JP2018016827A - Production method of organic coating, production method of semiconductor substrate and organic coating production apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of an organic coating capable of suppressing excessive thickness of the organic coating.SOLUTION: A production method of an organic coating has an organic coating formation step for forming an organic coating on the upper surface of a copper-containing metal layer by immersing a substrate having the copper-containing metal layer formed thereon into a solution of a nitrogen-based organic matter put into a bath. In the organic coating formation step, a copper concentration in the solution in the bath is set at 15 ppm or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing an organic film, a method for producing a conductive substrate, and an organic film production apparatus.

  The capacitive touch panel converts positional information of an adjacent object on the panel surface into an electric signal by detecting a change in electrostatic capacitance caused by the object adjacent to the panel surface. Since the conductive substrate used for the capacitive touch panel is installed on the surface of the display, the material of the conductive layer of the conductive substrate is required to have low reflectance and be difficult to be visually recognized.

  Therefore, as a material of the conductive layer used for the capacitive touch panel, a material having low reflectivity and not easily visible is used, and wiring is formed on a transparent substrate or a transparent film.

  For example, Patent Document 1 discloses a capacitive digital touch panel that includes a plurality of transparent sheet electrodes in which a signal pattern and a GND pattern are printed by an ITO film on a PET film.

  By the way, in recent years, the display screen including a touch panel has been enlarged, and in response to this, the conductive substrate for the touch panel is also required to have a large area. However, since ITO has a high electric resistance value and causes signal deterioration, there is a problem that a conductive substrate using ITO is not suitable for a large panel.

  Therefore, it has been studied to use a metal such as silver or copper in place of ITO as a material for the conductive layer. For example, Patent Document 2 discloses a technique in which a conductive sheet in which transparent electrodes each having a developed thin conductive silver wire are formed on both sides of a transparent support is used for a capacitive touch panel. However, a metal such as silver has a metallic luster, and there is a problem that the visibility of the display is lowered due to reflection.

  In order to solve this problem, a conductive substrate in which a blackened layer made of a black material is formed together with a metal layer containing a metal such as copper has been studied. For example, in Patent Document 3, a striped copper wiring is provided in each of the portions that need to be seen through on the front and back surfaces of the film, and a black copper oxide film (blackened layer) is formed on the side where the copper wiring on the front and back sides is viewed. A film-like touch panel sensor having the following is disclosed.

  Further, according to the method for manufacturing a film-like touch panel sensor disclosed in Patent Document 3, at least a resist layer is formed into a stripe-shaped wiring pattern by a step of forming a resist layer on a copper thin film supported by the film and a photolithography method. And a step of processing the lead wiring pattern, a step of removing the exposed copper thin film by etching to form a striped copper wiring and a lead copper wiring, and a step of blackening the copper wiring.

  However, in the method disclosed in Patent Document 3 in which the surface of the copper wiring is blackened after the copper wiring is formed, the number of steps is increased. For this reason, after forming a metal layer containing copper (hereinafter referred to as a copper-containing metal layer) on the substrate and a blackened layer whose surface is blackened, the copper-containing metal layer and the blackened layer are etched. However, a method for forming a conductive substrate has been studied.

JP 2004-213114 A JP 2012-230665 A JP 2013-206315 A

  However, when an organic coating or blackening layer is placed on the copper-containing metal layer, the organic coating should not be too thick so as not to reduce the adhesion between the copper-containing metal layer and the blackening layer. However, when an organic film is formed on the copper-containing metal layer, it is difficult to control the thickness of the organic film within a predetermined range.

  In view of the above-described problems of the prior art, an object of one aspect of the present invention is to provide a method for producing an organic coating that can suppress an excessive increase in the thickness of the organic coating.

In order to solve the above problems, in one aspect of the present invention,
An organic film forming step of forming an organic film on the upper surface of the copper-containing metal layer by immersing the base material on which the copper-containing metal layer is formed in a solution of a nitrogen-based organic material in a bath;
In the organic film forming step, the method for producing an organic film is characterized in that the copper concentration of the solution in the bath is 15 ppm or less.

  According to one aspect of the present invention, it is possible to provide a method for producing an organic coating that can suppress an excessive increase in the thickness of the organic coating.

The figure explaining the structural example (an example of an organic film manufacturing apparatus) of the manufacturing method of the organic film which concerns on embodiment of this invention. Sectional drawing of the electroconductive board | substrate which concerns on embodiment of this invention. Sectional drawing of the electroconductive board | substrate which concerns on embodiment of this invention. The top view of the electroconductive board | substrate provided with the mesh-shaped wiring which concerns on embodiment of this invention. Sectional drawing in the AA 'line of FIG. Explanatory drawing of the cut line formed when performing the adhesiveness test in an Example and a comparative example.

Hereinafter, an embodiment of an organic film manufacturing method, a conductive substrate manufacturing method, and an organic film manufacturing apparatus according to the present invention will be described.
(Method for producing organic coating)
First, a configuration example of the method for producing an organic coating according to this embodiment will be described.

  The manufacturing method of the organic film of this embodiment can have the following processes.

  An organic film forming step of forming an organic film on the upper surface of the copper-containing metal layer by immersing the base material on which the copper-containing metal layer is formed in a solution of a nitrogen-based organic material in a bathtub.

  In the organic film forming step, the copper concentration of the nitrogen-based organic solution in the bath is set to 15 ppm or less.

  When an organic film is formed on a copper-containing metal layer, for example, a copper-containing metal thin film is formed on a substrate such as a resin film by a dry method such as a sputtering method (hereinafter sometimes referred to as a dry plating method) or an electroless plating method. Form a layer. Thereafter, copper plating is performed on the copper-containing metal thin film layer by a wet method to form a copper-containing metal layer on the substrate. An adhesion layer may be formed between the substrate such as a resin film and the copper-containing metal thin film layer by a dry method or an electroless plating method.

  Thereafter, the base material on which the copper-containing metal layer is formed is dipped in a bath containing an organic solution to form an organic film on the base material on which the copper-containing metal layer is formed.

  According to the study by the inventors of the present invention, when the remaining copper plating solution is brought into a bath containing an organic solution, the copper ion concentration in the bath gradually increases. Moreover, when a copper component melts from the copper-containing metal layer formed on the base material in the bath containing the organic solution, the copper ion concentration in the bath may gradually increase. In this case, the higher the copper ion concentration in the bath, the higher the reactivity of the organic matter, so that the thickness of the organic coating was found to complete the present invention.

  Hereinafter, each process of the manufacturing method of the organic film of this embodiment is demonstrated.

  In the organic film forming step, the base material on which the copper-containing metal layer is formed is immersed in a nitrogen-based organic solution in the bath. Thereby, an organic film is formed in the copper content metal layer formed in the substrate.

  The kind of base material is not particularly limited, and a base material in which a copper-containing metal layer is formed on at least one surface can be used. For example, a long base material, a sheet-like base material, a transparent base material, etc. can be used.

  Moreover, a copper-containing metal layer will not be specifically limited if the material which comprises a copper-containing metal layer contains copper, The material which has the electrical conductivity which suited the use can be selected. For example, the material constituting the copper-containing metal layer is Cu and at least one metal selected from Zn, Ni, Mo, Sn, Ta, Ti, V, Cr, Fe, Mn, Co, and W. A copper alloy or a material containing copper is preferable. The copper-containing metal layer can be a copper layer made of copper.

  Further, the nitrogen-based organic material is not particularly limited, and can be arbitrarily selected from organic compounds containing nitrogen. Such a nitrogen-based organic substance preferably contains, for example, 1,2,3-benzotriazole or a derivative thereof. Specific examples of nitrogen-based organic substances used for the organic coating include 1,2,3-benzotriazole and 5-methyl-1H benzotriazole.

  Examples of the nitrogen-based organic solution include a rust preventive agent for copper, and examples of commercially available chemicals that can be preferably used include an OPC defenser (trade name, Okuno Pharmaceutical Co., Ltd.).

  The upper limit of the content of nitrogen-based organic matter in the organic coating to be formed is not particularly limited. However, to increase the content of nitrogenous organic matter in the organic coating, increase the concentration of the organic solution containing the nitrogenous organic matter used when forming the organic coating, or immerse it in the organic solution containing the nitrogenous organic matter. For example, it is necessary to lengthen the time to perform the operation. For this reason, if the content of nitrogen-based organic matter in the organic coating is excessively increased, the handling of the solution containing the nitrogen-based organic matter is reduced, the time required to form the organic coating is increased, and production May decrease.

Therefore, the content of the nitrogen-based organic substance in the organic coating is preferably, for example, 10 μg / cm ² or less, and the lower the content, the better the adhesion of the blackened layer, so that it is 1 μg / cm ² or less. More preferably, it is more preferably 0.5 μg / cm ² or less.

  The concentration of the nitrogen-based organic substance in the nitrogen-based organic substance solution is not particularly limited, and can be arbitrarily selected in consideration of the content of the nitrogen-based organic substance in the target organic film. For example, the lower limit of the concentration of the nitrogen-based organic substance in the organic solution is preferably 0.08 g / L or more, and more preferably 0.32 g / L or more. Moreover, it is preferable that an upper limit is 0.64 g / L or less.

  The temperature of the organic solution when the organic film is formed on the surface of the copper-containing metal layer by immersing the substrate in the organic solution is not particularly limited, considering the viscosity, operability, reactivity, etc. of the solution. Can be arbitrarily selected. For example, it is preferably 10 ° C. or higher, and more preferably 20 ° C. or higher. However, since the organic solution may react with other substances when the temperature increases, the temperature is preferably 40 ° C. or lower.

  The pH of the nitrogen-based organic substance solution is not particularly limited, and can be selected in consideration of, for example, the type of organic solution used and the reactivity of the solution. For example, the pH of the organic solution is preferably 2 or more, and more preferably 3 or more. However, when the pH is increased, for example, the content of nitrogen-based organic matter in the coating is lowered, so that the pH of the organic solution is preferably 4 or less.

  When forming an organic film on the surface of the copper-containing metal layer, the length of time for immersing the substrate in the organic solution (immersion time) is not particularly limited, and the type of organic solution used and the organic film to be formed It can be arbitrarily selected according to the thickness of the film. For example, the immersion time is preferably 3 seconds or more, and more preferably 4 seconds or more. However, if the immersion time is too long, the productivity may be lowered, and therefore it is preferably 10 seconds or less. In the above-described method for producing an organic coating, the immersion time can be set to a desired time by adjusting the conveyance speed of the substrate.

  In the organic coating forming step, the copper concentration of the nitrogen-based organic solution in the bath is adjusted to 15 ppm or less, preferably 8 ppm or less. Thus, even when the copper plating solution remaining on the base material when the copper-containing metal layer is formed is brought into the bathtub or when the copper component is dissolved out of the formed copper-containing metal layer in the bathtub, It can prevent that the copper concentration of the solution inside becomes high. Therefore, it can suppress that the thickness of an organic film becomes thick too much.

  Further, in the organic film forming step, the nitrogen-based organic solution can be replenished to the bathtub so that the copper concentration of the nitrogen-based organic solution in the bathtub is 15 ppm or less. In this case, it is easy to adjust the copper concentration of the solution in the bath to a low concentration of 15 ppm or less. Therefore, even when the plating solution remaining on the base material is brought into the bathtub or the copper component is dissolved in the bathtub from the formed copper-containing metal layer, the copper concentration of the solution in the bathtub is increased. It can be surely prevented. Therefore, it is possible to prevent the organic coating from becoming excessively thick with high accuracy.

  In addition, you may store the base material in which the organic film was formed, after washing with water and drying. The base material stored in this way can be used as a base material for a conductive substrate, for example.

  Moreover, in the manufacturing method of the organic film of this embodiment, the copper containing metal formation process may be included before the organic film formation process. In such a copper-containing metal layer forming step, a copper-containing metal layer is formed on at least one surface of the substrate.

  In the copper-containing metal layer forming step, for example, the copper-containing metal plating layer can be formed on the substrate by an electroplating method which is a kind of wet plating method. The copper-containing metal plating layer formed on the substrate can be constituted by the copper-containing metal plating layer thus formed.

  In addition, before performing the above-described copper-containing metal layer forming step, a copper-containing metal thin film layer (hereinafter referred to as a copper-containing metal thin film layer) is formed on the substrate in advance by a dry method such as sputtering or an electroless plating method. To do. By performing copper plating by a wet method in the copper-containing metal layer forming step using the copper-containing metal thin film layer as a power feeding layer, a copper-containing metal plating layer can be formed on the copper-containing metal thin film layer. The copper-containing metal thin film layer and the copper-containing metal plating layer thus formed can constitute a copper-containing metal layer formed on the substrate. Before the formation of the copper-containing metal thin film layer, the adhesion layer may be formed by a dry method such as sputtering or an electroless plating method.

  The substrate on which the copper-containing metal layer has been formed through the copper-containing metal layer forming step is then washed with water before the organic coating is formed in the organic coating forming step, and the water attached to the substrate is drained. May be performed. By performing such water washing and draining, it is possible to suppress the copper component from being brought into the organic film forming step, and thus it becomes easy to control the copper concentration of the nitrogen-based organic matter solution in the bath.

According to the method for producing an organic film of the present embodiment described above, it is possible to prevent the copper concentration of the nitrogen-based organic substance solution in the bathtub from increasing, and to prevent the organic film from becoming excessively thick. Can do.
(Organic coating production equipment)
Next, a configuration example of the organic film manufacturing apparatus according to this embodiment will be described.

  In addition, since the organic film manufacturing apparatus of this embodiment can be used suitably for the manufacturing method of the above-mentioned organic film, description is abbreviate | omitted about the matter already demonstrated in the manufacturing method of an organic film.

The organic film manufacturing apparatus of the present embodiment can have the following configuration.
Organic film forming means for immersing a base material on which a copper-containing metal layer is formed in a solution of a nitrogen-based organic material in a bath to form an organic film on the upper surface of the copper-containing metal layer.
An adjusting means provided in the organic coating forming means for adjusting the copper concentration of the nitrogen-based organic matter solution in the bathtub to 15 ppm or less.

  FIG. 1 is a diagram showing an example of an organic film manufacturing apparatus according to the present invention. In FIG. 1, the code | symbol 10 is an example of an organic film manufacturing apparatus. The organic film manufacturing apparatus 10 includes a copper-containing metal layer forming unit 11, an organic film forming unit 12, and an adjusting unit 13.

  The copper-containing metal layer forming means 11 can form a copper-containing metal layer on at least one surface of the base material 14 by a wet method. In addition, in the organic film manufacturing apparatus 10 of FIG. 1, although the copper containing metal layer forming means 11 is provided, providing a copper containing metal layer forming means is arbitrary. That is, in the organic film forming apparatus, without providing the copper-containing metal layer forming means, a base material on which the copper-containing metal layer is formed is prepared in advance, and the organic film forming means 12 forms the organic film on the base material. May be.

  The base material 14 is a long sheet-like base material. This sheet-like substrate 14 is conveyed in the direction of the block arrow 1 from the state wound on the unwinding roller 15, and is wound around the winding roller 16 via the copper-containing metal layer forming means 11 and the organic film forming means 12. Taken. In addition, FIG. 1 has shown the figure which looked at the sheet-like base material 14 in the horizontal direction orthogonal to the conveyance direction of the base material 14 conveyed.

  When the base material 14 is transported in the direction indicated by the block arrow 1 shown in FIG. 1, the base material 14 is held and transported in a state where the width direction is a direction orthogonal to the transport direction. In FIG. 1, the Y-axis direction (direction perpendicular to the paper surface) is the width direction of the base material 14, and the X-axis direction is the transport direction of the base material 14.

  In addition, although the example using the elongate sheet-like base material is shown in FIG. 1, it is not limited to the form which concerns. However, since it can be produced continuously, a long sheet is preferable.

  The copper-containing metal layer forming means 11 includes a plating bath 11a in which an electrode (not shown) is disposed, a plating solution 11b (copper sulfate solution) placed in the plating bath 11a, and transport rollers 11c to 11e. In the copper-containing metal layer forming means 11, the base material 14 is conveyed to the copper-containing metal layer forming means 11, and a copper-containing metal layer is formed on at least one surface of the base material 14.

  Specifically, the base material 14 unwound from the unwinding roller 15 passes through the plating bath 11a by the transport rollers 11c to 11e, and copper plating by a wet method is performed in the plating bath 11a. A copper-containing metal layer is formed on the substrate 14.

  In addition, the copper-containing metal thin film layer may be formed on the base material 14 in advance by a dry method such as sputtering before the copper-containing metal layer forming unit 11 performs copper plating by a wet method. A copper-containing metal plating layer can be formed on the copper-containing metal thin film layer by performing copper plating by the wet method using the copper-containing metal layer forming means 11 using the copper-containing metal thin film layer as a power feeding layer. The copper-containing metal thin film layer and the copper-containing metal plating layer thus formed can constitute a copper-containing metal layer formed on the substrate.

  In the copper-containing metal layer forming means 11 of FIG. 1, a horizontal type plating apparatus is used in which the base material 14 passes through the plating bath 11a so that the width direction of the base material 14 is along the Y-axis direction. When the copper-containing metal forming means is used as in this example, the configuration of the plating apparatus is not limited. For example, as a plating apparatus used in the copper-containing metal layer forming means, a suspension type plating apparatus in which the substrate 14 suspended so that the width direction of the substrate 14 is along the Z-axis direction passes through the plating bath 11a is used. Also good.

  Further, the base material 14 on which the copper-containing metal layer is formed by the copper-containing metal layer forming means 11 is then formed with an organic film by the organic film forming means 12. Prior to this, water washing means 17 and air knife 18 may be passed as shown in FIG. In the water washing means 17, the base material 14 on which the copper-containing metal layer is formed can be washed with water. Further, the air knife 18 can drain the water adhering to the base material 14. The base material 14 that has passed through the water washing means 17 and the air knife 18 is conveyed to the organic film forming means 12. By performing such water washing and draining, it is possible to suppress the copper component from being brought into the organic film forming means 12.

  The organic film forming unit 12 includes, for example, a bathtub 12a, a nitrogen-based organic solution 12b put in the bathtub 12a, and transport rollers 12c to 12e. In the organic coating forming means 12, the base material 14 on which the copper-containing metal layer is formed passes through the bathtub 12a and is immersed in the solution 12b in the bathtub 12a by the transport rollers 12c to 12e. Thereby, an organic film is formed on the copper-containing metal layer formed on the substrate 14.

  The organic coating formed in this manner can contain a nitrogen-based organic material. When an organic coating is used for a conductive substrate and placed between a copper-containing metal layer and a blackened layer, the adhesion between the blackened layer and the copper-containing metal layer and the organic coating that are the lower layer of the blackened layer is improved. In particular, it is possible to obtain a conductive substrate in which the adhesion between the copper-containing metal layer and the blackened layer is stable. As a result, since the peeling of the blackened layer can be suppressed, the etching property of the blackened layer can be improved. Moreover, the reflectance of a conductive substrate can be reduced because an organic film contains a nitrogen-type organic substance.

  In the organic film forming means 12, the copper concentration of the nitrogen-based organic matter solution 12b in the bathtub 12a is adjusted to 15 ppm or less, preferably 8 ppm or less. Thereby, even if the plating solution remaining on the base material 14 is brought into the bathtub 12a, the copper concentration of the solution 12b in the bathtub 12a can be prevented from increasing. Therefore, it is possible to prevent the organic coating from becoming excessively thick.

  The organic coating forming means 12 is provided with adjusting means 13 for adjusting the copper concentration of the solution 12b in the bathtub 12a. The adjusting means 13 includes a tank 13a, a nitrogen-based organic solution 13b stored in the tank 13a (hereinafter referred to as a replenishing solution), and a replenishment pipe 13c for replenishing the bathtub 12a with the replenishing solution 13b.

  In addition, the adjustment means 13 is not limited to said structure, What kind of structure may be sufficient if it is the structure which can adjust the copper concentration of the solution 12b in the bathtub 12a. For example, the adjusting means 13 is replenished with a sensor (not shown) for measuring the copper concentration in the bathtub 12a and the replenishing solution 13b so as to control the copper concentration in the bathtub 12a based on the copper concentration measured by the sensor. Control means (not shown) may be further provided.

  By this adjustment means 13, the replenishing solution 13b can be replenished to the bathtub 12a so that the copper concentration of the solution 12b in the bathtub 12a may be 15 ppm or less. In particular, the copper concentration of the solution 12b in the bathtub 12a can be adjusted to a low concentration of 15 ppm or less. Therefore, even if the plating solution remaining on the base material 14 is brought into the bathtub 12a, the copper concentration of the solution 12b in the bathtub 12a can be reliably prevented from increasing. Therefore, it is possible to prevent the organic coating from becoming excessively thick with high accuracy.

  In addition, in the organic film formation means 12 of FIG. 1, although the horizontal type immersion apparatus through which the base material 14 passes the inside of the bathtub 12a so that the width direction of the base material 14 follows a Y-axis direction is used, this example Thus, when using an immersion apparatus with an organic film formation means, the structure is not limited. For example, as the immersion device used in the organic film forming means, a suspension type immersion device in which the base material 14 passes through the bathtub 12a so that the width direction of the base material 14 is along the Z-axis direction may be used.

  Further, the base material 14 on which the organic coating film is formed by the organic coating film forming means 12 may then be washed with water after passing through the water washing means 19 and further dried through a drying means (not shown). The base material 14 thus washed and dried may be further wound around the winding roller 16. The base material 14 wound up in this way can be used for a conductive substrate described later.

According to the organic film manufacturing apparatus of this embodiment described above, it is possible to prevent the copper concentration of the nitrogen-based organic matter solution in the bath from becoming high. As a result, it is possible to prevent the organic coating from becoming excessively thick.
(Method for producing conductive substrate)
Next, a configuration example of the conductive substrate manufacturing method of the present embodiment will be described.

  In addition, since the manufacturing method of the electroconductive board | substrate of this embodiment can be implemented suitably using the manufacturing method and organic film manufacturing apparatus of an organic film as stated above, it already demonstrated in the manufacturing method of an electroconductive board | substrate. Description of matters is omitted.

  In the manufacturing method of the conductive substrate of this embodiment, an organic film can be formed between a copper containing metal layer and a blackening layer. And the manufacturing method of the electroconductive board | substrate of this embodiment can have the following processes.

  A copper-containing metal layer forming step of forming a copper-containing metal layer on at least one surface of the transparent substrate by a wet method.

  An organic film forming step of forming an organic film on the upper surface of the copper-containing metal layer by immersing the transparent base material on which the copper-containing metal layer is formed in a solution of a nitrogen-based organic material in a bathtub.

  A blackening layer forming step of forming a blackening layer on the upper surface of the organic coating.

  In the organic film forming step, the copper concentration of the nitrogen-based organic solution in the bath is set to 15 ppm or less.

  First, a configuration example of a conductive substrate obtained by the method for manufacturing a conductive substrate according to this embodiment will be described.

  The conductive substrate includes a transparent substrate, a copper-containing metal layer formed on at least one surface of the transparent substrate, an organic coating formed on the copper-containing metal layer, and a black formed on the organic coating. And a stratified layer.

  In addition, the conductive substrate in this embodiment is a substrate having a copper-containing metal layer, an organic coating, and a blackening layer on the surface of the transparent substrate before patterning the copper-containing metal layer and the like, and a copper-containing metal. A substrate on which a layer or the like is patterned, that is, a wiring substrate is included.

  First, each member included in the conductive substrate will be described below.

  The transparent substrate is not particularly limited, and a transparent substrate such as a resin substrate (resin film) that transmits visible light or a glass substrate can be preferably used.

  As a material for the resin substrate that transmits visible light, for example, a polyamide resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, a cycloolefin resin, a polyimide resin, a polycarbonate resin, or the like can be preferably used. In particular, PET (polyethylene terephthalate), COP (cycloolefin polymer), PEN (polyethylene naphthalate), polyamide, polyimide, polycarbonate, and the like can be more preferably used as the material for the resin substrate that transmits visible light.

  It does not specifically limit about the thickness of a transparent base material, It can select arbitrarily according to the intensity | strength, electrostatic capacitance, light transmittance, etc. which are required when it is set as an electroconductive board | substrate. The thickness of the transparent substrate can be, for example, 10 μm or more and 200 μm or less. In particular, when used for touch panel applications, the thickness of the transparent substrate is preferably 20 μm or more and 120 μm or less, and more preferably 20 μm or more and 100 μm or less. In the case of use for touch panel applications, for example, particularly in applications where it is required to reduce the thickness of the entire display, the thickness of the transparent substrate is preferably 20 μm or more and 50 μm or less.

  The total light transmittance of the transparent substrate is preferably higher. For example, the total light transmittance is preferably 30% or more, and more preferably 60% or more. When the total light transmittance of the transparent substrate is in the above range, the visibility of the display can be sufficiently ensured when used for, for example, a touch panel.

  In addition, the total light transmittance of a transparent base material can be evaluated by the method prescribed | regulated to JISK7361-1.

  Next, the copper-containing metal layer will be described.

  The material constituting the copper-containing metal layer is not particularly limited, and a material having electrical conductivity suitable for the application can be selected. For example, the materials constituting the copper-containing metal layer include Cu, Zn, Ni, Mo, A copper alloy with at least one metal selected from Sn, Ta, Ti, V, Cr, Fe, Mn, Co, and W, or a material containing copper is preferable. The copper-containing metal layer can be a copper layer made of copper.

  The method for forming the copper-containing metal layer on the transparent substrate is not particularly limited, but it is preferable not to arrange an adhesive between the transparent substrate and the copper-containing metal layer in order not to reduce the light transmittance. That is, the copper-containing metal layer is preferably directly formed on at least one surface of the transparent substrate. In addition, when arrange | positioning an adhesion layer between a transparent base material and a copper containing metal layer like the after-mentioned, it is preferable that the copper containing metal layer is directly formed on the upper surface of the adhesion layer.

  When the copper-containing metal layer is formed on the upper surface of the transparent substrate, as described above, the copper-containing metal thin film layer is formed by a dry method such as sputtering or an electroless plating method. Next, a copper-containing metal layer is formed by forming a copper-containing metal plating layer on the copper-containing metal thin film layer by a wet plating method. Thereby, a copper-containing metal layer can be directly formed on the transparent substrate without using an adhesive.

  The dry plating method will be described in detail later. For example, a sputtering method, a vapor deposition method, an ion plating method, or the like can be preferably used.

  Moreover, the film thickness of a copper containing metal layer can be thickened by comprising a copper containing metal layer from a copper containing metal thin film layer and a copper containing metal plating layer. The thickness of the copper-containing metal layer is not particularly limited, and when the copper-containing metal layer is used as a wiring, it can be arbitrarily selected according to the magnitude of current supplied to the wiring, the wiring width, etc. Can do.

  However, when the copper-containing metal layer is thick, it takes time to perform etching to form a wiring pattern, so that side etching is likely to occur, and it may be difficult to form a thin line. For this reason, it is preferable that the thickness of a copper containing metal layer is 5 micrometers or less, and it is more preferable that it is 3 micrometers or less.

  In particular, from the viewpoint of lowering the resistance value of the conductive substrate so that sufficient current can be supplied, for example, the copper-containing metal layer preferably has a thickness of 50 nm or more, more preferably 60 nm or more. More preferably, it is 150 nm or more.

  In addition, when the copper-containing metal layer has the copper-containing metal thin film layer and the copper-containing metal plating layer as described above, the sum of the thickness of the copper-containing metal thin film layer and the thickness of the copper-containing metal plating layer is the above. A range is preferable.

  When the copper-containing metal layer has a copper-containing metal thin film layer and a copper-containing metal plating layer, the thickness of the copper-containing metal thin film layer is not particularly limited, but is preferably, for example, 50 nm to 500 nm.

  As described later, the copper-containing metal layer can be used as a wiring by patterning it into a desired wiring pattern, for example. And since a copper containing metal layer can make an electrical resistance value lower than ITO conventionally used as a transparent conductive film, the electrical resistance value of an electroconductive board | substrate can be made small by providing a copper containing metal layer.

  Next, the organic coating will be described.

  The organic coating can be formed on the surface of the copper-containing metal layer facing a blackening layer described later. Therefore, when it is set as an electroconductive board | substrate, it can arrange | position between a copper containing metal layer and a blackening layer. The organic coating can contain a nitrogen-based organic material. This can particularly enhance the adhesion between the blackened layer, the copper-containing metal layer that is the lower layer of the blackened layer, and the organic coating because the organic coating contains a nitrogen-based organic substance. Therefore, a conductive substrate with stable adhesion between the copper-containing metal layer and the blackened layer can be obtained. In such a conductive substrate, peeling of the blackened layer can be suppressed, so that the etching property of the blackened layer can be improved. Moreover, the reflectance of a conductive substrate can be reduced because an organic film contains a nitrogen-type organic substance.

  The nitrogen-based organic substance used for the organic coating is not particularly limited, and can be arbitrarily selected from organic compounds containing nitrogen. The nitrogen-based organic material used for the organic coating preferably contains, for example, 1,2,3-benzotriazole or a derivative thereof. Specific examples of nitrogen-based organic substances used for the organic coating include 1,2,3-benzotriazole and 5-methyl-1H benzotriazole.

  Examples of the organic solution containing a nitrogen-based organic material that can be suitably used for the organic coating include a rust preventive agent for copper, and commercially available chemicals include, for example, an OPC defender (trade name, Okuno Pharmaceutical). Kogyo Co., Ltd.) can be preferably used.

The content of the nitrogen-based organic substance in the organic coating is preferably 0.2 μg / cm ² or more, and more preferably 0.3 μg / cm ² or more. According to the study by the inventors of the present invention, the reflectance of the conductive substrate can be significantly suppressed by setting the content of the nitrogen-based organic substance in the organic coating to 0.2 μg / cm ² or more. Because it can. In addition, when the content of nitrogenous organic matter in the organic coating increases, the a ^* and b ^* values when the color of the blackened layer is converted to the CIE (L ^* a ^* b ^* ) color system can be lowered. This is because the wiring of the conductive substrate can be made inconspicuous.

  The upper limit of the content of nitrogen-based organic matter in the organic coating is not particularly limited. However, to increase the content of nitrogenous organic matter in the organic coating, increase the concentration of the organic solution containing the nitrogenous organic matter used when forming the organic coating, or immerse it in the organic solution containing the nitrogenous organic matter. For example, it is necessary to lengthen the time to perform the operation. For this reason, if the content of nitrogen-based organic matter in the organic coating is excessively increased, the handling of the solution containing the nitrogen-based organic matter is reduced, the time required to form the organic coating is increased, and production May decrease.

Therefore, the content of the nitrogen-based organic substance in the organic coating is preferably, for example, 10 μg / cm ² or less, and the lower the content, the better the adhesion of the blackened layer, so that it is 1 μg / cm ² or less. More preferably, it is more preferably 0.5 μg / cm ² or less.

  The concentration of the nitrogen-based organic substance in the organic solution used when forming the organic film is not particularly limited, and can be arbitrarily selected in consideration of the content of the nitrogen-based organic substance in the target organic film. it can. For example, the lower limit of the concentration of the nitrogen-based organic substance in the organic solution is preferably 0.08 g / L or more, and more preferably 0.32 g / L or more. Moreover, it is preferable that an upper limit is 0.64 g / L or less.

  The temperature of the organic solution when the organic film is formed on the surface of the copper-containing metal layer by immersing the substrate in the organic solution is not particularly limited, considering the viscosity, operability, reactivity, etc. of the solution. Can be arbitrarily selected. For example, it is preferably 10 ° C. or higher, and more preferably 20 ° C. or higher. However, since the organic solution may react with other substances when the temperature increases, the temperature is preferably 40 ° C. or lower.

  The pH of the organic solution is not particularly limited, and can be selected in consideration of, for example, the type of organic solution used and the reactivity of the solution. For example, the pH of the organic solution is preferably 2 or more, and more preferably 3 or more. However, when the pH is increased, for example, the content of nitrogen-based organic matter in the coating is lowered, so that the pH of the organic solution is preferably 4 or less.

  When forming an organic film on the surface of the copper-containing metal layer, the length of time for immersing the substrate in the organic solution (immersion time) is not particularly limited, and the type of organic solution used and the organic film to be formed It can be arbitrarily selected according to the thickness of the film. For example, the immersion time is preferably 3 seconds or more, and more preferably 4 seconds or more. However, if the immersion time is too long, the productivity may be lowered, and therefore it is preferably 10 seconds or less. In the above-described method for producing an organic coating, the immersion time can be set to a desired time by adjusting the conveyance speed of the substrate.

  Next, the blackened layer will be described.

  The blackening layer can be formed on the top surface of the organic coating.

  The material of the blackening layer is not particularly limited, and any material that can suppress the reflection of light on the surface of the copper-containing metal layer can be suitably used.

  The blackening layer preferably contains at least one metal selected from, for example, Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. Further, the blackening layer may further contain one or more elements selected from carbon, oxygen, hydrogen, and nitrogen.

  The blackening layer can also include a metal alloy containing at least two metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. . Also in this case, the blackening layer may further contain one or more elements selected from carbon, oxygen, hydrogen, and nitrogen. At this time, as a metal alloy containing at least two kinds of metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn, a Cu—Ti—Fe alloy is used. Alternatively, a Cu—Ni—Fe alloy, Ni—Cu alloy, Ni—Zn alloy, Ni—Ti alloy, Ni—W alloy, Ni—Cr alloy, and Ni—Cu—Cr alloy can be preferably used. In particular, a Ni—Cu alloy can be used more preferably.

  The method for forming the blackening layer is not particularly limited, and the blackening layer can be formed by any method, for example, a dry method or a wet method.

  When the blackening layer is formed by a dry method, the specific method is not particularly limited, but for example, a dry plating method such as a sputtering method, an ion plating method or a vapor deposition method can be preferably used. When the blackening layer is formed by a dry method, it is more preferable to use a sputtering method because the film thickness can be easily controlled. Note that, as described above, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the blackened layer, and in this case, the reactive sputtering method can be more preferably used.

  When the blackened layer is formed by reactive sputtering, a target containing a metal species constituting the blackened layer can be used as the target. When the blackened layer contains an alloy, a target may be used for each metal species contained in the blackened layer, and the alloy may be formed on the surface of the film-deposited body such as a substrate, and is included in the blackened layer in advance It is also possible to use a target obtained by alloying a metal.

  Further, when the blackened layer contains one or more elements selected from carbon, oxygen, hydrogen, and nitrogen, these are added to the atmosphere when the blackened layer is formed, so that the blackened layer Can be added inside. For example, when adding carbon to the blackening layer, carbon monoxide gas and / or carbon dioxide gas is used, when adding oxygen, oxygen gas is used, and when adding hydrogen, hydrogen gas and / or water is used. In the case of adding nitrogen, nitrogen gas can be added to the atmosphere during sputtering. One or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the blackening layer by adding these gases to the inert gas when forming the blackening layer. Argon can be preferably used as the inert gas.

  When the blackened layer is formed by a wet method, it can be formed by, for example, an electroplating method using a plating solution corresponding to the material of the blackened layer.

  As described above, the blackening layer can be formed by either a dry method or a wet method, but when the blackening layer is formed, the material constituting the organic coating is dissolved in the plating solution, Since incorporation into the blackened layer may affect the color tone and other characteristics of the blackened layer, it is preferable to form a film by a dry method.

  Although the thickness of a blackening layer is not specifically limited, For example, it is preferable that it is 15 nm or more, and it is more preferable that it is 25 nm or more. This is because, when the thickness of the blackened layer is thin, reflection of light on the surface of the copper-containing metal layer may not be sufficiently suppressed, so that the thickness of the blackened layer is set to 15 nm or more as described above. It is because it is preferable to comprise so that reflection of the light in the copper containing metal layer surface can be suppressed especially.

  The upper limit of the thickness of the 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. Will be invited. For this reason, the thickness of the blackened layer is preferably 70 nm or less, and more preferably 50 nm or less.

  In addition, the conductive substrate may be provided with an arbitrary layer other than the above-described transparent substrate, copper-containing metal layer, organic coating, and blackening layer. For example, an adhesion layer can be provided.

  A configuration example of the adhesion layer will be described.

  As described above, the copper-containing metal layer can be formed on the transparent substrate, but when the copper-containing metal layer is directly formed on the transparent substrate, the adhesion between the transparent substrate and the copper-containing metal layer is It may not be enough. For this reason, when a copper containing metal layer is directly formed on the upper surface of a transparent base material, a copper containing metal layer may peel from a transparent base material at the time of a manufacture process or use.

  Therefore, in the conductive substrate of the present embodiment, an adhesion layer can be disposed on the transparent substrate in order to improve the adhesion between the transparent substrate and the copper-containing metal layer.

  By disposing the adhesion layer between the transparent substrate and the copper-containing metal layer, the adhesion between the transparent substrate and the copper-containing metal layer can be improved, and the copper-containing metal layer can be prevented from peeling from the transparent substrate. .

  Further, the adhesion layer can function as a blackening layer. For this reason, it becomes possible to also suppress reflection of the light of the copper containing metal layer by the light from the lower surface side of the copper containing metal layer, that is, the transparent base material side.

  The material constituting the adhesion layer is not particularly limited, the adhesion strength between the transparent substrate and the copper-containing metal layer, the required degree of suppression of light reflection on the surface of the copper-containing metal layer, and the conductivity. It can be arbitrarily selected according to the degree of stability to the environment (for example, humidity and temperature) in which the conductive substrate is used.

  The adhesion layer preferably contains at least one metal selected from, for example, Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. The adhesion layer can further include one or more elements selected from carbon, oxygen, hydrogen, and nitrogen.

  Note that the adhesion layer may include a metal alloy including at least two kinds of metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. Also in this case, the adhesion layer can further include one or more elements selected from carbon, oxygen, hydrogen, and nitrogen. At this time, as a metal alloy containing at least two kinds of metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn, a Cu—Ti—Fe alloy is used. Alternatively, a Cu—Ni—Fe alloy, Ni—Cu alloy, Ni—Zn alloy, Ni—Ti alloy, Ni—W alloy, Ni—Cr alloy, and Ni—Cu—Cr alloy can be preferably used. In particular, a Ni—Cu alloy can be used more preferably.

  The method for forming the adhesion layer is not particularly limited, but it is preferable to form the film by a dry plating method. As the dry plating method, for example, a sputtering method, an ion plating method, a vapor deposition method, or the like can be preferably used. In the case where the adhesion layer is formed by a dry method, it is more preferable to use a sputtering method because the film thickness can be easily controlled. Note that, as described above, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the adhesion layer, and in this case, a reactive sputtering method can be more preferably used.

  When the adhesion layer contains one or more elements selected from carbon, oxygen, hydrogen, and nitrogen, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen in the atmosphere when forming the adhesion layer Can be added to the adhesion layer. For example, when adding carbon to the adhesion layer, carbon monoxide gas and / or carbon dioxide gas, when adding oxygen, oxygen gas, when adding hydrogen, hydrogen gas and / or water, In the case of adding nitrogen, nitrogen gas can be added to the atmosphere when dry plating is performed.

  A gas containing one or more elements selected from carbon, oxygen, hydrogen, and nitrogen is preferably added to an inert gas and used as an atmosphere gas during dry plating. Although it does not specifically limit as an inert gas, For example, argon can be used preferably.

  By forming the adhesion layer by dry plating as described above, the adhesion between the transparent substrate and the adhesion layer can be enhanced. And since an adhesion layer can contain a metal as a main component, for example, adhesiveness with a copper content metal layer is also high. For this reason, peeling of a copper containing metal layer can be suppressed by arrange | positioning an adhesion layer between a transparent base material and a copper containing metal layer.

  The thickness of the adhesion layer is not particularly limited, but is preferably 3 nm to 50 nm, for example, more preferably 3 nm to 35 nm, and still more preferably 3 nm to 33 nm.

  When the adhesion layer also functions as a blackening layer, that is, when light reflection in the copper-containing metal layer is suppressed, the thickness of the adhesion layer is preferably 3 nm or more as described above.

  The upper limit value of the thickness of the adhesion 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. Will be invited. For this reason, the thickness of the adhesion layer is preferably 50 nm or less as described above, more preferably 35 nm or less, and further preferably 33 nm or less.

  Next, a configuration example of the conductive substrate will be described.

  As described above, the conductive substrate of this embodiment can have a transparent substrate, a copper-containing metal layer, an organic coating, and a blackening layer. Further, a layer such as an adhesion layer can be optionally provided.

  A specific configuration example will be described below with reference to FIG. FIG. 2 shows an example of a cross-sectional view of the conductive substrate of the present embodiment on a plane parallel to the lamination direction of the transparent base material, the copper-containing metal layer, the organic coating, and the blackening layer.

  The conductive substrate of this embodiment has, for example, a structure in which a copper-containing metal layer, an organic coating, and a blackening layer are laminated in that order from the transparent substrate side on at least one surface of the transparent substrate. Can do.

  Specifically, for example, like the conductive substrate 20A shown in FIG. 2A, the copper-containing metal layer 22, the organic coating 23, the blackening layer 24, and the like on the one surface 21a side of the transparent base material 21. Can be stacked one by one in that order. Moreover, like the electroconductive board | substrate 20B shown in FIG.2 (b), 22A of copper containing metal layers are respectively provided in the one surface 21a side of the transparent base material 21, and the other surface (other surface) 21b side. , 22B, organic coatings 23A, 23B, and blackening layers 24A, 24B can be stacked one by one in that order.

  Furthermore, as an arbitrary layer, for example, a configuration in which an adhesion layer is provided may be employed. In this case, for example, a structure in which an adhesion layer, a copper-containing metal layer, an organic coating, and a blackening layer are formed in that order on at least one surface of the transparent substrate from the transparent substrate side. .

  Specifically, for example, as in the conductive substrate 30A shown in FIG. 3A, the adhesion layer 25, the copper-containing metal layer 22, and the organic coating 23 are formed on one surface 21a side of the transparent base material 21. The blackening layer 24 can be stacked in that order.

  In this case as well, a configuration in which an adhesive layer, a copper-containing metal layer, an organic coating, and a blackening layer are laminated on both surfaces of the transparent substrate 21 can be employed. Specifically, as in the conductive substrate 30B shown in FIG. 3B, the adhesive layers 25A and 25B and the copper-containing layer are provided on one surface 21a side and the other surface 21b side of the transparent base material 21, respectively. Metal layers 22A and 22B, organic coatings 23A and 23B, and blackening layers 24A and 24B can be stacked in that order.

  In FIGS. 2B and 3B, when a copper-containing metal layer, an organic coating, a blackening layer, etc. are laminated on both surfaces of the transparent substrate, the transparent substrate 21 is used as a symmetrical surface. Although the example arrange | positioned so that the layer laminated | stacked on the upper and lower sides of 21 might become symmetrical was shown, it is not limited to the form which concerns. For example, in FIG. 3B, the configuration on the one surface 21a side of the transparent substrate 21 is the same as the configuration of FIG. 2B, and the copper-containing metal layer 22A and the organic coating 23A are provided without providing the adhesion layer 25A. And the blackened layer 24A may be stacked in that order, and the layers stacked above and below the transparent substrate 21 may be asymmetrical.

  In the conductive substrate of this embodiment, reflection of light by the copper-containing metal layer is suppressed by providing a copper-containing metal layer, an organic coating, and a blackening layer on the transparent substrate. The reflectance can be suppressed.

  The degree of reflectivity of the conductive substrate of the present embodiment is not particularly limited. For example, in order to increase the visibility of a display when used as a conductive substrate for a touch panel, the reflectivity is lower. Is good. For example, the average reflectance of light having a wavelength of 400 nm to 700 nm is preferably 20% or less, more preferably 17% or less, and particularly preferably 15% or less.

  The reflectance can be measured by irradiating the blackened layer of the conductive substrate with light. Specifically, for example, as shown in FIG. 2A, when the copper-containing metal layer 22, the organic coating 23, and the blackening layer 24 are sequentially laminated on the one surface 21 a side of the transparent base material 21, Measurement can be performed by irradiating the surface A of the blackened layer 24 with light so as to irradiate light. In the measurement, light having a wavelength of 400 nm or more and 700 nm or less is irradiated to the blackened layer 24 of the conductive substrate, for example, at a wavelength of 1 nm as described above, and the average value of the measured values is used as the reflectance of the conductive substrate. be able to.

  The conductive substrate of this embodiment can be preferably used as a conductive substrate for a touch panel. In this case, the conductive substrate can be configured to have mesh-like wiring.

  The conductive substrate provided with the mesh-like wiring can be obtained by etching the copper-containing metal layer, the organic coating, and the blackening layer of the conductive substrate 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. 4 shows a view of the conductive substrate 40 provided with mesh-like wiring as viewed from the upper surface side in the stacking direction of the copper-containing metal layer or the like. The layers other than the wirings 41A and 41B formed by patterning the contained metal layer are not shown. In addition, a wiring 41B that can be seen through the transparent substrate 21 is also shown.

  The conductive substrate 40 shown in FIG. 4 has a transparent base material 21, a plurality of wirings 41A parallel to the Y-axis direction in the drawing, and wirings 41B parallel to the X-axis direction. The wirings 41A and 41B are formed by etching a copper-containing metal layer, and an organic film and a blackening layer (not shown) are formed on the upper and / or lower surfaces of the wirings 41A and 41B. Further, the organic coating and the blackened layer are etched in the same shape as the wirings 41A and 41B in the cross section in a plane parallel to the surface (also referred to as the main surface of the transparent substrate) on which the wiring of the transparent substrate is formed. .

  The arrangement of the transparent substrate 21 and the wirings 41A and 41B is not particularly limited. A configuration example of the arrangement of the transparent base material 21 and the wiring is shown in FIGS. 5A and 5B correspond to cross-sectional views taken along the line AA ′ of FIG.

  First, as shown to Fig.5 (a), wiring 41A, 41B may be arrange | positioned at the upper and lower surfaces of the transparent base material 21, respectively. In FIG. 5A, organic coatings 42A and 42B and blackening layers 43A and 43B etched in the same shape as the wiring are disposed on the upper surface of the wiring 41A and the lower surface of 41B.

  Further, as shown in FIG. 5B, a pair of transparent base materials 21 is used, and wirings 41A and 41B are arranged on the upper and lower surfaces with one transparent base material 21 interposed therebetween, and one wiring 41B is You may arrange | position between the transparent base materials 21. FIG. Also in this case, organic coatings 42A and 42B and blackening layers 43A and 43B etched in the same shape as the wiring are arranged on the upper surfaces of the wirings 41A and 41B. As described above, an adhesion layer can be provided in addition to the copper-containing metal layer, the organic coating, and the blackening layer. Therefore, in either case of FIGS. 5A and 5B, for example, an adhesion layer can be provided between the wiring 41 </ b> A and / or the wiring 41 </ b> B and the transparent substrate 21. When the adhesion layer is provided, the adhesion layer is also preferably etched into the same shape as the wirings 41A and 41B.

  The conductive substrate having the mesh-like wiring shown in FIGS. 4 and 5A is, for example, copper-containing metal layers 22A and 22B and an organic coating 23A on both surfaces of the transparent base material 21 as shown in FIG. 2B. , 23B and a conductive substrate provided with blackening layers 24A, 24B.

  When the case where it forms using the conductive substrate of FIG.2 (b) is demonstrated to an example, first, the copper containing metal layer 22A, the organic coating 23A, and the blackening layer 24A of the one surface 21a side of the transparent base material 21 will be described. Etching is performed so that a plurality of linear patterns parallel to the Y-axis direction in FIG. 2B are arranged at predetermined intervals along the X-axis direction. In addition, the X-axis direction in FIG.2 (b) means the direction parallel to the width direction of each layer. Further, the Y-axis direction in FIG. 2 (b) means a direction perpendicular to the paper surface in FIG. 2 (b).

  Then, the copper-containing metal layer 22B, the organic coating 23B, and the blackening layer 24B on the other surface 21b side of the transparent base material 21 have a predetermined linear pattern parallel to the X-axis direction in FIG. Etching is performed so as to be arranged along the Y-axis direction at intervals.

  Through the above operation, the conductive substrate having the mesh-like wiring shown in FIGS. 4 and 5A can be formed. Note that the etching of both surfaces of the transparent substrate 21 can be performed simultaneously. That is, the etching of the copper-containing metal layers 22A and 22B, the organic coatings 23A and 23B, and the blackening layers 24A and 24B may be performed simultaneously. 5A, a conductive substrate having an adhesion layer patterned in the same shape as the wirings 41A and 41B between the wirings 41A and 41B and the transparent base material 21 is shown in FIG. It can be manufactured by performing etching in the same manner using the conductive substrate shown.

  The conductive substrate having the mesh-like wiring shown in FIG. 4 can be formed by using two conductive substrates shown in FIG. An example of the case where two conductive substrates shown in FIG. 2A are used will be described. For the two conductive substrates shown in FIG. 2A, a copper-containing metal layer 22, an organic coating 23, and The blackened layer 24 is etched so that a plurality of linear patterns parallel to the X-axis direction are arranged along the Y-axis direction with a predetermined interval. Then, the conductive substrate having mesh-like wiring is obtained by bonding the two conductive substrates so that the linear patterns formed on the respective conductive substrates intersect with each other by the etching process. be able to. The surface to be bonded when the two conductive substrates are bonded is not particularly limited. For example, the surface A in FIG. 2A in which the copper-containing metal layer 22 or the like is laminated and the other surface 21b in FIG. 2A in which the copper-containing metal layer 22 or the like is not laminated are bonded together. The structure shown in FIG. 5 (b) can also be obtained.

  Further, for example, the other surfaces 21b in FIG. 2A where the copper-containing metal layer 22 or the like of the transparent base material 21 is not laminated are bonded together so that the cross section has the structure shown in FIG. You can also.

  5 (a) and 5 (b), a conductive substrate having an adhesion layer that is further patterned in the same shape as the wirings 41A and 41B between the wirings 41A and 41B and the transparent base material 21, It can be manufactured by using the conductive substrate shown in FIG. 3A instead of the conductive substrate shown in FIG.

  The wiring width and the distance between the wirings in the conductive substrate having the mesh wiring shown in FIGS. 4 and 5 are not particularly limited, and may be selected according to the amount of current flowing through the wiring, for example. Can do.

  4 and 5 show examples in which a mesh-like wiring (wiring pattern) is formed by combining linear wirings, but the present invention is not limited to such a configuration, and a wiring pattern is configured. The wiring can have any shape. For example, the shape of the wiring constituting the mesh-like wiring pattern can be changed to various shapes such as jagged lines (zigzag straight lines) so that moire (interference fringes) does not occur between the images on the display.

  Thus, a conductive substrate having a mesh-like wiring composed of two layers of wiring can be preferably used as a conductive substrate for a projected capacitive touch panel, for example.

Among the steps included in the method for producing a conductive substrate, in the copper-containing metal layer forming step, the copper-containing metal layer 22 is formed on at least one surface 21a of the transparent substrate 21 by a wet method as shown in FIG. Is done. In addition,
The transparent base material 21 used for the copper-containing metal layer forming step can be prepared in advance. Although the kind of transparent base material to be used is not particularly limited, a transparent base material such as a resin substrate (resin film) that transmits visible light or a glass substrate can be preferably used as described above. The transparent base material can be cut into an arbitrary size in advance if necessary.

  The copper-containing metal layer can have a copper-containing metal plating layer as described above. Moreover, a copper containing metal layer can also have a copper containing metal thin film layer and a copper containing metal plating layer. For this reason, it can have the process of forming a copper content metal plating layer, for example by a wet plating method, before a copper content metal layer formation process. Moreover, a copper containing metal layer formation process can be performed after the process of forming a copper containing metal thin film layer by the dry-type plating method or the electroless-plating method previously. And it can be set as the process of forming a copper containing metal plating layer by the electroplating method which is a kind of wet-plating method by using this copper containing metal thin film layer as an electric power feeding layer.

  In addition, it does not specifically limit as a dry-type plating method used at the process of forming a copper containing metal thin film layer, For example, a vapor deposition method, sputtering method, or an ion plating method etc. can be used. In addition, as a vapor deposition method, a vacuum vapor deposition method can be used preferably. As the dry plating method used in the step of forming the copper-containing metal thin film layer, it is more preferable to use the sputtering method because the film thickness is particularly easy to control.

  Next, the process of forming a copper-containing metal plating layer will be described. In addition, the process of forming a copper containing metal plating layer is included in the copper containing metal layer forming process. The conditions in the step of forming the copper-containing metal plating layer by the wet plating method, that is, the conditions for the electroplating treatment are not particularly limited, and various conditions according to ordinary methods may be adopted. For example, a copper-containing metal plating layer can be formed by supplying a base material on which a copper-containing metal thin film layer is formed in a plating tank containing a metal plating solution and controlling the current density and the conveyance speed of the base material.

  Since materials that can be suitably used for the copper-containing metal layer, suitable thicknesses of the copper-containing metal layer, and the like have already been described, description thereof is omitted here.

  Next, an organic film formation process is demonstrated.

  In the organic film forming step, the transparent base material 21 on which the copper-containing metal layer 22 is formed is immersed in a solution of a nitrogen-based organic substance in the bath, thereby forming the copper-containing metal layer 22 formed on the transparent base material 21. An organic coating is formed. In addition, this organic film formation process can use the organic film production | generation means contained in the organic film formation process included in the manufacturing method of the above-mentioned organic film, or an organic film manufacturing apparatus.

  In the organic film forming step, the copper concentration of the nitrogen-based organic solution in the bath is adjusted to 15 ppm or less, preferably 8 ppm or less. Thereby, even if the plating solution which remained on the transparent base material 21 is brought into a bathtub, it can prevent that the copper concentration of the solution in a bathtub becomes high. Therefore, it is possible to prevent the organic coating from becoming excessively thick.

  In the organic film forming step, the replenishment solution can be replenished to the bath so that the copper concentration of the solution in the bath is 15 ppm or less. In this case, it is easy to adjust the copper concentration of the solution in the bath to a low concentration of 15 ppm or less. Therefore, even if the plating solution remaining on the transparent substrate 21 is brought into the bathtub, it is possible to reliably prevent the copper concentration of the solution in the bathtub from increasing. Therefore, it is possible to prevent the organic coating from becoming excessively thick with high accuracy.

  As described above, by providing an organic coating between the copper-containing metal layer and the blackening layer, it is possible to suppress the organic coating from becoming excessively thick. Therefore, while suppressing the reflectance of the conductive substrate, the adhesion of the blackened layer can be improved and the etching property can be improved.

  The organic coating can be formed by the method for producing an organic coating described above. Moreover, since the organic solution etc. used when forming an organic film are already described, description is abbreviate | omitted here.

  Next, the blackening layer forming process will be described.

  In the blackened layer forming step, a blackened layer can be formed on the upper surface of the organic coating. In the blackening layer forming step, the method for forming the blackening layer is not particularly limited, and can be formed by any method.

  As a method for forming the blackened layer in the blackened layer forming step, for example, a dry plating method such as a sputtering method, an ion plating method, or a vapor deposition method can be preferably used. In particular, the sputtering method is more preferable because the film thickness can be easily controlled. As described above, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the blackened layer, and in this case, the reactive sputtering method can be more preferably used.

  Further, as described above, the blackened layer can be formed by a wet method such as an electroplating method.

  However, when forming the blackened layer, the materials that make up the organic coating may be dissolved in the plating solution and taken into the blackened layer, which may affect the color tone and other characteristics of the blackened layer. Therefore, it is preferable to form a film by a dry method.

  Since the materials that can be suitably used for the blackened layer, the preferred thickness of the blackened layer, and the like have already been described, description thereof is omitted here.

  In the method for manufacturing a conductive substrate according to the present embodiment, an arbitrary step can be further performed in addition to the above-described steps.

  For example, when forming an adhesion layer between a transparent substrate and a copper-containing metal layer, an adhesion layer forming step of forming an adhesion layer on the surface of the transparent substrate on which the copper-containing metal layer is formed can be performed. When carrying out the adhesion layer forming step, the copper-containing metal layer forming step can be carried out after the adhesion layer forming step, and in the copper-containing metal layer forming step, the adhesion layer is formed on the transparent substrate in this step. A copper-containing metal thin film layer can be formed on the substrate.

  In the adhesion layer forming step, the method for forming the adhesion layer is not particularly limited, but it is preferable to form the film by a dry plating method. As the dry plating method, for example, a sputtering method, an ion plating method, a vapor deposition method, or the like can be preferably used. In the case where the adhesion layer is formed by a dry method, it is more preferable to use a sputtering method because the film thickness can be easily controlled. As described above, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the adhesion layer, and in this case, the reactive sputtering method can be more preferably used.

  Since materials that can be suitably used for the adhesion layer, suitable thicknesses of the adhesion layer, and the like have already been described, description thereof is omitted here.

  The conductive substrate obtained by the method for manufacturing a conductive substrate of the present embodiment can be used for various applications such as a touch panel. And when using for various uses, it is preferable that the copper containing metal layer, organic coating, and blackening layer which are contained in the electroconductive board | substrate of this embodiment are patterned. In addition, when providing an adhesion layer, it is preferable that the adhesion layer is also patterned. Copper-containing metal layers, organic coatings, and blackening layers, and in some cases, further adhesion layers can be patterned to match the desired wiring pattern, for example, copper-containing metal layers, organic coatings, and blackening layers. Depending on the case, it is preferable that the adhesion layer is further patterned in the same shape.

  For this reason, the manufacturing method of the electroconductive board | substrate of this embodiment can have the patterning process of patterning a copper containing metal layer, an organic film, and a blackening layer. When the adhesion layer is formed, the patterning step can be a step of patterning the adhesion layer, the copper-containing metal layer, the organic coating, and the blackening layer.

  The specific procedure of the patterning step is not particularly limited, and can be performed by an arbitrary procedure. For example, in the case of a conductive substrate 20A in which a copper-containing metal layer 22, an organic coating 23, and a blackening layer 24 are laminated on a transparent substrate 21 as shown in FIG. A mask placement step of placing a mask having a desired pattern can be performed. Next, an etching step of supplying an etching solution to the surface A on the blackened layer 24, that is, the surface side where the mask is disposed can be performed.

  The etchant used in the etching step is not particularly limited, and can be arbitrarily selected depending on the material constituting the layer to be etched. For example, the etching solution can be changed for each layer, and the copper-containing metal layer, the organic coating, and the blackening layer, and in some cases, the adhesion layer can be further etched with the same etching solution.

  Moreover, the electroconductivity which laminated | stacked copper containing metal layer 22A, 22B, organic coating 23A, 23B, and blackening layer 24A, 24B on the one surface 21a and the other surface 21b of the transparent base material 21 like FIG.2 (b). A patterning process for patterning the substrate 20B can also be performed. In this case, for example, a mask placement step of placing a mask having a desired pattern on the surface A and the surface B on the blackening layers 24A and 24B can be performed. Next, an etching step of supplying an etching solution to the surface A and the surface B on the blackening layers 24A and 24B, that is, the surface side where the mask is disposed can be performed.

  The pattern formed in the etching step is not particularly limited, and can be an arbitrary shape. For example, in the case of the conductive substrate 20A shown in FIG. 2A, as described above, the copper-containing metal layer 22, the organic coating 23, and the blackened layer 24 are formed by a plurality of straight lines or jagged lines (zigzag straight lines). ) Can be formed.

  In the case of the conductive substrate 20B shown in FIG. 2B, a pattern can be formed so as to form a mesh-like wiring with the copper-containing metal layer 22A and the copper-containing metal layer 22B. In this case, the organic coating 23A and the blackening layer 24A are patterned to have the same shape as the copper-containing metal layer 22A, and the organic coating 23B and the blackening layer 24B are patterned to have the same shape as the copper-containing metal layer 22B. It is preferable to carry out.

  In addition, for example, after patterning the copper-containing metal layer 22 and the like on the conductive substrate 20A described above in a patterning step, a stacking step of stacking two or more patterned conductive substrates can be performed. When laminating, for example, by laminating so that the patterns of the copper-containing metal layers of each conductive substrate intersect, it is also possible to obtain a laminated conductive substrate provided with mesh-like wiring.

  The method for fixing two or more laminated conductive substrates is not particularly limited, but can be fixed by, for example, an adhesive.

  The conductive substrate obtained by the conductive substrate manufacturing method of the present embodiment described above comprises an organic coating and a blackening layer on a copper-containing metal layer formed on at least one surface of a transparent substrate. It has a laminated structure. Moreover, since the organic film is manufactured by the method for manufacturing an organic film described above, a uniform film can be obtained.

  For this reason, the adhesion between the blackened layer and the copper-containing metal layer and the organic film, which are the lower layers of the blackened layer, can be particularly improved, and the blackened layer can be prevented from being peeled off. Can be increased. That is, by forming such an organic film between the blackening layer and the copper-containing metal layer, it is possible to prevent the organic film from becoming excessively thick. As a result, the adhesion of the blackened layer can be improved and the etching property can be improved.

  Furthermore, since fine wiring processing can be easily performed on a copper-containing metal layer, a blackened layer, and the like, it is possible to suppress the reflection of light on the surface of the copper-containing metal layer and to obtain a conductive substrate with a suppressed reflectance. it can. Therefore, when such a conductive substrate is used for applications such as a touch panel, the visibility of the display can be improved.

Specific examples and comparative examples will be described below, but the present invention is not limited to these examples.
(Evaluation method)
First, a method for evaluating the adhesion of the blackened layer of the obtained conductive substrate will be described.

  As shown in FIG. 6, using a cutting tool (Cross Cut Kit 1.0MM manufactured by Precision Gate & Tool Company) for the blackened layer of the conductive substrate formed up to the blackened layer, a vertical cut line having a length of 20 mm. Eleven 61a are formed in parallel with each other at intervals of 1.0 mm.

  Next, using the same cutting tool, eleven horizontal cutting lines 61b having a length of 20 mm are formed at intervals of 1.0 mm so as to be perpendicular to the previously formed vertical cutting lines 61a.

  Through the above steps, as shown in FIG. 6, a grid-like cut is formed in the blackened layer by 11 cut lines in the vertical and horizontal directions.

  Next, an adhesiveness evaluation tape (Elcometer 99 tape manufactured by Elcomometer Co., Ltd.) is applied so as to cover the grid-shaped cuts, and then sufficiently rubbed.

  After 30 seconds have passed since the adhesiveness evaluation tape was applied, the adhesiveness evaluation tape is quickly peeled off in the direction of 180 ° to the measurement surface as much as possible.

  After peeling off the adhesiveness evaluation tape, the copper-containing metal layer formed below the blackened layer in the evaluation region 62 in FIG. 6 surrounded by the grid-like vertical cut lines 61a and the horizontal cut lines 61b. The adhesion was evaluated based on the exposed area of the (organic material layer).

  5B when the exposed area of the copper-containing metal layer in the evaluation region is 0%, 4B when it is more than 0% and less than 5%, 3B when it is 5% or more and less than 15%, and 15% or more and less than 35% Was evaluated as 2B, 1B when 35% or more and less than 65%, and 0B when 65% or more. For such evaluation, 0B has the lowest adhesion of the blackened layer, and 5B has the highest adhesion of the blackened layer.

As a result of the adhesion test, it can be evaluated that the adhesion of the blackened layer is sufficient in the cases of 4B and 5B. That is, it shows that the organic coating is formed so that the thickness of the organic coating is a desired thickness that does not peel off the blackened layer.
(Sample preparation conditions)
As examples and comparative examples, conductive substrates were produced under the conditions described below and evaluated by the above-described evaluation method.
[Example 1]
(Adhesion layer forming process)
An adhesion layer was formed on one surface of a transparent substrate made of polyethylene terephthalate resin (PET), which is a long sheet having a width of 570 mm and a thickness of 50 μm. In addition, about the transparent base material made from the polyethylene terephthalate resin used as a transparent base material, when the total light transmittance was evaluated by the method prescribed | regulated to JISK7361-1, it was 97%.

  In the adhesion layer forming step, a Ni—Cu alloy layer containing oxygen was formed as an adhesion layer by a roll-to-roll sputtering apparatus equipped with a Ni-17 wt% Cu alloy target. The procedure for forming the adhesion layer will be described below.

  The above-mentioned transparent base material, which was previously heated to 60 ° C. to remove moisture, was placed in the chamber of the sputtering apparatus.

Next, after exhausting the inside of the chamber to 1 × 10 ⁻³ Pa, argon gas and oxygen gas were introduced, and the pressure in the chamber was set to 1.3 Pa. At this time, the atmosphere in the chamber is 30% oxygen by volume, and the remainder is argon.

Then, an electric power was supplied to the target in such an atmosphere, and an adhesion layer was formed on one surface of the transparent substrate so as to have a thickness of 20 nm while conveying the transparent substrate.
(Copper-containing metal layer forming process)
In the copper-containing metal layer forming step, the copper-containing metal plating layer forming step was performed.

  In addition, the copper containing metal thin film layer forming process was implemented before the copper containing metal layer forming process.

  First, the copper-containing metal thin film layer forming step will be described.

  In the copper-containing metal thin film layer forming step, a copper thin film layer was formed on the adhesion layer as a copper-containing metal thin film layer using a substrate in which the adhesion layer was formed on the transparent substrate in the adhesion layer forming step.

  The copper-containing metal thin film layer is the same as the case of the adhesive layer except that the copper target is used and the inside of the chamber in which the base material is set is evacuated and then an argon gas is supplied to form an argon atmosphere. The film was formed by a roll-to-roll sputtering apparatus.

  The copper thin film layer, which is a copper-containing metal thin film layer, was formed to have a film thickness of 150 nm. The base material on which the copper-containing metal thin film layer is formed is wound around an unwinding roller of an organic film manufacturing apparatus equipped with a roll-to-roll type transport means. And as shown in FIG. 1, the base material 14 wound up by the unwinding roller 15 is conveyed by the below-mentioned plating bath 11a with the conveyance speed of 3.5 m / min from the unwinding roller 15, and a copper containing metal layer formation is carried out. A process is performed.

  In the copper-containing metal layer forming step, a copper-containing metal layer is formed by forming a copper-containing metal plating layer by a wet plating method on the copper-containing metal thin film layer previously formed by sputtering in the copper-containing metal thin film layer forming step. did. Specifically, using the organic film manufacturing apparatus of FIG. 1, the base material 14 on which the copper-containing metal thin film layer is formed is passed through a plating bath 11a containing a plating solution 11b (copper sulfate solution), and electroplating is performed. A copper-containing metal plating layer was formed by a method such that the thickness of the copper-containing metal plating layer was 0.5 μm.

Thereafter, the base material 14 on which the copper-containing metal layer is formed is one surface on which the organic coating film of the base material 14 is formed by the water washing means 17 and the air knife 18 provided on the downstream side of the plating bath 11a. The copper-containing metal layer was washed and drained. The base material 14 that has been cleaned and drained is conveyed to a bathtub 12a containing a rust preventive agent described later, and an organic film forming step is performed.
(Organic film forming process)
In the organic coating forming step, an organic coating was formed on the copper-containing metal layer of the substrate on which the adhesion layer and the copper-containing metal layer were formed on the transparent substrate. In the organic film forming step, an organic film was formed using an example of the organic film manufacturing apparatus of FIG.

  In the organic film forming step, an aqueous solution (solution 12b) of a rust preventive agent (OPC diffuser, manufactured by Okuno Pharmaceutical Co., Ltd.) containing 1,2,3-benzotriazole, which is a nitrogen-based organic substance, is used as the organic solution. The base material 14 was immersed in this bath for 7 seconds. The organic solution was adjusted in advance so that the concentration of the rust inhibitor was 1.6 ml / L, the volume was 120 L, the bath temperature was 23 ° C., and the pH was 3.

  In addition, the bathtub 12a was replenished with 5 L of an aqueous solution of 6.5 ml / L of an anticorrosive treatment agent per hour and adjusted so that the copper concentration after operating continuously for 7 hours was 6 ppm or less. The replenishment of the antirust treatment agent was performed by replenishing the bath 12a with the replenishment solution 13b from the tank 13a in which the replenishment antirust treatment agent aqueous solution (replenishment solution 13b) was stored via the replenishment pipe 13c.

Thereafter, the base material 14 on which the organic film has been formed through the organic film forming step is further adhered to the surface of the base material 14 by the washing means 19 provided on the downstream side in the transport direction of the base material 14 (the direction of the block arrow 1). The organic solution was washed and removed, dried by a drying means (not shown), and the substrate on which the organic film was formed was taken up by a take-up roll (not shown).
(Blackening layer forming process)
In the blackened layer forming step, a Ni—Cu layer was formed as a blackened layer by sputtering on the organic coating formed on the substrate 14 in the organic coating forming step.

  In the blackening layer forming step, a Ni—Cu alloy layer was formed as a blackening layer by a roll-to-roll sputtering apparatus equipped with a target of Ni-35 wt% Cu alloy. The procedure for forming the blackened layer will be described below.

  First, the laminated body which laminated | stacked the contact | adherence layer, the copper containing metal layer, and the organic film on the transparent base material was set in the chamber of sputtering apparatus.

Next, after evacuating the inside of the chamber to 1 × 10 ⁻³ Pa, argon gas was introduced and the pressure in the chamber was set to 1.3 Pa.

  Then, power was supplied to the target in such an atmosphere, and a blackened layer was formed on the organic coating so as to have a thickness of 30 nm while transporting the base material.

  Through the above steps, a blackening layer is formed on the upper surface of the copper-containing metal layer, that is, the surface opposite to the surface facing the adhesion layer of the copper-containing metal layer via an organic coating, and is adhered to the transparent substrate. A conductive substrate in which a layer, a copper-containing metal layer, an organic coating, and a blackening layer were laminated in that order was obtained.

It was 5B when the adhesiveness test was implemented about the obtained electroconductive board | substrate.
[Example 2]
In the organic film forming process, using the above-mentioned organic film manufacturing apparatus, the bath was not replenished with an aqueous solution of a rust inhibitor, but it was operated continuously for 7 hours, and the copper concentration was adjusted to 10 ppm. A conductive substrate was produced in the same manner as in Example 1.

It was 4B when the adhesiveness test was implemented about the obtained electroconductive board | substrate.
[Comparative Example 1]
In the organic film forming step, using the above-mentioned organic film production apparatus, except that the bath was not replenished quantitatively with the aqueous solution of the anticorrosive treatment agent and operated continuously for 14 hours, and the copper concentration was adjusted to 18 ppm, A conductive substrate was produced in the same manner as in Example 1 except for the above.

  It was 3B when the adhesiveness test was implemented about the obtained electroconductive board | substrate.

  From the results of Example 1, Example 2, and Comparative Example 1, by adjusting the copper concentration of the aqueous solution of the rust preventive agent in the bath to 15 ppm or less, the result of the adhesion test becomes 4B or more, and the blackening layer It was confirmed that the adhesion can be improved. This result shows that the thickness of the organic coating was controlled to an appropriate thickness.

  Moreover, adjusting the copper concentration of the aqueous solution of the rust preventive agent in the bathtub to 8 ppm or less while replenishing the aqueous solution of the rust preventive agent in the bathtub from the results of Example 1, Example 2, and Comparative Example 1. Thus, the result of the adhesion test was 5B, and it was confirmed that the adhesion of the blackened layer could be further improved. This result shows that the thickness of the organic coating was controlled to a particularly appropriate thickness.

DESCRIPTION OF SYMBOLS 10 Organic film manufacturing apparatus 11 Copper containing metal layer formation means 12 Organic film formation means 12a Bath 12b Solution 13 Adjustment means 14 Sheet-like base material 20A, 20B, 30A, 30B, 40 Conductive substrate 21 Transparent base material 22, 22A, 22B Copper-containing metal layer 23, 23A, 23B, 42A, 42B Organic coating 24, 24A, 24B, 43A, 43B Blackening layer

Claims (6)

An organic film forming step of forming an organic film on the upper surface of the copper-containing metal layer by immersing the base material on which the copper-containing metal layer is formed in a solution of a nitrogen-based organic material in a bath;
In the organic film forming step, the copper concentration of the solution in the bath is adjusted to 15 ppm or less.   2. The method for producing an organic coating according to claim 1, wherein, in the organic coating forming step, the bath is supplemented with a nitrogen-based organic solution so that the copper concentration of the solution in the bath is 15 ppm or less. A copper-containing metal layer forming step of forming a copper-containing metal layer on at least one surface of the transparent substrate by a wet method;
An organic film forming step of immersing the transparent base material on which the copper-containing metal layer is formed in a solution of a nitrogen-based organic material in a bath to form an organic film on the upper surface of the copper-containing metal layer;
A blackening layer forming step of forming a blackening layer on the upper surface of the organic coating,
In the organic film forming step, the copper concentration of the solution in the bath is set to 15 ppm or less.   The method for producing a conductive substrate according to claim 3, wherein in the organic coating forming step, the bath is supplemented with a solution of a nitrogen-based organic material so that the copper concentration of the solution in the bath is 15 ppm or less. An organic film forming means for forming an organic film on the upper surface of the copper-containing metal layer by immersing the base material on which the copper-containing metal layer is formed in a solution of a nitrogen-based organic substance placed in a bathtub,
The said organic film formation means has an adjustment means which adjusts the copper concentration of the said solution in the said bath to 15 ppm or less, The organic film manufacturing apparatus characterized by the above-mentioned.   The said adjustment means is an organic film manufacturing apparatus of Claim 5 which replenishes the solution of a nitrogen-type organic substance to the said bathtub so that the copper concentration of the said solution in the said bath may be 15 ppm or less.

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