TWI707255B - Conductive substrate - Google Patents

Abstract

Provided is a conductive substrate having: an insulating substrate; a metal layer formed on at least one surface of the insulating substrate; an organic layer formed on the metal layer and containing nitrogen-based organics; and formed on the organic layer The metal layer has a plurality of granular protrusions on the surface on which the organic layer is formed, the average height of the plurality of granular protrusions is 8.00nm or more, and the metal layer is formed on the surface of the organic layer The surface has 70 or more granular protrusions per 10 μm.

Description

Conductive substrate

The present invention relates to a conductive substrate.

The capacitive touch panel detects the change in capacitance caused by an object close to the surface of the panel to convert the position information of the close object on the surface of the panel into an electrical signal. The conductive substrate used for the capacitive touch panel is provided on the surface of the display, so the material of the conductive layer of the conductive substrate is required to have low reflectivity and difficult to identify.

Therefore, as a material for the conductive layer of the capacitive touch panel, a material with low reflectivity and difficult to be recognized is used, and wiring is formed on a transparent substrate or a transparent film.

For example, Patent Document 1 discloses a transparent conductive film that contains a polymer film and a transparent conductive film composed of a metal oxide. The transparent conductive film composed of a metal oxide is formed on the polymer film by a vapor phase formation method. Above, the transparent conductive film composed of a metal oxide is composed of the following materials: a transparent conductive film composed of a first metal oxide, and a transparent conductive film provided on the first metal oxide and composed of a second metal oxide In addition, the conditions for forming the transparent conductive film made of the second metal oxide are different from the conditions for forming the transparent conductive film made of the first metal oxide. In addition, it is also disclosed that the transparent conductive film made of metal oxide is an indium oxide-tin oxide (ITO) film.

In addition, in recent years, a large screen of a display equipped with a touch panel is being developed, and accordingly, a large area of a conductive substrate for a touch panel is also required. However, high ITO resistance will occur The signal is degraded, so there is a problem that conductive substrates using ITO are not suitable for large panels.

In this regard, in order to suppress the resistance of the conductive substrate, a method of using a metal such as copper as a material of the conductive layer instead of ITO is being studied. However, since metal has metallic luster, there is a problem that the visibility of the display decreases due to reflection. Therefore, a conductive substrate in which a metal such as copper and a layer made of a black material are formed has been studied.

For example, Patent Document 2 discloses a thin-film touch panel sensor that has stripe-shaped copper wiring on the surface and back of the film that need to be seen through, and a black copper oxide film on the side where the copper wiring can be identified on the front and back. .

<Prior Technical Literature>

<Patent Literature>

Patent Document 1: Japanese Patent Application Publication No. 2003-151358

Patent Document 2: JP 2013-206315 A

However, in a conductive substrate, for example, when a metal layer and a blackened layer are formed using different devices, after the metal layer is formed, until the blackened layer is formed on the upper surface, it may be necessary to prevent the metal layer Rusty surface etc. In this regard, the inventors of the present invention have explored a method of forming an organic layer by performing rust prevention treatment to form an organic layer on the surface of the metal layer.

However, if the blackened layer is formed on the surface of the metal layer subjected to the rust prevention treatment, the adhesion between the blackened layer and the metal layer may decrease and the blackened layer may peel off.

In view of the above-mentioned problems of the prior art, an object of one aspect of the present invention is to provide a conductive material that forms an organic layer between the metal layer and the blackened layer and suppresses the peeling of the blackened layer. 性 substrate.

In order to solve the above-mentioned problem, one aspect of the present invention provides a conductive substrate having an insulating base material, a metal layer formed on at least one surface of the insulating base material, and a nitrogen-based organic substance formed on the metal layer The organic substance layer, the blackened layer formed on the organic substance layer, the metal layer has a plurality of granular protrusions on the surface on which the organic substance layer is formed, and the average height of the plurality of granular protrusions is 8.00nm or more, the The metal layer has 70/10 μm granular protrusions on the surface where 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 peeling of the blackened layer can be suppressed.

10A, 10B, 20A, 20B, 30‧‧‧Conductive substrate

11‧‧‧Insulating base material

11a‧‧‧One side of insulating base material

11b‧‧‧The opposite side of 11a

12, 12A, 12B‧‧‧Metal layer

13, 13A, 13B, 32A, 32B‧‧‧Organic layer

14, 14A, 14B, 33A, 33B‧‧‧Blackening layer

15, 15A, 15B‧‧‧Sealing layer

31A, 31B‧‧‧Wiring

51a‧‧‧Straight tangent

51b‧‧‧Cross-cut line

52‧‧‧Evaluation area

A, B‧‧‧The surface of the blackened layer

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

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

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

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

Fig. 3 is a plan view of a conductive substrate provided with grid-shaped wiring according to an embodiment of the present invention.

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

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

Fig. 5 is an explanatory diagram of the tangent line formed when the adhesion test is performed in the Examples and Comparative Examples.

Hereinafter, one embodiment of the conductive substrate and the conductive substrate manufacturing method of the present invention will be described.

(Conductive substrate)

The conductive substrate of the present embodiment may have an insulating base material, a metal layer formed on at least one surface of the insulating base material, an organic layer formed on the metal layer and containing nitrogen-based organics, and a black layer formed on the organic layer.化层。 The layer.

In addition, the metal layer may have a plurality of granular protrusions on the surface where the organic layer is formed. The average height of the plurality of granular protrusions can be set at 8.00 nm or more. In addition, the metal layer may have multiple granular protrusions of 70/10 μm or more on the surface where the organic layer is formed.

In addition, in this embodiment, the conductive substrate includes: a substrate having a metal layer, an organic layer, and a blackened layer on the surface of an insulating base material before patterning the metal layer, etc., and after patterning the metal layer, etc. The substrate is the wiring substrate.

Here, first, each member included in the conductive substrate will be described as follows.

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 the material for the resin substrate that allows visible light to pass through, for example, polyamide resins, polyethylene terephthalate resins, polyethylene naphthalate resins, cycloolefin resins, and polyamide resins can be preferably used. Resins such as imine resins, polycarbonate resins, and cellulose acetate resins. In particular, as the material for the resin substrate that allows visible light to pass through, PET (polyethylene terephthalate), COP (cycloolefin copolymer), PEN (polyethylene naphthalate), and poly Amide, polyamide, polycarbonate, TAC (triacetyl cellulose), etc.

The thickness of the insulating substrate is not particularly limited, and it can be The required strength, electrostatic capacity, light transmittance, etc. for the board can be arbitrarily selected. The thickness of the insulating base material may be 10 μm or more and 200 μm or less, for example. Particularly 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. When it is used for touch panel applications, for example, when it is used for applications that require a reduction in the overall thickness of the display, the thickness of the insulating substrate is preferably 20 μm or more and 50 μm or less.

The insulating base material preferably has a higher total light transmittance. For example, the total light transmittance is preferably 30% or more, more preferably 60% or more. When the total light transmittance of the insulating base material is in the above range, for example, when it is used for touch panel applications, it is possible to sufficiently ensure the visibility of the display.

Here, the total light transmittance of the insulating base material can be evaluated according to the method specified in JIS K 7361-1.

Hereinafter, the metal layer will be described.

The material constituting the metal layer is not particularly limited, and a material whose conductivity is suitable for its purpose can be selected. For example, the material constituting the metal layer is preferably Cu and Ni, Mo, Ta, Ti, V, Cr, Fe, Mn, Co, W A copper alloy of at least one metal selected from the group, or a copper-containing material. In addition, the metal layer may be a copper layer made of copper.

The method of forming the metal layer on the insulating substrate is not particularly limited. In order to avoid a decrease in light transmittance, it is better not to arrange an adhesive between the insulating substrate and the metal layer. That is, it is preferable to form a metal layer directly on at least one surface of the insulating base material. In addition, when the adhesion layer is arranged between the insulating base material and the metal layer as described below, it is preferable to directly form the metal layer on the upper surface of the adhesion layer.

In order to directly form a metal layer on the upper surface of the insulating base material, the metal layer preferably has a metal thin film layer. In addition, 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 the metal layer. Thus, the metal layer can be directly formed on the insulating base material without interposing the adhesive. Here, as the dry plating method, for example, a sputtering method, a vapor deposition method, an ion plating method, etc. can be preferably used.

In addition, when the film thickness of the metal layer is to be increased, the metal thin film layer is used as the power supply layer, and the metal plating method is formed by the electroplating method, which is one of the wet plating methods, to obtain the metal layer having the metal thin film layer and the metal plating layer. Since the metal layer has a metal thin film layer and a metal plating layer, in this case, the metal layer can be directly formed on the insulating substrate without interposing an adhesive.

In addition, the conductive substrate of the present embodiment may have a plurality of granular protrusions on the surface of the metal layer on which the organic layer is formed.

As described above, when an organic layer is formed on the surface of a 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 will decrease, and the blackened layer may peel off . In response to this, the inventors of the present invention have studied diligently a method of suppressing peeling of the blackened layer in a conductive substrate in which an organic layer is formed between the metal layer and the blackened layer. As a result, it was found that by forming a plurality of granular protrusions with an average height of 8.00nm or more (hereinafter also referred to as "plural granular protrusions") 70/10μm or more on the organic layer of the metal layer, the blackness can be improved. The adhesion of the organic layer of the chemical layer to the metal layer is 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.

The reason is that, as described above, according to the research of the inventors of the present invention, by making the average height of a plurality of granular protrusions 8.0 nm or more, the peeling of the blackened layer can be suppressed.

The upper limit of the average height of a plurality of granular protrusions is not particularly limited, but is preferably 15.0 nm or less, and more preferably 14.0 nm or less. The reason is that when the average height of a plurality of granular protrusions exceeds 15.0 nm, when the organic layer and the blackened layer are formed on the metal layer, the surface roughness of the blackened layer surface may increase, which may affect the blackened layer. The surface hue affects and affects the function of the blackened layer.

On the surface of the metal layer where the organic layer is formed, it is preferable to form a plurality of granular protrusions having a size of 70/10 μm or more, and more preferably, a plurality of granular protrusions having a size of 70/10 μm or more may be formed. Here, the above-mentioned numerical value indicates the number of granular protrusions based on the line profile measured at an arbitrary position on the organic layer forming the metal layer, that is, the number of granular protrusions per unit length.

The reason is that by forming a plurality of granular protrusions of 70/10μm or more on the surface of the metal layer where the organic layer is formed, the adhesion between the blackened layer and the metal layer forming the organic layer can be improved, and blackening can be suppressed. The layer is peeled off.

Here, for example, an AFM (Atomic Force Microscope) can be used to measure the surface of the metal layer on which the organic layer is formed, and calculate the average height of a plurality of granular protrusions and the number per unit length based on the measurement result. When measuring and calculating the average height of a plurality of granular protrusions and the number per unit length, you can first use AFM to determine a specific length (for example, a length of 10 μm) at any position on the surface of the metal layer where the organic layer is formed. Measure the surface profile linearly. Then, based on the result of the measured line profile, the average height and the number of granular protrusions existing in the measurement range can be calculated.

However, for the measurement and calculation of the average height of the granular protrusions on the surface of the metal layer on which the organic layer is formed, and the number per unit length, if the AFM is used to evaluate after the metal layer is formed and before the organic layer is formed, the metal The surface of the layer is oxygenated by the oxygen in the atmosphere It is not possible to make a correct evaluation. Therefore, it is preferable to perform measurement and evaluation using AFM after the formation of the metal layer and the formation of the organic layer. As described below, by supplying and coating a nitrogen-containing organic liquid on the metal layer and drying it, an organic layer can be formed, and the surface of the organic layer reflects the state of the metal layer surface. Therefore, the measurement result on the surface of the organic layer is consistent with the measurement result on the surface of the metal layer.

Therefore, in the description of the measurement and calculation method of the average height and the number per unit length of the plurality of granular protrusions, the surface of the metal layer on which the organic layer is formed may also be referred to as the surface of the organic layer. In this way, the line profile of the surface of the organic layer is measured at any position of the organic layer, and the results are used to calculate the average height of the plurality of granular protrusions and the number per unit length, so that the organic layer reflecting the metal layer can be obtained. The result of the state of the multiple granular protrusions on the surface.

The material of the plurality of granular protrusions is not particularly limited, and it is preferable to use the same material as the metal layer.

The method of forming a plurality of granular protrusions on the surface of the metal layer where the organic layer is formed is not particularly limited. For example, a method of surface-treating the surface of the metal layer after forming the metal layer can be mentioned. As a specific example, a method of performing etching treatment or sand blasting treatment on the surface of the metal layer after forming the metal layer can be cited.

In addition, as another method of forming a plurality of granular protrusions on the surface of the metal layer on which the organic layer is formed, a method of adjusting the formation conditions when forming the metal layer can be cited. For example, a method of changing the current density (Dk value) when forming the metal plating layer by the electroplating method in forming the metal plating layer can be mentioned.

More specifically, for example, after the formation of the metal plating layer, a specific current density The degree Dk1 performs the formation of the metal plating layer, and reduces to the current density Dk2 within a certain time before the completion of the formation of the metal plating layer, whereby a plurality of granular protrusions can be formed on the surface of the metal layer where the organic layer is formed. Here, there is a relationship of Dk1>Dk2.

A case where the metal layer is a copper layer will be described as an example. First, a copper plating layer as a metal plating layer can be formed with a current density Dk1. Then, the metal plating layer is formed by reducing the current density to the current density Dk2 within a predetermined time of 7 seconds or more and 30 seconds or less before the completion of the copper plating layer formation, thereby forming a plurality of granular protrusions on the surface of the metal layer Things. Here, the current density Dk1 is preferably 1 A/dm ² or more and 2 A/dm ² or less. Further, the current density is preferably Dk2 0.1A / dm ² or more 0.2A / ² or less dm, more preferably from 0.1A / dm ² or more 0.15A / dm ² or less.

The reason is that by setting the current density Dk2 just before the completion of the copper plating layer formation to 0.1 A/dm ² or more and 0.2 A/dm ² or less, the current density can be made smaller than the current density Dk1 when the copper plating layer is formed before. On the other hand, granular materials are deposited on the plating layer.

However, if the current density during the formation of the metal plating layer is kept at Dk2, the density of the metal plating layer may sometimes be lowered, which is not good. Therefore, the time for electroplating at the current density Dk2 is preferably 30 seconds or less before the completion of the formation of the metal plating layer. In addition, in order to form a plurality of granular protrusions at a desired density on the surface of the metal layer, it is preferable to set the "time for electroplating in the range of current density Dk2" to be 7 seconds or more before the completion of the formation of the metal plating layer.

Among the methods for forming a plurality of granular protrusions on the surface of the metal layer described above, from the viewpoint of suppressing the number of manufacturing steps of the conductive substrate, it is preferable to form on the surface of the metal layer by adjusting the formation conditions when forming the metal layer. Multiple granular protrusion methods. Among them, according to the above-mentioned in the formation of the metal plating layer, the current density (Dk The method of changing the value) can form a plurality of granular protrusions on the surface of the metal layer only by changing the current density, so this method is preferred.

In addition, the value of SAD (Surface Area Different) calculated by the following formula (1) based on the projected area S1 of the surface of the metal layer where the organic layer is formed and the surface area S2 of the surface of the metal layer where the organic layer is formed is preferably 5% the above.

SAD=100×(S2-S1)/S1‧‧‧(1)

The SAD value calculated from the above formula is a value obtained by dividing the surface area of the organic layer forming surface of the metal layer, that is, the difference between the measured area S2 and the projected area S1 of the organic layer forming surface of the metal layer by the projected area S1. Therefore, as the size of the plurality of granular protrusions and the number per unit area of the plurality of granular protrusions increase, the SAD value increases. In addition, according to studies by the inventors of the present invention, when the SAD value is 5% or more, the size and the number per unit area of the plurality of granular protrusions formed on the surface of the metal layer where the organic layer is formed becomes It can meet the sufficient size required to improve the adhesion of the blackened layer.

For example, AFM can be used to measure the surface area S2 of the surface of the metal layer on which the organic substance layer is formed for calculating the SAD value. In addition, the projected area S1 can be calculated from the size of the metal layer.

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

In addition, the surface roughness Ra of the surface of the metal layer on which the organic layer is formed is preferably less than 20.0 nm. As described above, in the conductive substrate of the present 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 the organic substance layer is provided.

However, when the surface roughness of the organic layer of the metal layer is too large, it will The effect of providing a plurality of granular protrusions is reduced, and the effect of improving the adhesion of the blackened layer by the plurality of granular protrusions may decrease. Therefore, the surface roughness Ra of the surface of the metal layer on which the organic layer is formed is preferably less than 20.0 nm.

Here, JIS B 0601 (2013) specifies the surface roughness Ra as the arithmetic average roughness. As a measuring method of surface roughness Ra, it can evaluate by a stylus method, an optical method, etc., Specifically, it can evaluate using, for example, AFM (atomic force microscope).

The lower limit of the surface roughness Ra is not particularly limited. For example, it is preferably 15.0 nm or more, 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 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 thickened, when etching is performed to form a wiring pattern, the etching takes more time, and therefore side etching is likely to occur, which sometimes causes problems such as difficulty in forming thin lines. Therefore, 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 to provide sufficient current, for example, the thickness of the metal layer is preferably 50 nm or more, more preferably 60 nm or more, and even more preferably 150 nm or more.

Here, when the metal layer has a metal thin film layer and a metal plating layer as described above, the total thickness of the thickness of the metal thin film layer and the thickness of the metal plating layer is preferably within the above-mentioned range.

In addition, the plurality of granular protrusions as described above may be composed of the same material as the metal layer. In addition, when the plurality of granular protrusions and the metal layer are made of the same material, the thickness of the metal layer also includes the height of the plurality of granular protrusions.

Regardless of the case where the metal layer is composed of a metal thin film In the case of the film layer and the metal plating layer, the thickness of the metal thin film layer is not particularly limited. For example, it is preferably 50 nm or more and 500 nm or less.

As described below, the metal layer can be used as a wiring by forming a desired wiring pattern by patterning, for example. In addition, the metal layer can lower the resistance value compared with ITO that has been used as a transparent conductive film conventionally. Therefore, by providing the metal layer, the resistance value of the conductive substrate can be reduced.

Hereinafter, the organic substance layer will be described.

An organic layer may be formed on the surface of the metal layer opposite to the blackened layer described below. Therefore, in the case of a conductive substrate, an organic layer can be arranged between the metal layer and the blackened layer. The organic substance layer may contain nitrogen-based organic substances.

The nitrogen-based organic substance contained in the organic substance layer is not particularly limited, and it can be arbitrarily selected and used from nitrogen-containing organic compounds. The nitrogen-based organic substance preferably contains, for example, 1,2,3-benzotriazole or a derivative thereof. As the nitrogen-based organic substance, more specifically, for example, 1,2,3-benzotriazole or 5-methyl-1H benzotriazole can be contained.

The method of forming the organic substance layer is not particularly limited, and for example, a method of supplying and applying a solution containing a nitrogen-based organic substance on the surface of the metal layer where the organic substance layer is formed and drying is mentioned.

As the nitrogen-containing organic substance solution, for example, a nitrogen-containing organic substance-containing rust preventive treatment agent for copper can be preferably used. As a commercially available antirust treatment agent for copper, for example, OPC Defensor (trade name, Okuno Pharmaceutical Co., Ltd.) etc. can be preferably used. Here, as the solution of the nitrogen-containing organic substance, for example, an aqueous solution of the nitrogen-containing organic substance can be preferably used.

As the metal layer of the base material forming the organic layer, the nitrogen-containing Examples of the method of the organic solution include a spray method, a flowing method, and a dipping method.

The spray method is a method of using a sprayer to provide a nitrogen-containing organic solution to the surface of the metal layer of the base material forming the organic layer.

The impulse flow method is a method in which a nitrogen-containing organic solution flows from above to below to form a film-like flow, so that the nitrogen-containing organic solution flow and the surface of the base metal layer forming the organic layer become substantially parallel and in contact , The method of transporting the substrate forming the organic layer.

In addition, the immersion method refers to a method of immersing the substrate forming the organic substance layer in a nitrogen-containing organic substance solution. Here, the formation of the organic layer substrate described above refers to a substrate in which a metal layer is formed on a transparent substrate, or an adhesion layer and a metal layer are formed.

Hereinafter, the blackened layer will be described.

A blackened layer can be formed on the upper surface of the organic layer.

The material of the blackening layer is not particularly limited, and it can be suitably used as long as it can suppress light reflection on the surface of the metal layer.

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

Here, the blackening layer may also include a metal alloy, the metal alloy system containing at least two selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn Of the metal. In this case, the blackened layer may contain one or more elements selected from carbon element, oxygen element, hydrogen element, and nitrogen element. In this case, as a metal alloy containing at least two metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn, Cu-Ti can be preferably used -Fe alloy, Cu-Ni-Fe alloy, Ni-Cu Alloy, Ni-Zn alloy, Ni-Ti alloy, Ni-W alloy, Ni-Cr alloy, or Ni-Cu-Cr alloy. In particular, Ni-Cr alloy or Ni-Cu alloy can be preferably used.

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

When the blackened layer is formed by a dry method, the specific method is not particularly limited. 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 the case of forming the blackened layer by the dry method, it is more preferable to use the sputtering method in consideration of easy control of the film thickness. Here, one or more elements selected from carbon element, oxygen element, hydrogen element, and nitrogen element may be added to the blackening layer as described above. In this case, it is more preferable to use a reactive sputtering method.

In the case of forming the blackened layer by the reactive sputtering method, as a target, a metal-based target containing the blackened layer can be used. When the blackening layer contains an alloy, a target of each metal contained in the blackening layer can be used, and then the alloy can be formed on the surface of the film-forming body such as a substrate, or the blackening layer can be preliminarily made Metal alloyed target.

In addition, when one or more elements selected from carbon, oxygen, hydrogen, and nitrogen are to be contained in the blackened layer, these can be added to the environment when the blackened layer is formed in advance. It is added to the blackened layer. For example, in the case of adding carbon element to the blackening layer, carbon monoxide gas and/or carbon dioxide gas can be added to the environment during sputtering in advance; in the case of adding oxygen element, oxygen can be added to the sputtering environment in advance. The environment during plating; if hydrogen is to be added, hydrogen and/or water can be added to the environment during sputtering in advance; if nitrogen is to be added, nitrogen can be added to the environment during sputtering in advance Environment. By adding these gases to the inert gas when forming the blackened layer, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the blackened layer. Here, make As an inert gas, argon can be preferably used.

In the case of forming the blackened layer by a wet method, a plating solution corresponding to the material of the blackened layer may be used, and for example, the blackened layer may be formed by an electroplating method.

Either dry method or wet method can be used to form the blackened layer as described above. However, when the blackened layer is formed, the nitrogen-based organic matter contained in the organic layer will dissolve into the plating solution and enter the blackened layer. In the layer, the color tone and other characteristics of the blackened layer may be affected, so it is preferably formed by a dry method.

The thickness of the blackening layer is not particularly limited. For example, it is preferably 5 nm or more, and more preferably 15 nm or more. The reason is that when the thickness of the blackened layer is thin, the reflection of light on the surface of the metal layer may not be sufficiently suppressed. Therefore, it is preferable to set the thickness of the blackened layer to 5 nm or more as described above. In particular, a structure capable of suppressing light reflection on the surface of the metal layer.

The upper limit of the thickness of the blackened layer is not particularly limited. However, an unnecessary increase in thickness will increase the time required for the formation of the blackened layer and the time required for etching when forming the wiring, resulting in an increase in cost. Therefore, the thickness of the blackening layer is preferably 50 nm or less, and more preferably 30 nm or less.

In addition to the above-mentioned insulating base material, metal layer, organic layer, and blackening layer, any other layers may be provided on the conductive substrate. For example, an adhesive 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 base material, and when the metal layer is directly formed on the insulating base material, the adhesion between the insulating base material and the metal layer may be insufficient. Therefore, when the metal layer is directly formed on the upper surface of the insulating base material, the metal layer may peel from the insulating base material during the manufacturing process or during use.

In this regard, in the conductive substrate of this embodiment, in order to improve the insulating substrate Adhesion to the metal layer can be provided with an adhesive layer on the insulating base material.

By disposing the adhesion layer between the insulating base material and the metal layer, the adhesion between the insulating base material and the metal layer can be improved, and peeling of the metal layer from the insulating base material can be suppressed.

In addition, the adhesion layer can also function as a blackening layer. Thereby, it is also possible to suppress light reflection from the metal layer by light from the lower surface side of the metal layer, that is, from the side of the insulating base material.

The material constituting the adhesion layer is not particularly limited, and it can be based on the adhesion of the insulating base material and the metal layer, the degree of suppression of light reflection on the surface of the metal layer required, or the use environment of the conductive substrate (for example, humidity or The degree of stability of temperature) can be selected arbitrarily.

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

Here, the adhesion layer may also include a metal alloy containing at least two or more selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn Metal person. In this case, the adhesion layer may still contain one or more elements selected from carbon element, oxygen element, hydrogen element, and nitrogen element. At this time, as a metal alloy containing at least two metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn, Cu-Ti- Fe alloy or Cu-Ni-Fe alloy, Ni-Cu alloy, Ni-Zn alloy, Ni-Ti alloy, Ni-W alloy, Ni-Cr alloy, Ni-Cu-Cr alloy. In particular, Ni-Cr alloy or Ni-Cu alloy can be preferably used.

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

When the adhesion layer contains one or more elements selected from carbon element, oxygen element, hydrogen element, and nitrogen element, it is possible to preliminarily add elements containing carbon element, oxygen element, and oxygen element to the environment when the adhesion layer is formed. A gas of one or more elements selected from element, hydrogen element, and nitrogen element, and these elements are added to the adhesion layer. For example, in the case of adding carbon to the adhesion layer, carbon monoxide gas and/or carbon dioxide gas can be pre-added to the environment during dry plating; in the case of adding oxygen, oxygen can be pre-added to the dry plating. When adding hydrogen, hydrogen and/or water can be added to the environment during dry plating; when adding nitrogen, nitrogen can be added to the environment during dry plating. Environment.

Preferably, a gas containing one or more elements selected from the group consisting of carbon element, oxygen element, hydrogen element, and nitrogen element is added to the inert gas as an ambient gas during dry plating. The inert gas is not particularly limited. For example, argon can be preferably used.

By forming the adhesion layer by the dry plating method as described above, the adhesion between the insulating base material and the adhesion layer can be improved. In addition, the adhesion layer may contain, for example, a metal as its main component, so its adhesion to the metal layer is also high. Therefore, by disposing the adhesion layer between the insulating base material and the metal layer, peeling of the metal layer can be suppressed.

The thickness of the adhesion layer is not particularly limited, but is preferably, for example, 5 nm or more and 50 nm or less, more preferably 5 nm or more and 35 nm or less, and still more preferably 5 nm or more and 33 nm or less.

When the adhesion layer functions as a blackening layer, that is, when the light reflection of the metal layer is suppressed, the thickness of the adhesion layer is preferably 5 nm or more as described above.

The upper limit of the thickness of the adhesion layer is not particularly limited. However, if the thickness exceeds the necessary thickness, the time required for forming the adhesion layer and the time required for etching during wiring formation are prolonged, resulting in an increase in cost. Therefore, as described above, the thickness of the adhesion layer is preferably 50 nm or less, more preferably 35 nm or less, and still more preferably 33 nm or less.

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

As described above, the conductive substrate of the present embodiment may have an insulating base material, a metal layer, an organic layer, and a blackening layer. In addition, layers such as an adhesion layer can be arbitrarily provided.

The specific configuration examples are described below with reference to FIG. 1A, FIG. 1B, FIG. 2A, and FIG. 2B. 1A, 1B, 2A, and 2B illustrate cross-sectional views of the conductive substrate of the present embodiment on a plane parallel to the stacking direction of the insulating base material, the metal layer, the organic layer, and the blackened layer.

The conductive substrate of the present embodiment may have, for example, a structure in which a metal layer, an organic layer, and a blackened layer are sequentially laminated on at least one surface of the insulating base material from the insulating base material side.

Specifically, for example, it is a conductive substrate 10A shown in FIG. 1A, in which a metal layer 12, an organic layer 13, and a blackened layer 14 can be laminated on one surface 11a side of the insulating base material 11 in this order.

In addition, the conductive substrate of the present embodiment may also have a structure in which a metal layer, an organic layer, and a blackened layer are sequentially formed on one surface of the insulating base material and the other surface opposite to the one surface. Specifically, for example, the structure shown in FIG. 1B or FIG. 2B described later may be used. For example, in the case of the conductive substrate 10B shown in FIG. 1B, one of the insulating base materials 11 On one surface 11a and on the other surface (the other surface) 11b opposite to the one surface 11a, metal layers 12A and 12B, organic layers 13A and 13B, and blackened layers 14A and 14B may be sequentially laminated, respectively. Here, the metal layer, the organic layer, and the blackened layer may be formed in one layer each as shown in FIG. 1B, for example.

In addition, it may be a structure in which, for example, an adhesive layer is provided as an arbitrary layer. In this case, for example, it may be a structure in which an adhesion layer, a metal layer, an organic layer, and a blackened layer are sequentially formed on at least one surface of the insulating base material from the insulating base material side.

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 blackened layer 14 may be laminated on the one surface 11a side of the insulating base material 11 in this order.

In this case, a structure in which an adhesion layer, a metal layer, an organic layer, and a blackened layer are layered on both areas of the insulating base material 11 may be used. Specifically, the conductive substrate 20B shown in FIG. 2B can be laminated on one surface 11a side and the other surface 11b side of the insulating base material 11, respectively, and adhesion layers 15A and 15B, metal layers 12A and 12B, and an organic layer 13A and 13B, blackened layers 14A and 14B.

In addition, Figures 1B and 2B show that in the case of a two-area metal layer, an organic layer, and a blackened layer of an insulating base material, the insulating base material 11 is used as the plane of symmetry, and the laminated layers are closely connected. An example in which the layers on the upper and lower sides of the substrate 11 are symmetrically arranged with each other, but the aspect of the present invention is not limited to this. For example, in Figure 2B, the structure on the side 11a of the insulating base material 11 may be the same as that in Figure 1B. The adhesion layer 15A is not provided, but the metal layer 12A, the organic layer 13A, and the blackening layer are sequentially laminated. The form of the layer 14A is such that the layers laminated on the upper and lower sides of the insulating base material 11 have an asymmetric structure.

However, in the conductive substrate of this embodiment, by forming an insulating substrate Providing a metal layer, an organic layer, and a blackening layer can suppress light reflection due to the metal layer, thereby suppressing the reflectance of the conductive substrate.

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

The reflectance can be measured by irradiating light to the blackened layer of the conductive substrate. Specifically, for example, as shown in FIG. 1A, when the metal layer 12, the organic layer 13, and the blackened layer 14 are sequentially laminated on the side 11a of the insulating base material 11, the blackened layer 14 can be irradiated with light. In the method, the surface A of the blackened layer 14 is irradiated with light and measured. During the measurement, light with a wavelength of 400 nm or more and 700 nm or less can be irradiated to the blackened layer 14 of the conductive substrate at intervals of, for example, 1 nm in wavelength as described above, and the average value of the measured values can be used as the reflection of the conductive substrate rate.

The conductive substrate of this embodiment can be preferably used as a conductive substrate for touch panels. In this case, the conductive substrate may have a structure with grid-like wiring.

By etching the metal layer, the organic layer, and the blackened layer of the conductive substrate of the present embodiment described above, a conductive substrate having grid-like wiring can be obtained.

For example, grid-like wiring can be formed by two layers of wiring. The specific configuration is shown in Figure 3 for example. Figure 3 shows a view of the conductive substrate 30 with grid-like wiring viewed from the upper surface side in the stacking direction of the metal layer, etc. In order to make the wiring pattern easy to understand, the insulating base material 11 and the patterning of the metal layer are omitted Layers other than the wirings 31A and 31B formed by chemical conversion. In addition, the wiring 31B visible 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 figure, and wirings 31B parallel to the X-axis direction. Here, wirings 31A and 31B are formed by etching the metal layer, and an organic layer and a blackening layer (not shown) are formed on the upper and/or lower surfaces of the wirings 31A and 31B. In addition, the organic layer and the blackened layer are etched into the same shape as the wirings 31A and 31B.

The arrangement of the insulating base material 11 and the wirings 31A and 31B is not particularly limited. The arrangement configuration of the insulating base material 11 and the wiring is shown in FIGS. 4A and 4B, for example. Figures 4A and 4B correspond to the cross-sectional views taken along the line A-A' in Figure 3.

First, as shown in FIG. 4A, wirings 31A and 31B may be arranged on the upper and lower surfaces of the insulating base material 11, respectively. Here, in FIG. 4A, organic layers 32A and 32B and blackened layers 33A and 33B etched into the same shape as the wiring are arranged on the upper surface of the wiring 31A and the lower surface of the wiring 31B.

In addition, as shown in FIG. 4B, a set of insulating base materials 11 can be used. Wirings 31A and 31B are arranged on the upper and lower surfaces with one insulating base 11 sandwiched therebetween, and one wiring 31B is arranged on the insulating base 11 between. In this case, organic layers 32A and 32B and blackened layers 33A and 33B etched into the same shape as the wiring are arranged on the upper surfaces of the wirings 31A and 31B. Here, as described above, in addition to the metal layer, the organic layer, and the blackened layer, an adhesion layer may be provided. Therefore, in either case of FIGS. 4A and 4B, for example, an adhesive layer may be provided between the wiring 31A and/or the wiring 31B and the insulating base material 11. When providing an adhesion layer, it is preferable to etch the adhesion layer also into the same shape as the wiring 31A, 31B.

For example, according to a conductive substrate provided with metal layers 12A and 12B, organic layers 13A and 13B, and blackened layers 14A and 14B on both sides of an insulating base material 11 as shown in FIG. 1B, To form a conductive substrate with grid-like wiring shown in Figs. 3 and 4A.

Taking the case of forming using the conductive substrate of FIG. 1B as an example, first, the metal layer 12A, the organic layer 13A, and the blackened layer 14A on the side 11a of the insulating substrate 11 are aligned along the X axis. The etching is performed in such a manner that a plurality of linear patterns parallel to the Y-axis direction in Fig. 1B are arranged at predetermined intervals in the direction. Here, the X-axis direction in FIG. 1B indicates a direction parallel to the width direction of each layer. In addition, the Y-axis direction in FIG. 1B indicates a direction perpendicular to the paper surface in FIG. 1B.

Then, the metal layer 12B, the organic layer 13B, and the blackened layer 14B on the other surface 11b side of the insulating base material 11 are arranged at specific intervals along the Y axis direction parallel to the X axis direction in Figure 1B Etching is performed in a plurality of linear patterns.

Through the above operations, it is possible to form a conductive substrate having grid-like wiring as shown in FIGS. 3 and 4A. In addition, both surfaces of the insulating base material 11 may be etched at the same time. That is, the metal layers 12A and 12B, the organic layers 13A and 13B, and the blackened layers 14A and 14B can be simultaneously etched. In addition, in Fig. 4A, by performing the same etching using the conductive substrate shown in Fig. 2B, it is possible to produce a patterned pattern between the wirings 31A, 31B and the insulating base material 11 as well as the wirings 31A, 31B. Conductive substrates with adhesion layers of the same shape.

By using two conductive substrates as shown in Fig. 1A or Fig. 2A, it is possible to form a conductive substrate with grid-like wiring as shown in Fig. 3. Taking the case of using two conductive substrates shown in Fig. 1A as an example for description, for the two conductive substrates shown in Fig. 1A, the metal layer 12, the organic layer 13, and the blackened layer 14, respectively, The etching is performed in such a manner that a plurality of linear patterns parallel to the X-axis direction are arranged at specific intervals along the Y-axis direction. Then, the linear patterns formed on each conductive substrate by the above-mentioned etching process are crossed with each other. In this way, two conductive substrates are bonded together to obtain a conductive substrate with grid-like wiring. When bonding two conductive substrates, the bonding surface is not particularly limited. For example, the surface A in Figure 1A on which the metal layer 12 and the like are laminated and the other surface 11b in Figure 1A on which the metal layer 12 and the like are not laminated can be bonded to form the structure shown in Figure 4B.

In addition, for example, the other surface 11b in FIG. 1A, which is the surface of the transparent substrate 11 where the metal layer 12 and the like are not laminated, may be bonded to each other to have a cross-section as shown in FIG. 4A.

In addition, the conductive substrate shown in Fig. 2A can be used instead of the conductive substrate shown in Fig. 1A, and the conductive substrate shown in Fig. 4A and Fig. 4B can also be produced between the wiring 31A and 31B and the transparent substrate 11. The conductive substrate of the adhesion layer is patterned to have the same shape as the wiring 31A and 31B.

The width of the wiring and the distance between the wirings of the conductive substrate with grid-like wiring shown in FIGS. 3, 4A, and 4B are not particularly limited. For example, it can be determined based on the amount of current flowing through the wiring. select.

In addition, FIGS. 3, 4A, and 4B show examples of combining linear wirings to form grid-shaped wirings (wiring patterns). However, the present embodiment is not limited to this, and the wirings constituting the wiring patterns may be It is of arbitrary shape. For example, in order not to generate moire (interference fringes) between the images of the display, the shapes of the wires constituting the grid-like wiring pattern may be various shapes such as zigzag curved lines (z-shaped straight lines).

Such a conductive substrate having grid-shaped wiring composed of two layers of wiring can be preferably used as, for example, a conductive substrate for a touch panel of a projection type capacitance system.

According to the conductive substrate of this embodiment described above, it has an insulating base A structure in which an organic substance layer containing a nitrogen-based organic substance and a blackened layer are laminated on a metal layer formed on at least one surface of the material. In addition, a plurality of granular protrusions having a predetermined average height are formed on the surface of the metal layer on which the organic layer is formed, and a predetermined number is formed per unit length. Thereby, even when an organic substance layer is formed, peeling of the blackened layer can be suppressed, and a conductive substrate with high quality stability can be provided.

Furthermore, since the conductive substrate of the present embodiment is provided with a blackening layer that suppresses peeling, the light reflection on the surface of the metal layer can be surely suppressed, and a conductive substrate with low reflectance can be obtained. In addition, when used in applications such as touch panels, the visibility of the display can be improved.

(Method of manufacturing conductive substrate)

Hereinafter, a configuration example of the manufacturing method of the conductive substrate of this embodiment will be described.

The manufacturing method of the conductive substrate of this embodiment may have the following steps.

A metal layer forming step of forming a metal layer on at least one surface of the insulating base material.

An organic substance layer forming step of forming an organic substance layer containing a nitrogen-based organic substance on the metal layer.

A blackening layer forming step of forming a blackening layer on the organic layer.

The metal layer formed in the metal layer forming step may have a plurality of granular protrusions on the surface where the organic layer is formed. In addition, the average height of the plurality of granular protrusions can be set to 8.00 nm or more. In addition, the metal layer may have a plurality of granular protrusions of 70/10 μm or more on the surface where the organic layer is formed.

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

Here, the manufacturing method of the conductive substrate of this embodiment can be suitably used for manufacturing the said conductive substrate. Therefore, in addition to the content described below, it can be set as the same as the above The conductive substrate has the same structure, so part of its description is omitted.

The insulating base material to be provided in the metal layer forming step may be prepared in advance. The type of the insulating base material used is not particularly limited, and it can be as described above, but it is preferable to use a transparent base material such as a resin substrate (resin film) that transmits visible light and a glass substrate. If necessary, the insulating base material can be cut into any size in advance.

In addition, as described above, the metal layer preferably has a metal thin film layer. In addition, the metal layer may also have a metal thin film layer and a metal plating layer. Therefore, the metal layer forming step may include, for example, a step of forming a metal thin film layer by a dry plating method. In addition, the metal layer forming step may further include: forming a metal thin film layer by a dry plating method, and using the metal thin film layer as a power supply layer to form a metal plating layer by an electroplating method, which is one of the wet plating methods. step.

The dry plating method used in the step of forming the metal thin film layer is not particularly limited, and for example, a vapor deposition method, a sputtering method, an ion plating method, etc. can be used. In addition, as the vapor deposition method, a vacuum vapor deposition method can be preferably used. Since the sputtering method is particularly easy to control the film thickness, it is preferable to use the sputtering method as the dry plating method used in the step of forming the metal thin film layer.

Hereinafter, the steps of forming the metal plating layer will be described. Regarding the conditions in the step of forming the metal plating layer by the wet plating method, that is, the conditions of the electroplating treatment are not particularly limited, and each condition in a common method may be adopted. For example, a substrate on which a metal thin film layer is formed can be placed in a plating tank containing a metal plating solution, and the current density and the conveying speed of the substrate can be controlled to form a metal plating layer.

Regarding the conductive substrate of the present embodiment, the metal layer may have a plurality of granular protrusions on the surface where the organic layer is formed.

The above-mentioned multiple granular protrusions are formed on the surface of the metal layer where the organic layer is formed The method of is not particularly limited, and for example, a method of surface-treating the surface of the metal layer after forming the metal layer can be mentioned. As a specific example, a method of performing etching treatment or sandblasting treatment on the surface of the metal layer after forming the metal layer can be mentioned. Therefore, after forming the metal thin film layer or after forming the metal thin film layer and the metal plating layer, a step of etching or sandblasting the surface of the metal layer on which the organic layer is formed can also be provided.

In addition, as another method of forming the plurality of granular protrusions on the surface of the metal layer where the organic layer is formed, a method of adjusting the formation conditions when forming the metal layer can be cited. For example, a method of changing the current density (Dk value) when the metal plating layer is formed by the electroplating method during the formation of the metal plating layer can be cited. Thus, when a plurality of granular protrusions are formed on the surface of the metal layer on which the organic layer is formed by the above method, the current density can be changed in the step of forming the metal plating layer. The specific control example of the current density has been described above, so the description is omitted.

Hereinafter, the organic substance layer formation step will be described.

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

The method of forming the organic layer is not particularly limited. For example, a nitrogen-containing organic substance solution, for example, an aqueous solution of a nitrogen-containing organic substance, is provided, coated on the metal layer, and dried to form the organic substance layer.

The method of supplying and coating the nitrogen-containing organic substance solution on the metal layer is not particularly limited, and any method can be adopted. For example, a spray method, a flush method, a dipping method, etc. can be mentioned. The respective methods have been explained above, so the explanation is omitted here.

Here, after applying the nitrogen-based organic solution, in order to remove the remaining nitrogen-based The organic substance solution can be washed with water, and the washing system uses water to wash the substrate coated with the nitrogen-based organic solution.

Next, the step of forming the blackened layer will be described.

In the blackening layer forming step, the method for forming the blackening layer is not particularly limited, and any method can be used for formation.

As a method of 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, since the sputtering method is easy to control the film thickness, it is more preferable to use the sputtering method. Here, as described above, one or more elements selected from carbon element, oxygen element, hydrogen element, and nitrogen element may be added to the blackening layer. In this case, it is more preferable to use a reactive sputtering method.

In addition, as described above, the blackened layer can be formed by a wet method such as a plating method.

However, when the blackened layer is formed, the nitrogen-based organics contained in the organic layer will dissolve into the plating solution and enter the blackened layer, which may affect the color tone and other characteristics of the blackened layer, so it is preferable It is formed by dry method.

In the manufacturing method of the conductive substrate of this embodiment, in addition to the above-mentioned steps, arbitrary steps can be implemented.

For example, in the case of forming an adhesive layer between an insulating base material and a metal layer, an adhesive layer forming step of forming an adhesive layer on the surface of the insulating base material where the metal layer is formed may be implemented. In the case of performing the adhesion layer forming step, the metal layer forming step may be performed after the adhesion layer forming step. In the metal layer forming step, the adhesive layer may be formed on the insulating substrate in this step. A metal thin film layer is formed on it.

In the adhesion layer forming step, the method of forming the adhesion layer is not particularly limited. It is preferably formed by a dry plating method. As the dry plating method, for example, a sputtering method, an ion plating method, or a vapor deposition method can be preferably used. When the adhesion layer is formed by a dry method, it is more preferable to use a sputtering method in terms of easy control of the film thickness. In addition, as described above, one or more elements selected from carbon element, oxygen element, hydrogen element, and nitrogen element may be added to the adhesion layer. In this case, the reactive sputtering method is more preferably used.

The conductive substrate obtained by the manufacturing method of the conductive substrate of the present embodiment can be used for various applications such as touch panels. In addition, when used in various applications, it is preferable to pattern the metal layer, the organic layer, and the blackened layer contained in the conductive substrate of the present embodiment. Moreover, when providing an adhesive layer, it is preferable to pattern an adhesive layer also. For example, the metal layer, the organic layer, and the blackened layer can be patterned according to the desired wiring pattern, and the adhesion layer may also be patterned according to the situation. Preferably, the metal layer, the organic layer, and the blackened layer are in the same shape. The adhesion layer is patterned.

Therefore, the manufacturing method of the conductive substrate of this embodiment may have the patterning process of patterning a metal layer, an organic substance layer, and a black layer. In addition, when the adhesion layer is formed, this patterning step can be a step of patterning the adhesion layer, the organic layer, the metal layer, and the blackened layer.

The specific order of the patterning step is not particularly limited, and can be performed in any order. For example, as shown in Figure 1A, in the case of a conductive substrate 10A on which a metal layer 12, an organic layer 13 and a blackened layer 14 are laminated on an insulating base material 11, a mask placement step may be performed first. The mask placement The step is to arrange a mask having a desired pattern on the surface A on the blackened layer 14. Secondly, an etching step may be performed, which is to provide an etching solution to the surface A on the blackened layer 14, that is, the side where the mask is disposed.

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 may be changed for each layer, or the same etching solution may be used to simultaneously etch the metal layer, the organic layer, and the blackened layer, and optionally also the adhesion layer.

In addition, as shown in FIG. 1B, a conductive substrate 10B in which metal layers 12A and 12B, organic layers 13A and 13B, and blackened layers 14A and 14B are laminated on one surface 11a and the other surface 11b of the insulating base material 11, The patterning step can also be implemented. In this case, for example, a mask arranging step of arranging a mask having a desired pattern on the surface A and the surface B on the blackened 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 blackened layers 14A and 14B, that is, the side on which the mask is disposed.

The pattern formed in the etching step is not particularly limited, and may have any shape. For example, in the case of the conductive substrate 10A shown in FIG. 1A, the metal layer 12, the organic layer 13, and the blackened layer 14 can be formed in a pattern including a plurality of straight lines or zigzag-shaped curved lines (z-shaped straight lines) as described above. .

In addition, in the case of the conductive substrate 10B shown in FIG. 1B, the metal layer 12A and the metal layer 12B may be patterned so that the metal layer 12A and the metal layer 12B form grid-like wiring. In this case, it is preferable to pattern the organic layer 13A and the blackened layer 14A into the same shape as the metal layer 12A and the organic layer 13A and the blackened layer 14B into the same shape as the metal layer 12B.

In addition, for example, after the metal layer 12 or the like is patterned by the patterning step on the conductive substrate 10A described above, a step of laminating two or more patterned conductive substrates may be performed. When layering, for example, the pattern of the metal layer of each conductive substrate is crossed. By stacking, a build-up conductive substrate with grid-like wiring can be obtained.

The method of fixing two or more laminated conductive substrates is not particularly limited. For example, it can be fixed with an adhesive or the like.

The conductive substrate obtained by the method of manufacturing the conductive substrate of the present embodiment described above has an organic layer containing nitrogen-containing organics laminated on a metal layer formed on at least one surface of an insulating base material, and a black The structure of the layer. In addition, on the surface of the metal layer where the organic layer is formed, a plurality of granular protrusions having a specific average height are formed so as to become a specific number per unit length. Therefore, even when an organic substance layer is formed, peeling of the blackened layer can be suppressed, and a conductive substrate with high quality stability can be obtained.

In addition, the conductive substrate obtained by the method of manufacturing the conductive substrate of the present embodiment is provided with a blackening layer that suppresses peeling, so that light reflection on the surface of the metal layer can be more reliably suppressed, and conductivity with suppressed reflectivity can be obtained. Substrate. Therefore, when used for applications such as a touch panel, the visibility of the display can be improved.

[Example]

The following description is made based on specific examples and comparative examples, but the present invention is not limited to these examples.

(Evaluation method)

First, the evaluation method of the obtained conductive substrate will be described.

(1) The average height of the granular protrusions, the number of granular protrusions based on the line profile, the surface roughness of the metal layer surface, and the SAD value

In the following examples and comparative examples, after forming the adhesion layer, the metal layer, and the organic layer on the insulating substrate, AFM (brand name manufactured by Bruker AXS) is used for the surface of the organic layer: Dimension Icon, nanoScope V), measured the surface state of the metal layer after the organic layer was formed. Here, when the measurement is performed, immediately after the formation of the organic layer, the surface profile of a line with a length of 10 μm is measured at any position on the surface of the organic layer, and the average height of a plurality of granular protrusions on the surface of the metal layer is calculated from the measured value. , The number of granular protrusions based on the line profile and the surface roughness of the metal layer surface. In addition, the SAD value was also calculated based on the measurement result using AFM.

Here, the SAD value was calculated according to the following formula (1), the surface area of the surface of the metal layer on which the organic layer was formed was taken as S2, and the value measured by AFM was applied.

SAD=100×(S2-S1)/S1 (1)

Projected area of the surface of the metal layer where the organic layer is formed: S1

Surface area of the metal layer on which the organic layer is formed: S2

(2) Adhesion test of the blackened layer

According to ASTM D3359, the adhesion test of the blackened layer was specifically implemented in the following procedure.

As shown in Figure 5, for the blackened layer of the conductive substrate until the blackened layer is formed, a cutting tool (Cross Cut Kit 1.0MM manufactured by Precision Gate & Tool Company) is used to form a length of 20 mm at intervals of 1.0 mm and parallel to each other. 11 straight tangent lines 51a.

Then, using the same cutting tool, 11 transverse tangent lines 51b with a length of 20 mm were formed in a manner orthogonal to the previously formed straight tangent line 51a and at 1.0 mm intervals and parallel to each other.

Through the above steps, 11 tangent lines are formed in the vertical direction and the horizontal direction of the blackened layer shown in FIG. 5, respectively, to form lattice-shaped cuts.

Next, the adhesive force evaluation tape is applied so as to cover the grid-shaped cuts (Elcometer 99 tape manufactured by Elcometer), and rub it sufficiently.

After 30 seconds have elapsed since the adhesive force evaluation tape was applied, the adhesive force evaluation tape was quickly peeled off in a direction of as much as possible 180° with respect to the measurement surface.

After peeling off the adhesive force evaluation tape, the metal layer (organic layer) formed under the blackened layer is exposed in the evaluation area 52 in Figure 5 enclosed by the grid-shaped straight tangent line 51a and the transverse tangent line 51b The area was evaluated for adhesion.

The case where the exposed area of the metal layer in the evaluation area is 0% is rated as 5B, the case of greater than 0% and less than 5% is rated as 4B, the case of 5% or more and less than 15% is rated as 3B, and 15% is rated The cases above and less than 35% are rated as 2B, the cases above 35% and less than 65% are rated as 1B, and the cases above 65% are rated as 0B. In the above evaluation, 0B indicates that the blackened layer has the lowest adhesiveness, and 5B indicates that the blackened layer has the highest adhesiveness.

As a result of the adhesion test, the case of 5B was evaluated as adhesion "○", and the other cases were evaluated as "x".

(Preparation conditions of sample)

As an example and a comparative example, a conductive substrate was produced under the conditions described below, and evaluated according to the above-mentioned evaluation method.

[Example 1]

(Adhesion layer forming step)

An adhesive layer was formed on one surface of an insulating substrate made of polyethylene terephthalate resin (PET) with a height of 500 mm × a width of 500 mm and a thickness of 50 μm. Here, regarding the insulating base material made of polyethylene terephthalate resin used as the insulating base material, the total light transmittance was evaluated according to the method specified in JIS K 7361-1, and the result was 97%.

In the adhesion layer forming step, a sputtering apparatus equipped with a target of Ni-17 wt% Cu alloy was used to form an oxygen-containing Ni-Cu alloy layer as the adhesion layer. Hereinafter, the procedure for forming the adhesion layer will be described.

The above-mentioned insulating base material which has been heated to 60° C. and removed moisture in advance is set in the cavity of the sputtering device.

Then, exhaust is performed to make the chamber 1×10 ^-3 Pa, and then argon and oxygen are introduced to make the pressure in the chamber 1.3 Pa. Here, according to the volume ratio of the cavity, 30% is oxygen and the remaining part is argon.

Then, power was supplied to the target in this environment, and an adhesion layer with a thickness of 20 nm was formed on one surface of the insulating base material.

(Metal layer forming step)

In the metal layer forming step, the metal thin film layer forming step and the metal plating layer forming step are implemented.

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

In the metal thin film layer forming step, a base material in which an adhesive layer was formed on an insulating substrate in the adhesive layer forming step was used as a substrate, and a copper thin film layer as a metal thin film layer was formed on the adhesive layer .

When forming the metal thin film layer, a copper target is used, and after evacuating the cavity provided with the substrate, argon gas is supplied to form an argon atmosphere, except that the adhesion layer is formed using a sputtering device in the same manner as the adhesion layer.

The copper thin film layer as the metal thin film layer was formed so that the film thickness became 80 nm.

Next, in the metal plating layer forming step, a copper plating layer is formed as a metal plating layer. Floor. The copper plating layer is formed by the electroplating method so that the thickness of the copper plating layer becomes 0.5 μm.

In the metal plating layer formation step, the current density (Dk value) at the beginning of the metal plating layer formation step was 1 A/dm ² , and the current density (Dk value) 7 seconds before the end of the metal plating layer formation step was 0.1 A/dm ² . Here, the plating time before the end of the metal layer forming step is referred to as the final plating time hereinafter.

(Organic layer formation step)

In the organic substance layer forming step, an organic substance layer is formed on the metal layer of the laminate of the adhesion layer and the metal layer on the insulating base material.

In the organic substance layer forming step, first, the laminate was immersed in an OPC diffuser (manufactured by Okuno Pharmaceutical Co., Ltd.) solution containing 1,2,3-benzotriazole as a nitrogen-containing organic substance for 7 seconds. Here, in the OPC diffuser solution used, the concentration of 1,2,3-benzotriazole is adjusted in advance to 3mL/L.

And, after removing the solution attached to the upper surface of the metal layer, that is, removing the solution attached to the side opposite to the surface of the metal layer opposite to the adhesion layer, it is dried, thereby forming organic matter on the metal layer Floor.

After the organic layer was formed, the average height of the granular protrusions, the number of granular protrusions based on the line profile, the surface roughness of the metal layer surface, and the SAD value were evaluated.

(Blackening layer formation step)

In the blackening layer forming step, a Ni—Cu layer as a blackening layer is formed by a sputtering method on the organic substance layer formed by the organic substance layer forming step.

In the blackening layer forming step, a Ni-Cu alloy layer as the blackening layer was formed using a sputtering device equipped with a target of Ni-35% by weight Cu alloy. The following is about the formation of the black layer The order will be explained.

First, a laminate in which an adhesion layer, a metal layer, and an organic layer are laminated on an insulating base material is installed in the cavity of the sputtering device.

Next, vent the chamber to 1×10 ^-3 Pa, and then introduce argon to make the pressure in the chamber 1.3 Pa.

Then, power was supplied to the target in this environment, and a blackened layer was formed on the organic layer so that the thickness became 20 nm.

Through the above steps, on the upper surface of the metal layer, that is, on the side opposite to the surface of the metal layer opposite to the adhesion layer, a blackened layer is formed through the organic layer, and the adhesion layer is sequentially laminated on the insulating substrate. Layer, metal layer, organic layer and blackened layer conductive substrate.

The obtained conductive substrate was subjected to the adhesion test as described above.

The results are shown in Table 1.

[Example 2, Example 3]

The final plating time was the time shown in Table 1, and the production and evaluation of a conductive substrate were performed under the same conditions as in Example 1.

The results are shown in Table 1.

[Comparative Examples 1, 2]

The final plating time was the time shown in Table 1, and the production and evaluation of the conductive substrate were performed under the same conditions as in Example 1.

The results are shown in Table 1.

According to the results shown in Table 1, it was confirmed that "the average height of the plurality of granular protrusions formed on the surface of the metal layer is 8.00 nm or more, and the grains of the granular protrusions based on the line profile on the surface of the metal layer where the organic layer is formed In Examples 1 to 3 in which the number is 70/10 μm or more", the evaluation of these adhesion tests was "○".

On the other hand, it was confirmed that "the average height of a plurality of granular protrusions formed on the surface of the metal layer and/or the number of granular protrusions based on the line profile does not meet the above range" of Comparative Examples 1 and 2 was confirmed. The evaluation of the adhesion test was "×", and peeling of the blackened layer was observed.

In the above, the conductive substrate has been described based on the embodiments and examples, but the present invention is not limited to the above embodiments and examples. Various modifications and changes can be made within the scope of the gist of the present invention described in the scope of patent claims.

This application claims priority based on patent application No. 2015-152898 filed with the Japan Patent Office on July 31, 2015, and quotes the entire content of patent application No. 2015-152898.

10A‧‧‧Conductive substrate

11‧‧‧Insulating base material

11a‧‧‧One side of insulating base material

11b‧‧‧The opposite side of 11a

12‧‧‧Metal layer

13‧‧‧Organic layer

14‧‧‧Black layer

A‧‧‧The surface of the blackened layer

Claims (5)

A conductive substrate having: an insulating substrate; a metal layer formed on at least one surface of the insulating substrate; an organic layer formed on the metal layer and containing nitrogen-based organics; and a blackening layer , Which is formed on the organic layer, the metal layer has a plurality of granular protrusions on the surface where the organic layer is formed, the average height of the plurality of granular protrusions is 8.00nm or more, and the metal layer forms the organic The surface of the layer has 70 or more granular protrusions per 10 μm. For example, the conductive substrate of the first item of the patent claim, wherein, according to the projected area S1 of the surface of the metal layer on which the organic layer is formed, and the surface area S2 of the surface of the metal layer on which the organic layer is formed, the following formula ( 1) The calculated SAD (Surface Area Different) value is 5% or more, and SAD=100×(S2-S1)/S1 (1). For example, in the conductive substrate of item 1 or 2, the nitrogen-based organic substance contains 1,2,3-benzotriazole or its derivatives. For example, the conductive substrate of item 1 or 2 of the scope of patent application, wherein the metal layer and the organic substance are respectively formed on one surface of the insulating substrate and the other surface opposite to the one surface. Layer and the blackened layer. Such as the conductive substrate of item 3 of the scope of patent application, wherein, on one surface of the insulating substrate and the other surface opposite to the one surface, respectively The metal layer, the organic layer and the blackened layer are sequentially formed.

Images