h, heater 59, etc. may be arbitrarily provided on the transportation path of the blackened layer film-forming substrate.

The unwinding roller 52, the film forming roller 53, the feed roller 55a, and the winding roller 57 can be powered by a servo motor. Through the torque control of the powder clutch, etc., the unwinding roller 52 and the winding roller 57 can maintain the tension balance of the blackened layer film-forming substrate.

The structure of the film forming roller 53 is not particularly limited. For example, it is preferable that the surface is processed with a hard chromium plating, and a refrigerant or heat medium from the outside of the housing 51 circulates inside to maintain a substantially constant temperature.

The tension rollers 56a and 56b are preferably processed with hard chromium plating on the surface, for example, And has a tension sensor. In addition, it is also preferable that the surfaces of the feed forward roller 55a, the rear feed roller 55b, and the guide rollers 58a to 58h be processed with a hard chromium plating.

The sputtering cathodes 54 a to 54 d are preferably of a magnetron cathode type, and are arranged opposite to the film forming roller 53. The size of the sputtering cathodes 54a to 54d is not particularly limited, but it is preferable that the size of the sputtering cathodes 54a to 54d along the width direction of the blackened layer film-forming substrate is larger than the width of the blackened layer film-forming substrate.

The substrate used for forming the blackened layer is transported to the roll-to-roll sputtering device 50 as a roll-to-roll vacuum film forming device, and the black film is formed at the sputtering cathode 54a~54d opposite to the film forming roll 53化层。 The layer.

Hereinafter, the procedure for forming a blackened layer using the roll-to-roll sputtering device 50 will be described.

First, for the case 51 where the nickel-copper alloy target is mounted on the sputtering cathode 54a to 54d, and the base material for blackening layer film formation is set in the unwinding roll 52, vacuum pumps 60a, 60b are used, and A vacuum pump 60c can be added as appropriate for vacuum exhaust.

Here, in the process of conveying the substrate from the unwinding roller 52 to the winding roller 57, layers of different compositions can be continuously formed on the substrate, specifically, for example, a blackened layer and a copper thin film layer. As described above, when the blackened layer and the copper thin film layer are continuously formed, for example, a nickel-copper alloy target may be provided on the sputtering cathodes 54a, 54b, and a copper target may be provided on the sputtering cathodes 54c, 54d.

Then, an inert gas such as argon and oxygen as sputtering gas are introduced into the casing 51 from the gas supply portion 61a.

The structure of the gas supply part 61a is not particularly limited, and it may have a gas storage tank not shown. And, in order to be able to control the amount of supply of each gas to the housing 51, you can Between the gas storage tank and the housing 51, mass flow controllers (MFC) 611a, 611b, and valves 612a, 612b are provided according to the gas type. Figure 5 shows an example of the installation of two sets of mass flow controllers and valves, but the number of settings is not particularly limited, and the number of settings can be selected according to the number of gas types used.

When introducing inert gas and oxygen into the housing from the gas supply unit 61a, it is preferable to adjust the oxygen partial pressure through the mass flow controller 6112, 611b, etc., so that Γ(O ₂ )/Γ(Ni) meets the specified range as described above .

When the sputtering gas is supplied into the casing 51 from the gas supply portion 61a, it is preferable to adjust the flow rate of the sputtering gas and the opening of the pressure regulating valve 62a provided between the vacuum pump 60b and the casing 51 to maintain the inside of the casing, for example 0.13Pa or more and 1.3Pa or less, and film formation.

In this state, the base material is transported from the unwinding roller 52 at a speed of 1 m or more and 20 m or less per minute, and sputtering discharge is performed by supplying power from a sputtering DC power supply connected to the sputtering cathodes 54a to 54d. In this way, a desired blackened layer can be continuously formed on the substrate.

In the roll-to-roll sputtering device 50, in addition to the above, various components can be arranged as needed. For example, pressure gauges 63a and 63b and vent valves 64a and 64b for measuring the pressure in the housing 51 can be provided.

In addition, as described above, during the process of conveying the base material from the unwinding roll 52 to the winding roll 57, the blackened layer and the copper thin film layer can be continuously formed on the base material. When the blackened layer and the copper thin film layer are continuously formed on the substrate, it is preferable to adopt a structure capable of controlling the area 51a on the sputtering cathode 54a, 54b side and the area 51b on the sputtering cathode 54c, 54d side into different environments. Specifically, it is preferable to control the two areas into different environments by providing partition 65, for example. In this case, in addition to the gas supply part 61a, a gas supply part 61b can be provided. Set up gas supply In the case of the portion 61b, the gas supply portion 61b may have the same structure as the gas supply portion 61a, for example, may include a mass flow controller 611c and a valve 612c. FIG. 5 shows an example in which one set of mass flow controllers 611c and 612c is provided, but it is not limited to this form, and the number of installations can be selected according to the number of types of gas provided.

In addition, a vacuum pump 60c and a pressure regulating valve 62b may be pre-installed on the side of the region 51b, and the pressure in the region 51b can be controlled according to the flow rate of the sputtering gas from the gas supply part 61b and the opening of the pressure regulating valve 62b.

When there is no need to form areas with different environments in the housing, the partition 65, gas supply portion 61b, vacuum pump 60c, and pressure regulating valve 62b need not be provided, and the area 51a and the area 51b can be controlled to the same environment.

In addition, in addition to the step of forming the blackened layer, the method of manufacturing the laminate substrate of the present embodiment may have the following steps.

The transparent substrate preparation step of preparing the transparent substrate.

A copper layer forming step of forming a copper layer on at least one surface side of the transparent substrate by a film forming means of depositing copper.

As described above, in the laminate substrate of the present embodiment, there is no particular limitation on the order of the laminate when the copper layer and the blackened layer are arranged on the transparent base material. In addition, the copper layer and the blackened layer may be formed into plural layers, respectively. Therefore, the order of performing the copper layer forming step and the blackened layer forming step is not particularly limited, and it can be performed at any number of times and timing according to the structure of the laminated substrate to be formed.

The step of preparing a transparent substrate for preparing a transparent substrate, for example, is a step of preparing a transparent substrate composed of an insulator film, a glass substrate, etc. that can penetrate visible light. The operation is not particularly limited. For example, it can be cut into any size according to the needs of each step provided in the subsequent steps.

Next, the steps of forming the copper layer will be described.

The copper layer is as described above, and it is preferable to form the copper layer using a dry plating method. In addition, when it is desired to further increase the thickness of the copper layer, it is preferable to use a wet plating method after the dry plating.

Therefore, 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 also 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.

As described above, it is preferable to form the copper layer by using only the dry plating method or the combination of the dry plating method and the wet plating method, so that the copper layer can be directly formed on the transparent substrate or the blackened layer without using an adhesive.

The dry plating method is not particularly limited. For example, a sputtering method, an ion plating method, a vapor deposition method, or the like can be preferably used. In particular, as a dry plating method for forming a copper thin film layer, since it is easy to control the film thickness, it is more preferable to use a sputtering method. That is, the film forming means for depositing copper in the copper layer forming step is preferably a sputtering film forming means (sputtering method).

For example, the above-mentioned roll-to-roll sputtering device 50 can be used to form a copper thin film layer preferably. Regarding the structure of the roll-to-roll sputtering device, it has been described in the foregoing, and the details are omitted here.

Regarding the conditions in the step of forming the copper plating layer by the wet plating method, that is, the conditions of the electroplating treatment are not particularly limited, and conditions in common methods can be adopted. For example, the substrate on which the copper thin film layer is formed is supplied to a plating tank containing a copper plating solution, and the copper plating layer can be formed by controlling the current density and the conveying speed of the substrate.

Then, the multilayer substrate manufactured by the above-mentioned manufacturing method of the multilayer substrate, As with the above-mentioned laminate substrate, the thickness of the copper layer is preferably 80 nm or more, more preferably 100 nm or more, and still more preferably 150 nm or more. In addition, the upper limit of the thickness of the copper layer is not particularly limited, but is preferably 5000 nm or less, more preferably 3000 nm or less, and still more preferably 1200 nm or less.

In addition, the thickness of the blackened layer is not particularly limited in the laminate substrate obtained by the above-described method of manufacturing the laminate substrate, and it is preferably 15 nm or more, and more preferably 20 nm or more. The upper limit of the thickness of the blackening layer is not particularly limited, but it is preferably 60 nm or less, and more preferably 50 nm or less.

In addition, the average reflectivity of the laminated substrate obtained through the above-described method of manufacturing the laminated substrate to light having a wavelength of 400 nm or more and 700 nm or less is preferably 40% or less, and more preferably 30% or less. Especially preferably, it is 20% or less.

In addition, it is possible to produce a conductive substrate with thin metal wires by using a laminate substrate obtained by the method for producing a laminate substrate described above. When the copper layer and the blackened layer are etched to produce a conductive substrate using the laminated substrate prepared by the method of manufacturing the laminated substrate of this embodiment, in addition to the above steps, it may also have a copper layer, black The wiring processing step of wiring processing on the chemical layer. That is, the manufacturing method of the conductive substrate of this embodiment may have a wiring processing step of performing wiring processing on the multilayer substrate manufactured by the manufacturing method of the multilayer substrate of this embodiment.

When performing this wiring processing step, for example, first, a protective layer may be formed on the outermost surface of the laminate substrate, and the protective layer may have an opening corresponding to a portion to be removed by etching.

When using the laminate substrate shown in Figure 1A to produce a conductive substrate, you can A protective layer is formed on the exposed surface A of the blackened layer 13 arranged in the laminate substrate. Here, the method for forming the protective layer is not particularly limited. For example, it can be formed by photolithography, and the protective layer has an opening corresponding to the portion to be removed by etching.

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

Here, as shown in FIG. 1B, when the copper layer and the blackened layer are arranged on both sides of the transparent base material 11, the protection of openings having a predetermined shape can be formed on the surface A and the surface B of the laminate substrate. The copper layer and the blackened layer formed on both sides of the transparent substrate 11 are simultaneously etched.

In addition, the copper layer and the blackened layer formed on both sides of the transparent substrate 11 may also be etched separately on each side. That is, for example, after the copper layer 12A and the blackened layer 13A are etched, the copper layer 12B and the blackened layer 13B may be etched.

The blackened layer contained in the laminate substrate of this embodiment shows the same etching solution reactivity as the copper layer. Therefore, the etching solution used in the wiring processing step is not particularly limited, and general copper layer etching can be preferably used. The etching solution used. As the etching solution, for example, a mixed aqueous solution of ferric chloride and hydrochloric acid can be preferably used. The content of ferric chloride and hydrochloric acid in the etching solution is not particularly limited. For example, the content of ferric chloride is preferably 5% by weight to 50% by weight, and more preferably 10% by weight to 30% by weight. . In addition, the content ratio of hydrochloric acid in the etching solution is preferably 1% by weight or more and 50% by weight or less, and more preferably 1% by weight or more and 20% by weight or less. Here, the remaining part may be water.

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

The thin metal wires obtained through the above wiring processing steps, for example, may have a grid-like wiring pattern. The specific form has been described above, and the details are omitted here.

In addition, regarding the laminate substrate having a copper layer and a blackened layer on one side of the transparent substrate 11 shown in FIG. 1A or FIG. 2A, etching is performed through the wiring processing step, and the obtained two conductive substrates are pasted Together, a conductive substrate with a grid-like wiring pattern is formed. In this case, there may be a step of bonding the conductive substrate.

In the step of bonding the conductive substrates, the method of bonding the two conductive substrates is not particularly limited. For example, an adhesive can be used for bonding.

The manufacturing method of the laminated body board|substrate and the manufacturing method of a conductive board|substrate of this embodiment were demonstrated above.

The copper layer and the blackened layer of the laminated substrate obtained by the method of manufacturing the laminated substrate have almost the same reactivity to the etching solution. Therefore, the copper layer and the blackened layer can be etched at the same time, making it easy to form the desired Thin metal wires.

In addition, the blackened layer that contains oxygen, copper, and nickel, and the film thickness and the atomic ratio of oxygen atoms to nickel atoms in the blackened layer are within the specified range is black, so when the blackened wiring layer is formed by etching, It can suppress the light reflection of the copper wiring layer. Therefore, when the obtained conductive substrate is used for, for example, a conductive substrate for a touch panel, it is possible to suppress a decrease in visibility.

[Example]

Hereinafter, the present invention will be described in further detail based on the examples and comparative examples of the present invention, but these examples are not meant to limit the present invention.

(Evaluation method)

(1) Reflectivity

Reflectance measurements were performed on the laminate substrates produced in the following examples and comparative examples.

The reflectance measurement unit was installed in an ultraviolet-visible spectrophotometer (Model: UV-2550 manufactured by Shimadzu Corporation) and measured.

In each embodiment and comparative example, a laminate substrate having the structure shown in FIG. 2A was produced, and the surface A exposed to the outside of the second blackened layer 132 in FIG. 2A was set at an incident angle of 5° and a light receiving angle. 5° irradiated with light in the wavelength range from 400nm to 700nm, and measured the reflectance. Here, the measurement was performed while changing the wavelength of the light irradiated to the laminate substrate in the range of 400 nm to 700 nm in units of 1 nm, and the average of the measurement results was taken as the average reflectance of the laminate substrate.

(2) The ratio of oxygen, nickel and copper atoms in the blackened layer

For the laminate substrates produced in the following Examples and Comparative Examples, XPS (Model: Versa Probe II manufactured by ULVAC PHI) was used to measure the ratio of oxygen, nickel, and copper atoms in the second blackened layer.

(3) Etching

The laminate substrates produced in the following examples and comparative examples were immersed in an etching solution of 10% by weight of ferric chloride, 10% by weight of hydrochloric acid, and water for the remainder for 1 minute, and the etching properties were evaluated. The laminate substrate with no residue remaining on the transparent base material was judged to have good etching properties.

(Production conditions of sample)

The following shows the manufacturing conditions of the laminate substrates in the respective examples and comparative examples.

[Example 1]

A laminate substrate 20A having the structure shown in FIG. 2A was produced.

First, a transparent base material of polyethylene terephthalate resin (PET) with a width of 500 mm and a thickness of 100 μm is set in the roll-to-roll sputtering device 50 shown in FIG. 5. And splashing The plating cathodes 54a and 54b are equipped with Ni-40 mass% Cu targets for forming the blackened layer, and the sputtering cathodes 54c and 54d are equipped with copper targets for forming the copper layer.

Next, the heater 59 of the roll-to-roll sputtering device 50 is heated to 100° C. to heat the transparent substrate to remove water contained in the substrate.

Next, the inside of the casing 51 was exhausted to 1×10 ^-4 Pa, and the gas supply portion 61a was introduced into the area 51a on the side of the sputtering cathodes 54a and 54b in the casing 51 separated by the partition 65 at 360 sccm Argon gas, oxygen gas was introduced at 40 sccm. In addition, the opening degree of the pressure regulating valve 62a provided between the gas supply part 61a and the vacuum pump 60b and the housing 51 is adjusted to adjust the pressure in the area 51a to 0.4 Pa. At this time, the oxygen partial pressure in the region 51a is 0.04Pa. Here, the oxygen partial pressure in the region 51a when the blackened layer is formed is shown in Table 1 as the O ₂ partial pressure when the blackened layer is formed.

Similarly, 400 sccm of argon was introduced from the gas supply portion 61b to the region 51b on the side of the sputtering cathodes 54c and 54d in the casing 51. In addition, the opening degree of the pressure regulating valve 62b provided between the gas supply part 61b and the vacuum pump 60c and the housing 51 was adjusted so that the pressure in the area 51ba became 0.4 Pa.

Then, the unwinding roller 52 transports the transparent substrate at a speed of 2m per minute, and at the same time, the sputtering DC power supply connected to the sputtering cathode 54a to 54d provides power to perform sputtering discharge, and continuously form a black film on the substrate. Chemical layer and copper layer. Through this operation, a first blackened layer 131 with a thickness of 20 nm and a copper layer with a thickness of 100 nm were formed on the transparent substrate.

Next, the roll-to-roll sputtering device 50 was transported in the reverse direction, and the base material on which the first blackened layer and the copper layer were laminated on the transparent base material was transported from the winding roller 57 to the unwinding roller 52. In addition, under the same conditions as above, a copper layer with a thickness of 100 nm and a second blackened layer 132 with a thickness of 20 nm were formed.

After the above-mentioned two film formation, the copper layer became a layer with a total thickness of 200 nm.

In addition, Γ(O ₂ )/Γ(Ni) when the first blackened layer 131 and the second blackened layer 132 were formed was 5.8.

When measuring the reflectance of the second blackened layer of the fabricated laminate substrate, the exposed surface A of the second blackened layer 132, that is, where the second blackened layer 132 is not opposed to the copper layer 12 The surface was irradiated with light, and the average reflectance of light with a wavelength of 400nm to 700nm was measured. As a result, the average reflectivity of the second blackened layer of the fabricated laminate substrate was 25%.

In addition, the atomic ratio of oxygen, nickel, and copper in the second blackened layer was evaluated by XPS, and the O/Ni ratio in the second blackened layer was calculated. The O/Ni ratio of the second blackened layer was 0.34. Here, as described above, since the first blackened layer and the second blackened layer are formed under the same conditions, the two blackened layers have the same composition.

[Example 2~Example 7]

Regarding Examples 2 to 4, as the Γ(O ₂ )/Γ(Ni) during the formation of the first and second blackened layers and the nickel and copper content of the target for the formation of blackened layers, The ratio and content rate shown in Table 1 were other than the same conditions as in Example 1 to prepare a laminate substrate and evaluate it.

Regarding Examples 5 to 7, as the Γ(O ₂ )/Γ(Ni) during the film formation of the first and second blackened layers, and the nickel and copper content ratios in the target for the formation of the blackened layer, use The ratio and content rate shown in Table 1 were used, and the film thickness of the first and second blackened layers was 30 nm. Otherwise, a laminate substrate was produced under the same conditions as in Example 1, and evaluated.

Here, in order to make Γ(O ₂ )/Γ(Ni) at the time of forming the first and second blackened layers into the predetermined ratio shown in Table 1, the roll-to-roll sputtering device 50 was also changed. The amount of oxygen supplied by the gas supply portion 61a to the region 51a where the blackened layer is formed. Therefore, the O ₂ partial pressure during the film formation of the blackened layer also changes.

The evaluation results are shown in Table 1.

[Comparative example 1~Comparative example 4]

Regarding Comparative Example 1 to Comparative Example 3, the Γ(O ₂ )/Γ(Ni) during the film formation of the first and second blackened layers were changed. Otherwise, a laminate substrate was prepared under the same conditions as in Example 1, and proceeded. Evaluation.

Regarding Comparative Example 4, the film thickness of the first and second blackened layers was set to 10 nm, and otherwise under the same conditions as in Example 1, a laminate substrate was produced and evaluated.

Here, in order to make the Γ(O ₂ )/Γ(Ni) during the film formation of the first blackened layer and the second blackened layer into the predetermined ratio shown in Table 1, the gas supplied by the roll-to-roll sputtering device 50 The oxygen supply amount provided by the portion 61a to the region 51a where the blackened layer is formed is also changed. Therefore, the O ₂ partial pressure during the film formation of the blackened layer also changes.

Especially in Comparative Example 1, when the first blackened layer and the second blackened layer were formed, oxygen was not supplied to the region 51a but only argon was supplied.

The evaluation results are shown in Table 1.

【Table 1】

According to the results shown in Table 1, the blackening layer has a thickness of 15nm or more and the atomic ratio of oxygen atoms to nickel atoms O/Ni contained in the blackening layer is 0.1 or more and 0.8 or less for Examples 1 to 7, etching The result of the evaluation of sex was good. In addition, the reflectivity of the blackened layer is below 40%, and it was confirmed that the blackened layer has sufficient function as a blackened layer that suppresses light reflection on the surface of the copper layer. Thus, it was confirmed that a laminate substrate having a copper layer and a blackened layer that can be etched at the same time was obtained.

In contrast, in Comparative Examples 1 and 2 in which the atomic ratio of oxygen atoms to nickel atoms contained in the blackened layer O/Ni is less than 0.1, the reflectance of the blackened layer exceeds 40%. The function of the blackened layer is insufficient.

In addition, in Comparative Example 3 in which the atomic ratio of oxygen atoms to nickel atoms contained in the blackened layer, O/Ni, exceeded 0.8, the results of the etching performance evaluation showed that residues were present. That is, it was confirmed that it cannot be used as a laminate substrate provided with a copper layer and a blackened layer that can be simultaneously etched.

Regarding Comparative Example 4, since the thickness of the blackened layer is less than 15nm, the thickness of the blackened layer The reflectivity was as high as 42%, and it was confirmed that the function as a blackening layer that suppresses light reflection on the surface of the copper layer is insufficient.

As mentioned above, the laminated body substrate, the laminated body substrate manufacturing method, the conductive substrate, and the conductive substrate manufacturing method have been described through the embodiments and examples, but the present invention is not limited to the above-mentioned 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 Patent Application No. 2015-204642 filed with the Japan Patent Office on October 16, 2015, and cites the entire content of Patent Application No. 2015-204642.

10A: Multilayer substrate

11: Transparent substrate

11a: One side

11b: another side

12: Copper layer

13: Blackened layer

A: Surface

X, Y: X axis, Y axis

Claims (10)

A laminated body substrate comprising: a transparent base material and a laminated body formed on at least one surface side of the transparent base material; the laminated body having a blackened layer containing oxygen, copper, and nickel, and a copper layer, the The film thickness of the blackened layer is 15 nm or more, and the atomic ratio O/Ni of oxygen atoms to nickel atoms contained in the blackened layer satisfies the following formula (1), 0.1≦O/Ni≦0.8 (1). For example, the laminated substrate of item 1 in the scope of patent application, wherein the ratio of copper in the blackened layer to the total of copper and nickel in the blackened layer is 20% or more and 80% or less by mass. For example, the laminated substrate of item 1 or 2 of the scope of patent application, wherein the thickness of the copper layer is 80 nm or more and 5000 nm or less. For example, the laminated substrate of item 1 or 2 of the scope of patent application, wherein the average reflectivity of the blackened layer to light with a wavelength of 400 nm or more and 700 nm or less is 40% or less. For example, the laminated substrate of item 3 of the scope of patent application, wherein the average reflectivity of the blackened layer to light with a wavelength of 400 nm or more and 700 nm or less is 40% or less. A method for manufacturing a laminate substrate, which is a method for manufacturing a laminate substrate according to any one of items 1 to 5 in the scope of the patent application, the manufacturing method comprising: forming the blackened layer by a dry plating method The layer formation step. In the blackened layer forming step, when the blackened layer is formed, the number of oxygen molecules (Γ(O ₂ )) injected into the blackened layer and deposited on the blackened layer The number of nickel atoms (Γ(Ni)) satisfies the following formula (2), 2≦Γ(O ₂ )/Γ(Ni)≦10 (2). A conductive substrate comprising: a transparent substrate and a thin metal wire formed on at least one surface side of the transparent substrate; the thin metal wire is a laminate having a blackened wiring layer and a copper wiring layer; the blackened wiring The layer contains oxygen, copper, and nickel. The thickness of the blackened wiring layer is 15nm or more. The atomic ratio of oxygen atoms to nickel atoms contained in the blackened wiring layer O/Ni satisfies the following formula (1), 0.1≦O/Ni ≦0.8 (1). For example, the conductive substrate of item 7 in the scope of patent application, wherein the ratio of copper in the blackened wiring layer to the total of copper and nickel in the blackened wiring layer is 20% or more and 80% or less by mass ratio. For example, the conductive substrate of item 7 or 8 in the scope of patent application, wherein the average reflectivity of the blackened wiring layer to light with a wavelength of 400 nm or more and 700 nm or less is 40% or less. A method for manufacturing a conductive substrate includes a wiring processing step, which performs wiring processing on a laminate substrate obtained by the method for manufacturing a laminate substrate of the sixth patent application.

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