JP6417964B2 - LAMINATED BOARD, WIRING BOARD AND METHOD FOR PRODUCING THEM - Google Patents

Description

  The present invention relates to a wiring board and a method for manufacturing the wiring board.

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

  By the way, in recent years, the display screen including a touch panel has been increased in screen size, and in response to this, a wiring board such as a transparent conductive film for a touch panel is required to have a large area. However, since ITO has a high electric resistance value, there is a problem that it cannot cope with an increase in the area of the wiring board.

  For this reason, for example, as disclosed in Patent Documents 2 and 3, it is considered to use a wiring board provided with a wiring pattern of a fine metal wire (metal film) having a mesh structure such as copper instead of an ITO film. . However, for example, when copper is used for the wiring layer, since copper has a metallic luster, there is a problem that the visibility of the display decreases due to reflection.

  Therefore, when the transparent conductive film is compared with a metal thin wire (metal film), the transparent conductive film has an advantage that the circuit pattern such as an electrode is hardly visually recognized because it is excellent in transparency in the visible wavelength region. Since the electric resistance value is higher than that of the (metal film), there is a disadvantage that is not suitable for increasing the size of the touch panel and increasing the response speed. On the other hand, thin metal wires (metal films) are suitable for increasing the size of touch panels and increasing the response speed due to their low electrical resistance, but they have high reflectivity in the visible wavelength region, so they are processed into a fine mesh structure. Even if it is done, a circuit pattern may be visually recognized under high-intensity illumination, and it has the fault of reducing a product value.

  Therefore, blackening made of metal oxide or metal nitride between the transparent substrate made of resin film and the metal fine wire (metal film) in order to take advantage of the characteristics of the above-mentioned metal fine wire (metal film) with low electrical resistance. There has been proposed a method of reducing reflection of a fine metal wire (metal film) observed from the transparent substrate side with a layer interposed (see Patent Documents 4 and 5).

  In general, in order to obtain a wiring substrate having a wiring pattern, an etching is performed on a multilayer substrate including a multilayer film in which a wiring layer and a blackening layer are formed on at least one surface of a transparent substrate. Thus, a desired pattern is formed.

JP 2003-151358 A JP 2011-018194 A JP 2013-0669261 A JP 2014-142462 A JP 2013-225276 A

  In order to obtain a wiring substrate for use in a touch panel, a desired pattern is formed by etching a multilayer substrate including a multilayer film in which a wiring layer and a blackening layer formed on at least one surface of a transparent substrate are laminated. There is a need. However, there is a problem that the reactivity to the etching solution is different between the wiring layer and the blackened layer. That is, if the wiring layer and the blackened layer are simultaneously etched, there is a problem that any one of the layers cannot be etched into a target shape. In addition, when the wiring layer etching and the blackening layer etching are performed in separate steps, there is a problem that the number of steps increases.

  SUMMARY OF THE INVENTION In view of the above-described problems of the prior art, an object of the present invention is to provide a laminate substrate and a wiring substrate having a copper layer and a blackening layer that can be simultaneously etched, and a method for manufacturing them.

  The inventors of the present application, when the (111) orientation degree index of the crystal is 1.2 or more in the copper layer on the blackened layer side, is generated when trying to simultaneously etch the wiring layer and the blackened layer. The inventors have found that the problem that any of the layers cannot be etched into a desired shape can be suppressed, and have arrived at the present invention. That is, the inventors of the present application can slow the etching rate of the copper layer on the blackened layer side by setting the (111) orientation degree index of the crystal to 1.2 or more in the copper layer on the blackened layer side. It was found that side etching of the copper layer can be suppressed, and the occurrence of problems such as peeling of the blackened layer can be suppressed.

A first aspect of the present invention includes a transparent substrate and a conductive laminate provided on at least one surface of the transparent substrate, and the laminate is laminated on the surface of the copper layer and the copper layer. The surface blackening layer is the most surface, the copper layer has a laminated structure, and the (111) orientation degree index of the crystal of the copper layer on the transparent substrate side is less than 1, and the surface blackening The laminated substrate is characterized in that the (111) orientation degree index of the copper layer crystal on the conversion layer side is 1.2 or more and the thickness of the surface blackening layer is 10 nm or more and 100 nm or less .

According to a second aspect of the present invention, the copper layer in the first aspect is a first copper film as a dry plating layer, and a second copper film as a copper electroplating layer by PR current using the first copper film as a feeding layer. It is a laminated substrate characterized by including these.

A third aspect of the present invention, the thickness of the second copper layer in the second invention, a laminate substrate, characterized in that at 100nm or more.

The fourth invention of the present invention is the first blackened layer formed on the surface of the transparent substrate, and the copper formed on the surface of the first blackened layer in the first to third inventions. It is a laminated substrate characterized by having a laminated structure comprising a layer and the surface blackening layer formed on the surface of the copper layer .

In a fifth aspect of the present invention, the first blackening layer and the surface blackening layer in the fourth invention are selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Ni, and Cu. It is a laminate substrate characterized by being a nitride or oxide containing one or more kinds of metals .

According to a sixth aspect of the present invention , there is provided a laminate substrate according to any one of the first to fifth aspects , wherein the thickness of the copper layer is 100 nm or more and the thickness of the surface blackening layer is 20 nm or more. is there.

7th invention of this invention is a manufacturing method of the laminated body board in 1st-6th invention , and includes the process of forming into a film by the electroplating method by PR electric current the copper layer in the said surface blackening layer side Is a method for manufacturing a laminated substrate.

8th invention of this invention is a manufacturing method of the laminated body board in 1st-6th invention, and forms all or one part of the copper layer in the said transparent substrate side among the said copper layers by the dry-type plating method And a step of forming the copper layer on the surface blackening layer side by electroplating using a PR current after the step (a) and the step (a). is there.

According to a ninth aspect of the present invention, there is provided a transparent substrate and a wiring having a laminated structure provided on at least one surface of the transparent substrate, wherein the wiring is laminated on the surface of the copper layer and the copper layer. The surface blackening layer is on the most surface, the copper layer has a laminated structure, and the (111) orientation degree index of the crystal of the copper layer on the transparent substrate side is less than 1, The wiring substrate is characterized in that the (111) orientation index of the copper layer crystal on the surface blackening layer side is 1.2 or more and the thickness of the blackening layer is 10 nm or more and 100 nm or less .

According to a tenth aspect of the present invention, the copper layer in the ninth aspect comprises a first copper film as a dry plating layer and a second copper film as a copper electroplating layer by PR current using the first copper film as a power feeding layer. The wiring board characterized by including .

Eleventh aspect of the present invention, the thickness of the second copper film in the invention of the ninth through 10, a wiring substrate characterized in that at 100nm or more.

In a twelfth aspect of the present invention, the laminate according to the ninth to eleventh aspects is formed on the surface of the first blackened layer and the first blackened layer formed on the surface of the transparent substrate. A wiring board having a laminated structure comprising a copper layer and the surface blackening layer formed on the surface of the copper layer .

In a thirteenth aspect of the present invention, the first blackening layer and the surface blackening layer in the twelfth aspect are selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Ni, and Cu. A wiring board characterized by being a nitride or oxide containing one or more metals .

A fourteenth aspect of the present invention is a wiring board characterized in that in the ninth to thirteenth aspects, the thickness of the copper layer is 100 nm or more, and the thickness of the surface blackening layer is 10 nm or more. is there.

According to a fifteenth aspect of the present invention, there is provided a method for manufacturing a wiring board, comprising processing the laminated substrate according to the first to sixth aspects into a wiring by etching.

  According to the present invention, since the side etching of the copper layer provided under the blackened layer can be suppressed, peeling of the blackened layer can be prevented. Further, according to the present invention, it is possible to suppress the occurrence of a problem that any layer cannot be etched into a target shape, which occurs when the wiring layer and the blackening layer are simultaneously etched. And the blackened layer can be etched simultaneously. Further, it is not necessary to perform the etching of the wiring layer and the etching of the blackened layer in separate steps, and the number of steps can be reduced and the cost can be reduced.

It is sectional drawing of the wiring board which concerns on embodiment of this invention, (a) is an example which provided the copper layer and the surface blackening layer on the single side | surface of a transparent substrate, (b) is a copper layer and surface on both surfaces of a transparent substrate. This is an example in which a blackening layer is provided. It is sectional drawing of the wiring board which concerns on embodiment of this invention, (a) is an example which provided the 1st blackening layer, the copper layer, and the surface blackening layer in the single side | surface of a transparent substrate, (b) is a transparent substrate This is an example in which a first blackening layer, a copper layer, and a surface blackening layer are provided on both sides. It is a top view of the wiring board provided with the mesh-shaped wiring which concerns on embodiment of this invention. (A) is sectional drawing in the AA 'line of FIG. 3, is an example which provided the copper layer and the surface blackening layer on both surfaces of the transparent substrate, (b) is between a pair of transparent substrates, It is another example which provided the copper layer and the surface blackening layer in each surface where two transparent substrates oppose. It is explanatory drawing of one structural example of the roll-to-roll sputtering apparatus which concerns on this invention. It is explanatory drawing of one structural example of the roll-to-roll plating apparatus which concerns on this invention. It is the figure which showed typically the time and current density of PR current in this invention.

  Hereinafter, an embodiment of a wiring board and a manufacturing method of the wiring board according to the present invention will be described.

(Wiring board)
The wiring board of the present embodiment includes a transparent substrate and a wiring having a laminated structure provided on at least one surface of the transparent substrate, and the wiring is a surface blackening layer laminated on the surface of the copper layer and the copper layer, The surface blackening layer is arranged on the surface most. And the wiring board which concerns on this invention processes a laminated body board | substrate which concerns on this invention into wiring by processes, such as an etching.

  The laminate substrate according to the present invention is a surface blackening layer in which at least one surface of a transparent substrate is covered with a laminate, and the laminate is laminated on the surface of a copper layer and a copper layer. Is arranged on the most surface. A blackened layer may be provided between the transparent substrate and the copper layer.

  First, each member included in the wiring board of the present embodiment will be described below.

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

  As the insulator film that transmits visible light, for example, a polyamide film, a polyethylene terephthalate film, a polyethylene naphthalate film, a resin film such as a cycloolefin film, and the like can be preferably used.

  The thickness of the transparent substrate is not particularly limited, and can be arbitrarily selected according to the strength required for the wiring substrate, the light transmittance, and the like. The thickness of the transparent substrate can be, for example, 20 μm or more and 200 μm or less. In particular, when used for touch panel applications, it is preferably 40 μm or more and 120 μm or less.

  The wiring is a surface blackening layer laminated on the surface of the copper layer and the copper layer, and the surface blackening layer is arranged on the surface most.

  Although it does not specifically limit also about a copper layer, In order not to reduce the light transmittance, it is preferable not to arrange | position an adhesive agent between a copper layer and a transparent substrate or between a copper layer and a surface blackening layer. That is, the copper layer is preferably formed directly on the upper surface of another member.

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

  Moreover, when making a copper layer thicker, it is preferable to use a wet-plating method after dry-type plating. That is, for example, a copper thin film layer is formed by a dry plating method on a transparent substrate or a blackening layer provided as necessary, and a copper plating layer is formed by a wet plating method using the copper thin film layer as a power feeding layer. Can do.

  Directly without an adhesive on a transparent substrate or a blackened layer provided as necessary by forming a copper layer by dry plating alone or in combination with dry plating and wet plating as described above It is preferable because a copper layer can be formed.

The 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, the thickness of the copper layer can be, for example, 100 nm so that sufficient current can be supplied, and the thickness is preferably 110 nm or more, and more preferably 150 nm or more.
The upper limit value of the thickness of the copper layer is not particularly limited. However, when the copper layer is thick, side etching occurs because etching takes time when performing etching to form a wiring, and the resist peels off during the etching. Etc. are likely to occur. For this reason, it is preferable that the thickness of a copper layer is 3000 nm or less, and it is more preferable that it is 1200 nm or less. In addition, when a copper layer has a copper thin film layer and a copper plating layer as mentioned above, it is preferable that the sum total of the thickness of a copper thin film layer and the thickness of a copper plating layer is the said range.

The copper layer on the surface blackening layer side has a (111) plane orientation degree index of 1.2 or more, and the transparent substrate side copper layer has a (111) plane orientation degree index of less than 1, thereby providing a laminate substrate. The surface blackening layer can be prevented from being peeled off by side etching when wiring is processed on the wiring board. The thickness of the copper layer on the surface blackening layer side having an orientation degree index of (111) plane of 1.2 or more is preferably 100 nm or more and 1500 nm or less, and on the transparent substrate side having an orientation degree index of (111) plane of less than 1. The thickness of the copper layer is preferably 100 nm or more and 1500 nm or less.
Further, the (111) orientation degree index of the crystal of the copper layer on the transparent substrate side may be less than 1.

Next, the surface blackening layer will be described.
Since the copper layer has a metallic luster, the copper reflects light as described above only by forming the wiring obtained by etching the copper layer on the transparent substrate. For example, when used as a wiring substrate for a touch panel, the visibility of the display There was a problem that decreased. Thus, methods for providing a surface blackening layer have been studied.

  In the wiring board of this embodiment, the surface blackening layer is made of a nitride or oxide of one or more metals selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Ni, and Cu. is there. By appropriately selecting the degree of oxidation of the metal or oxide of the surface blackening layer 13 and the degree of nitridation of the nitride, etching can be performed using the same etching solution as that for the copper layer. For this reason, a copper layer and a surface blackening layer can be etched simultaneously.

  The method for forming the surface blackening layer is not particularly limited, and the film can be formed by any method. However, since the surface blackening layer can be formed relatively easily, it is preferable to form the film by sputtering.

  The surface blackening layer can be formed by sputtering using a metal sputtering target for forming the blackening layer and supplying nitrogen gas or oxygen gas in addition to argon gas into the chamber. In particular, it is preferable to adjust the partial pressure of nitrogen and oxygen by simultaneously supplying argon gas and nitrogen gas into the chamber so that the amount of nitrogen and oxygen supplied to the blackening layer can be adjusted.

  Although the thickness of a surface blackening layer is not specifically limited, For example, it is preferable that it is 10 nm or more, and it is more preferable that it is 30 nm or more. The surface blackening layer is black as described above and functions as a blackening layer that suppresses reflection of light by the copper layer. However, when the surface blackening layer is thin, sufficient blackness is In some cases, reflection of light by the copper layer cannot be sufficiently suppressed. On the other hand, it is preferable to make the thickness of the surface blackened layer in the above range because the reflection of the copper layer can be more reliably suppressed.

  The upper limit value of the thickness of the surface blackening layer is not particularly limited, but even if it is thicker than necessary, the time required for film formation and the time required for etching when forming the wiring are increased, resulting in an increase in cost. It will cause a rise. For this reason, the thickness of the surface blackening layer is preferably 100 nm or less, and more preferably 60 nm or less.

Next, a configuration example of the wiring board of this embodiment will be described.
As described above, the wiring board of this embodiment includes a transparent substrate, a copper layer, and a surface blackening layer. A plurality of copper layers and surface blackening layers can be formed. In order to suppress the reflection of light on the surface of the copper layer, a blackening layer is disposed on the surface of the copper layer on which the reflection of light is particularly desired to be suppressed. In particular, it has a laminated structure in which the blackened layer is formed on the surface of the copper layer. That is, it is more preferable that the copper layer has a structure sandwiched between the transparent substrate and the surface blackening layer.

  A specific configuration example will be described below with reference to FIGS. 1 and 2 show examples of cross-sectional views of the wiring board of the present embodiment on a plane parallel to the lamination direction of the transparent substrate 11, the copper layer 12, and the surface blackening layer 13.

  For example, like the wiring board 10A shown in FIG. 1A, the copper layer 12 and the surface blackening layer 13 can be laminated one by one on the one surface 11a side of the transparent substrate 11. Moreover, like the wiring board 10B shown in FIG.1 (b), copper layer 12A, 12B on the one surface 11a side of the transparent substrate 11, and the other surface (other surface) 11b side, respectively, The surface blackening layers 13A and 13B can be stacked one by one in that order.

  Further, for example, a configuration in which a plurality of blackening layers are provided on one surface side of the transparent substrate 11 may be employed. For example, like the wiring board 20A shown in FIG. 2A, the first blackened layer 131, the copper layer 12, and the surface blackened layer 132 are arranged in this order on one surface 11a side of the transparent substrate 11. Can be stacked.

  In this case as well, a configuration in which a copper layer, a first blackening layer, and a surface blackening layer are laminated on both surfaces of the transparent substrate 11 can be adopted. Specifically, like the wiring board 20B shown in FIG. 2B, the first blackening layer is formed on one surface 11a side of the transparent substrate 11 and on the other surface (the other surface) 11b side, respectively. 131A, 131B, copper layers 12A, 12B, and surface blackening layers 132A, 132B can be laminated in that order.

  In FIGS. 1B and 2B, when a copper layer and a surface blackening layer are laminated on both surfaces of the transparent substrate 11, the transparent substrate 11 is laminated on the upper and lower sides of the transparent substrate 11 with the symmetry surface as a symmetry plane. Although the example which arrange | positioned so that the layer which became symmetrical may be shown, it is not limited to the form which concerns. For example, in FIG. 2B, the configuration on the one surface 11a side of the transparent substrate 11 is a form in which a copper layer and a blackened layer are laminated in that order in the same manner as the configuration of FIG. The layers stacked above and below 11 may be asymmetrical.

  The wiring board of this embodiment has been described so far. However, in the wiring board of this embodiment, a copper layer and a surface blackening layer functioning as a blackening layer are provided on a transparent substrate. The reflection of light by the layer can be suppressed.

The degree of light reflection of the wiring board of this embodiment is not particularly limited. For example, in the wiring board of this embodiment, the average reflectance of light having a wavelength of 400 nm to 700 nm is 55% or less. It is preferably 40% or less. The average reflectance of light having a wavelength of 400 nm to 700 nm is more preferably 30% or less, and particularly preferably 20% or less.
This is because, when the average reflectance of light having a wavelength of 400 nm or more and 700 nm or less is 55% or less, for example, when it is used as a wiring board for a touch panel, a decrease in display visibility can be particularly suppressed.

  The reflectance can be measured by irradiating the blackened layer with light. That is, measurement can be performed from the surface blackened layer side of the copper layer and the surface blackened layer included in the wiring board.

  Specifically, for example, as shown in FIG. 1A, when the copper layer 12 and the surface blackening layer 13 are laminated in this order on one surface 11a of the transparent substrate 11, the surface blackening layer 13 can be irradiated with light. It can be measured from the surface side indicated by A in the figure.

  Further, the arrangement of the copper layer 12 and the surface blackening layer 13 is changed from that in the case of FIG. 1A, and the surface blackening layer 13 and the copper layer 12 are laminated in this order on one surface 11 a of the transparent substrate 11. The reflectance can be measured from the surface 11b side of the transparent substrate 11 so that the blackened layer 13 can be irradiated with light.

  As will be described later, the wiring substrate can be formed by etching the copper layer and the surface blackening layer of the multilayer substrate. However, the above-mentioned reflectance is on the outermost surface when the transparent substrate is excluded from the wiring substrate. The reflectance of the surface of the blackening layer disposed on the light incident side is shown. For this reason, if it is before an etching process or after performing an etching process, it is preferable that the measured value in the part in which the copper layer and the blackening layer remain satisfy | fills the said range.

  In addition, the average of the reflectance of light means the average value of the measurement result at the time of measuring by changing a wavelength within the range of 400 nm or more and 700 nm or less. In the measurement, the width for changing the wavelength is not particularly limited. For example, it is preferable to measure the light in the wavelength range by changing the wavelength every 10 nm, and changing the wavelength every 1 nm to change the wavelength in the wavelength range. More preferably, the measurement is performed on light.

  The wiring board of this embodiment can be preferably used as a wiring board for touch panels, for example, as described above. In this case, the wiring board can be configured to include mesh-like wiring.

  The wiring board provided with the mesh-like wiring can be obtained by etching the copper layer and the surface blackening layer of the wiring board of the present embodiment described so far.

  For example, a two-layer wiring can be used as a mesh wiring. A specific configuration example is shown in FIG. FIG. 3 shows a view of the wiring board 30 provided with mesh-like wiring as viewed from the upper surface side in the stacking direction of the copper layer and the surface blackening layer. The wiring board 30 shown in FIG. 3 has a transparent substrate 11, a plurality of wirings 31A parallel to the X-axis direction in the drawing, and wirings 31B parallel to the Y-axis direction. The wirings 31A and 31B are formed by etching a copper layer, and a surface blackening layer (not shown) is formed on the upper surface and / or the lower surface of the wirings 31A and 31B. The surface blackening layer is etched in the same shape as the wirings 31A and 31B.

  The arrangement of the transparent substrate 11 and the wirings 31A and 31B is not particularly limited. 4A and 4B show a configuration example of the arrangement of the transparent substrate 11 and the wirings 31A and 31B. FIG. 4A corresponds to a cross-sectional view taken along the line AA ′ of FIG.

  First, as illustrated in FIG. 4A, wirings 31 </ b> A and 31 </ b> B may be disposed on the upper and lower surfaces of the transparent substrate 11, respectively. In this case, surface blackening layers 32A and 32B etched in the same shape as the wiring are arranged on the upper surfaces of the wirings 31A and 31B.

  Further, as shown in FIG. 4B, a pair of transparent substrates 11 may be used, and wirings 31 </ b> A and 31 </ b> B may be arranged on the surface of each transparent substrate 11 between the pair of transparent substrates 11. . Also in this case, surface blackening layers 32A and 32B etched in the same shape as the wiring are arranged on the upper surfaces of the wirings 31A and 31B.

  However, the surface blackening layers 32 </ b> A and 32 </ b> B are preferably arranged on the surface of the copper layer surface where light reflection is particularly desired to be suppressed. For this reason, in the wiring board shown in FIG. 4B, for example, when it is necessary to suppress reflection of light from the lower surface side in the figure, the position of the surface blackening layer 32B and the position of the wiring 31B are set. The reverse is preferred. Further, in addition to the surface blackening layer 32B, a first blackening layer may be further provided between the wiring 31B and the transparent substrate 11.

  The wiring board having the mesh-like wirings 31A and 31B shown in FIGS. 3 and 4A is, for example, copper layers 12A and 12B on both surfaces of the transparent substrate 11 as shown in FIGS. 1B and 2B. And a wiring board provided with surface blackening layers 13A and 13B (copper layers 131A and 132A and surface blackening layers 131B and 132B in FIG. 2B).

  The case where it is formed using the wiring substrate of FIG. 1B will be described as an example. First, the copper layer 12A and the surface blackening layer 13A on the one surface 11a side of the transparent substrate 11 are shown as X in FIG. Etching is performed so that a plurality of linear patterns parallel to the axial direction are arranged at predetermined intervals. The X-axis direction in FIG. 1 (b) means a direction parallel to the width direction of each layer in FIG. 1 (b).

  A plurality of linear patterns parallel to the Y-axis direction in FIG. 1B are arranged at predetermined intervals on the copper layer 12B and the surface blackening layer 13B on the other surface 11b side of the transparent substrate 11. Etching is performed so that In addition, the Y-axis direction in FIG.1 (b) means the direction perpendicular | vertical to a paper surface.

  Through the above operation, the wiring board having the mesh-like wiring shown in FIGS. 3 and 4A can be formed. Note that the etching of both surfaces of the transparent substrate 11 can be performed simultaneously. That is, the etching of the copper layers 12A and 12B and the surface blackening layers 13A and 13B may be performed simultaneously.

  The wiring board having the mesh-like wiring shown in FIG. 3 can also be formed by using two wiring boards shown in FIG. 1 (a) or FIG. 2 (a). The case where the wiring board of FIG. 1A is used will be described as an example. For the two wiring boards shown in FIG. 1A, a plurality of copper layers 12 and blackening layers 13 are parallel to the X-axis direction. Etching is performed so that the linear patterns are arranged at predetermined intervals. And it can be set as a wiring board provided with the mesh-like wiring by aligning direction so that the linear pattern formed in each wiring board by the above-mentioned etching process may cross each other, and bonding two wiring boards. . The surface to be bonded when the two wiring boards are bonded is not particularly limited, and the surface A in FIG. 1A in which the copper layer 12 and the like are stacked as shown in FIG. The surface 11b in FIG. 1A on which 12 or the like is not laminated may be bonded.

  Further, for example, the surfaces 11b in FIG. 1A on which the copper layer 12 or the like of the transparent substrate 11 is not laminated may be bonded together so that the cross section has the structure shown in FIG.

  Note that the width of the wiring and the distance between the wirings in the wiring substrate having the mesh-like wiring shown in FIGS. 3 and 4 are not particularly limited, and are selected according to the amount of current flowing through the wiring, for example. be able to.

  A wiring board having a mesh-like wiring composed of two layers of wirings can be preferably used as a wiring board for a projected capacitive touch panel, for example.

(Manufacturing method of laminated substrate)
First, the manufacturing method of the wiring board of this embodiment is shown.
The method for manufacturing a wiring board includes a transparent substrate preparing step for preparing the transparent substrate 11, a copper layer forming step for forming the copper layer 12 by a film forming means for depositing copper on at least one surface side of the transparent substrate 11, and a transparent substrate. And a blackening layer forming step of forming a surface blackening layer 13 by a film forming means for depositing a metal nitride or oxide on at least one surface side of the substrate 11.

  In addition, when performing a copper layer formation process by the dry-type plating method, implementing in a pressure-reduced atmosphere is preferable. Moreover, it is preferable to implement also in a reduced pressure atmosphere also in a blackening layer formation process.

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

  As described above, in the laminate substrate of the present embodiment, the order of lamination when the copper layer and the blackened layer are arranged on the transparent substrate is not particularly limited. Further, a plurality of copper layers and blackening layers can be formed. For this reason, the order in which the copper layer forming step and the blackened layer forming step are performed and the number of times of performing the steps are not particularly limited, and can be performed at any number of times according to the structure of the wiring board to be formed. Can be implemented.

  The step of preparing the transparent substrate is a step of preparing a transparent substrate made of, for example, an insulating film that transmits visible light, a glass substrate, or the like, and the specific operation is not particularly limited. For example, in order to use for each process in a latter process, it can cut | disconnect etc. to arbitrary sizes as needed.

Next, the copper layer forming step will be described.
The method of forming the copper layer is not particularly limited as long as the copper layer can be formed so that the (111) orientation degree index of the crystal of the copper layer on the surface blackening layer side is 1.2 or more. For example, dry plating The method may include a step of forming a copper thin film layer by a method. Moreover, the copper layer forming step may include a step of forming a copper thin film layer by a dry plating method and a step of forming a copper plating layer by a wet plating method using the copper thin film layer as a power feeding layer. .

  As described above, the copper layer is preferably formed using a dry plating method. Moreover, when making a copper layer thicker, it is preferable to use a wet-plating method after dry-type plating.

  As described above, the copper layer can be formed directly on the transparent substrate or the surface blackening layer without using an adhesive by forming the copper layer only by the dry plating method or by combining the dry plating method and the wet plating method. preferable.

Although it does not specifically limit as a dry-type plating method, For example, sputtering method, an ion plating method, a vapor deposition method etc. can be used preferably. In particular, as the dry plating method used for forming the copper thin film layer, it is more preferable to use the sputtering method because the film thickness can be easily controlled. That is, the film forming means for depositing copper in the copper layer forming step is preferably a sputtering film forming means (sputtering film forming method).
The copper thin film layer can be suitably formed using, for example, a roll-to-roll sputtering apparatus 50.

The process of forming a copper thin film layer will be described taking the case of using a roll-to-roll sputtering apparatus as an example.
FIG. 5 shows a configuration example of the roll-to-roll sputtering apparatus 50.
The roll-to-roll sputtering apparatus 50 includes a housing 51 that houses most of the components.
In FIG. 5, the shape of the housing 51 is shown as a rectangular parallelepiped shape, but the shape of the housing 51 is not particularly limited, and may be any shape depending on the device accommodated therein, the installation location, the pressure resistance performance, and the like. It can be. For example, the shape of the housing 51 can be a cylindrical shape.

However, in order to remove residual gas not related to film formation at the start of film formation, it is preferable that the inside of the casing 51 can be depressurized to 10 ⁻⁴ Pa or less, and more preferably 10 ⁻³ Pa or less. Note that it is not necessary that the entire interior of the casing 51 can be reduced to the above pressure, and it can be configured such that only the lower region in the figure in which a can roll 53 (to be described later) where sputtering is performed can be reduced to the above pressure. .

In the housing 51, an unwinding roll 52, a can roll 53, sputtering cathodes 54a to 54d, a front feed roll 55a, a rear feed roll 55b, tension rolls 56a and 56b, which supply a base material for forming a copper thin film layer, A winding roll 57 can be arranged.
In addition to the above rolls, guide rolls 58a to 58h, a heater 61, a pressure adjustment valve 62, a vacuum gauge 63, a vent valve 64, and the like are optionally provided on the transport path of the base material on which the copper thin film layer is formed. You can also.

  The unwinding roll 52, the can roll 53, the front feed roll 55a, and the winding roll 57 can be provided with power by a servo motor. The unwinding roll 52 and the winding roll 57 are configured to maintain the tension balance of the base material on which the copper thin film layer is formed by torque control using a powder clutch or the like.

  The configuration of the can roll 53 is not particularly limited. For example, the surface of the can roll 53 is finished with hard chrome plating, and a coolant and a heating medium supplied from the outside of the casing 51 are circulated inside the can roll 53 so as to be adjusted to a substantially constant temperature. It is preferable to be configured to be able to.

  For example, the tension rolls 56a and 56b are preferably finished with hard chrome plating and provided with a tension sensor.

  Further, the front feed roll 55a, the rear feed roll 55b, and the guide rolls 58a to 58h are preferably finished with hard chrome plating.

  The sputtering cathodes 54 a to 54 d are preferably magnetron cathode types and arranged to face the can roll 53. The size of the sputtering cathodes 54a to 54d is not particularly limited, but the width-wise dimension of the substrate on which the copper thin film layer of the sputtering cathodes 54a to 54d is formed may be wider than the width of the substrate on which the copper thin film layer is formed. preferable.

  The base material on which the copper thin film layer is formed is transported through a roll-to-roll sputtering apparatus 50 which is a roll-to-roll vacuum film forming apparatus, and the copper thin film is formed by sputtering cathodes 54 a to 54 d facing the can roll 53. A layer is deposited.

  In the case where a copper thin film layer is formed using the roll-to-roll sputtering apparatus 50, a copper target is mounted on the sputtering cathodes 54a to 54d, and a substrate on which the copper thin film layer is formed is set on the unwinding roll 52 The inside is evacuated by vacuum pumps 60a and 60b. Thereafter, a sputtering gas such as argon is introduced into the casing 51 by the gas supply means 59. At this time, the flow rate of the sputtering gas and the opening of the pressure adjusting valve provided between the vacuum pump 60b and the casing 51 are adjusted to maintain the inside of the apparatus at, for example, 0.13 Pa or more and 1.3 Pa or less. It is preferable to perform film formation.

  In this state, while discharging the base material from the unwinding roll 52 at a speed of, for example, 1 m or more and 20 m or less per minute, power is supplied from a sputtering DC power source connected to the sputtering cathodes 54a to 54d to perform sputtering discharge. Thereby, a desired copper thin film layer can be continuously formed on a base material.

  As an example of a manufacturing method in which the crystal orientation on the surface blackening layer side of the copper layer is (111) orientation, a film forming method by a wet plating method will be described. If the (111) orientation degree index of the crystal on the surface blackening layer side in the copper layer is 1.20 or more, the production method is not limited. In addition to the (111) orientation, the copper layer also includes the (200), (220), and (311) orientations, of which the (111) orientation occupies the most and the degree of crystal orientation The index is 1.20 or more.

  Although 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, FIG. 6 shows a roll-to-roll method that can be used for the wet plating method according to the present invention. -It is an example of a roll continuous electroplating apparatus (hereinafter referred to as plating apparatus 20).

  The transparent substrate F2 with the copper thin film layer obtained by forming the copper thin film layer is unwound from the unwinding roll 22 and continuously conveyed while being repeatedly immersed in the plating solution 28 in the electroplating tank 21. . Incidentally, 28a indicates the surface of the plating solution.

  In the transparent substrate F2 with a copper thin film layer, a copper layer is formed on the surface of the metal thin film by electroplating while being immersed in the plating solution 28, and a copper layer having a predetermined thickness is formed. As shown in FIG. In addition, the conveyance speed of the transparent substrate F2 with a copper thin film layer is preferably in a range of 0.1 m to several tens m / min.

  More specifically, the transparent substrate F2 with a copper thin film layer is unwound from the unwinding roll 22 and immersed in the plating solution 28 in the electroplating tank 21 through the power supply roll 26a. The transparent substrate F2 with the copper thin film layer that has entered the electroplating tank 21 is reversed in the transport direction through the reversing roll 23, and is drawn out of the electroplating tank 21 by the power feeding roll 26b.

In this way, the transparent substrate F2 with a copper thin film layer forms a copper layer on the metal thin film of the transparent substrate F2 with a copper thin film layer while the immersion in the plating solution is repeated a plurality of times (10 times in FIG. 6). It is.
A power source (not shown) is connected between the power supply roll 26a and the anode 24a.
An electroplating circuit is configured by the power supply roll 26a, the anode 24a, the plating solution, the polyimide film F2 with a copper thin film layer, and the power source. The insoluble anode does not require a special one, and may be a known anode whose surface is coated with a conductive ceramic. A mechanism for supplying copper ions to the plating solution 28 is provided outside the electroplating tank 21.

  The copper ions are supplied to the plating solution 28 using an aqueous copper oxide solution, an aqueous copper hydroxide solution, an aqueous copper carbonate solution, or the like. Alternatively, there is a method in which a small amount of iron ions is added to the plating solution to dissolve the oxygen-free copper balls and supply the copper ions. Any of the above methods can be used as a method for supplying copper.

The current density during plating is increased stepwise from the anode 24a toward the downstream in the transport direction so that the maximum current density is reached at 24t from the anode 24o.
Thus, discoloration of the copper layer can be prevented by increasing the current density. In particular, when the current density is high when the copper layer is thin, discoloration of the copper layer is likely to occur. Therefore, the current density during plating is 0.1 A / dm ^{2 to} 8 A except for the reverse current of Periodic Reverse current described later. / Dm ² is desirable. When the current density is increased, a poor appearance of the copper electroplating layer occurs.

In order to manufacture the wiring board according to the present invention, it is formed using a PR current in a range of 100 nm or more from the surface of the copper electroplating layer.
In the case of using a periodic reverse current (hereinafter also referred to as a PR current), it is preferable to add a current that is 1 to 9 times as large as the positive current.
The reversal current time ratio is preferably about 1 to 10%.
Further, the period in which the reversal current next to the PR current flows is desirably 10 milliseconds or more, and more desirably 20 milliseconds to 300 milliseconds.
FIG. 7 schematically shows PR current time and current density.
In addition, what is necessary is just to adjust a plating voltage suitably so that the above-mentioned current density is realizable.

  In order to manufacture the wiring board according to the present invention with a roll-to-roll continuous electroplating apparatus (plating apparatus 20), a PR current may be passed through one or more anodes from the downstream side of the transport path. The number of anodes to flow is determined by the ratio of the range in which the film is formed with the PR current from the surface of the copper electroplating layer to the transparent substrate side. That is, at least the anode 24t causes a PR current to flow, and if necessary, the PR current flows to the anode 24s, the anode 24r, and the anode 24q.

  Although a PR current may be supplied to all the anodes, a manufacturing cost increases because a rectifier for PR current is expensive. Therefore, in the wiring board according to the present invention, if a film thickness of 100 nm or more and 1500 nm or less is formed with a PR current from the surface of the copper electroplating layer to the transparent substrate, the crystal orientation index of the (111) plane of the copper plating is 1. .2 or more, as a result, side etching can be suppressed.

  The reason why copper electroplating using a PR current is desirable is that when the current is reversed, the copper electroplating dissolves, and the orientation other than the readily soluble (111) plane preferentially dissolves, the atomic density is the highest, and it is difficult to dissolve. (111) plane crystals can be preferentially grown.

  In general, in the electroplating method, the deposited copper is affected by the surface of the base material to be plated with copper, but the crystal orientation can be controlled by forming a film with a thickness of 100 nm or more from the surface of the copper electroplating layer with a PR current. If the thickness of the copper electroplating layer of the wiring board is 100 nm or more and the crystal orientation index of the (111) plane is 1.2 or more, the surface black due to side etching is formed when wiring is formed by etching. The effect which suppresses peeling of a chemical layer is acquired, and the subject of this invention can be achieved.

Next, the surface blackening layer forming process formed on the surface of the copper layer will be described.
As described above, the surface blackening layer forming step is a step of forming a surface blackening layer by a film forming means for depositing a metal nitride or oxide on the surface of the copper layer. The film forming means for depositing nitride or oxide in the surface blackening layer forming step is not particularly limited, but for example, a sputtering film forming means (sputtering film forming method) is preferable.

  When forming a surface blackening layer of copper nitride using the roll-to-roll sputtering apparatus 50 (FIG. 5), a copper target is attached to the sputtering cathodes 54a to 54d, and a base material for forming the blackening layer is formed. The inside of the apparatus set on the unwinding roll 52 is evacuated by the vacuum pumps 60a and 60b. Thereafter, a sputtering gas composed of argon and nitrogen is introduced into the casing 51 by the gas supply means 59. At this time, by adjusting the flow rate of the sputtering gas and the opening of the pressure adjustment valve 62 provided between the vacuum pump 60b and the housing 51, the inside of the apparatus is maintained at, for example, 0.13 Pa or more and 13 Pa or less, It is preferable to perform film formation.

  In this state, while discharging the base material from the unwinding roll 52 at a speed of about 0.5 to 10 m per minute, for example, power is supplied from the sputtering DC power source connected to the sputtering cathodes 54a to 54d to cause sputtering discharge. Do. Thereby, a desired surface blackening layer can be continuously formed on the substrate.

  In the case of providing the first blackened layer, it may be formed according to the procedure for forming the surface blackened layer before forming the copper thin film layer.

  And the laminated body board | substrate obtained by the manufacturing method of the laminated body board | substrate demonstrated here can be used as the wiring board provided with the mesh-shaped wiring. In this case, in addition to the above-described steps, an etching step of forming a wiring can be further provided by etching the copper layer and the surface blackening layer.

  In the etching process, for example, first, a resist having an opening corresponding to a portion to be removed by etching is formed on the outermost surface of the wiring board. In the case of the wiring substrate shown in FIG. 1A, a resist can be formed on the exposed surface A of the surface blackening layer 13 disposed on the wiring substrate. Note that a method for forming a resist having an opening corresponding to a portion to be removed by etching is not particularly limited. For example, the resist can be formed by a photolithography method.

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

  When the copper layers 12A and 12B and the surface blackening layers 13A and 13B are arranged on both surfaces of the transparent substrate 11 as shown in FIG. 1B, each of the outermost surfaces A and B of the wiring substrate has a predetermined shape. A resist having an opening may be formed, and the copper layers 12A and 12B and the surface blackening layers 13A and 13B formed on both surfaces of the transparent substrate 11 may be etched simultaneously.

  In addition, the copper layers 12A and 12B and the surface blackening layers 13A and 13B formed on both sides of the transparent substrate 11 can be etched one by one. That is, for example, after the copper layer 12A and the surface blackening layer 13A are etched, the copper layer 12B and the surface blackening layer 13B can be etched.

  In the laminate of the laminate substrate according to the present invention, the crystal of the copper layer 12 on the surface blackening layer side has a (111) orientation degree index of 1.20 or more. The copper layer 12 on the side is not easily subjected to side etching, and peeling of the surface blackened layer due to side etching can be suppressed. Since the surface blackened layer is a metal nitride or oxide, the etching rate is slower than that of the copper layer 12, and the copper layer 12 is side-etched before the surface blackened layer is etched and the surface blackened layer is peeled off. The laminated substrate according to the present invention can solve the problem.

The etching solution used in the etching step is not particularly limited as long as the copper layer 12 and the surface blackened layer or the first blackened layer can be etched, and an etching solution generally used for etching the copper layer 12 is preferably used. Can do. As the etching solution, for example, a mixed aqueous solution of ferric chloride and hydrochloric acid can be used more preferably. The contents of ferric chloride and hydrochloric acid in the etching solution are not particularly limited. For example, ferric chloride is preferably contained in a proportion of 5 wt% to 50 wt%, and preferably 10 wt%. More preferably, it is contained in a proportion of 30% by weight or less.
Further, for example, the etching solution preferably contains hydrochloric acid in a proportion of 1 wt% or more and 50 wt% or less, and more preferably contains 1 wt% or more and 20 wt% or less. The remainder can be water.

  Although the etching solution can be used at room temperature, it is preferably heated to increase the reactivity, and for example, it is preferably heated to 40 ° C. or more and 50 ° C. or less.

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

  Further, as described above, two wiring boards having a copper layer 12 and a blackened layer are bonded to one surface side of the transparent substrate 11 shown in FIGS. 1A and 2A to form a mesh. In the case of a wiring board provided with the wiring, a step of bonding the wiring boards can be further provided. At this time, the method of bonding the two wiring boards is not particularly limited, and for example, the bonding can be performed using an adhesive or the like.

  In the above, the manufacturing method of the laminated body board | substrate and wiring board of this embodiment was demonstrated. According to such a laminate substrate, the copper layer and the surface blackening layer exhibit substantially the same reactivity with the etching solution, so that a desired wiring can be easily formed. In addition, since the blackened layer is black, it functions as a blackened layer and can suppress reflection of light by the copper layer. For example, when a wiring board for a touch panel is used, a reduction in visibility is suppressed. it can.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited to these Examples.

(Evaluation method)
(1) Reflectance The reflectance was measured for the wiring boards produced in the following examples.
The measurement was performed by installing a reflectance measurement unit in an ultraviolet-visible spectrophotometer (Shimadzu Corporation model: UV-2550).
As the wiring board, a wiring board having the structure of FIG. 2A was manufactured, but the reflectance was measured at an incident angle of 5 ° with respect to the surface exposed to the outside of the second blackening layer 132 in FIG. The light receiving angle was 5 °, and irradiation was performed with light having a wavelength in the range of 400 nm to 700 nm. In addition, the light irradiated to the wiring board was measured by changing the wavelength every 1 nm within a range of 400 nm to 700 nm, and the average of the measurement results was taken as the average reflectance of the wiring board.

(2) Wiring evaluation by etching A photoresist wiring is provided on the wiring board, and an etching solution composed of 10% by weight of ferric chloride, 10% by weight of hydrochloric acid, and the balance is water is sprayed by a spray nozzle. Formed.

(3) Crystal orientation Crystal orientation was measured by X-ray diffraction using Wilson's orientation degree index.

(Sample preparation conditions)
The manufacturing conditions of the wiring board in Example 1 are shown below.
A wiring board having the structure shown in FIG.
First, a blackened layer having a thickness of 40 nm was formed on a transparent substrate made of polyethylene terephthalate resin (PET) having a width of 500 mm and a thickness of 100 μm on the transparent substrate using the roll-to-roll sputtering apparatus shown in FIG.
Subsequently, a copper layer having a thickness of 200 nm was formed on the upper surface of the first blackened layer by a roll-to-roll sputtering apparatus.
Then, after depositing 200 nm of the first copper plating layer with a direct current power supply by electroplating, the copper layer 12 was formed by depositing 200 nm of the second copper plating layer with a PR power supply at the anodes 24g and 24h.
For the PR current, the negative current time ratio was set to 10%.
Then, the second blackened layer 132 was formed again on the upper surface of the copper layer 12 under the same conditions as the first blackened layer 131.

Light having a wavelength of 400 nm or more and 700 nm or less is irradiated by irradiating light from the exposed surface side of the second blackening layer 132, that is, the surface side not facing the copper layer 12. When the average reflectance was measured, the average reflectance was 17.9%.
When a photoresist wiring for forming a pattern having a wiring width of 5 μm and an inter-wiring space of 300 μm was applied to this wiring board and subjected to an etching process, the wiring was formed.

  The crystal orientation of the copper layer was measured by X-ray diffraction after the first copper plating layer was formed and after the second copper plating layer was formed, and the (111) orientation degree index of the crystal of the first copper plating layer was 0. 84, and the (111) orientation index of the second copper plating layer was 1.31.

[Comparative Example 1]
When wiring was formed on the wiring board in the same manner as in Example 1 except that the copper layer 12 was formed by depositing a 400 nm copper plating film with a direct current power source by electroplating, the wiring side surface was excessively etched. As a result, wiring processing was not possible. In any of the examples, the blackening layer is formed under the same filming conditions when the first blackening layer 131 is formed and when the second blackening layer 132 is formed. ing.
The crystal orientation of the copper layer was measured by X-ray diffraction after forming the copper plating layer, and the (111) orientation degree index of the crystal of the copper plating layer was 0.84.

10A, 10B, 20A, 20B, 30 Wiring substrate 11 Transparent substrate 12, 12A, 12B Copper layer 13, 13A, 13B, 131, 132, 131A, 131B, 132A, 132B, 32A, 32B Blackening layer 31A, 31B Wiring

Claims (15)

A transparent substrate;
Comprising a conductive laminate provided on at least one surface of the transparent substrate;
The laminated body is a surface blackened layer laminated on the surface of the copper layer and the copper layer, the surface blackened layer is on the most surface,
The copper layer has a laminated structure,
The (111) orientation degree index of the crystal of the copper layer on the transparent substrate side is less than 1,
(111) orientation index of the copper layer crystal on the surface blackening layer side is 1.2 or more,
A laminate substrate, wherein the surface blackening layer has a thickness of 10 nm or more and 100 nm or less . The copper layer, according to claim 1, characterized in that it comprises a first copper layer of dry plating layer, a second copper layer of a copper electroplating layer by PR current the first copper layer and the power feeding layer Laminated substrate. The laminate substrate according to claim 2 , wherein the thickness of the second copper film is 100 nm or more. The laminate is
A first blackening layer formed on the surface of the transparent substrate;
The copper layer formed on the surface of the first blackening layer;
Laminate substrate according to any one of claims 1 3, characterized in that a laminated structure comprising the said surface blackening layer formed on the surface of the copper layer. The first blackening layer and the surface blackening layer are nitrides or oxides containing one or more metals selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Ni, and Cu. The laminate substrate according to claim 4 , wherein the laminate substrate is a product. The copper layer has a thickness of 100 nm or more;
The laminate substrate according to any one of claims 1 to 5 , wherein a thickness of the surface blackening layer is 20 nm or more. It is a manufacturing method of the layered product substrate according to any one of claims 1 to 6 ,
A method of manufacturing a laminate substrate, comprising a step of forming a copper layer on the surface blackening layer side by electroplating using a PR current. It is a manufacturing method of the layered product substrate according to any one of claims 1 to 6 ,
Step (a) of depositing all or part of the copper layer on the transparent substrate side of the copper layer by a dry plating method;
After the step (a), the method for producing a laminate substrate which comprises a step of forming a copper layer on said surface blackening layer side electroplating by PR current. A transparent substrate;
A wiring having a laminated structure provided on at least one surface of the transparent substrate,
Wherein the wiring is a laminate comprising a surface blackening layer laminated on the surface of the copper layer and the copper layer located at the surface blackening layer is most superficial,
The copper layer has a laminated structure,
The (111) orientation degree index of the crystal of the copper layer on the transparent substrate side is less than 1,
(111) orientation degree index of the crystal of the copper layer on the surface blackening layer side is 1.2 or more ,
The wiring board, wherein the blackened layer has a thickness of 10 nm or more and 100 nm or less . The copper layer, according to claim 9, characterized in that it comprises a first copper layer of dry plating layer, a second copper layer of a copper electroplating layer by PR current the first copper layer and the power feeding layer Wiring board. The circuit board according to claim 9 or 10 before Symbol thickness of the second copper layer, characterized in that at 100nm or more. The laminate is
A laminate comprising a first blackening layer formed on the surface of the transparent substrate, the copper layer formed on the surface of the first blackening layer, and the surface blackening layer formed on the surface of the copper layer. It is a structure, The wiring board of any one of Claim 9 to 11 characterized by the above-mentioned. The first blackening layer and the surface blackening layer are nitrides or oxides containing one or more metals selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Ni, and Cu. The wiring board according to claim 12 , wherein the wiring board is a thing. The copper layer has a thickness of 100 nm or more.
The wiring board according to claim 9 , wherein a thickness of the surface blackening layer is 10 nm or more. A method of manufacturing a wiring board, comprising processing the laminated substrate according to any one of claims 1 to 6 into a wiring by etching.

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