TW201728444A - Laminate substrate, method for manufacturing laminate substrate, electroconductive substrate, and method for manufacturing electroconductive substrate - Google Patents

Abstract

Provided is a laminate substrate that is provided with a transparent base material and a laminate formed on at least one surface of the transparent base material. The laminate includes: a blackened layer containing oxygen, copper, and nickel; and a copper layer. The film thickness of the blackened layer is 15 nm or greater, and the mass ratio O/Ni of the oxygen atoms and nickel atoms contained in the blackened layer satisfies formula (1). Formula (1): 0.1 ≤ O/Ni ≤ 0.8.

Description

Method for producing laminated substrate, laminated substrate, conductive substrate, and method for producing conductive substrate

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

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

Here, the display screen including the touch panel tends to be large in the recent years, and accordingly, the conductive substrate such as the transparent conductive film for the touch panel is required to have a large area. However, since the ITO resistance value is high, there is a problem that it is impossible to cope with the increase in the area of the conductive substrate.

On the other hand, for example, Patent Documents 2 and 3 disclose a technical study using a metal thin wire formed by processing a metal foil such as copper instead of the ITO film. However, in the case where, for example, copper is used for the thin metal wires, since copper has a metallic luster, there is a problem that reflection causes a decrease in the visibility of the display screen.

Therefore, it has been studied to form a laminated body substrate having a blackened layer together with a copper layer, the copper layer is made of a metal foil such as copper, and the blackened layer is made of a black material. In order to process the laminated substrate into a conductive substrate having a wiring pattern of metal thin wires, it is necessary to etch the copper layer and the blackened layer after forming a copper layer and a blackened layer having optical characteristics such as a desired reflectance. To form a place The pattern of hope.

However, there is a problem that the reactivity of the copper layer and the blackening layer to the etching liquid is different. That is, if the copper layer and the blackened layer are simultaneously etched, it is impossible to etch one of the layers into a desired shape. Further, if the copper layer etching and the blackening layer etching are separately performed as separate steps, the number of steps is increased.

<Previous Technical Literature> <Patent Literature>

Patent Document 1: Japanese Laid-Open Patent Publication No. 2003-151358

Patent Document 2: JP-A-2011-018194

Patent Document 3: Japanese Laid-Open Patent Publication No. 2013-069261

In view of the above problems in the prior art, it is an object of the present invention to provide a laminate substrate having a copper layer and a blackening layer which can be simultaneously subjected to etching treatment.

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 And a copper layer having a film thickness of 15 nm or more, wherein the blackening layer contains a mass ratio of oxygen atoms to nickel atoms O/Ni satisfying 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 black which can be simultaneously subjected to etching treatment The layered substrate of the layer.

10A, 10B, 20A, 20B‧‧‧ laminated substrate

11‧‧‧Transparent substrate

12, 12A, 12B‧‧‧ copper layer

13, 13A, 13B, 131, 132, 131A, 131B, 132A, 132B‧‧‧ blackening layer

30‧‧‧Electrically conductive substrate

31A, 31B‧‧‧ copper wiring layer

32A, 32B‧‧‧ blackened wiring layer

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

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

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

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

3 is a plan view of a conductive substrate having a mesh wiring pattern according to an embodiment of the present invention.

Fig. 4A is a cross-sectional view taken along line A-A' of Fig. 3.

Fig. 4B is a cross-sectional view taken along line A-A' of Fig. 3.

Figure 5 is an explanatory view of a roll-to-roll sputtering apparatus.

Hereinafter, an embodiment of a laminated substrate, a method for producing a laminated substrate, a conductive substrate, and a method for producing a conductive substrate of the present invention will be described.

(Laminated substrate, 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. Further, the laminate may have a blackening layer and a copper layer containing oxygen, copper, and nickel. Further, the film thickness of the blackening layer is 15 nm or more, and the mass ratio O/Ni of the oxygen atom to the nickel atom contained in the blackening layer preferably satisfies the following formula (1).

0.1≦O/Ni≦0.8 (1)

Here, the laminated substrate of the present embodiment means that the surface of the transparent substrate has a copper layer and black. The layered body of the layer and the substrate before etching the copper layer or the like. The conductive substrate refers to a substrate in which a copper layer and a blackened layer are etched to form metal thin wires.

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

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

As the insulator film which can transmit visible light, for example, a polyimide film, a polyethylene terephthalate (PET) film, a polyethylene naphthalate film, a cycloolefin film, or a polycondensation can be preferably used. A resin film such as a quinone imine film or a polycarbonate film.

The thickness of the transparent substrate is not particularly limited, and can be arbitrarily selected depending on the required strength, light transmittance, and the like for the conductive substrate. The thickness of the transparent substrate may be, for example, 10 μm or more and 250 μm or less. In particular, in the case of use for a touch panel, it is preferably 20 μm or more and 200 μm or less, and more preferably 20 μm or more and 120 μm or less. In the case of use for a touch panel, for example, in the case where it is particularly necessary to reduce the thickness of the entire display screen, 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 not particularly limited. However, in order not to lower the light transmittance, it is preferable that no binder is disposed 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 member.

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

In addition, in order to further thicken the copper layer, it is preferable to make it after the dry plating 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 a copper plating layer can be formed by wet plating using the copper thin film layer as a power supply layer. In this case, the copper thin film layer and the copper plating layer may constitute a copper layer.

As described above, by forming the copper layer by only the dry plating method or by the combination of the dry plating method and the wet plating method, it is possible to form the copper layer directly on the transparent substrate or the blackening layer without using the binder. The above method.

The film thickness of the copper layer is not particularly limited, and when the copper layer is used as a wiring, it can be arbitrarily selected according to the magnitude of the current supplied to the wiring, the wiring width, and the like. In particular, in order to provide a sufficient current, the film thickness of the copper layer is preferably 80 nm or more, more preferably 100 nm or more, still more preferably 150 nm or more. The upper limit of the film thickness of the copper layer is not particularly limited. However, when the copper layer is thickened, 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 5,000 nm or less, more preferably 3,000 nm, still more preferably 1200 nm or less. Further, as described above, in the case where 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 thickness of the copper plating layer are preferably within the above range.

Next, the blackening layer will be described. In the laminated substrate of the present embodiment, the blackening layer may contain oxygen, copper, and nickel.

A metal thin wire which is formed only by a copper layer and is subjected to wiring processing without a blackening layer, and the copper layer of the wiring has a metallic luster, and the copper reflects light, for example, when used as a wiring substrate for a touch panel, display occurs. The problem of reduced visibility of the screen. In this regard, the method of setting the blackening layer is studied.

In order to suppress light reflection on the surface of the copper layer, and to form a copper layer on the transparent substrate After the blackening layer is subjected to wiring processing, the blackening layer is required to have both low reflectance and etchability capable of simultaneously etching the copper layer and the blackened layer into a desired shape.

The inventors of the present invention have studied a blackened layer containing oxygen, copper, and nickel in order to obtain a blackened layer having both low reflectance and etching properties. It has been found that the reactivity of the blackening layer to the etching liquid, that is, the etching property, may be insufficient depending on the ratio of the number of metal atoms constituting the blackening layer to the number of oxygen atoms.

Further, it has been found that the film thickness of the blackening layer containing oxygen, copper, and nickel is 15 nm or more, and the mass ratio (O/Ni) of the oxygen atom to the nickel atom contained in the blackening layer satisfies the following formula (1). The blackening layer can have both low reflectance and etchability.

0.1≦O/Ni≦0.8 (1)

For example, a blackening layer containing oxygen, copper, or nickel in the laminated substrate of the present embodiment can be formed by a dry plating method. Further, when a blackening layer containing oxygen, copper or nickel is formed by a dry plating method using a nickel-copper alloy and oxygen is added to an inert gas such as argon gas, nickel is preferentially oxidized.

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

Further, when the O/Ni ratio of the above formula (1) is more than 0.8, the oxidation of nickel is enhanced, and the Ni-Cu-O film formed as a blackening layer becomes transparent, and the transmittance may be improved. Therefore, in the case where 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 is increased, and as a result, the reflectance is increased. Further, when the O/Ni ratio of the above formula (1) is more than 0.8, the etching property may be lowered.

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

Here, the state of each atom contained in the blackening layer is not particularly limited, and for example, a non-stoichiometric nickel-copper oxide may be contained, and a part of nickel and copper may also be used as an oxide. Atom containing a non-stoichiometric oxide is contained therein.

Further, the composition of oxygen, nickel, and copper contained in the blackening layer can be found by XPS.

The ratio of copper to nickel in the blackened layer of the laminated substrate of the present embodiment is not particularly limited, and the ratio of copper in the blackened layer to the total of copper and nickel in the blackened layer is preferably a mass ratio. 20% or more and 80% or less.

The reason for this is that the etching ratio of the blackening layer can be particularly improved by making the ratio of copper in the blackening layer to the total of copper and nickel in the blackening layer 20% by mass or more. However, when the ratio of copper in the blackening layer to the total of copper and nickel in the blackening layer is more than 80% by mass, the reflectance of the blackening layer is improved, and it is used as a conductive substrate for a touch panel. In this case, the visibility of the display screen may be lowered, so it is preferably 80% or less.

The ratio of the copper in the blackening layer to the total of copper and nickel in the blackening layer is more preferably 30% or more and 50% or less by mass ratio.

Here, in the case where the blackening layer is formed by a sputtering method using a sputtering target of a nickel-copper alloy, the ratio of copper to nickel in the blackening layer and the ratio of copper to nickel in the sputtering target can be made substantially Become equal. Therefore, when the blackening layer is formed by sputtering, the ratio of copper to nickel in the blackened layer can be changed by the composition of the sputtering target.

The film formation method of the blackening layer is not particularly limited, and can be carried out by any method. For film formation, for example, film formation can be suitably carried out by dry plating. In particular, when a nickel-copper alloy from the sputtering target is oxidized by a sputtering method using a sputtering target of a nickel-copper alloy, a blackened layer containing oxygen, copper, or nickel can be easily formed. Therefore, it is preferable to perform film formation of a blackening layer by a sputtering method.

When the blackening layer of the laminated substrate of the present embodiment is formed by sputtering, a nickel-copper alloy target can be used, and an inert gas and oxygen gas are supplied into the chamber, and a film is formed by sputtering. Here, as the inert gas, for example, argon gas can be used.

When the blackening layer is formed by sputtering, a mixed gas of an inert gas and oxygen may be supplied to the chamber in advance. Alternatively, an inert gas and oxygen may be supplied to the chamber separately, and the partial pressure of each gas may be adjusted. In particular, in order to be able to adjust the amount of oxygen supplied to the blackening layer, it is preferred to simultaneously supply the inert gas and oxygen to the chamber and adjust the oxygen partial pressure in the chamber.

As described above, when the blackening layer is formed by dry plating such as sputtering by supplying an inert gas and oxygen to the chamber, the ratio of the inert gas to the oxygen supplied to the chamber is not limited. However, when the blackening layer is formed, the number of oxygen molecules (Γ(O ₂ )) incident on the surface to be formed and the number of nickel atoms (Γ(Ni)) deposited on the surface to be formed 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 yttrium (O ₂ )/niobium (Ni) is 2 or more, the blackened layer can be sufficiently blackened, and in particular, the reflectance of the blackened layer of the laminated substrate can be reduced, and the conductive substrate can be used as the conductive substrate. In particular, the visibility of the display screen can be improved.

In addition, when cerium (O ₂ )/germanium (Ni) is 10 or less, it is possible to suppress excessive oxidation of nickel contained in the blackening layer, thereby suppressing the problem that the nickel oxide becomes transparent and the blackening layer transmittance is increased. Therefore, in the laminate substrate in which the blackening layer and the copper layer are laminated, the blackening layer suppresses light reflection on the surface of the copper layer, and the reflectance of the laminated substrate can be lowered. Further, in particular, the etching property of the blackening layer can be improved, and the etching process can be surely performed simultaneously on the copper layer and the blackening layer.

Thus, a black layer deposition, as described _{above, Γ (O 2) / Γ} (Ni) is preferably 2 or more and 10 or less, more preferably 4 or more than 8.

And the incident surface of the O ₂ film formation is not the whole molecule reacts with Ni atoms, forming a portion of the incident surface of the O ₂ molecules react with Ni atoms occurs. Therefore, considering the probability of reaction between the O ₂ molecule and the Ni atom, the relationship between the number of O ₂ molecules (Γ(O ₂ )) incident on the surface to be formed and the number of atoms (Γ(Ni)) deposited on the surface to be formed is considered. Preferably, the formula (2) is satisfied.

The film-forming surface of the blackening layer refers to the outermost surface portion when the blackening layer is formed. When the blackening layer is formed, it means that the blackening layer is formed under the film, that is, the surface of the transparent substrate or The surface of the copper layer. Further, the film formation of the blackening layer means the outermost surface of the blackening layer in the film formation.

The number of O ₂ molecules (O ₂ ) of the film formation surface of the blackening layer in the above formula (2) can be determined according to the following formula (3).

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

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

The number of nickel atoms (Γ(Ni)) deposited on the film-forming surface of the blackening layer in the above formula (1) can be calculated from the mass of nickel deposited in the 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) [个/(m ² s)] (4)

Among them, W: mass of Ni, Na: Yafo 厥 constant, M: atomic amount of Ni, A: film formation area, t: film formation time.

The thickness of the blackening layer is not particularly limited, and is, for example, preferably 15 nm or more, and more preferably 20 nm or more. As described above, the blackening layer is black, and has an effect of suppressing light reflection of the copper layer. However, when the thickness of the blackening layer is thin, sufficient black cannot be obtained, and light reflection of the copper layer may not be sufficiently suppressed. On the other hand, when the thickness of the blackening layer is set to the above range, the reflection of the copper layer can be more reliably suppressed, which is preferable.

The upper limit of the thickness of the blackening layer is not particularly limited. However, if the thickness is increased beyond the necessary thickness, the time required for film formation is prolonged, the time required for etching during wiring formation is prolonged, and the cost is increased. Therefore, the thickness of the blackening layer is preferably 60 nm or less, and more preferably 50 nm or less.

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

As described above, the laminated substrate of the present embodiment includes a transparent substrate, a copper layer, and a blackened layer. Here, the order of lamination when the copper layer and the blackened layer are disposed on the transparent substrate is not particularly limited. In addition, the copper layer and the blackening layer may form a plurality of layers, respectively. Further, in order to suppress light reflection on the surface of the copper layer, it is preferable to dispose a blackening layer on a surface of the surface of the copper layer which is particularly intended to suppress light reflection. In particular, a laminated structure in which a blackened layer is formed on the surface of the copper layer is more preferable, that is, a structure in which a copper layer is sandwiched between the blackened layers is more preferable.

A specific configuration example of the laminated substrate of the present embodiment will be described with reference to FIGS. 1A, 1B, 2A, and 2B. 1A, 1B, 2A, and 2B are cross-sectional views illustrating a laminated substrate of the present embodiment, which is a plane parallel to a lamination direction of a transparent substrate, a copper layer, and a blackened layer.

For example, like the laminated body substrate 10A shown in FIG. 1A, each of the copper layer 12 and the blackening layer 13 may be laminated on the one surface 11a side of the transparent substrate 11. Further, as shown in the laminated substrate 10B shown in FIG. 1B, the copper layers 12A and 12B and the blackening layers 13A and 13B may be sequentially laminated on the one surface 11a side and the other surface (the other surface) 11b side of the transparent substrate 11. Each floor. Here, the order of lamination of the copper layers 12 (12A, 12B) and the blackening layer 13 (13A, 13B) is not limited to the example of FIGS. 1A and 1B, and the blackening layer 13 may be pressed from the side of the transparent substrate 11. The layers (13A, 13B) and the copper layers 12 (12A, 12B) are laminated.

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

In this case, the structure of the copper layer, the first blackening layer, and the second blackening layer in the two regions of the transparent substrate 11 may be employed. Specifically, as shown in FIG. 2B, the first blackening layer 131A, 131B and the copper layer 12A may be sequentially laminated on one surface 11a side and the other surface (other surface) 11b side of the transparent substrate 11 respectively. 12B and second blackening layers 132A and 132B.

1B and 2B show a case where the copper substrate and the blackening layer are formed on the two regions of the transparent substrate, and the transparent substrate 11 is used as a plane of symmetry, and the layers laminated on the lower surface of the transparent substrate 11 are symmetrically arranged. Examples are not limited to this form. For example, in FIG. 2B, the structure of one side of the surface 11a of the transparent substrate 11 can be the same as that of FIG. 1A, and the copper layer 12 and the blackening layer 13 are sequentially laminated to form a layer on the transparent substrate 11. The lower layer becomes an asymmetrical structure.

Thus, the laminated substrate of the present embodiment has been described. In the laminated substrate of the present embodiment, since the copper layer and the blackened layer are provided on the transparent substrate, the copper layer can be suppressed. Reflection of light.

The degree of light reflection of the laminated substrate of the present embodiment is not particularly limited. For example, the average thickness of the reflectance (positive reflectance) of the blackened layer of the multilayered substrate of the present embodiment with respect to light having a wavelength of 400 nm or more and 700 nm or less is preferably 40. %the following. In particular, the average of the reflectance of the blackened layer of the laminated substrate of the present embodiment with respect to light having a wavelength of 400 nm or more and 700 nm or less is more preferably 30% or less, further preferably 20% or less. The reason for the fact that the surface of the blackened layer of the laminated substrate of the present embodiment has an average reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 40% or less, for example, when used as a conductive substrate for a touch panel. It is possible to suppress the visibility of the display screen from being lowered.

By irradiating light to the blackening layer, the reflectance of the blackened layer of the laminated substrate can be measured. That is, it can be measured from the side of the blackening layer among the copper layer and the blackening layer contained in the laminated body substrate.

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

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

Here, the average of the light reflectances means an average value of the measurement results of the reflectance measurement while changing the wavelength in the range of 400 nm or more and 700 nm or less for the same sample. In the measurement, the range in which the wavelength is changed is not particularly limited, and for example, it is preferably In the wavelength range, the wavelength is changed in units of 10 nm and the light is measured. More preferably, the wavelength is changed in units of 1 nm in the above wavelength range, and the light is measured.

As described above, the laminated substrate of the present embodiment may have a structure in which a copper layer and a blackened layer are disposed on a transparent substrate. Further, the copper layer and the blackened layer disposed on the transparent substrate are etched according to the desired wiring pattern to form a metal thin wire, that is, a wiring, and can be used as a conductive substrate.

Therefore, the conductive substrate of the present embodiment can include a transparent substrate and metal thin wires formed on at least one surface side of the transparent substrate. Further, the fine metal wires may be a laminate having a blackened wiring layer and a copper wiring layer, and the blackened wiring layer contains oxygen, copper, and nickel.

Further, the film thickness of the blackened wiring layer can be set to 15 nm or more. Further, the mass ratio O/Ni of the oxygen atom to the nickel atom 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, for example, as a conductive substrate for a touch panel. 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 laminated substrate of the present embodiment described above, a conductive substrate having a mesh 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 FIG. FIG. 3 is a view showing the conductive substrate 30 having a mesh-shaped wiring pattern as viewed from the upper side along the lamination direction of the copper wiring layer and the blackened wiring layer. The conductive substrate 30 shown in FIG. 3 has a transparent substrate 11, a plurality of copper wiring layers 31A parallel to the Y-axis direction in the drawing, and a copper wiring layer 31B parallel to the X-axis direction. Further, the 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 surface and/or the lower surface of the copper wiring layers 31A and 31B. The blackened wiring layer can be formed by etching the blackened layer, and 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. The arrangement structure of the transparent substrate 11 and the copper wiring layer is as shown in, for example, FIGS. 4A and 4B. 4A and 4B are cross-sectional views taken along line A-A' of Fig. 3.

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

Further, as shown in FIG. 4B, a pair of transparent substrates 11 are used, and one of the transparent substrates 11 is interposed therebetween to have copper wiring layers 31A, 31B disposed thereon, and a copper wiring layer 31B can be disposed on the transparent substrate. 11 between. In this case, blackened wiring layers 32A and 32B which are etched into the same shape as the copper wiring layer are also disposed on the upper surfaces of the copper wiring layers 31A and 31B.

Further, the arrangement of the blackened wiring layer and the copper wiring layer is not limited. Therefore, in any of FIGS. 4A and 4B, the arrangement of the blackened wiring layers 32A and 32B and the copper wiring layers 31A and 31B can be reversed. Further, it is also possible to provide, for example, a blackened wiring layer of a plurality of layers.

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

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

The case where the laminated substrate of FIG. 1B is used will be described as an example. First, the copper layer 12A and the blackened layer 13A on the one surface 11a side of the transparent substrate 11 are etched to form the X along 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 the direction perpendicular to the paper surface.

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

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

In addition, in FIG. 4A, when a blackened wiring layer is also disposed between the copper wiring layers 31A and 31B and the transparent substrate 11, the laminated substrate of FIG. 1B can be replaced with the laminated substrate of FIG. In this case, the first blackening layers 131A and 131B including the laminated substrate of FIG. 2B can be etched in the same manner as described above to form a conductive substrate.

A conductive substrate having a grid-like wiring pattern as shown in FIG. 3 can also be formed by using two conductive substrates as shown in FIG. 1A or FIG. 2A. The case where the laminated substrate shown in FIG. 1A is used will be described as an example. The two layers of the laminated substrate shown in FIG. 1A are etched by the copper layer 12 and the blackened layer 13 to form along the Y-axis. A plurality of linear patterns whose directions are apart from each other and are arranged in parallel with the X-axis direction. Then, it will be processed through the above etching process The linear patterns formed on the respective conductive substrates are disposed so as to intersect each other, and two conductive substrates are bonded to each other, whereby a conductive substrate having mesh wiring can be obtained.

The bonding surface when the two conductive substrates are bonded together is not particularly limited. For example, the surface 11b of the transparent substrate 11 which is not laminated with the copper layer 12, that is, the surface 11b of FIG. 1A is bonded to each other, and the same structure as the conductive substrate shown in FIG. 4A can be obtained.

Further, for example, a surface of the etched laminated body substrate having the surface of the copper layer 12 or the like, that is, the surface A in FIG. 1A and the un-laminated copper layer 12 of the other etched laminated substrate may be used. 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 disposed in the surface of the copper layer, and it is particularly necessary to suppress the surface of light reflection.

Therefore, in the conductive substrate shown in FIG. 4B, it is necessary to suppress the position of the blackened wiring layers 32A, 32B and the positions of the copper wiring layers 31A, 31B in the case where it is necessary to suppress the reflection of light from the lower side in the drawing. Configuration. In this case, when the conductive substrate is produced, the laminated substrate substrate in which the copper layer 12 and the blackening layer 13 are arranged upside down in FIG. 1A can be used instead of the laminated substrate 10A shown in FIG. 1A to fabricate the conductive substrate. .

Further, 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 substrate 11. In this case, when the conductive substrate is produced, the laminate substrate 10A shown in FIG. 2A can be used instead of the laminate substrate 10A shown in FIG. 1A to produce a conductive substrate.

Here, the width of the metal thin wires or the distance between the thin metal wires in the conductive substrate having the mesh wiring pattern shown in FIGS. 3 , 4A, and 4B is not particularly limited, and examples thereof are not particularly limited. For example, it can be selected according to the amount of current flowing through the thin metal wires or the like. In consideration of the visibility when the conductive substrate for a touch panel is displayed, the width of the fine metal wires is preferably 20 μm or less.

As described above, the conductive substrate of the present embodiment can be produced by etching the copper layer and the blackened layer of the laminate substrate in accordance with a desired wiring pattern. . Therefore, the copper wiring layer and the blackened wiring layer of the conductive substrate of the present embodiment each have the same characteristics as the copper layer and the blackened layer of the laminated substrate.

Here, for example, the ratio of the 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.

Further, the average of the reflectance 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, still more preferably 20% or less. The reason why the blackened wiring layer of the conductive substrate of the present embodiment has an average reflectance of 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 a touch panel, Extra suppression shows that the visibility of the screen is reduced.

The reflectance refers to the reflectance of the surface on the light incident side of the blackened wiring layer disposed on the outermost surface when the transparent substrate in the conductive substrate is removed. Therefore, the reflectance of the blackened wiring layer of the conductive substrate can be measured by light irradiation of the blackened wiring layer of the fine metal wires remaining after etching the blackened layer or the like of the laminated substrate.

The specific measurement method of the reflectance can be measured in the same manner as the reflectance of the blackened layer of the laminated substrate, and thus the description thereof is omitted.

Further, 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 laminated substrate.

Further, although the example in which the metal thin wires of the straight line shape are combined to form the mesh-shaped wiring pattern is shown in FIG. 3, FIG. 4A and FIG. 4B, the present invention is not limited to this embodiment, and the metal thin wires constituting the wiring pattern may have any shape. For example, the shape of the metal thin wires constituting the mesh-shaped wiring pattern may be various shapes such as a zigzag-shaped curved line (z-shaped straight line) to prevent occurrence of moiré (interference pattern) between the images of the display screen.

The conductive substrate having the mesh-shaped wiring pattern composed of the two-layered metal thin wires described above can be preferably used as a conductive substrate for a touch panel of a projection type electrostatic capacitance type.

(Method for Producing Laminate Substrate, Method for Manufacturing Conductive Substrate)

Hereinafter, a configuration example of a method for producing a laminate substrate and a method for producing a conductive substrate according to the present embodiment will be described.

Here, the above-described laminated substrate can be manufactured by the method for producing a laminated substrate of the present embodiment, and the conductive substrate can be manufactured by the method for producing a conductive substrate of the present embodiment. Therefore, the same configurations as those of the laminated substrate and the conductive substrate described above can be employed except for the following description, and thus some descriptions thereof will be omitted.

The method for producing a laminated substrate of the present embodiment may have a blackening layer forming step of forming a blackened layer by a dry plating method such as a sputtering method. Further, in the blackening layer forming step, when the blackening layer is formed, the number of oxygen molecules (Γ(O ₂ )) incident on the film-forming surface of the blackening layer and the number of copper atoms deposited in the blackening layer (Γ) (Ni)) preferably satisfies the following formula (2).

2≦Γ(O ₂ )/Γ(Ni)≦10 (2)

In the blackening layer forming step, a blackening layer containing oxygen, copper, or nickel may be formed on at least one surface side of the transparent substrate. Further, in the blackening layer forming step, the film forming step of the blackening layer can be performed by, for example, a film forming means for depositing a non-stoichiometric nickel-copper oxide. About the blackening layer formation step The film forming means for depositing the non-stoichiometric nickel-copper alloy oxide 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 blackening layer forming step of the method for producing a laminated substrate of the present embodiment, when a blackening layer is formed by a dry plating method such as a sputtering method, a nickel-copper alloy target can be used in the chamber. Film formation is carried out while providing an inert gas and oxygen. Here, as the inert gas, for example, argon gas can be used.

Further, when the blackening layer is formed by a dry plating method such as sputtering by supplying an inert gas and oxygen to the chamber, the ratio of the inert gas to the oxygen supplied to the chamber is not limited. However, when the blackening layer is formed, the number of oxygen molecules (Γ(O ₂ )) incident on the surface to be formed and the number of nickel atoms (Γ(Ni)) deposited on the surface to be formed preferably satisfy the above formula (2). ).

The reason is that when yttrium (O ₂ )/niobium (Ni) is 2 or more, the blackening layer can be sufficiently blackened, and the reflectance of the blackened layer of the laminated substrate can be particularly lowered, and the conductive substrate can be particularly used as a conductive substrate. Improve the visibility of the display screen.

Further, when yttrium (O ₂ )/niobium (Ni) is 10 or less, it is possible to suppress excessive oxidation of nickel contained in the blackening layer, thereby suppressing the problem that the transmittance of the blackened layer due to the transparency of the nickel oxide is improved. Therefore, in the laminate substrate in which the blackening layer and the copper layer are laminated, the blackening layer can suppress light reflection on the surface of the copper layer and reduce the reflectance of the laminated substrate. Further, in particular, the etching property of the blackening layer can be improved, and the copper layer and the blackening layer can be more reliably etched simultaneously.

Therefore, when the blackening layer is formed, as described above, cerium (O ₂ ) / cerium (Ni) is preferably 2 or more and 10 or less, and more preferably 4 or more and 8 or less.

When the blackening layer is formed by the dry plating method, for example, the roll-to-roll sputtering apparatus 50 shown in Fig. 5 can be used for film formation. Next, use the roll-to-roller sputtering device. As an example, the blackening layer forming step will be explained.

Fig. 5 shows an example of the configuration of the roll-to-roll sputtering apparatus 50. The roll-to-roll sputtering apparatus 50 has a casing 51 capable of accommodating almost all of its constituent members. The shape of the casing 51 in FIG. 5 is shown as a rectangular shape. However, the shape of the casing 51 is not particularly limited, and any shape may be adopted depending on the apparatus, the installation position, the pressure resistance, and the like accommodated therein. For example, the shape of the housing 51 may be a cylindrical shape. However, in order to eliminate residual gas irrespective of film formation at the start of film formation, it is preferable to reduce the pressure inside the casing 51 to 1 Pa or less, more preferably to 10 ^-3 Pa or less, and further preferably to 10 ^-4 Pa or less. . Here, it is not necessary to reduce the pressure inside the casing 51 to the above pressure, and it is possible to reduce the pressure to the pressure in the lower region 51a and the region 51b in the drawing in which the deposition roller 53 described below is disposed, which is used for sputtering.

In the casing 51, a take-up roll 52 for providing a blackened layer film-forming substrate, a film forming roll 53, a sputtering cathode 54a to 54d, a feedforward roller 55a, a feedforward roller 55b, a tension roller 56a, and the like, may be disposed. 56b, take-up roll 57.

Further, on the transport path of the blackened layer film-forming substrate, in addition to the above-described rolls, the guide rolls 58a to 58h, the heater 59, and the like may be arbitrarily provided.

Power can be supplied to the take-up roll 52, the film forming roll 53, the feed roller 55a, and the take-up roll 57 by a servo motor. The take-up roll 52 and the take-up roll 57 can maintain the tension balance of the blackened layer film-forming substrate by the torque control of the powder clutch or the like.

The structure of the film formation roller 53 is not particularly limited. For example, it is preferable that the surface is subjected to hard chrome plating, and a refrigerant or a heat medium from outside the casing 51 is circulated therein to maintain a substantially constant temperature.

For example, the tension rolls 56a, 56b are preferably subjected to hard chrome plating on the surface thereof. And has a tension sensor. Further, it is preferable that the feedforward roller 55a, the feedforward roller 55b, and the guide rollers 58a to 58h are surface-treated with hard chrome plating.

The sputtering cathodes 54a to 54d are preferably of a magnetron cathode type and disposed opposite to the film forming roller 53. The size of the sputtering cathodes 54a to 54d is not particularly limited. However, it is preferable that the thickness 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 blackening layer film-forming substrate.

The substrate for film formation of the blackening layer is conveyed into a roll-to-roll sputtering apparatus 50 as a roll-to-roll vacuum film forming apparatus, and is formed black at the sputtering cathodes 54a to 54d opposite to the film forming roller 53. Layer.

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

First, a vacuum pump 60a, 60b is used in the case 51 in which the nickel-copper alloy target is mounted on the sputtering cathodes 54a to 54d, and the winding roller 52 is provided with a substrate for forming a blackened layer. The vacuum pump 60c may be added as needed to perform vacuum evacuation.

Here, in the process of transporting the substrate from the take-up roll 52 to the take-up roll 57, a layer of a different composition can be continuously formed on the substrate, specifically, for example, a blackened layer and a copper thin film layer. As described above, in the case where the blackening 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 and 54b, and a copper target may be provided on the sputtering cathodes 54c and 54d.

Then, the gas supply unit 61a introduces an inert gas such as argon and oxygen gas as a sputtering gas into the casing 51.

The structure of the gas supply unit 61a is not particularly limited, and may include a gas storage tank (not shown). Moreover, in order to be able to control the amount of supply of each gas into the casing 51, Between the gas storage tank and the casing 51, mass flow controllers (MFC) 611a, 611b, and valves 612a, 612b are provided in accordance with the type of gas. Fig. 5 shows an example in which the mass flow controller and the valve are set in two groups. However, the number of the settings is not particularly limited, and the number of the types can be selected depending on the number of gases used.

When introducing the inert gas and the oxygen into the casing by the gas supply unit 61a, it is preferable to adjust the oxygen partial pressure by the mass flow controllers 611a and 611b so that Γ(O ₂ )/Γ(Ni) satisfies the predetermined range as described above. .

When the gas supply unit 61a supplies the sputtering gas to the inside of the casing 51, it is preferable to adjust the flow rate of the sputtering gas and the opening degree of the pressure regulating valve 62a provided between the vacuum pump 60b and the casing 51 so as to hold the inside of the casing, for example. 0.13 Pa or more and 1.3 Pa or less, and film formation is performed.

In this state, the substrate is transported from the unwinding roller 52 at a speed of, for example, 1 m or more and 20 m or less per minute, and is supplied with electric power from a sputtering DC power source connected to the sputter cathodes 54a to 54d to perform sputtering discharge. Thereby, a desired blackened layer can be continuously formed on the substrate.

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

Further, as described above, in the process of transporting the substrate from the take-up roll 52 to the take-up roll 57, the blackened layer and the copper thin film layer can be continuously formed on the substrate. When the blackening layer and the copper thin film layer are continuously formed on the substrate, it is preferable to adopt a configuration in which the region 51a on the side of the sputtering cathodes 54a and 54b and the region 51b on the side of the sputtering cathodes 54c and 54d are controlled to have different environments. Specifically, for example, it is preferable to control the two regions to have different environments by providing the partition walls 65. In this case, in addition to the gas supply portion 61a, the gas supply portion 61b can be provided. Set gas supply In the case of the portion 61b, the gas supply portion 61b may have the same configuration as the gas supply portion 61a, and may include, for example, a mass flow controller 611c and a valve 612c. Although an example in which one set of mass flow controllers 611c and 612c are provided is shown in Fig. 5, the present invention is not limited to this embodiment, and the number of installations may be selected in accordance with the number of types of gas supplied.

Further, the vacuum pump 60c and the pressure adjusting valve 62b may be provided in advance on the side of the region 51b, and the pressure in the region 51b may be controlled based on the flow rate of the sputtering gas from the gas supply portion 61b and the opening degree of the pressure regulating valve 62b.

When it is not necessary to form a region of a different environment in the casing, it is not necessary to provide the partition wall 65, the gas supply portion 61b, the vacuum pump 60c, and the pressure regulating valve 62b, and the region 51a and the region 51b can be controlled to the same environment.

Further, in the method for producing a laminate substrate of the present embodiment, in addition to the blackening layer forming step, the following steps may be employed.

A transparent substrate preparation step of preparing a 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 method of depositing copper.

As described above, in the laminated substrate of the present embodiment, the order of lamination when the copper layer and the blackened layer are disposed on the transparent substrate is not particularly limited. In addition, the copper layer and the blackening layer may be formed into a plurality of layers, respectively. Therefore, the number of times of implementation of the above-described copper layer forming step and blackening layer forming step is not particularly limited, and can be carried out in any number of times and timing depending on the structure of the laminated body substrate to be formed.

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

Next, the copper layer forming step will be described.

Copper Layer As described above, it is preferable to form a copper layer by dry plating. Further, in order to further thicken the copper layer, it is preferred to use a wet plating method after the dry plating.

Therefore, the copper layer forming step may also have, for example, a step of forming a copper thin film layer by dry plating. Further, the copper layer forming step may have a step of forming a copper thin film layer by dry plating, and a step of forming a copper plating layer by wet plating using the copper thin film layer as a power supply layer.

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

The dry plating method is not particularly limited, and 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, in the copper layer forming step, the film forming means for depositing copper is preferably a sputtering film forming means (sputtering method).

For example, by using the above-described roll-to-roll sputtering apparatus 50, film formation of a copper thin film layer can be preferably performed. The structure of the roll-to-roller sputtering apparatus has been described above, and a detailed description is omitted here.

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

Then, the laminate substrate manufactured by the method for producing a laminate substrate described above is used. Similarly to the laminated substrate described above, the thickness of the copper layer is preferably 80 nm or more, more preferably 100 nm or more, 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 3,000 nm or less, still more preferably 1200 nm or less.

In addition, the thickness of the blackened layer in the laminated substrate obtained by the method for producing a laminated substrate described above is not particularly limited, and is preferably 15 nm or more, and more preferably 20 nm or more. The upper limit of the thickness of the blackened layer is not particularly limited, but is preferably 60 nm or less, and more preferably 50 nm or less.

In addition, the average of the reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 40% or less, and more preferably 30% or less, of the laminate substrate obtained by the method for producing a laminated substrate described above. It is especially preferably 20% or less.

Further, a conductive substrate having metal thin wires can be produced by using the laminated body substrate obtained by the method for producing a laminated substrate described above. When the laminate substrate obtained by the method for producing a laminate substrate of the present embodiment is used to etch the copper layer and the blackened layer to form a conductive substrate, in addition to the above steps, the copper layer and the black layer may be provided. The wiring layer processing step of wiring processing. In other words, the method for producing a conductive substrate of the present embodiment may include a wiring processing step of performing wiring processing on the laminated body substrate obtained by the method for producing a laminated substrate of the present embodiment.

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

When a conductive substrate is produced using the laminated body substrate shown in FIG. 1A, A protective layer is formed on the exposed surface A of the blackened layer 13 disposed in the laminated substrate. Here, the method for forming the protective layer is not particularly limited, and for example, it may be formed by a photolithography method, and the protective layer has an opening corresponding to a portion to be removed by etching.

Next, etching of the copper layer 12 and the blackening layer 13 can be performed by supplying an etching liquid from the upper surface of the protective layer.

Here, as shown in FIG. 1B, when a copper layer or a blackened layer is disposed on both surfaces of the transparent substrate 11, protection of an opening having a predetermined shape can be formed on the surface A and the surface B of the laminated substrate, respectively. The layer and the copper layer and the blackened layer formed on both surfaces of the transparent substrate 11 are simultaneously etched.

Further, the copper layer and the blackened layer formed on both surfaces of the transparent substrate 11 may be subjected to etching treatment on each side. That is, for example, the copper layer 12A and the blackened layer 13A may be etched, and then the copper layer 12B and the blackened layer 13B may be etched.

The blackening layer contained in the laminated substrate of the present embodiment shows the same etching liquid reactivity as the copper layer. Therefore, the etching liquid used in the wiring processing step is not particularly limited, and a general copper layer etching can be preferably used. The etching solution used. As the etching liquid, for example, a mixed aqueous solution of ferric chloride and hydrochloric acid can be preferably used. The content of the ferric chloride and the hydrochloric acid in the etching solution is not particularly limited. For example, the content ratio of the ferric chloride is preferably 5% by weight or more and 50% by weight or less, and more preferably 10% by weight or more and 30% by weight or less. . Further, the content ratio of hydrochloric acid in the etching liquid 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 portion may be water.

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

The metal thin wires obtained by the above-described wiring processing step may have, for example, a grid-like wiring pattern, and the specific form thereof has been described above, and a detailed description thereof is omitted here.

In addition, the laminate substrate having the copper layer and the blackening layer on one surface side of the transparent substrate 11 shown in FIG. 1A or FIG. 2A is etched by a wiring processing step, and the obtained two conductive substrates are pasted. In combination, a conductive substrate having a grid-like wiring pattern is formed. In this case, it is also possible to have a step of bonding the conductive substrate.

In the step of bonding the conductive substrate, the method of bonding the two conductive substrates is not particularly limited, and for example, bonding can be performed using a binder or the like.

The method for producing the laminated substrate of the present embodiment and the method for producing the conductive substrate have been described above.

In the laminated body substrate obtained by the method for producing a laminated substrate, the copper layer and the blackened layer have almost the same reactivity with respect to the etching liquid. Therefore, the copper layer and the blackened layer can be simultaneously etched, and the desired layer can be easily formed. Fine metal wire.

In addition, in the case where the blackening layer containing oxygen, copper, and nickel and the film thickness and the mass ratio of the oxygen atom to the nickel atom in the blackening layer is within a predetermined range is black, the blackened wiring layer is formed by etching. It is possible to suppress 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 deterioration in visibility.

[Examples]

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

(evaluation method)

(1) Reflectance

The reflectance of the laminated substrate produced in each of the following Examples and Comparative Examples was measured.

The reflectance measuring unit was set in an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV-2550) for measurement.

In each of the examples and comparative examples, a laminate substrate having the structure shown in FIG. 2A was produced and passed through the exposed surface A of the second blackening layer 132 in FIG. 2A at an incident angle of 5° and a light receiving angle. The light having a wavelength in the range of 400 nm or more and 700 nm or less was irradiated at 5°, and the reflectance was measured. Here, the wavelength of the light irradiated onto the laminated substrate is measured while being changed in the range of 400 nm or more and 700 nm or less in units of 1 nm, and the average of the measurement results is used as the average of the reflectances of the laminated substrate.

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

The ratio of oxygen, nickel, and copper atoms in the second blackening layer was measured using XPS (manufactured by ULVAC PHI Co., Ltd.: Versa Probe II) on the laminated substrate produced in the following Examples and Comparative Examples.

(3) Etchability

The laminate substrate produced in the following Examples and Comparative Examples was immersed in an etching solution of 10% by weight of ferric chloride and 10% by weight of hydrochloric acid, and the remainder was water, and the etching property was evaluated. The laminate substrate having no residue remaining on the transparent substrate was judged to have good etching properties.

(production conditions of the sample)

The production conditions of the laminate substrate in each of the examples and the comparative examples are shown below.

[Example 1]

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

First, a transparent substrate of polyethylene terephthalate resin (PET) having a width of 500 mm and a thickness of 100 μm was placed in the roll-to-roll sputtering apparatus 50 shown in Fig. 5 . And, splashing The plating cathodes 54a and 54b are provided with a Ni-40 mass% Cu target for film formation of a blackened layer, and a copper target for copper film formation is provided on the sputtering cathodes 54c and 54d.

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

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

Similarly, argon gas was introduced into the region 51b on the side of the sputtering cathodes 54c and 54d in the casing 51 by the gas supply portion 61b at 400 sccm. Further, the opening degree of the pressure regulating valve 62b provided between the gas supply portion 61b and the vacuum pump 60c and the casing 51 is adjusted so that the pressure in the region 51ba becomes 0.4 Pa.

Then, the transparent substrate is transported by the take-up roll 52 at a speed of 2 m per minute, while power is supplied from a DC power source for sputtering connected to the sputter cathodes 54a to 54d, and sputtering discharge is performed to continuously form a black film on the substrate. Layer and copper layer. Through this operation, the first blackening layer 131 having a thickness of 20 nm and the copper layer having a thickness of 100 nm were formed on the transparent substrate.

Next, the roll-to-roll sputtering apparatus 50 is transported in the reverse direction, and the base material in which the first blackening layer and the copper layer are laminated on the transparent substrate is conveyed from the take-up roll 57 to the take-up roll 52. Further, under the same conditions as above, a copper layer having a thickness of 100 nm and a second blackening layer 132 having a thickness of 20 nm were formed.

The film was formed twice as described above, and the copper layer was a layer having a total thickness of 200 nm.

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

When the reflectance of the second blackening layer of the laminated substrate is measured, the exposed surface A of the second blackening layer 132, that is, the second blackening layer 132 is not opposed to the copper layer 12. The surface was irradiated with light, and the average of the reflectances of light having a wavelength of 400 nm or more and 700 nm or less was measured. As a result, the average reflectance of the second blackened layer of the laminated substrate produced was 25%.

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

[Example 2 to Example 7]

In the examples 2 to 4, the content of nickel (or copper) in the target for film formation of the blackened layer (O ₂ )/Γ (Ni) and the film for forming the blackened layer is used as the first and second blackened layers. The laminate and the ratio shown in Table 1 were prepared in the same manner as in Example 1 and evaluated.

In the fifth to seventh embodiments, the content of nickel (O ₂ )/Γ (Ni) in the film formation of the first and second blackening layers and the target for film formation of the blackened layer is used. The film thickness of the first and second blackening layers was set to 30 nm, and the laminate substrate was produced under the same conditions as in Example 1 and evaluated.

Here, in order to form the first blackening layer and the second blackening layer, the Γ(O ₂ )/Γ(Ni) has a predetermined ratio shown in Table 1, and the roll-to-roll sputtering apparatus 50 is also changed. The gas supply portion 61a supplies the oxygen supply amount to the region 51a where the blackening layer is formed. Therefore, the O ₂ partial pressure at the time of film formation of the blackened layer also changes.

The evaluation results are shown in Table 1.

[Comparative Example 1 to Comparative Example 4]

In Comparative Example 1 to Comparative Example 3, the enthalpy (O ₂ )/Γ (Ni) was changed in the film formation of the first and second blackening layers, and the laminate substrate was produced under the same conditions as in Example 1 and was carried out. Evaluation.

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

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

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

The evaluation results are shown in Table 1.

【Table 1】

According to the results shown in Table 1, the film thickness of the blackening layer is 15 nm or more, and the mass ratio O/Ni of the oxygen atom to the nickel atom in the blackening layer is 0.1 or more and 0.8 or less, and Examples 1 to 7 are The evaluation of the etching property was good. Further, the reflectance of the blackened layer was 40% or less, and it was confirmed that the blackened layer which suppresses light reflection on the surface of the copper layer has a sufficient function. Therefore, it was confirmed that a laminate substrate having a copper layer and a blackening layer which can be simultaneously subjected to etching treatment was obtained.

On the other hand, in Comparative Examples 1 and 2 in which the mass ratio of oxygen atoms to nickel atoms contained in the blackening layer is less than 0.1, the reflectance of the blackening layer exceeds 40%, and it is confirmed that light reflection as a surface of the copper layer is suppressed. The blackening layer has insufficient functions.

In addition, in Comparative Example 3 in which the mass ratio O/Ni of the oxygen atom to the nickel atom contained in the blackening layer exceeded 0.8, the etching property was evaluated, and it was confirmed that the residue was present. In other words, it was confirmed that it was not possible to use a laminate substrate having a copper layer and a blackening layer which can be simultaneously subjected to etching treatment.

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

In the above, the method of manufacturing the laminated substrate, the laminated substrate, the conductive substrate, and the method for producing the conductive substrate will be described with reference to the embodiments and the examples. However, the present invention is not limited to the above-described embodiments and examples. Various modifications and changes can be made without departing from the spirit and scope of the invention.

The present application claims priority to Japanese Patent Application No. 2015-204642, filed on Jan.

10A‧‧‧Laminated substrate

11‧‧‧Transparent substrate

11a‧‧‧One side

11b‧‧‧ another side

12‧‧‧ copper layer

13‧‧‧Blackening layer

A‧‧‧ surface

X, Y‧‧‧X-axis, Y-axis

Claims (9)

A laminated body substrate comprising: a transparent substrate; and a laminate formed on at least one surface side of the transparent substrate; the laminate having a blackened layer containing oxygen, copper, nickel, and a copper layer; The film thickness of the blackening layer is 15 nm or more, and the mass ratio O/Ni of the oxygen atom to the nickel atom contained in the blackening layer satisfies the following formula (1), 0.1 ≦O/Ni ≦ 0.8 (1). The laminate substrate according to the first aspect of the invention, wherein a ratio of copper in the blackening layer to a total of copper and nickel in the blackening layer is 20% or more and 80% or less by mass. The laminate substrate according to claim 1 or 2, wherein the copper layer has a thickness of 80 nm or more and 5000 nm or less. The laminate substrate according to any one of claims 1 to 3, wherein the blackening layer has an average reflectance of 40% or less for light having a wavelength of 400 nm or more and 700 nm or less. A method for producing a laminated substrate, which is a method for producing a laminated substrate according to any one of claims 1 to 4, which has a blackening of the blackened layer by a dry plating method. a layer forming step of forming a blackening layer, a number of oxygen molecules (Γ(O ₂ )) incident on a film formation surface of the blackening layer, and depositing on the blackening layer in the blackening layer forming step The number of copper 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 metal thin wire formed on at least one surface side of the transparent substrate; the metal thin wire is a laminated body having a blackened wiring layer and a copper wiring layer; the blackened wiring layer contains oxygen, copper, nickel, The film thickness of the blackened wiring layer is 15 nm or more, and the mass ratio O/Ni of the oxygen atom to the nickel atom contained in the blackened wiring layer satisfies the following formula (1) and 0.1 ≦O/Ni ≦ 0.8 (1). The conductive substrate of the sixth aspect of the invention, wherein a ratio of copper in the blackened wiring layer to a total of copper and nickel in the blackened wiring layer is 20% or more and 80% or less by mass. The conductive substrate according to claim 6 or 7, wherein the blackened wiring layer has an average reflectance of light of 40% or more and 700 nm or less of 40% or less. A method for producing a conductive substrate, comprising: a wiring processing step of performing wiring processing on a laminate substrate obtained by the method for producing a laminate substrate according to claim 5 of the patent application.