JPWO2017022539A1 - Conductive substrate, method for manufacturing conductive substrate - Google Patents

Abstract

An insulating substrate;
A metal layer formed on at least one surface of the insulating substrate;
An organic material layer containing a nitrogen-based organic material formed on the metal layer;
A blackening layer formed on the organic layer,
Provided is a conductive substrate in which the contact angle of pure water on the surface of the organic layer facing the blackened layer is 60 ° or less.

Description

  The present invention relates to a conductive substrate and a method for manufacturing a conductive substrate.

  The capacitive touch panel converts information on the position of an adjacent object on the panel surface into an electrical 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 for the conductive layer used in the capacitive touch panel, a material having low reflectivity and hardly 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 having a plurality of transparent sheet electrodes in which a signal pattern and a GND pattern are printed with an ITO film on a touch panel portion on a PET film.

  By the way, in recent years, the display screen including a touch panel has been increased in screen size. Correspondingly, a conductive substrate such as a transparent conductive film for a touch panel is required to have a large area. However, since ITO has a high electric resistance value and causes signal deterioration, there is a problem that ITO is not suitable for a large panel.

  Therefore, it has been studied to use a metal such as copper in place of ITO as a material for the conductive layer. However, since the metal has a metallic luster, there is a problem that the visibility of the display decreases due to reflection. For this reason, a conductive substrate in which a blackened layer that suppresses reflection of light on the surface of the metal layer is formed together with a metal layer that is a conductive layer using a metal such as copper.

Japanese Unexamined Patent Publication No. 2004-213114

  By the way, in the conductive substrate, for example, when the metal layer and the blackened layer are formed by different apparatuses, after the metal layer is formed and before the blackened layer is formed on the upper surface, the surface of the metal layer is formed. In some cases, it was required to prevent rust and the like from occurring. Therefore, it is conceivable to carry out a rust prevention treatment that forms an organic layer on the surface of the metal layer. There was a problem that the performance decreased.

  In view of the above-described problems of the prior art, according to one aspect of the present invention, in a conductive substrate in which an organic layer is formed between a metal layer and a blackened layer, a conductive substrate with high adhesion of the blackened layer is provided. With the goal.

In order to solve the above problems, in one aspect of the present invention,
An insulating substrate;
A metal layer formed on at least one surface of the insulating substrate;
An organic material layer containing a nitrogen-based organic material formed on the metal layer;
A blackening layer formed on the organic layer,
Provided is a conductive substrate in which the contact angle of pure water on the surface of the organic layer facing the blackened layer is 60 ° or less.

  According to one aspect of the present invention, in a conductive substrate in which an organic layer is formed between a metal layer and a blackened layer, a conductive substrate with high adhesion of the blackened layer can be provided.

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. 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. 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. Explanatory drawing of the relationship between the contact angle of the organic substance layer in an Example and a comparative example, and adhesiveness.

Hereinafter, an embodiment of a conductive substrate and a method for manufacturing the conductive substrate of the present invention will be described.
(Conductive substrate)
The conductive substrate of the present embodiment includes an insulating base, a metal layer formed on at least one surface of the insulating base, an organic layer containing a nitrogen-based organic material formed on the metal layer, A blackening layer formed on the organic material layer. And the contact angle of the pure water in the surface which opposes the blackening layer of an organic substance layer can be 60 degrees or less.

  Note that the conductive substrate in this embodiment is a pattern in which a substrate having a metal layer, an organic material layer, and a blackened layer on the surface of the insulating base before patterning the metal layer, and the metal layer is patterned. A substrate, that is, a wiring substrate.

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

  The insulating 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), polyimide, polyamide, polycarbonate, and the like can be more preferably used as the material for the resin substrate that transmits visible light.

  The thickness of the insulating base material is not particularly limited, and can be arbitrarily selected according to strength, capacitance, light transmittance, and the like required when the substrate is a conductive substrate. The thickness of the insulating 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 insulating 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 insulating substrate is preferably 20 μm or more and 50 μm or less.

  The total light transmittance of the insulating 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 insulating 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 an insulating base material can be evaluated by the method prescribed | regulated to JISK7361-1.

  Next, the metal layer will be described.

  Although the material which comprises a metal layer is not specifically limited, The material which has the electrical conductivity according to the application can be selected, For example, the material which comprises a metal layer is Cu, Ni, Mo, Ta, Ti, V, Cr , Fe, Mn, Co and W are preferably a copper alloy with at least one metal selected from the group consisting of copper, or a material containing copper. The metal layer can be a copper layer made of copper.

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

  In order to directly form the metal layer on the upper surface of the insulating substrate or the like, the metal layer preferably has a metal thin film layer. Moreover, the metal layer may have a metal thin film layer and a metal plating layer.

  For example, a metal thin film layer can be formed on an insulating substrate by a dry plating method, and the metal thin film layer can be used as a metal layer. Thereby, a metal layer can be directly formed on an insulating substrate without using an adhesive. As the dry plating method, for example, a sputtering method, a vapor deposition method, an ion plating method, or the like can be preferably used.

  In addition, when increasing the thickness of the metal layer, the metal thin film layer and the metal plating layer are formed by forming the metal plating layer by electroplating, which is a kind of wet plating method, using the metal thin film layer as a power feeding layer. It can also be a metal layer. Since the metal layer has the metal thin film layer and the metal plating layer, the metal layer can be directly formed on the insulating base material without using an adhesive.

  In addition, when a metal layer is formed on the adhesion layer, the metal layer can be directly formed on the adhesion layer in the same manner.

  The thickness of the metal layer is not particularly limited, and when the metal layer is used as a wiring, it can be arbitrarily selected according to the magnitude of the current supplied to the wiring, the wiring width, and the like.

  However, when the 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 fine lines. For this reason, the thickness of the metal layer is preferably 5 μm or less, and more preferably 3 μm or less.

  In particular, from the viewpoint of reducing the resistance value of the conductive substrate and supplying a sufficient current, for example, the metal layer preferably has a thickness of 50 nm or more, more preferably 60 nm or more, and 150 nm. More preferably, it is the above.

  In addition, when a metal layer has a metal thin film layer and a metal plating layer as mentioned above, it is preferable that the sum total of the thickness of a metal thin film layer and the thickness of a metal plating layer is the said range.

  In any case where the metal layer is composed of a metal thin film layer or has a metal thin film layer and a metal plating layer, the thickness of the metal thin film layer is not particularly limited. The following is preferable.

  As will be described later, the metal layer can be used as a wiring by patterning it into a desired wiring pattern, for example. And since a 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 metal layer.

  Next, the organic layer will be described.

  The organic material layer can be formed on the surface of the metal layer facing a blackening layer described later. Therefore, when a conductive substrate is used, it can be disposed between the metal layer and the blackened layer.

  By forming the organic layer on the upper surface of the metal layer, it is possible to prevent rust or the like from being generated on the surface of the metal layer.

  The organic material layer can contain a nitrogen-based organic material. And it is preferable that the nitrogen type organic substance used for an organic substance layer contains 1,2,3-benzotriazole or its derivative (s), for example. Specific examples of the nitrogen-based organic material used for the organic layer include 1,2,3-benzotriazole and 5-methyl-1H benzotriazole.

  As a chemical | medical agent containing the nitrogen type organic substance used for an organic substance layer, the rust preventive agent for copper can be used preferably, for example, As a chemical | medical agent marketed, for example, an OPC defenser (brand name, Okuno Pharmaceutical Co., Ltd.) Etc. can be preferably used.

  As described above, when the blackened layer is formed after the organic material layer is formed, the adhesion of the blackened layer may not be sufficient. Therefore, the inventors of the present invention examined a method for increasing the adhesion of the blackened layer, and by setting the contact angle of pure water on the surface of the organic layer facing the blackened layer to 60 ° or less, The inventors have found that the adhesion of the blackened layer can be improved and completed the present invention.

  According to the study of the inventors of the present invention, when a uniform film in which the metal layer and the organic layer are bonded cannot be formed, and the organic matter is simply deposited on the surface of the metal layer, the adhesion of the blackened layer is In some cases it was not enough. When the organic matter is thus deposited on the surface of the metal layer, the contact angle with respect to the pure water of the surface of the organic matter layer facing the blackened layer exceeds 60 °.

  On the other hand, when the organic layer is formed, if a uniform film in which the metal layer and the organic layer are combined is formed, the contact angle of pure water on the surface of the organic layer facing the blackened layer Is 60 ° or less. Then, by forming a uniform film in which the metal layer and the organic layer are combined, the adhesion of the blackened layer can be enhanced when the blackened layer is formed on the organic layer.

  For this reason, as described above, the contact angle of pure water on the surface of the organic layer facing the blackened layer is preferably 60 ° or less.

  The method of setting the contact angle of pure water on the surface of the organic material layer facing the blackened layer to 60 ° or less is not particularly limited, The method of supplying the nitrogen type organic substance solution used as the raw material of a layer with respect to the surface of a metal layer is mentioned.

  The method for supplying the nitrogen-based organic substance solution is not particularly limited, and can be supplied by any method. For example, applying a solution containing a material constituting the organic layer on the metal layer by applying a nitrogen-based organic solution by spraying or immersing an insulating base material in which the metal layer is formed in the nitrogen-based organic solution. Can do.

  However, when the nitrogen-based organic solution is supplied, it is preferable to supply the nitrogen-based organic solution uniformly to the surface of the metal layer so that a uniform film in which the metal layer and the organic layer are combined is obtained. For this reason, for example, a nitrogen-based organic substance solution is simultaneously supplied to the surface of the metal layer on the side where the blackened layer is formed by two or more types of means, or the side on which the blackened layer of the metal layer is formed. It is preferable to repeatedly supply the nitrogen-based organic substance solution in a plurality of times to the surface.

  The condition of the nitrogen-based organic solution when supplying the nitrogen-based organic solution to the surface of the metal layer on which the blackening layer is formed is not particularly limited, depending on the type of the nitrogen-based organic solution, etc. Can be arbitrarily selected. Specifically, the concentration of nitrogen-based organic matter in the nitrogen-based organic matter solution used when forming the organic matter layer is not particularly limited, and the content of nitrogen-based organic matter in the target organic matter layer and operability It can be arbitrarily selected in consideration of the above.

  However, the lower limit of the concentration of the nitrogenous organic substance in the nitrogenous organic solution is preferably 1 mL / L or more, and more preferably 2 mL / L or more. The upper limit is preferably 4 mL / L or less. This is because by setting the concentration of the nitrogen-based organic substance in the nitrogen-based organic substance solution to 1 mL / L or more, a uniform film in which the metal layer and the organic layer are combined can be more reliably formed. However, if the concentration of the nitrogen-based organic substance in the nitrogen-based organic substance solution exceeds 4 mL / L, the excess solution may not be removed by washing with water, and it is preferably 4 mL / L or less.

  The temperature of the nitrogen-based organic solution when supplying the nitrogen-based organic solution to the surface of the metal layer is not particularly limited, and may be arbitrarily selected in consideration of the viscosity, operability, reactivity, etc. of the solution. Can do. For example, it is preferably 10 ° C. or higher, and more preferably 20 ° C. or higher. However, since the nitrogenous organic substance contained may react with other substances when the temperature increases, the temperature is preferably set to 40 ° C. or lower.

  Further, the pH of the nitrogen-based organic substance solution is not particularly limited, and can be selected in consideration of the type of nitrogen-based organic substance used, the reactivity of the solution, and the like. For example, the pH of the nitrogen-based organic substance solution is 2 It is preferable that it is above, and it is more preferable that it is 3 or more. However, since the content of nitrogen-based organic matter in the film decreases as the pH increases, the pH of the nitrogen-based organic matter solution is preferably 4 or less.

  The length of the treatment time for supplying and reacting the nitrogen-based organic solution to the metal layer surface is not particularly limited, depending on the type of nitrogen-based organic solution used, the thickness of the organic layer to be formed, etc. Can be arbitrarily selected. For example, the treatment time is preferably 5 seconds or more, and more preferably 6 seconds or more. However, if the treatment time is too long, productivity may be lowered, and therefore it is preferably 10 seconds or less.

  The inventors of the present invention have also found that the reflectance of the conductive substrate can be suppressed by disposing an organic material layer containing a nitrogen-based organic material between the metal layer and the blackening layer.

In order to suppress the reflectance of the conductive substrate, the content of nitrogen-based organic matter in the organic layer 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 greatly suppressed by setting the content of the nitrogen-based organic matter in the organic layer to 0.2 μg / cm ² or more. Because it can. In addition, when the content of nitrogenous organic matter in the organic matter layer increases, the a ^* value and b ^* value 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 matter layer is not particularly limited. However, in order to increase the content of nitrogenous organic matter in the organic matter layer, increase the concentration of the nitrogenous organic matter solution used when forming the organic matter layer, increase the supply time of the nitrogenous organic matter solution, etc. It becomes. For this reason, if the content of the nitrogenous organic matter in the organic matter layer is excessively increased, the handleability of the nitrogenous organic matter solution is lowered or the time required for forming the organic matter layer is increased, resulting in a decrease in productivity. There is a fear. Therefore, the content of the nitrogen-based organic compound in the organic layer is preferably set to 0.5 μg / cm ² or less, for example.

  Next, the blackened layer will be described.

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

  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 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 include 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. . 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 formation method of a blackening layer is not specifically limited, It can form by arbitrary methods, For example, it can form into a film by 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, the target may be formed 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 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 blackened layer can be formed by either a dry method or a wet method, but when forming the blackened layer, the nitrogen-based organic matter contained in the organic layer is dissolved in the plating solution. However, it may be taken into the blackened layer and may affect the color tone and other characteristics, so that 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 metal layer may not be sufficiently suppressed. Therefore, the thickness of the blackened layer is set to 15 nm or more as described above. This is because it is preferable to configure so that reflection of light on the surface of the layer can be particularly suppressed.

  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.

  Further, the conductive substrate can be provided with any layer other than the above-described insulating base material, metal layer, organic material layer, 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 metal layer can be formed on the insulating substrate, but when the metal layer is directly formed on the insulating substrate, the adhesion between the insulating substrate and the metal layer is not sufficient. There is a case. For this reason, when a metal layer is directly formed on the upper surface of the insulating substrate, the metal layer may be peeled off from the insulating substrate during the manufacturing process or use.

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

  By disposing the adhesion layer between the insulating substrate and the metal layer, the adhesion between the insulating substrate and the metal layer can be improved, and the metal layer can be prevented from peeling from the insulating substrate.

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

  The material constituting the adhesion layer is not particularly limited, the adhesion strength between the insulating base and the metal layer, the degree of suppression of light reflection on the surface of the required metal layer, and the conductive substrate. It can be arbitrarily selected according to the degree of stability to the environment (for example, humidity and temperature) to be 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 may further contain one or more elements selected from carbon, oxygen, hydrogen, and nitrogen.

  The adhesion layer can 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 insulating substrate and the adhesion layer can be enhanced. And since an adhesion layer can contain a metal as a main component, for example, its adhesiveness with a metal layer is also high. For this reason, peeling of a metal layer can be suppressed by arrange | positioning an adhesion layer between an insulating base material and a 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 on the 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 the present embodiment can have an insulating substrate, a metal layer, an organic material layer, 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 FIGS. 1A, 1B, 2A, and 2B. FIG. 1A, FIG. 1B, FIG. 2A, and FIG. 2B show examples of cross-sectional views in the plane parallel to the stacking direction of the insulating substrate, metal layer, organic layer, and blackening layer of the conductive substrate of this embodiment. ing.

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

  Specifically, for example, like the conductive substrate 10A shown in FIG. 1A, the metal layer 12, the organic material layer 13, and the blackening layer 14 are formed one by one on the one surface 11a side of the insulating base material 11. They can be stacked in that order. Moreover, like the electroconductive board | substrate 10B shown to FIG. 1B, metal layer 12A, 12B on the one surface 11a side of the insulating base material 11, and the other surface (other surface) 11b side, respectively, The organic layers 13A and 13B and the blackening layers 14A and 14B 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 metal layer, an organic material layer, and a blackening layer are formed in that order from the insulating substrate side on at least one surface of the insulating substrate can be employed. .

  Specifically, for example, like the conductive substrate 20A shown in FIG. 2A, the adhesion layer 15, the metal layer 12, the organic layer 13, and the blackening layer 14 are formed on one surface 11a side of the insulating base material 11. Can be stacked in that order.

  In this case as well, a configuration in which an adhesive layer, a metal layer, an organic material layer, and a blackening layer are laminated on both surfaces of the insulating substrate 11 can also be adopted. Specifically, as in the conductive substrate 20B shown in FIG. 2B, the adhesion layers 15A and 15B and the metal layer 12A on the one surface 11a side and the other surface 11b side of the insulating base material 11, respectively. 12B, organic layers 13A and 13B, and blackening layers 14A and 14B can be stacked in that order.

  In FIG. 1B and FIG. 2B, when a metal layer, an organic material layer, a blackening layer, etc. are laminated on both surfaces of the insulating base material, the insulating base material 11 is laminated on the upper and lower sides of the insulating base material 11 with the symmetrical surface. Although the example which arrange | positioned so that the layer which became symmetrical may be shown, it is not limited to the form which concerns. For example, in FIG. 2B, the configuration on the one surface 11a side of the insulating substrate 11 is similar to the configuration of FIG. 1B, without providing the adhesion layer 15A, the metal layer 12A, the organic layer 13A, and the blackening layer 14A. It is good also as a form laminated | stacked in that order, and it is good also as an asymmetrical structure the layer laminated | stacked on the upper and lower sides of the insulating base material 11.

  By the way, in the electroconductive board | substrate of this embodiment, reflection of the light by a metal layer is suppressed by providing a metal layer, an organic substance layer, and a blackening layer on an insulating base material, and reflection of an electroconductive board | substrate. The rate can also 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, when the metal layer 12, the organic material layer 13, and the blackened layer 14 are laminated in this order on one surface 11a side of the insulating base material 11 as shown in FIG. 1A, the blackened layer 14 is irradiated with light. The surface A of the blackened layer 14 can be irradiated with light and measured. In the measurement, light having a wavelength of 400 nm or more and 700 nm or less is irradiated to the surface A of the blackened layer 14 of the conductive substrate, for example, at a wavelength of 1 nm as described above, and the average value of the measured values is reflected on the conductive substrate. Rate.

  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 wiring.

  The conductive substrate provided with the mesh-like wiring can be obtained by etching the metal layer, the organic material layer, 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. 3 shows a view of the conductive substrate 30 provided with mesh-like wiring as viewed from the upper surface side in the stacking direction of the metal layer or the like. In order to make the wiring pattern easy to understand, the insulating substrate 11 and the metal layer Layers other than the wirings 31A and 31B formed by patterning are omitted. In addition, a wiring 31B that can be seen through the insulating substrate 11 is also shown.

  The conductive substrate 30 shown in FIG. 3 has an insulating base material 11, a plurality of wirings 31A parallel to the Y-axis direction in the drawing, and wirings 31B parallel to the X-axis direction. The wirings 31A and 31B are formed by etching a metal layer, and an organic material layer and a blackening layer (not shown) are formed on the upper surface or the lower surface of the wirings 31A and 31B. The organic material layer and the blackened layer are etched in the same shape as the wirings 31A and 31B.

  The arrangement of the insulating substrate 11 and the wirings 31A and 31B is not particularly limited. A configuration example of the arrangement of the insulating base material 11 and the wiring is shown in FIGS. 4A and 4B. 4A and 4B correspond to cross-sectional views taken along the line AA ′ of FIG.

  First, as illustrated in FIG. 4A, wirings 31 </ b> A and 31 </ b> B may be disposed on the upper and lower surfaces of the insulating base material 11, respectively. In FIG. 4A, organic layers 32A and 32B and blackening layers 33A and 33B etched in the same shape as the wiring are arranged on the upper surface of the wiring 31A and the lower surface of 31B.

  Further, as shown in FIG. 4B, a pair of insulating base materials 11 is used, wirings 31A and 31B are arranged on the upper and lower surfaces with one insulating base material 11 interposed therebetween, and one wiring 31B is insulated. May be disposed between the conductive substrates 11. Also in this case, organic layers 32A and 32B and blackening layers 33A and 33B etched in the same shape as the wiring are arranged on the upper surfaces of the wirings 31A and 31B. As described above, an adhesion layer can be provided in addition to the metal layer, the organic material layer, and the blackening layer. Therefore, in either case of FIG. 4A or FIG. 4B, for example, an adhesion layer can be provided between the wiring 31 </ b> A and / or the wiring 31 </ b> B and the insulating substrate 11. When the adhesion layer is provided, it is preferable that the adhesion layer is also etched in the same shape as the wirings 31A and 31B.

  The conductive substrate having the mesh-like wiring shown in FIGS. 3 and 4A is, for example, a metal layer 12A, 12B, an organic layer 13A, 13B, and a blackening layer on both sides of the insulating base 11 as shown in FIG. 1B. 14A and 14B can be formed from a conductive substrate.

  The case where it is formed using the conductive substrate of FIG. 1B will be described as an example. First, the metal layer 12A, the organic layer 13A, and the blackening layer 14A on the one surface 11a side of the insulating base 11 are shown in FIG. 1B. Etching is performed so that a plurality of linear patterns parallel to the Y-axis direction are arranged at predetermined intervals along the X-axis direction. In addition, the X-axis direction in FIG. 1B means a direction parallel to the width direction of each layer. Further, the Y-axis direction in FIG. 1B means a direction perpendicular to the paper surface in FIG. 1B.

  A plurality of linear patterns parallel to the X-axis direction in FIG. 1B are spaced apart from each other on the metal layer 12B, the organic material layer 13B, and the blackening layer 14B on the other surface 11b side of the insulating substrate 11 by a predetermined interval. Etching is performed so as to be arranged along the Y-axis direction.

  Through the above operation, the conductive substrate having the mesh-like wiring shown in FIGS. 3 and 4A can be formed. In addition, the etching of both surfaces of the insulating substrate 11 can be performed simultaneously. That is, the etching of the metal layers 12A and 12B, the organic layers 13A and 13B, and the blackening layers 14A and 14B may be performed simultaneously. 4A, the conductive substrate having an adhesion layer patterned in the same shape as the wirings 31A and 31B between the wirings 31A and 31B and the insulating base material 11 is the conductive substrate shown in FIG. 2B. It can be produced by etching in the same manner.

  The conductive substrate having the mesh-like wiring shown in FIG. 3 can also be formed by using two conductive substrates shown in FIG. 1A or 2A. A case where the two conductive substrates shown in FIG. 1A are used will be described as an example. For the two conductive substrates shown in FIG. 1A, the metal layer 12, the organic material layer 13, and the blackening layer 14 are respectively formed on the X axis. Etching is performed so that a plurality of linear patterns parallel to the direction are arranged along the Y-axis direction at predetermined intervals. 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. 1A in which the metal layer 12 or the like is laminated and the other surface 11b in FIG. 1A in which the metal layer 12 or the like is not laminated are bonded together so that the structure shown in FIG. 4B is obtained. You can also.

  Further, for example, the other surfaces 11b in FIG. 1A where the metal layer 12 or the like of the insulating base material 11 is not laminated may be bonded together so that the cross section has the structure shown in FIG. 4A.

  4A and 4B, the conductive substrate having an adhesion layer patterned in the same shape as the wirings 31A and 31B between the wirings 31A and 31B and the insulating base material 11 is shown in FIG. 1A. It can be manufactured by using the conductive substrate shown in FIG. 2A instead of the conductive substrate.

  The width of the wiring and the distance between the wirings in the conductive substrate having the mesh-like wiring shown in FIG. 3, FIG. 4A and FIG. 4B are not particularly limited. You can choose.

  3, 4 </ b> A, and 4 </ b> B 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 form. The wiring that constitutes can be of 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.

According to the conductive substrate of the present embodiment described above, the contact angle of pure water on the surface facing the blackening layer on the metal layer formed on at least one surface of the insulating base is 60 ° or less. An organic material layer containing a nitrogen-based organic material is disposed. For this reason, it can be set as the electroconductive board | substrate with high adhesiveness of a blackening layer. Moreover, since the blackening layer is arrange | positioned on the organic substance layer, when it uses for uses, such as a touch panel, the visibility of a display can be improved.
(Method for producing conductive substrate)
Next, a configuration example of the method for manufacturing the conductive substrate according to the present embodiment will be described.

The manufacturing method of the conductive substrate of this embodiment can have the following processes.
A metal layer forming step of forming a metal layer on at least one surface of the insulating substrate.
An organic material layer forming step of forming an organic material layer containing a nitrogen-based organic material on the metal layer.
A blackened layer forming step of forming a blackened layer on the organic material layer.

  In the organic layer forming step, the organic layer is preferably formed so that the contact angle of pure water on the surface of the organic layer facing the blackening layer is 60 ° or less.

  The manufacturing method of the conductive substrate of this embodiment will be specifically described below.

  In addition, the above-mentioned electroconductive board | substrate can be suitably manufactured with the manufacturing method of the electroconductive board | substrate of this embodiment. For this reason, since it can be set as the structure similar to the case of the above-mentioned electroconductive board | substrate except the point demonstrated below, description is abbreviate | omitted partially.

  The insulating base material used for the metal layer forming step can be prepared in advance. Although the kind of insulating 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 insulating base material can be cut into an arbitrary size in advance if necessary.

  And as above-mentioned, it is preferable that a metal layer has a metal thin film layer. The metal layer can also have a metal thin film layer and a metal plating layer. For this reason, a metal layer formation process can have a process of forming a metal thin film layer, for example by a dry-type plating method. The metal layer forming step includes a step of forming a metal thin film layer by a dry plating method, a step of forming a metal plating layer by an electroplating method which is a kind of wet plating method, using the metal thin film layer as a power feeding layer, You may have.

  The dry plating method used in the step of forming the metal thin film layer is not particularly limited, and for example, an evaporation method, a sputtering method, an ion plating method, or the like 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 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 metal plating layer will be described. The conditions in the step of forming the metal plating layer by the wet plating method, for example, the conditions for the electroplating treatment are not particularly limited, and various conditions according to ordinary methods may be adopted. When forming a metal plating layer by electroplating, it can be formed by, for example, supplying a base material on which a 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 metal layer, suitable thicknesses of the metal layer, and the like have already been described, description thereof is omitted here.

  Next, the organic layer forming step will be described.

  In the organic material layer forming step, an organic material layer containing a nitrogen-based organic material can be formed on the metal layer.

  As described above, when an organic layer is provided between a metal layer and a blackened layer, blackening is achieved by supplying a nitrogen-based organic solution so that a uniform film is formed by combining the metal layer and the organic layer. The adhesion of the layer can be increased.

  The method for forming the organic layer is not particularly limited, and the organic layer can be formed by supplying a nitrogen-based organic solution onto the metal layer and drying it.

  The method for supplying the nitrogen-based organic substance solution is not particularly limited, and can be supplied by any method. For example, applying a solution containing a material constituting the organic layer on the metal layer by applying a nitrogen-based organic solution by spraying or immersing an insulating base material in which the metal layer is formed in the nitrogen-based organic solution. Can do.

  However, when the nitrogen-based organic solution is supplied, it is preferable to supply the nitrogen-based organic solution uniformly to the surface of the metal layer so that a uniform film in which the metal layer and the organic layer are combined is obtained. For this reason, for example, a nitrogen-based organic substance solution is simultaneously supplied to the surface of the metal layer on the side where the blackened layer is formed by two or more types of means, or the side on which the blackened layer of the metal layer is formed. It is preferable to repeatedly supply the nitrogen-based organic substance solution in a plurality of times to the surface.

  Although the nitrogen type organic substance used for an organic substance layer is not specifically limited, For example, it is preferable that a 1,2,3- benzotriazole or its derivative is included. Specific examples of the nitrogen-based organic material used for the organic layer include 1,2,3-benzotriazole and 5-methyl-1H benzotriazole.

  In the organic layer forming step, the organic layer can be formed using, for example, a nitrogen-based organic solution that is a drug containing the nitrogen-based organic material.

  As a chemical | medical agent containing the nitrogen type organic substance used for an organic substance layer, the rust preventive agent for copper can be used preferably, for example, As a chemical | medical agent marketed, for example, an OPC defenser (brand name, Okuno Pharmaceutical Co., Ltd.) Etc. can be preferably used.

  Since the suitable conditions for supplying the nitrogen-based organic solution on the metal layer have already been described, the description thereof is omitted here.

  In addition, after apply | coating a nitrogen type organic substance solution, in order to remove the adhering excess nitrogen type organic substance solution, the water washing which wash | cleans the base material which apply | coated the nitrogen type organic substance solution with water can also be implemented.

  Next, the blackening layer forming process will be described.

  In the blackening layer forming step, 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. 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 nitrogen-based organic matter contained in the organic layer starts to dissolve in the plating solution and is taken into the blackened layer, affecting the color tone and other characteristics of the blackened layer. Since there is a fear, 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 an insulating substrate and a metal layer, an adhesion layer forming step of forming an adhesion layer on the surface of the insulating substrate on which the metal layer is formed can be performed. When carrying out the adhesion layer forming step, the metal layer forming step can be carried out after the adhesion layer forming step, and in the metal layer forming step, the substrate having the adhesion layer formed on the insulating substrate in this step. A metal thin film layer can be formed.

  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 metal layer, organic substance layer, 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. The metal layer, the organic material layer, and the blackening layer, and in some cases, the adhesion layer can be patterned in accordance with, for example, a desired wiring pattern, and the metal layer, the organic material layer, and the blackening layer, and in some cases, further adhesion. The layers are preferably 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 metal layer, an organic substance layer, and a blackening layer. When the adhesion layer is formed, the patterning step can be a step of patterning the adhesion layer, the metal layer, the organic material layer, 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 the conductive substrate 10A in which the metal layer 12, the organic material layer 13, and the blackening layer 14 are laminated on the insulating base 11 as shown in FIG. 1A, first, a desired pattern is formed on the surface A on the blackening layer 14. A mask placement step of placing a mask having it can be performed. Next, an etching step of supplying an etching solution to the surface A on the blackened layer 14, 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 metal layer, the organic material layer, and the blackening layer, and in some cases, the adhesion layer can be etched simultaneously with the same etching solution.

  Further, as shown in FIG. 1B, the conductive substrate 10B in which the metal layers 12A and 12B, the organic layers 13A and 13B, and the blackening layers 14A and 14B are stacked on the one surface 11a and the other surface 11b of the insulating base 11 is also used. A patterning process for patterning can 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 14A and 14B can be performed. Next, an etching step of supplying an etching solution to the surface A and the surface B on the blackening layers 14A and 14B, 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 10A shown in FIG. 1A, as described above, the metal layer 12, the organic material layer 13, and the blackened layer 14 include a plurality of straight lines or jagged lines (zigzag straight lines). A pattern can be formed.

  In the case of the conductive substrate 10B shown in FIG. 1B, a pattern can be formed so that the metal layer 12A and the metal layer 12B form a mesh-like wiring. In this case, the organic material layer 13A and the blackening layer 14A may be patterned to have the same shape as the metal layer 12A, and the organic material layer 13B and the blackening layer 14B may be patterned to have the same shape as the metal layer 12B. preferable.

  In addition, for example, after the metal layer 12 or the like is patterned on the conductive substrate 10A described above in a patterning step, a lamination step of laminating two or more patterned conductive substrates can be performed. When laminating, for example, by laminating so that the pattern of the metal layer of each conductive substrate intersects, a laminated conductive substrate provided with mesh-like wiring can be obtained.

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

  According to the conductive substrate obtained by the conductive substrate manufacturing method of the present embodiment described above, the pure surface on the surface facing the blackening layer is formed on the metal layer formed on at least one surface of the insulating base material. An organic material layer containing a nitrogen-based organic material having a water contact angle of 60 ° or less is disposed. For this reason, it can be set as the electroconductive board | substrate with high adhesiveness of a blackening layer. Moreover, since the blackening layer is arrange | positioned on the organic substance layer, when it uses for uses, such as a touch panel, the visibility of a 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 obtained conductive substrate will be described.
(1) Contact angle When the conductive substrates prepared in the following examples and comparative examples are prepared, the contact angle of pure water on the surface of the organic layer is measured after forming the organic layer and before forming the blackened layer. went.

  The measurement was performed using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd .: DM-301).

After forming the organic layer, 1.0 μL of pure water was supplied to the surface of the organic layer on which the blackened layer was formed, and the contact angle was measured.
(2) Adhesion test As shown in FIG. 5, a cutting tool (Cross Cut Kit 1.0MM manufactured by Precision Gate & Tool Company) was used for the blackening layer of the conductive substrate formed up to the blackening layer. Eleven vertical cut lines 51a having a length of 20 mm are formed at intervals of 1.0 mm so as to be parallel to each other.

  Next, using the same cutting tool, eleven horizontal cutting lines 51b having a length of 20 mm are formed at intervals of 1.0 mm so as to be orthogonal to the previously formed vertical cutting lines 51a.

  Through the above steps, as shown in FIG. 5, 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 adhesion evaluation tape, a metal layer (organic matter) formed under the blackened layer in the evaluation region 52 in FIG. 5 surrounded by the grid-like vertical cut lines 51a and the horizontal cut lines 51b. The adhesion was evaluated based on the exposed area of the layer.

  5B when the exposed area of the 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 2B when it is 15% or more and less than 35% The case of 35% or more and less than 65% was evaluated as 1B, and the case of 65% or more was evaluated as 0B. 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 case of 5B.
(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 an insulating base made of polyethylene terephthalate resin (PET) having a length of 500 mm × width of 500 mm and a thickness of 50 μm. In addition, about the insulating base material made from the polyethylene terephthalate resin used as an insulating 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 sputtering apparatus equipped with a Ni-17 wt% Cu alloy target. The procedure for forming the adhesion layer will be described below.

  The above-described insulating 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, electric power was supplied to the target in such an atmosphere, and an adhesion layer was formed on one surface of the insulating base so as to have a thickness of 20 nm.
(Metal layer forming process)
In the metal layer forming step, a metal thin film layer forming step and a metal plating layer forming step were performed.

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

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

  The metal thin film layer is a sputtering apparatus as in the case of the adhesion layer except that a copper target is used and the inside of the chamber in which the substrate is set is evacuated and then an argon gas is supplied to form an argon atmosphere. Was formed.

  The copper thin film layer which is a metal thin film layer was formed so as to have a film thickness of 150 nm.

Next, in the metal plating layer forming step, a copper plating layer was formed as the metal plating layer. The copper plating layer was formed by electroplating so that the thickness of the copper plating layer was 0.5 μm.
(Organic layer formation process)
In the organic layer forming step, an organic layer was formed on the metal layer of the laminate in which the adhesion layer and the metal layer were formed on the insulating base material.

  In the organic layer forming step, first, the above laminate was immersed in an OPC diffuser (Okuno Pharmaceutical Co., Ltd.) solution containing 1,2,3-benzotriazole as a nitrogen-based organic substance for 7 seconds. The OPC diffuser solution used was adjusted in advance so that the concentration of 1,2,3-benzotriazole was 3 mL / L, and the bath temperature was 30 ° C. and pH 3.

  And after removing the solution adhering except the upper surface of a metal layer, ie, the surface on the opposite side to the surface which opposes the adhesion layer of a metal layer, it dried and formed the organic substance layer on the metal layer.

In addition, after the organic substance layer formation process, a part of board | substrate was cut out and it used for evaluation of the above-mentioned contact angle.
(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 layer formed in the organic layer forming step.

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

  First, the laminated body which laminated | stacked the contact | adherence layer, the metal layer, and the organic substance layer on the insulating base material was set in the chamber of the sputtering device.

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 layer so as to have a thickness of 30 nm.

  Through the above steps, a blackening layer is formed on the upper surface of the metal layer, that is, the surface opposite to the surface facing the adhesion layer of the metal layer through the organic material layer, and the adhesion layer, the metal is formed on the insulating substrate. A conductive substrate in which a layer, an organic material layer, and a blackening layer were laminated in that order was obtained.

  An adhesion test was performed on the obtained conductive substrate.

The results are shown in Table 1.
[Example 2 and Example 3]
The conductive layer was formed in the same manner as in Example 1 except that the contact angle of the organic layer surface was changed by changing the concentration of the OPC diffuser solution, the bath temperature, and the pH when forming the organic layer. A conductive substrate was produced.

  The above-described adhesion test was performed on the obtained conductive substrate.

The results are shown in Table 1.
[Comparative Examples 1 to 3]
The conductive layer was formed in the same manner as in Example 1 except that the contact angle of the organic layer surface was changed by changing the concentration of the OPC diffuser solution, the bath temperature, and the pH when forming the organic layer. A conductive substrate was produced.

  The above-described adhesion test was performed on the obtained conductive substrate.

  The results are shown in Table 1.

表１に示した有機物層の接触角と、黒化層の密着性の評価結果との関係をグラフにしたものを図６に示す。

FIG. 6 is a graph showing the relationship between the contact angle of the organic layer shown in Table 1 and the evaluation result of the adhesion of the blackened layer.

  As is apparent from the results of Table 1 and FIG. 6, it can be confirmed that the results of the adhesion test are 5B for Examples 1 to 3 where the contact angle of the organic layer surface is 60 ° or less. It was. On the other hand, for Comparative Examples 1 to 3 in which the contact angle of the organic layer exceeded 60 °, the result of the adhesion test was 3B or 4B, and peeling of the blackened layer was confirmed.

  From the above results, in the conductive substrate in which the organic layer is formed between the metal layer and the blackened layer, the contact angle of the surface of the organic layer is set to 60 ° or less so that the adhesion of the blackened layer is high. It was confirmed that the substrate could be used.

  Although the conductive substrate and the method for manufacturing the conductive substrate have been described in the above embodiments and examples, the present invention is not limited to the above embodiments and examples. Various modifications and changes are possible within the scope of the gist of the present invention described in the claims.

  This application claims priority based on Japanese Patent Application No. 2015-152896 filed with the Japan Patent Office on July 31, 2015. The entire contents of Japanese Patent Application No. 2015-152896 are incorporated herein by reference. Incorporate.

10A, 10B, 20A, 20B, 30 Conductive substrate 11 Insulating substrate 12, 12A, 12B Metal layer 13, 13A, 13B, 32A, 32B Organic layer 14, 14A, 14B, 33A, 33B Blackening layer

Claims (4)

An insulating substrate;
A metal layer formed on at least one surface of the insulating substrate;
An organic material layer containing a nitrogen-based organic material formed on the metal layer;
A blackening layer formed on the organic layer,
The electroconductive board | substrate whose contact angle of the pure water in the surface facing the said blackening layer of the said organic substance layer is 60 degrees or less.   The conductive substrate according to claim 1, wherein the nitrogen-based organic substance contains 1,2,3-benzotriazole or a derivative thereof. A metal layer forming step of forming a metal layer on at least one surface of the insulating substrate;
An organic material layer forming step of forming an organic material layer containing a nitrogenous organic material on the metal layer;
A blackening layer forming step of forming a blackening layer on the organic material layer,
In the organic layer forming step, the organic substrate is formed so that a contact angle of pure water on the surface of the organic layer facing the blackening layer is 60 ° or less.   The method for producing a conductive substrate according to claim 3, wherein the nitrogen-based organic substance contains 1,2,3-benzotriazole or a derivative thereof.

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