WO2017022573A1 - Conductive substrate - Google Patents

Abstract

Provided is a conductive substrate which includes: an insulating base material; a metal layer formed on at least one surface of the insulating base material; an organic substance layer which is formed on the metal layer and contains a nitrogen-containing organic substance; and a blackened layer formed on the organic substance layer. The metal layer has multiple granular protrusions on a surface thereof where the organic substance layer is formed, the average height of the multiple granular protrusions being 8.00 nm or greater. The metal layer has 70 pieces or more/10 μm of the multiple granular protrusions on the surface where the organic substance layer is formed.

Description

Conductive substrate

The present invention relates to 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 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 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 transparent conductive film including a polymer film and a transparent conductive film made of a metal oxide provided thereon by a vapor deposition method, and the transparent conductive film made of a metal oxide. Is made of a transparent conductive film made of the first metal oxide and a transparent conductive film made of the second metal oxide provided thereon, and the transparent conductive film made of the second metal oxide is the first A transparent conductive film characterized by being formed under conditions different from the film forming conditions of a transparent conductive film made of a metal oxide is disclosed. It is also disclosed that the transparent conductive film made of a metal oxide is an indium oxide-tin oxide (ITO) film.

By the way, in recent years, a display having a touch panel has been enlarged, and in response to this, a conductive substrate for the 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 a conductive substrate using ITO is not suitable for a large panel.

Therefore, in order to suppress the electrical resistance of the conductive substrate, it has been studied to use a metal such as copper instead of ITO as the material of 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 layer composed of a black material is formed together with a metal such as copper has been studied.

For example, Patent Document 2 discloses a film-like touch panel sensor that includes a striped copper wiring on each of the portions that need to be seen through on the front and back surfaces of the film, and has a black copper oxide film on the side where the copper wiring on the front and back sides is visually recognized. It is disclosed.

Japanese Unexamined Patent Publication No. 2003-151358 Japanese Unexamined Patent Publication No. 2013-206315

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, the inventors of the present invention studied to form an organic layer by performing a rust prevention treatment for forming an organic layer on the surface of the metal layer.

However, when a blackened layer is formed on the surface of the metal layer which has been subjected to rust prevention treatment, there is a problem in that the adhesion between the blackened layer and the metal layer is lowered, and the blackened layer may peel off.

In view of the above-described problems of the prior art, according to one aspect of the present invention, there is provided a conductive substrate in which an organic layer is formed between a metal layer and a blackened layer, and the blackened layer is prevented from peeling off. The purpose is to do.

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 layer containing nitrogen-based organic matter formed on the metal layer;
A blackening layer formed on the organic layer,
The metal layer has a plurality of granular protrusions on the surface on which the organic layer is formed,
An average height of the plurality of granular protrusions is 8.00 nm or more;
The metal layer provides a conductive substrate having 70/10 μm or more of the plurality of granular protrusions on a surface on which the organic layer is formed.

According to one aspect of the present invention, it is possible to provide a conductive substrate in which an organic layer is formed between a metal layer and a blackened layer, and the blackened layer is prevented from peeling off.

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.

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 substrate, a metal layer formed on at least one surface of the insulating substrate, and an organic material layer containing a nitrogen-based organic material formed on the metal layer. And a blackening layer formed on the organic material layer.
The metal layer can have a plurality of granular protrusions on the surface on which the organic layer is formed. The average height of the plurality of granular projections can be 8.00 nm or more. Further, the metal layer can have a plurality of granular protrusions of 70/10 μm or more on the surface on which the organic layer is formed.

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.

Here, 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.

The resin substrate material that transmits visible light is preferably a resin such as a polyamide resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, a cycloolefin resin, a polyimide resin, a polycarbonate resin, or an acetyl cellulose resin. Can be used. In particular, PET (polyethylene terephthalate), COP (cycloolefin polymer), PEN (polyethylene naphthalate), polyimide, polyamide, polycarbonate, TAC (triacetyl cellulose), and the like are more preferably used as the material for the resin substrate that transmits visible light. be able to.

The thickness of the insulating base material is not particularly limited, and can be arbitrarily selected according to the strength, capacitance, light transmittance, and the like required for 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 base material 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.

The total light transmittance of the insulating substrate can be evaluated by the method specified in JIS K 7361-1.

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 W, or a material containing copper. The metal layer can be a copper layer made of copper.

The method for forming the metal layer on the insulating substrate is not particularly limited, but it is preferable not to place an adhesive between the insulating substrate and the metal layer in order not to reduce the light transmittance. 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, 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.

The conductive substrate of this embodiment can have a plurality of granular protrusions on the surface on which the organic layer of the metal layer is formed.

As described above, when an organic layer is formed on the surface of the metal layer and a blackened layer is formed on the organic layer, the adhesion between the blackened layer and the metal layer on which the organic layer is formed is reduced. In some cases, the chemical layer peeled off. Accordingly, the inventors of the present invention have made extensive studies on a method for suppressing the peeling of the blackened layer in the conductive substrate in which the organic layer is formed between the metal layer and the blackened layer. As a result, a plurality of granular protrusions having an average height of 8.00 nm or more (hereinafter also simply referred to as “a plurality of granular protrusions”) were formed on the surface of the metal layer on which the organic material layer was formed. It has been found that by forming 10 μm or more, the adhesion of the blackened layer to the organic material layer and the metal layer can be improved and peeling can be suppressed.

The average height of the plurality of granular protrusions is preferably 8.0 nm or more, and more preferably 8.5 nm or more.

This is because, as described above, according to the study of the inventors of the present invention, it is possible to prevent the blackened layer from peeling by setting the average height of the plurality of granular projections to 8.0 nm or more. It is.

The upper limit of the average height of the plurality of granular projections is not particularly limited, but is preferably 15.0 nm or less, and more preferably 14.0 nm or less. This is because when the average height of the plurality of granular protrusions exceeds 15.0 nm, the surface roughness of the surface of the blackened layer is reduced when the organic material layer and the blackened layer are formed on the metal layer. This is because it increases, affects the color of the surface of the blackened layer, and may affect the function of the blackened layer.

The surface of the metal layer on which the organic layer is formed is preferably formed with a plurality of granular projections of 70/10 μm or more, more preferably 80/10 μm or more. This indicates the number of granular protrusions from the line profile measured at an arbitrary position on the surface of the metal layer on which the organic layer is formed, that is, the number of granular protrusions included per unit length. .

This is to increase the adhesion between the blackened layer and the metal layer on which the organic material layer is formed by forming a plurality of granular projections on the surface of the metal layer on which the organic material layer is formed by 70/10 μm or more. It is because it can suppress that a blackening layer peels.

The average height and the number per unit length of the plurality of granular protrusions are calculated from the measurement results obtained by, for example, measuring the surface of the metal layer on which the organic layer is formed using an AFM (atomic force microscope). can do. In measuring and calculating the average height of the plurality of granular protrusions and the number per unit length, first, a predetermined length, for example, a length of 10 μm, is formed at an arbitrary position on the surface of the metal layer on which the organic layer is formed. The surface profile can be measured linearly by AFM. Then, the average height and the number of granular protrusions existing in the measurement range can be calculated from the measured line profile result.

However, the average height of the granular projections on the surface of the metal layer on which the organic layer is formed and the number of units per unit length are measured and calculated by AFM after forming the metal layer and before forming the organic layer. If the evaluation is to be performed, the surface of the metal layer may be oxidized by oxygen in the atmosphere and may not be evaluated accurately. For this reason, it is preferable to measure and evaluate by AFM after forming a metal layer and further forming an organic layer. As described later, the organic material layer can be formed by supplying, applying and drying a liquid containing a nitrogen-based organic material on the metal layer, and the surface of the organic material layer reflects the state of the surface of the metal layer. Become. For this reason, it is because the measurement result on the surface of an organic substance layer corresponds with the measurement result on the surface of a metal layer.

Therefore, the measurement of the average height of the plurality of granular projections and the number per unit length and the calculation method in the description of the calculation method should be read as the surface of the organic layer. Can do. Thus, by measuring the line profile on the surface of the organic material layer at an arbitrary location of the organic material layer, by using the result, calculating the average height of the plurality of granular projections, and the number per unit length, A result reflecting the state of a plurality of granular protrusions existing on the surface of the metal layer on which the organic layer is formed can be obtained.

The material of the plurality of granular protrusions is not particularly limited, but it is preferable that the plurality of granular protrusions are made of the same material as the metal layer.

The method for forming a plurality of granular protrusions on the surface of the metal layer on which the organic material layer is formed is not particularly limited, and examples thereof include a method of surface-treating the surface of the metal layer after forming the metal layer. As a specific example, there is a method in which after the metal layer is formed, the surface of the metal layer is subjected to etching treatment or sand blast treatment.

Further, as another method of forming a plurality of granular protrusions on the surface of the metal layer on which the organic material layer is formed, there is a method of adjusting film forming conditions when forming the metal layer. For example, there is a method of changing the current density (Dk value) when forming the metal plating layer by electroplating during the formation of the metal plating layer.

More specifically, for example, after starting the formation of the metal plating layer, the metal plating layer is formed at a predetermined current density Dk1, and the current density is reduced to a current density Dk2 for a certain period of time before the end of the formation of the metal plating layer. Thus, a plurality of granular protrusions can be formed on the surface of the metal layer on which the organic layer is formed. Note that Dk1> Dk2.

The case where the metal layer is a copper layer will be described as an example. First, as the current density Dk1, a copper plating layer which is a metal plating layer can be formed. A plurality of metal plating layers are formed on the surface of the metal layer by reducing the current density to the current density Dk2 for a predetermined time of 7 seconds or more and 30 seconds or less before the completion of the copper plating layer formation. Granular projections can be formed. The current density Dk1 is preferably 1 A / dm ² or more and 2 A / dm ² or less. The current density Dk2 is more preferably preferably at most 0.1 A / dm ² or more 0.2 A / dm ^2, at 0.1 A / dm ² or more 0.15 A / dm ² or less.

This film formation immediately before the end of the current density Dk2 of the copper plating layer as a 0.1 A / dm ² or more 0.2 A / dm ² or less, current than the current density Dk1 when the copper plating layer was deposited up to that It is because a granular material can be deposited on the plating surface by reducing the density.

However, if the current density during the formation of the metal plating layer is continuously set to Dk2, the density of the metal plating layer may decrease, which is not preferable. For this reason, it is preferable that the time for performing electroplating as the current density Dk2 is 30 seconds or less before the end of the formation of the metal plating layer. In addition, in order to form a plurality of granular projections with a desired density on the surface of the metal layer, the time for performing electroplating within the range of the current density Dk2 should be 7 seconds or more before the end of the formation of the metal plating layer. Is preferred.

Of the methods for forming a plurality of granular protrusions on the surface of the metal layer described so far, the plurality of granular protrusions are formed on the surface of the metal layer by adjusting the film formation conditions when forming the metal layer. The method of forming is preferable from the viewpoint of suppressing an increase in the number of manufacturing steps of the conductive substrate. In particular, according to the method of changing the current density (Dk value) when the metal plating layer is formed by the electroplating method described above during the formation of the metal plating layer, it is only necessary to change the current density. It is more preferable because a plurality of granular protrusions can be formed on the surface.

Further, the SAD (Surface Area Differentiate) value calculated by the following equation (1) is calculated from the projected area S1 of the surface of the metal layer forming the organic material layer and the surface area S2 of the surface of the metal layer forming the organic material layer. It is preferably 5% or more.

SAD = 100 × (S2-S1) / S1 (1)
The SAD value calculated by the above formula is obtained by calculating the difference between the surface area of the surface of the metal layer forming the organic material layer, that is, the measured area S2 of the surface of the metal layer forming the organic material layer, and the projected area S1 by The value is divided. Accordingly, the SAD value increases as the size of the plurality of granular projections and the number of the plurality of granular projections per unit area increase. According to the study of the inventors of the present invention, when the SAD value is 5% or more, the size of the plurality of granular protrusions formed on the surface of the metal layer on which the organic layer is formed, and the unit area Is preferably large enough to increase the adhesion of the blackened layer.

The surface area S2 of the surface on which the organic layer of the metal layer for calculating the SAD value can be measured using, for example, AFM. Further, the projected area S1 can be calculated from the size of the metal layer.

The upper limit value of the SAD value is not particularly limited, but is preferably 20% or less, for example.

Further, the surface roughness Ra of the surface on which the organic layer of the metal layer is formed is preferably less than 20.0 nm. As described above, in the conductive substrate of this embodiment, a plurality of granular protrusions are formed on the surface of the metal layer on which the organic layer is formed. In addition, since a plurality of granular protrusions are formed, it is possible to suppress the peeling of the blackened layer even when an organic layer is provided.

However, if the surface roughness of the surface on which the organic layer of the metal layer is formed becomes too large, the effect of providing a plurality of granular projections is reduced, and the adhesion of the blackened layer by the plurality of granular projections is increased. The effect may be reduced. For this reason, it is preferable that surface roughness Ra of the surface which forms the organic substance layer of a metal layer is less than 20.0 nm.

The surface roughness Ra is defined as an arithmetic average roughness in JIS B 0601 (2013). As a measuring method of the surface roughness Ra, it can be evaluated by a stylus method or an optical method. Specifically, for example, it can be evaluated by an AFM (atomic force microscope).

The lower limit of the surface roughness Ra is not particularly limited, but is preferably 15.0 nm or more, for example, and more preferably 18.0 nm or more.

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, if 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.

Also, as described above, the plurality of granular protrusions can be made of the same material as the metal layer. When the plurality of granular projections and the metal layer are made of the same material, the thickness of the metal layer includes the height of the plurality of granular projections.

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

The nitrogen-based organic material included in the organic layer is not particularly limited, and can be arbitrarily selected from organic compounds containing nitrogen. As the nitrogen-based organic substance, for example, it is preferable to contain 1,2,3-benzotriazole or a derivative thereof. More specifically, for example, 1,2,3-benzotriazole, 5-methyl-1H benzotriazole and the like can be contained as the nitrogen-based organic substance.

The method for forming the organic material layer is not particularly limited, and examples thereof include a method of supplying, applying, and drying a solution containing a nitrogen-based organic material on the surface of the metal layer on which the organic material layer is formed.

As the solution containing nitrogen-based organic material, for example, a rust preventive for copper containing nitrogen-based organic material can be preferably used. As a commercially available copper anticorrosive treatment agent, for example, an OPC defender (trade name, Okuno Pharmaceutical Co., Ltd.) or the like can be preferably used. In addition, as a solution containing nitrogen-type organic substance, the aqueous solution containing nitrogen-type organic substance can be used preferably, for example.

Examples of a method for supplying and applying a solution containing a nitrogen-based organic material on the metal layer of the base material forming the organic material layer include a spray method, a pouring method, and an immersion method.

The spray method is a method of supplying a solution containing a nitrogen-based organic material to the surface of the metal layer of the base material on which the organic material layer is formed using a spray.

In the pouring method, a solution containing a nitrogenous organic substance is flowed from the top to the bottom to form a film-like flow, and the flow of the solution containing the nitrogenous organic substance and the base metal for forming the organic matter layer It refers to a method of transporting a base material that forms an organic layer so that the surface of the layer is substantially parallel to and in contact with the surface of the layer.

Also, the dipping method refers to a method of dipping a base material for forming an organic material layer in a solution containing a nitrogenous organic material. In addition, the base material which forms the organic substance layer by description so far means the base material which formed the metal layer or the contact | adherence layer and the metal layer on the transparent base material.

Next, the blackened layer will be described.

The blackening layer can be formed on the upper 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 may contain 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. Good. 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. In addition, 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—Cr alloy or a Ni—Cu alloy can be used more preferably.

The method for forming the blackened layer is not particularly limited, and can be formed by any method, for example, 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. In this case, a reactive sputtering method can be more preferably used.

When forming the blackened layer by the reactive sputtering method, 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 blackened layer can be formed by either a dry method or a wet method. However, when forming the blackened layer, the nitrogen-based organic matter contained in the organic layer is dissolved in the plating solution. Incorporation into the blackened layer may affect the color tone and other characteristics of the blackened layer. Therefore, it is preferable to form a film by a dry method.

The thickness of the blackening layer is not particularly limited, but is preferably 5 nm or more, for example, and more preferably 15 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 5 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 50 nm or less, and more preferably 30 nm or less.

Also, the conductive substrate can be provided with any layer other than the above-mentioned 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 off from the insulating substrate.

Also, 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 also 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 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. In addition, 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—Cr alloy or 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, for example, 5 nm to 50 nm, more preferably 5 nm to 35 nm, and still more preferably 5 nm to 33 nm.

When the adhesion layer also functions as a blackening layer, that is, when light reflection in the metal layer is suppressed, the thickness of the adhesion layer is preferably 5 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 base, a metal layer, an organic layer, and a blackening layer. Further, a layer such as an adhesion layer can be optionally provided.

Specific configuration examples 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.

In addition, for the conductive substrate of the present embodiment, a metal layer, an organic material layer, and a blackening layer are formed on one surface of the insulating base and on the other surface facing the one surface, respectively. It can also be set as the structure formed in that order. Specifically, for example, it can be configured as shown in FIG. 1B or FIG. 2B described later. For example, in the case of the conductive substrate 10B shown in FIG. 1B, the other surface (the other surface) on one surface 11a of the insulating base 11 and opposite to the one surface 11a, that is, on the opposite side. The metal layers 12A and 12B, the organic layers 13A and 13B, and the blackening layers 14A and 14B can be stacked in this order on the surface 11b. The metal layer, the organic material layer, and the blackening layer can be formed one by one as shown in FIG. 1B, for example.

Further, as an optional layer, for example, an adhesion layer may be provided. 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 structure in which an adhesion layer, a metal layer, an organic material layer, and a blackening layer are laminated on both surfaces of the insulating substrate 11 can be employed. 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 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 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 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 metal layer, the organic material layer, and the blackening layer of the conductive substrate of the present embodiment described so far.

For example, a mesh-like wiring can be formed by two-layer 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 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 and / 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 base 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 are cross-sectional views taken along line AA ′ of FIG.

First, as shown in FIG. 4A, wirings 31A and 31B 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.

By 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.

3 can also be formed by using two conductive substrates shown in FIG. 1A or FIG. 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 can 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 as described above, the organic material layer containing the nitrogen-based organic material and the blackening layer are stacked on the metal layer formed on at least one surface of the insulating base material. It has a structure. A plurality of granular protrusions having a predetermined average height are formed on the surface of the metal layer on which the organic material layer is formed so that a predetermined number per unit length. For this reason, even when the organic material layer is formed, the blackened layer can be prevented from peeling off, and a conductive substrate having high quality stability can be obtained.

Furthermore, since the blackened layer which suppressed peeling is provided in the conductive substrate of this embodiment, reflection of light on the surface of the metal layer is more reliably suppressed, and a conductive substrate with reduced reflectance is obtained. be able to. For this reason, when it uses for uses, such as a touch panel, for example, 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 this 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.

The metal layer formed in the metal layer forming step can have a plurality of granular protrusions on the surface on which the organic layer is formed. And the average height of a some granular protrusion can be 8.00 nm or more. Further, the metal layer can have a plurality of granular protrusions of 70/10 μm or more on the surface on which the organic layer is formed.

Hereinafter, the manufacturing method of the conductive substrate of the present embodiment will be specifically described.

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.

The metal layer preferably has a metal thin film layer as described above. 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 preferable to use a sputtering method because the film thickness can be easily controlled.

Next, the process for forming the metal plating layer will be described. The conditions in the step of forming the 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 metal plating layer can be formed by 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.

The conductive substrate of the present embodiment can have a plurality of granular protrusions on the surface on which the organic layer of the metal layer is formed.

The method for forming a plurality of granular protrusions related to the surface of the metal layer on which the organic layer is to be formed is not particularly limited, and examples thereof include a method for surface-treating the surface of the metal layer after the metal layer is formed. As a specific example, there is a method in which after the metal layer is formed, the surface of the metal layer is subjected to etching treatment or sand blast treatment. For this reason, after forming a metal thin film layer, or a metal thin film layer and a metal plating layer, the process which performs the etching process and the sandblasting process about the surface which forms the organic substance layer of a metal layer can also be provided.

Further, as another method of forming a plurality of granular protrusions related to the surface of the metal layer on which the organic material layer is formed, there is a method of adjusting film forming conditions when forming the metal layer. For example, there is a method of changing the current density (Dk value) when forming the metal plating layer by electroplating during the formation of the metal plating layer. For this reason, when forming a some granular protrusion on the surface which forms the organic substance layer of a metal layer by the method which concerns, a current density can be changed in the process of forming a metal plating layer. Since the specific control example of the current density has already been described, the description thereof is omitted here.

Next, the organic layer forming process 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.

The method for forming the organic material layer is not particularly limited. For example, the organic material layer may be formed by supplying, applying, and drying a solution containing a nitrogen-based organic material, for example, an aqueous solution containing the nitrogen-based organic material, on the metal layer. it can.

The method for supplying and applying a solution containing a nitrogenous organic substance on the metal layer is not particularly limited, and any method can be used. For example, the spray method, the pouring method, the dipping method, etc. are mentioned. Since each method has already been described, a description thereof will be omitted.

In addition, in order to remove the adhering excess nitrogen-based organic matter solution after applying the nitrogen-based organic matter solution, it is possible to perform water washing in which the base material coated with the nitrogen-based organic matter solution is washed with water.

Next, the blackening layer forming process will be described.

In the blackened layer forming step, the method for forming the blackened 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 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.

In the method for manufacturing a conductive substrate according to the present embodiment, an optional 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.

The conductive substrate obtained by the conductive substrate manufacturing method 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 conductive substrate of the present embodiment can include a patterning step of patterning the metal layer, the organic material layer, and the 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 side on which the mask is disposed can be performed.

The etching solution used in the etching step is not particularly limited, and can be arbitrarily selected according to 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.

Further, in the case of the conductive substrate 10B shown in FIG. 1B, a pattern can be formed by the metal layer 12A and the metal layer 12B so as to 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.

Further, for example, after the metal layer 12 and the like are patterned on the above-described conductive substrate 10A in the patterning step, a lamination step of laminating two or more patterned conductive substrates may 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 of 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 includes an organic material layer containing a nitrogen-based organic material on a metal layer formed on at least one surface of an insulating base, and a black And a laminated structure. A plurality of granular protrusions having a predetermined average height are formed on the surface of the metal layer on which the organic material layer is formed so that a predetermined number per unit length. For this reason, even when the organic material layer is formed, the blackened layer can be prevented from peeling off, and a conductive substrate having high quality stability can be obtained.

Furthermore, in the conductive substrate obtained by the manufacturing method of the conductive substrate of this embodiment, since the blackening layer which suppressed peeling is provided, reflection of the light in the metal layer surface is suppressed more reliably, and reflection It can be set as the electroconductive board | substrate which suppressed the rate. For this reason, when it uses for uses, such as a touch panel, for example, 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 methods)
First, a method for evaluating the obtained conductive substrate will be described.
(1) The average height of granular protrusions, the number of granular protrusions from the line profile, the surface roughness of the metal layer surface, the SAD value In the following examples and comparative examples, on the insulating substrate, After forming the adhesion layer, the metal layer, and the organic layer, the surface of the organic layer is measured using AFM (trade name: Dimension Icon, nanoScope V, manufactured by Bruker AXS), and the surface state of the metal layer after the formation of the organic layer is measured. It was. In addition, immediately after the formation of the organic material layer, the measurement is performed by measuring the surface profile in a linear shape having a length of 10 μm at an arbitrary location on the surface of the organic material layer. The height, the number of granular projections from the line profile, and the surface roughness of the metal layer surface were calculated. Further, the SAD value was also calculated from the measurement result using AFM.

The SAD value was calculated by the following formula (1), and the value measured by AFM was used as the surface area S2 of the surface of the metal layer on which the organic layer is formed.

SAD = 100 × (S2-S1) / S1 (1)
Projected area of the surface on which the organic layer of the metal layer is formed: S1
Surface area of the surface on which the organic layer of the metal layer is formed: S2
(2) Adhesion test of blackened layer The blackened layer adhesion test was carried out based on ASTM D3359, specifically according to the following procedure.

As shown in FIG. 5, 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 pieces of 51a are formed parallel to each other at intervals of 1.0 mm.

Next, using the same cutting tool, 11 horizontal cutting lines 51b having a length of 20 mm are formed in parallel with each other at intervals of 1.0 mm so as to be orthogonal to the previously formed vertical cutting lines 51a.

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

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

¡After adhering the adhesive strength evaluation tape, 30 seconds later, peel the adhesive strength evaluation tape as quickly as possible in the direction of 180 ° to the measurement surface.

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, the evaluation of adhesion was evaluated as ◯ in the case of 5B, and x was evaluated in other cases.
(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. Note that the total light transmittance of the insulating base material made of polyethylene terephthalate resin used as the insulating base material was evaluated by the method prescribed in JIS K 7361-1, and found to be 97%.

In the adhesion layer forming step, a Ni—Cu alloy layer containing oxygen was formed as an adhesion layer using 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-mentioned insulating base material, which was previously heated to 60 ° C. to remove moisture, was placed in the chamber of the sputtering apparatus.

Next, after evacuating 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 process will be described.

In the metal thin film layer forming step, a copper thin film layer was formed as a metal thin film layer on the adhesion layer using a substrate in which the adhesion layer was 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 to a thickness of 80 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.

In the metal plating layer forming step, the current density (Dk value) is 1 A / dm ² at the start of the metal plating layer forming step, and the current density (Dk value) is 0.1 A for 7 seconds before the end of the metal plating layer forming step. / Dm ² . The plating time before the end of the metal layer forming step is hereinafter referred to as the final plating time.
(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 material 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 material 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.

Then, the organic material layer was formed on the metal layer by removing the solution adhering to the surface other than the upper surface of the metal layer, that is, the surface opposite to the surface opposite to the adhesion layer of the metal layer, and then drying.

After the organic layer was formed, the average height of the granular protrusions, the number of granular protrusions from the line profile, the surface roughness of the metal layer surface, and the SAD value were evaluated.
(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, a laminated body in which an adhesion layer, a metal layer, and an organic layer were laminated on an insulating substrate was set in a chamber of a 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 blackening layer was formed on the organic layer so as to have a thickness of 20 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.

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

The results are shown in Table 1.
[Example 2 and Example 3]
A conductive substrate was prepared and evaluated in the same manner as in Example 1 except that the final plating time was the time shown in Table 1.

The results are shown in Table 1.
[Comparative Examples 1 and 2]
A conductive substrate was prepared and evaluated in the same manner as in Example 1 except that the final plating time was the time shown in Table 1.

The results are shown in Table 1.

According to the results shown in Table 1, the average height of the plurality of granular projections formed on the surface of the metal layer is 8.00 nm or more, and the granularity from the line profile on the surface of the metal layer on which the organic layer is formed is It was confirmed that Examples 1 to 3 in which the number of protrusions was 70/10 μm or more were evaluated as “good” in the adhesion test.

On the other hand, for Comparative Examples 1 and 2 in which the average height of the plurality of granular protrusions formed on the surface of the metal layer and / or the number of granular protrusions from the line profile does not satisfy the above range It was confirmed that the adhesion test was evaluated as x and peeling of the blackened layer was observed.

Although the conductive substrate has been described in the embodiment and examples, the present invention is not limited to the above-described embodiment 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. 2015-152898 filed with the Japan Patent Office on July 31, 2015. The entire contents of Japanese Patent Application No. 2015-152898 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)

1. An insulating substrate;
   A metal layer formed on at least one surface of the insulating substrate;
   An organic layer containing nitrogen-based organic matter formed on the metal layer;
   A blackening layer formed on the organic layer,
   The metal layer has a plurality of granular protrusions on the surface on which the organic layer is formed,
   An average height of the plurality of granular protrusions is 8.00 nm or more;
   The metal layer is a conductive substrate having the plurality of granular protrusions of 70/10 μm or more on a surface on which the organic layer is formed.
2. From the projected area S1 of the surface of the metal layer on which the organic material layer is formed and the surface area S2 of the surface of the metal layer on which the organic material layer is formed, SAD (Surface Area Different) calculated by the following equation (1) The conductive substrate according to claim 1, wherein the value is 5% or more.
   SAD = 100 × (S2-S1) / S1 (1)
3. The conductive substrate according to claim 1 or 2, wherein the nitrogen-based organic substance contains 1,2,3-benzotriazole, or a derivative thereof.
4. On one surface of the insulating substrate and on the other surface facing the one surface,
   The conductive substrate according to any one of claims 1 to 3, wherein the metal layer, the organic material layer, and the blackening layer are formed in that order.

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