TWI701134B - Conductive substrate, manufacturing method of conductive substrate - Google Patents

Abstract

Provided is a conductive substrate having: an insulating base material, a metal layer formed on at least one surface of the insulating base material, an organic substance layer formed on the metal layer and containing a nitrogen-based organic substance, and an organic substance layer formed on the organic substance layer On the upper blackened layer, the contact angle of pure water on the surface of the organic layer facing the blackened layer is 60° or less.

Description

Conductive substrate and manufacturing method of conductive substrate

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

The capacitive touch panel detects changes in capacitance caused by objects approaching the surface of the panel, thereby converting the position information of the approaching objects on the surface of the panel into electrical signals. Since the conductive substrate used for the capacitive touch panel is provided on the surface of the display, the material of the conductive layer of the conductive substrate is required to have low reflectivity and is difficult to visually confirm.

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

For example, Patent Document 1 discloses a capacitive digital touch panel, the touch panel portion of which is composed of a plurality of transparent sheet electrodes printed with a signal pattern and a GND pattern on a PET film using an ITO film.

However, in recent years, the larger screens of displays equipped with touch panels have been increasing. Correspondingly, conductive substrates such as transparent conductive films for touch panels have also been required to have larger areas. However, ITO has a problem that it is not suitable for large-scale panels due to its high resistance value and signal degradation.

Therefore, as a material for the conductive layer, research is underway to use metals such as copper instead of ITO. However, since metal has metallic luster, there is a problem that the visibility of the display decreases due to reflection. Therefore, a conductive substrate is being studied, which is formed with a metal layer and The blackened layer of light reflection on the surface of the metal layer, wherein the metal layer is a conductive layer using metals such as copper.

Patent Document 1: Japanese Patent Application Publication No. 2004-213114

However, on conductive substrates, for example, when the metal layer and the blackened layer are formed by another device, after the metal layer is formed, it is sometimes sought to prevent the metal layer before the blackened layer is formed on it. The surface is rusty. Therefore, it is considered to perform anti-rust 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 anti-rust treatment, the adhesion between the blackened layer and the metal layer will decrease. problem.

In view of the above-mentioned problems of the prior art, in one aspect of the present invention, an object is to provide a conductive substrate in which an organic layer is formed between a metal layer and a blackened layer, and the blackened layer has high adhesion.

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

According to one aspect of the present invention, 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 has high adhesion.

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

11‧‧‧Insulating base material

12, 12A, 12B‧‧‧Metal layer

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

14, 14A, 14B, 33A, 33B‧‧‧Blackening 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.

3 is a plan view of a conductive substrate provided with mesh wiring according to the embodiment of the present invention.

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

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

Fig. 5 is an explanatory view of a cutting line formed when an adhesion test is performed in an example and a comparative example.

6 is an explanatory diagram of the relationship between the contact angle of the organic layer and the adhesiveness in Examples and Comparative Examples.

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

(Conductive substrate)

The conductive substrate of this embodiment may have 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 black layer formed on the organic layer.化层。 The layer. In addition, the contact angle of pure water on the surface of the organic substance layer facing the blackened layer may be 60° or less.

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

Hereinafter, each member included in the conductive substrate will be described first.

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

As the material for the resin substrate that transmits visible light, for example, polyamide resins, polyethylene terephthalate resins, polyethylene naphthalate resins, cycloolefin resins, Polyimide resins, polycarbonate resins and other resins. In particular, as a material for a resin substrate that transmits visible light, PET (polyethylene terephthalate), COP (cycloolefin polymer), PEN (polyethylene naphthalate), and poly(ethylene naphthalate) can be more preferably used. Amine, polyamide, polycarbonate, etc.

The thickness of the insulating base material is not particularly limited, and can be arbitrarily selected according to the required strength, capacitance, and light transmittance when used as a conductive substrate. As the thickness of the insulating base material, for example, it can be 10 μm or more and 200 μm or less. In particular, when used for touch panel applications, the thickness of the insulating base material 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 a use for a touch panel, for example, when a thinning of the thickness of the entire display is sought, the thickness of the insulating substrate is preferably 20 μm or more and 50 μm or less.

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

In addition, 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.

The material constituting the metal layer is not particularly limited, and a material having electrical conductivity depending on the application can be selected. For example, the material constituting the metal layer is preferably Cu and selected from Ni, Mo, Ta, Ti, V, Cr, A copper alloy of at least one metal of Fe, Mn, Co, and W, or a material containing copper. In addition, the metal layer may be a copper layer made of copper.

The method of forming the metal layer on at least one surface of the insulating base material is not particularly limited. In order to reduce the light transmittance, it is preferable not to arrange an adhesive between the insulating base material and the metal layer. In other words, the metal layer is preferably formed directly on at least one surface of the insulating substrate. In addition, when the adhesion layer is arranged between the insulating base material and the metal layer as described below, the metal layer is preferably formed directly on the adhesion layer.

In order to form a metal layer directly on an insulating substrate or the like, 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.

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. Thereby, a metal layer can be formed directly on the insulating base material without passing through an adhesive agent. In addition, as a dry plating method, for example, a sputtering method, an evaporation method, an ion plating method, etc. can be preferably used.

In addition, when the film thickness of the metal layer is increased, the metal thin film layer can also be used as a power supply layer to form a metal plating layer by electroplating (a kind of wet plating method), thereby forming a metal with a metal thin film layer and a metal plating layer. Floor. By making the metal layer have 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 using an adhesive.

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

The thickness of the metal layer is not particularly limited. When the metal layer is used as wiring, it can be It can be arbitrarily selected according to the magnitude of the current supplied to the wiring or the wiring width.

However, if the metal layer becomes thicker, problems such as the following may occur: when etching is performed to form a wiring pattern, since the etching takes time, side etching is likely to occur and it is difficult to form thin lines. Therefore, the thickness of the metal layer is preferably 5 μm or less, more preferably 3 μm or less.

In addition, from the viewpoint of particularly lowering the resistance value of the conductive substrate to allow sufficient current to be supplied, for example, the thickness of the metal layer is preferably 50 nm or more, more preferably 60 nm or more, and still more preferably 150 nm or more.

In addition, when the metal layer has the metal thin film layer and the metal plating layer as described above, the total thickness of the metal thin film layer and the metal plating layer is preferably in the above range.

Even in the case where the metal layer is composed of a metal thin film layer, or when it has a metal thin film layer and a metal plating layer, the thickness of the metal thin film layer is not particularly limited. For example, it is preferably set to 50 nm or more and 500 nm or less .

As described below, for example, the metal layer can be patterned into a desired wiring pattern and used as wiring. In addition, since the metal layer can lower the resistance value than ITO used as a transparent conductive film in the past, the resistance value of the conductive substrate can be reduced by providing the metal layer.

Next, the organic substance layer will be described.

The organic layer may be formed on the side of the metal layer facing the blackening layer (described later). Therefore, when used as a conductive substrate, it can be arranged between the metal layer and the blackened layer.

By forming the organic layer on top of the metal layer, rust and the like on the surface of the metal layer can be prevented.

The organic substance layer may contain nitrogen-based organic substances. Furthermore, the nitrogen-based organic substance used for the organic substance layer preferably contains, for example, 1,2,3-benzotriazole or a derivative thereof. As the nitrogen system used in the organic layer Specific examples of the organic substance include 1,2,3-benzotriazole, 5-methyl-1H benzotriazole, and the like.

As the agent containing the nitrogen-based organic substance used in the organic substance layer, for example, an antirust treatment agent for copper can be preferably used, and as a commercially available drug, for example, OPC-DEFENSER (trade name, Okuno Pharmaceutical Co., Ltd.) can be preferably used. Wait.

As described above, if the blackened layer is formed after the organic layer is formed, the adhesion of the blackened layer may be insufficient. Therefore, the inventors of the present invention have studied methods for improving the adhesion of the blackened layer, and found that the blackened layer can be improved by making the contact angle of pure water on the surface of the organic layer facing the blackened layer 60° or less. The adhesiveness, and completed the present invention.

According to studies by the inventors of the present invention, when a uniform coating film combining the metal layer and the organic layer cannot be formed, and the organic matter is only deposited on the surface of the metal layer, the adhesion of the blackened layer may be insufficient. In addition, when organic matter is deposited on the surface of the metal layer, the contact angle of the surface of the organic matter facing the blackened layer to pure water exceeds 60°.

In contrast, when an organic layer is formed, if a uniform coating film combining the metal layer and the organic layer can be formed, the contact angle of pure water on the surface of the organic layer facing the blackened layer will be 60° or less. In addition, by forming a uniform coating film in which the metal layer and the organic layer are bonded, the adhesion of the black layer can be improved when the black layer is formed on the organic layer.

Therefore, it is preferable that the contact angle of pure water on the surface of the organic substance layer facing the blackened layer is 60° or less as described above.

The method for making the contact angle of pure water on the surface of the organic layer facing the blackened layer 60° or less is not particularly limited, and it may be used to form a uniform coating on the surface of the metal layer and the organic layer. Nitrogen-based organic solution method of the raw material of the organic layer.

The method for supplying the nitrogen-based organic solution is not particularly limited, and any Method to supply. For example, by applying a nitrogen-based organic solution using a spray or immersing an insulating substrate on which a metal layer is formed in the nitrogen-based organic solution, a solution containing a material constituting the organic layer can be applied to the metal layer.

However, when supplying the nitrogen-based organic solution, it is preferable to uniformly supply the nitrogen-based organic solution to the surface of the metal layer so as to form a uniform coating film combining the metal layer and the organic layer. Therefore, it is preferable, for example, to supply the nitrogen-based organic solution to the surface of the metal layer on the side where the blackened layer is formed by two or more methods at the same time, or to repeatedly supply the surface on the side where the blackened layer of the metal layer is formed. Nitrogen-based organic solution.

In addition, the conditions of the nitrogen-based organic solution when the nitrogen-based organic solution is supplied to the surface of the metal layer forming the blackened layer are not particularly limited, and can be arbitrarily selected according to the type of the nitrogen-based organic solution and the like. Specifically, the concentration of the nitrogen-based organic substance in the nitrogen-based organic substance solution used when forming the organic substance layer is not particularly limited, and it can be arbitrarily selected in consideration of the content of the nitrogen-based organic substance in the target organic substance layer, workability, etc. .

However, the lower limit of the concentration of the nitrogen-based organic substance in the nitrogen-based organic substance solution is preferably 1 mL/L or more, and more preferably 2 mL/L or more. The upper limit is preferably 4 mL/L or less. This is because by setting the concentration of the nitrogen-based organic substance in the nitrogen-based organic substance solution to 1 mL/L or more, it is possible to more reliably form a uniform film in which the metal layer and the organic substance layer are bonded. However, if the concentration of the nitrogen-based organic matter in the nitrogen-based organic matter solution exceeds 4 mL/L, it may not be possible to remove the remaining solution by washing with water, so it is preferably 4 mL/L or less.

In addition, the temperature of the nitrogen-based organic solution when the nitrogen-based organic solution is supplied to the surface of the metal layer is not particularly limited, and can be arbitrarily selected in consideration of the viscosity, operability, and reactivity of the solution. For example, it is preferably 10°C or higher, more preferably 20°C or higher. However, because if the temperature rises, The nitrogen-based organic substance contained may react with other substances, so it is preferably 40°C or lower.

In addition, the pH value of the nitrogen-based organic solution is not particularly limited, and it can be selected in consideration of the type of nitrogen-based organic substance used or the reactivity of the solution. For example, the pH value of the nitrogen-based organic solution is preferably 2 or more, more preferably For 3 or more. However, as the pH value increases, the content of nitrogen-based organic matter in the film will decrease, so the pH value of the nitrogen-based organic matter solution is preferably 4 or less.

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

In addition, the inventors of the present invention have also discovered that by disposing an organic layer containing a nitrogen-based organic substance between the metal layer and the blackened layer, the reflectance of the conductive substrate can be suppressed.

In order to suppress the reflectance of the conductive substrate, in particular, the content of the nitrogen-based organic substance in the organic layer is preferably 0.2 μg/cm ² or more, more preferably 0.3 μg/cm ² or more.

This is because according to the research of the inventors of the present invention, the reflectance of the conductive substrate can be significantly suppressed by setting the content of the nitrogen-based organic substance in the organic layer to be 0.2 μg/cm ² or more. In addition, if the content of nitrogen-based organic matter in the organic matter layer increases, the a* value and b* value when the color of the blackened layer is converted into the CIE (L*a*b*) color system can be reduced, and in particular, it can be made conductive The wiring of the flexible substrate is not conspicuous, so it is preferable.

The upper limit of the content of the nitrogen-based organic substance in the organic substance layer is not particularly limited. However, in order to increase the nitrogen-based organic matter content of the organic matter layer, the concentration of the nitrogen-based organic matter solution used when the organic matter layer is formed is increased, or the supply time of the nitrogen-based organic matter solution is extended. Therefore, if the content of the nitrogen-based organic substance in the organic substance layer is excessively increased, the operability of the nitrogen-based organic substance solution may decrease, or the time required to form the organic substance layer may become longer, and productivity may decrease. Therefore, the content of the nitrogen-based organic substance in the organic substance layer is preferably set to 0.5 μg/cm ² or less, for example.

Next, the blackened layer will be described.

The blackening layer may be formed on the organic layer.

The material of the blackening layer is not particularly limited, as long as it is a material that 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 blackened layer may further contain one or more elements selected from carbon, oxygen, hydrogen, and nitrogen.

In addition, the blackening layer may contain a metal alloy containing at least two metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. At this time, the blackened 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 metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn, Cu-Ti- Fe alloy, 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-Cu alloy can be used more preferably.

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 into a film 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 an evaporation method can be preferably used. Since the film thickness of the blackened layer can be easily controlled by the dry method, the sputtering method is more preferable. Alternatively, you can also The blackening layer is added with one or more elements selected from carbon, oxygen, hydrogen, and nitrogen as described above. In this case, a reactive sputtering method can be more preferably used.

When the blackened layer is formed into a film by the reactive sputtering method, as a target, a target containing a metal species constituting the blackened layer can be used. When the blackened layer contains an alloy, the target can also be used for each metal species contained in the blackened layer to form an alloy on the surface of the film-forming body such as the substrate, or the metal contained in the blackened layer can be used in advance. Alloyed target.

In addition, when the blackened layer contains at least one element selected from carbon, oxygen, hydrogen, and nitrogen, these can be added to the blackened layer by pre-adding to the environment when the blackened layer is formed. . For example, when carbon is added to the blackened layer, carbon monoxide gas and/or carbon dioxide gas can be added to the environment during sputtering in advance. When oxygen is added to the blackened layer, oxygen can be added in advance. In the sputtering environment, when hydrogen is added to the blackened layer, hydrogen and/or water can be added to the environment during sputtering in advance. When nitrogen is added to the blackened layer, nitrogen can be added in advance In the environment during sputtering. One or more elements selected from carbon, oxygen, hydrogen, and nitrogen can be added to the blackened layer by adding these gases to the inert gas when forming the blackened film. In addition, argon can be preferably used as the inert gas.

When the blackened layer is formed into a film by a wet method, a plating solution can be used according to the material of the blackened layer. For example, the film can be formed by an electroplating method.

As mentioned above, the blackened layer can be formed by any method of dry method or wet method. However, when the blackened layer is formed, the nitrogen-based organic matter contained in the organic layer will dissolve in the plating solution and enter the blackened layer. In this case, the color tone or other characteristics may be affected, so it is preferable to use the dry method to form the film.

The thickness of the blackening layer is not particularly limited, for example, preferably 15nm or more, more preferably It is 25nm or more. This is because when the thickness of the blackened layer is thin, the light reflection on the surface of the metal layer may not be sufficiently suppressed. Therefore, it is preferable to configure the blackened layer to have a thickness of 15 nm or more as described above. Suppress light reflection on the surface of the metal layer.

The upper limit of the thickness of the blackened layer is not particularly limited, and even if it is thicker than necessary, the time required for film formation or the time required for etching when forming wiring becomes longer, which incurs an increase in cost. Therefore, the thickness of the blackened layer is preferably 70 nm or less, and more preferably 50 nm or less.

In addition, the conductive substrate may be provided with any layers other than the above-mentioned insulating base material, metal layer, organic layer, and blackened layer. For example, an adhesive layer can be provided.

An example of the structure of the adhesion layer will be described.

As described above, the metal layer can be formed on the insulating base material, but 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 insulating base material, the metal layer may peel off from the insulating base material during the manufacturing process or during use.

Therefore, in the conductive substrate of the present embodiment, in order to improve the adhesion between the insulating base material and the metal layer, an adhesion layer may be arranged on the insulating base material.

By disposing the adhesive layer between the insulating base material and the metal layer, the adhesiveness of the insulating base material and the metal layer can be improved, and the metal layer can be prevented from peeling off the insulating base material.

In addition, the adhesion layer can also function as a blackening layer. Therefore, it is also possible to suppress light reflection of the metal layer due to 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, and it can be based on the adhesion between the insulating base material and the metal layer or the degree of suppression of light reflection on the surface of the metal layer required, and the resistance to conductivity The degree of stability of the use environment (for example, humidity or temperature) of the flexible substrate can be arbitrarily selected.

The adhesive 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 further contain one or more elements selected from carbon, oxygen, hydrogen, and nitrogen.

In addition, the adhesion layer may contain a metal alloy containing at least two metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. Even in this case, the adhesion 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 metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn, for example, Cu-Ti can be preferably used -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-Cu alloy can be better used.

The film forming method of the adhesion layer is not particularly limited, and 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, or a vapor deposition method can be preferably used. Since it is easy to control the film thickness when the adhesive layer is formed by the dry method, the sputtering method is preferably used. In addition, one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen as described above may be added to the adhesive layer. In this case, the reactive sputtering method can be more preferably used.

When the adhesive layer contains one or more elements selected from carbon, oxygen, hydrogen, and nitrogen, it can be prepared by adding one or more elements selected from carbon, oxygen, hydrogen, and nitrogen to the environment when the adhesive layer is formed. The elements of the gas are added in the adhesion layer. For example, when carbon is added to the adhesion layer, carbon monoxide gas and/or carbon dioxide gas can be added to the environment during dry plating in advance, and when oxygen is added to the adhesion layer, the dry plating can be added beforehand. Oxygen is added to the environment of, when hydrogen is added to the adhesion layer, it can be in the environment of dry plating in advance Hydrogen and/or water are added, and when nitrogen is added to the adhesion layer, nitrogen can be added to the environment during dry plating in advance.

A gas containing one or more elements selected from carbon, oxygen, hydrogen, and nitrogen is preferably added to an 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 adhesive layer into a film by the dry plating method as described above, the adhesiveness between the insulating base material and the adhesive layer can be improved. In addition, since the adhesion layer may contain metal as a main component, for example, the adhesion to the metal layer is also high. Therefore, by disposing the adhesive 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. For example, it is preferably 3 nm or more and 50 nm or less, more preferably 3 nm or more and 35 nm or less, and still more preferably 3 nm or more and 33 nm or less.

When the adhesion layer also 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 3 nm or more as described above.

The upper limit of the thickness of the adhesion layer is not particularly limited, and even if it is thicker than necessary, the time required for film formation or the time required for etching during wiring formation will become longer, leading to an increase in cost. Therefore, the thickness of the adhesion layer is preferably 50 nm or less as described above, more preferably 35 nm or less, and still more preferably 33 nm or less.

Next, a structural 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 adhesion layers may be arbitrarily provided.

Regarding specific configuration examples, the following description uses FIGS. 1A, 1B, 2A, and 2B. Figures 1A, 1B, 2A, and 2B show the conductive substrate plane of this embodiment An example of a cross-sectional view of the plane in 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, in the conductive substrate 10A shown in FIG. 1A, the metal layer 12, the organic layer 13, and the blackened layer 14 can be sequentially laminated on the side 11a of the insulating base material 11 layer by layer. In addition, the conductive substrate 10B shown in FIG. 1B may have metal layers 12A, 12B, organic layers 13A, 13B, and blackened layers 14A, 14B layered on one side 11a of the insulating base material 11, respectively. Side and the other side (other side) 11b side.

Moreover, it can also be set as the structure which provided an adhesive layer as an arbitrary layer further, for example. In this case, for example, a structure in which an adhesive 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, a conductive substrate 20A as shown in FIG. 2A may have an adhesive layer 15, a metal layer 12, an organic layer 13, and a blackened layer 14 laminated in this order on the side 11a of the insulating base material 11.

In this case, it is also possible to form a structure in which an adhesive layer, a metal layer, an organic layer, and a blackened layer are laminated on both surfaces of the insulating base material 11. 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 the adhesion layers 15A, 15B, the metal layers 12A, 12B, and the organic layer 13A, 13B and blackened layers 14A, 14B.

In addition, in FIGS. 1B and 2B, although it is disclosed that when a metal layer, an organic layer, a blackened layer, etc. are laminated on both sides of an insulating base material, the insulating base material 11 is used as a symmetry plane to The layer laminated on the top and bottom of the insulating base material 11 is an example in which the layers are arranged symmetrically, but it is not limited to this form. For example, in FIG. 2B, the structure on the side 11a of the insulating base material 11 may be the same as the structure in FIG. 1B. The adhesive layer 15A is not provided and 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 stacked above and below the insulating base 11 have an asymmetric configuration.

In addition, in the conductive substrate of this embodiment, by providing a metal layer, an organic layer, and a blackening layer on the insulating base material, the light reflection caused by the metal layer can be suppressed, and the reflectance of the conductive substrate can be suppressed. .

The degree of reflectivity of the conductive substrate of the present embodiment is not particularly limited. For example, when the visibility of a display is to be improved when it is used as a conductive substrate for a touch panel, the reflectance is preferably low. 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 the blackened layer of the conductive substrate with light. Specifically, for example, when the metal layer 12, the organic layer 13, and the blackened layer 14 are sequentially laminated on the side 11a of the insulating substrate 11 as shown in FIG. 1A, the blackened layer 14 can be irradiated with light. The surface A of the blackened layer 14 is irradiated with light for measurement. In addition, during the measurement, light having a wavelength of 400 nm or more and 700 nm or less may be irradiated to the surface A of the blackened layer 14 of the conductive substrate at intervals of 1 nm in wavelength, for example, as described above, and the average value of the measured values may be regarded as the conductivity The reflectivity of the substrate.

The conductive substrate of this embodiment can be preferably used as a conductive substrate for touch panels. In this case, the conductive substrate may be formed to have a configuration with mesh-shaped wiring.

The conductive substrate provided with the mesh wiring can be obtained by etching the metal layer, the organic layer, and the blackened layer of the conductive substrate of the present embodiment described above.

For example, two layers of wiring can be used to form mesh wiring. A specific configuration example is shown in FIG. 3. 3 illustrates a view of the conductive substrate 30 provided with mesh wiring viewed from the upper side in the laminating direction of the metal layer, etc. In order to facilitate understanding of the wiring pattern, the insulating base material 11 and the patterning of the metal layer are omitted. Description of layers other than wiring 31A, 32B. In addition, the wiring 31B that can be seen through the insulating base material 11 is also disclosed.

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. In addition, the wirings 31A and 31B are formed by etching a metal layer, and an organic substance layer and a blackening layer (not shown) are formed on the upper 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. A configuration example of the arrangement of the insulating base material 11 and wiring is shown in FIGS. 4A and 4B. 4A and 4B correspond to cross-sectional views on the line A-A' in FIG. 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. In addition, in FIG. 4A, organic layers 32A, 32B, and blackened layers 33A, 33B etched into the same shape as the wiring are arranged on the upper surface and the lower surface of the wiring 31A.

In addition, as shown in FIG. 4B, a set of insulating base materials 11 may also be used. One insulating base material 11 is sandwiched, and wirings 31A and 31B are arranged on the upper and lower sides, and one wiring 31B is arranged on the insulating base 11 between. In this case, the organic layer 32A, 32B and the blackened layer 33A, 33B etched into the same shape as the wiring are also arranged on the upper surface of the wiring 31A, 31B. In addition, 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, the wiring 31A and/or the wiring 31B and the insulating substrate 11 may be Set up a close layer between. When an adhesive layer is provided, it is preferable that the adhesive layer is also etched into the same shape as the wiring 31A, 31B.

The conductive substrate with mesh wiring shown in FIGS. 3 and 4A can be provided with metal layers 12A, 12B, organic layers 13A, 13B, and blackened layers 14A on both sides of an insulating base material 11 as shown in FIG. 1B, for example. , 14B conductive substrate is formed.

Taking the case of using the conductive substrate of FIG. 1B as an example for description, first, a plurality of linear patterns parallel to the Y-axis direction in FIG. 1B are arranged at predetermined intervals along the X-axis direction, and the insulation The metal layer 12A, the organic layer 13A, and the blackened layer 14A on the side 11a of the flexible substrate 11 are etched. In addition, the X-axis direction in FIG. 1B means a direction parallel to the width direction of each layer. In addition, the Y-axis direction in FIG. 1B means a direction perpendicular to the paper surface in FIG. 1B.

Next, a plurality of linear patterns parallel to the X-axis direction in FIG. 1B are arranged along the Y-axis direction with a predetermined interval, and the insulating substrate 11 on the other surface 11b side of the metal layer 12B, organic layer 13B and black The chemical layer 14B is etched.

Through the above operations, it is possible to form a conductive substrate having mesh wiring as shown in FIGS. 3 and 4A. In addition, the etching on both sides of the insulating substrate 11 may be performed simultaneously. In other words, the metal layers 12A, 12B, the organic layers 13A, 13B, and the blackened layers 14A, 14B may be etched simultaneously. In addition, in FIG. 4A, a conductive substrate having an adhesion layer patterned into the same shape as the wiring 31A, 31B between the wiring 31A, 31B and the insulating base material 11 can be obtained by using the conductive substrate shown in FIG. 2B The sexual substrate is produced by etching in the same way.

The conductive substrate with mesh wiring shown in FIG. 3 can also be formed using two conductive substrates shown in FIG. 1A or FIG. 2A. If the conductive substrate of Figure 1A is used to form As an example, two conductive substrates as shown in FIG. 1A are arranged in the Y-axis direction with a plurality of linear patterns parallel to the X-axis direction at predetermined intervals, and the metal layers 12, The organic layer 13 and the blackened layer 14 are etched. Next, the two conductive substrates can be bonded together by aligning the directions so that the linear patterns formed on the conductive substrates intersect each other by the above-mentioned etching process, thereby making a conductive substrate provided with mesh wiring. The surface to be bonded when bonding two conductive substrates is not particularly limited. For example, the surface A in FIG. 1A on which the metal layer 12 and the like are laminated may be bonded to the other surface 11b in FIG. 1A on which the metal layer 12 and the like are not laminated to form the structure shown in FIG. 4B.

Moreover, for example, the other surface 11b in FIG. 1A in which the metal layer 12 etc. are not laminated|stacked of the insulating base material 11 may be bonded together, and it may become a cross section as the structure shown to FIG. 4A.

In addition, in FIGS. 4A and 4B, between the wiring 31A, 31B and the insulating base material 11, a conductive substrate further having an adhesion layer patterned into the same shape as the wiring 31A, 31B can be used as shown in FIG. 2A Instead of the conductive substrate shown in FIG. 1A, the conductive substrate shown was produced.

The wiring width or the distance between the wirings in the conductive substrate with mesh wiring shown in FIGS. 3, 4A, and 4B is not particularly limited, and can be selected according to the amount of current flowing through the wiring, for example.

In addition, in FIGS. 3, 4A, and 4B, an example of combining linear wirings to form a mesh wiring (wiring pattern) is shown, but it is not limited to this form, and the wiring constituting the wiring pattern may be arbitrary shape. For example, it is also possible to form the shapes of the wires constituting the mesh wiring pattern into various shapes such as zigzag curved lines (saw-tooth straight lines) so that no moiré (interference fringes) occurs between the image on the display .

The conductive substrate having the mesh wiring composed of such two-layer wiring can be preferably used as a conductive substrate for a projection type capacitive touch panel, for example.

According to the conductive substrate of the present embodiment described above, the metal layer formed on at least one surface of the insulating substrate is provided with an organic layer containing nitrogen-based organics, and the contact angle of the pure water on the surface of the organic layer facing the blackened layer is Below 60°. Therefore, it is possible to obtain a conductive substrate with high adhesion of the blackened layer. In addition, since the blackened layer is arranged on the organic layer, it is possible to improve the visibility of the display when it is used in applications such as touch panels.

(Method of manufacturing conductive substrate)

Next, 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 can have the following steps.

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

Organic substance layer forming step: forming an organic substance layer containing nitrogen-based organic substances on the metal layer.

Blackening layer formation step: forming a blackening layer on the organic layer.

Furthermore, in the organic substance layer forming step, it is preferable to form the organic substance layer so that the contact angle of pure water on the surface of the organic substance layer facing the blackened layer is 60° or less.

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

In addition, the above-mentioned conductive substrate can be suitably manufactured using the conductive substrate manufacturing method of this embodiment. Therefore, except for the points described below, since it can be formed into the same configuration as in the case of the above-mentioned conductive substrate, part of the description is omitted.

The insulating base material used in the metal layer formation step can be prepared in advance. The type of insulating substrate used is not particularly limited. As mentioned above, a resin that transmits visible light can be preferably used. Transparent substrates such as substrates (resin films) or glass substrates. The insulating base material may be cut into any size in advance as needed.

Also, 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 also include a step of forming a metal thin film layer by a dry plating method, and a step of using the metal thin film layer as a power supply layer to use an electroplating method (a type of wet plating method) to form a metal plating layer.

The dry plating method used in the step of forming the metal thin film layer is not particularly limited. 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. As the dry plating method used in the step of forming the metal thin film layer, since it is particularly easy to control the film thickness, the sputtering method is preferably used.

Next, 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, for example, the conditions of the electroplating treatment are not particularly limited, and conditions according to the usual method may be adopted. When the metal plating layer is formed by electroplating, it can be formed by, for example, supplying a substrate on which a metal thin film layer is formed to a plating tank filled with a metal plating solution, and controlling the current density or the transfer speed of the substrate.

The materials applicable to the metal layer, the appropriate thickness of the metal layer, etc. are as described above, so the description thereof is omitted here.

Next, the organic substance layer forming step will be described.

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

As mentioned above, when the organic layer is placed between the metal layer and the blackened layer, by By supplying the nitrogen-based organic substance solution so as to become a uniform film in which the metal layer and the organic substance layer are bonded, the adhesion of the blackened layer can be improved.

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

The method of supplying the nitrogen-based organic substance solution is not particularly limited, and it can be supplied by any method. For example, by applying a nitrogen-based organic solution using a sprayer or the like, or by immersing an insulating substrate formed with a metal layer in the nitrogen-based organic solution, a solution containing the material constituting the organic layer can be applied on the metal layer.

However, when supplying the nitrogen-based organic solution, it is preferable to uniformly supply the nitrogen-based organic solution to the surface of the metal layer so as to form a uniform coating film combining the metal layer and the organic layer. Therefore, it is preferable, for example, to supply the nitrogen-based organic solution to the surface of the metal layer on the side where the blackened layer is formed by two or more methods at the same time, or divide the surface on the side where the blackened layer is formed on the metal layer to repeat Supply a nitrogen-based organic solution.

The nitrogen-based organic substance used in the organic substance layer is not particularly limited, and for example, it preferably contains 1,2,3-benzotriazole or a derivative thereof. Specific examples of the nitrogen-based organic substance used for the organic substance layer include 1,2,3-benzotriazole, 5-methyl-1H benzotriazole, and the like.

In addition, in the organic substance layer forming step, for example, a nitrogen-based organic substance solution (a drug containing the aforementioned nitrogen-based organic substance) can be used to form the organic substance layer.

As the agent containing the nitrogen-based organic substance used in the organic substance layer, for example, an antirust treatment agent for copper can be preferably used, and as a commercially available drug, for example, OPC-DEFENSER (trade name, Okuno Pharmaceutical Co., Ltd. )Wait.

The better conditions for supplying nitrogen-based organic solution to the metal layer It has been explained, so the explanation is omitted here.

In addition, after the nitrogen-based organic solution is applied, in order to remove the adhered remaining nitrogen-based organic solution, a water washing step of washing the substrate coated with the nitrogen-based organic solution with water may be performed.

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 it can be formed by any method. For example, a dry method or a wet method can be used to form a film.

When the blackened layer is formed into a film 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 an evaporation method can be preferably used. In particular, since it is easy to control the film thickness, the sputtering method is preferably used. In addition, as described above, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen may be added to the blackened layer. In this case, the reactive sputtering method may be more preferably used.

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

However, when the blackened layer is formed, the nitrogen-based organic matter contained in the organic layer will dissolve in the plating solution and enter the blackened layer, which may affect the color tone or other characteristics of the blackened layer, so it is better to use Dry method to form film.

Since the materials applicable to the blackening layer, the suitable thickness of the blackening layer, etc. have already been described, the description is omitted here.

In the manufacturing method of the conductive substrate of this embodiment, in addition to the above-mentioned steps, you may implement further arbitrary steps.

For example, when an adhesive layer is formed between an insulating base material and a metal layer, a step of forming an adhesive layer in which the metal layer is formed on the insulating base material may be performed. When implementing close bonding In the case of the layer formation step, the metal layer formation step may be performed after the adhesion layer formation step. In the metal layer formation step, the metal thin film layer may be formed on the insulating substrate with the adhesion layer formed in this step.

In the adhesive layer forming step, the method of forming the adhesive layer is not particularly limited, and 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, or a vapor deposition method can be preferably used. When the adhesive layer is formed into a film by a dry method, since it is easy to control the film thickness, the sputtering method is preferably used. In addition, one or more elements selected from carbon, oxygen, hydrogen, and nitrogen may be added to the adhesion layer as described above. In this case, the reactive sputtering method can be more preferably used.

Since the materials applicable to the adhesive layer, the preferable thickness of the adhesive layer, etc. have already been explained, the explanation is omitted here.

The conductive substrate obtained by the conductive substrate manufacturing method of this embodiment can be used for various applications such as touch panels. In addition, when used in various applications, it is preferable that the metal layer, the organic layer, and the blackened layer included in the conductive substrate of this embodiment have been patterned. In addition, when the adhesive layer is provided, it is preferable to pattern the adhesive layer. For the metal layer, organic layer, blackened layer, and optionally the adhesive layer, for example, it can be patterned according to the desired wiring pattern, preferably the metal layer, organic layer, blackened layer, and optionally the adhesive layer is patterned Into the same shape.

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

The specific procedure of the patterning step is not particularly limited, and can be implemented by any procedure. For example, as shown in FIG. 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, the first can be implemented on the surface A on the blackened layer 14. A mask placement step of placing a mask with a desired pattern. Next, an etching step of supplying an etching solution to the upper surface of the blackened layer 14, that is, the side where the mask is disposed, can be performed.

The etching liquid 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 same etching solution can also be used to etch the metal layer, the organic layer, the blackened layer, and the adhesion layer as appropriate.

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

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 may be treated in a manner that contains a plurality of straight lines or zigzag-shaped curved lines (saw-tooth straight lines) as described above. 14 form a pattern.

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 as a mesh wiring. In this case, it is preferable to pattern each of the organic layer 13A and the blackened layer 14A into the same shape as the metal layer 12A, and the organic layer 13B and the blackened layer 14B have the same shape as the metal layer 12B.

In addition, for example, after patterning the metal layer 12 or the like on the conductive substrate 10A in the patterning process, a lamination step of laminating two or more patterned conductive substrates may be performed. When performing lamination, for example, by lamination so that the pattern of the metal layer of each conductive substrate cross|intersects, you may obtain the laminated conductive substrate provided with mesh wiring.

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

According to the conductive substrate obtained by the conductive substrate manufacturing method of the present embodiment described above, an organic layer is disposed on the metal layer formed on at least one surface of the insulating base material, and the organic layer faces one of the surfaces of the blackened layer. The contact angle of pure water is 60° or less and contains nitrogen-based organic matter. Therefore, it is possible to obtain a conductive substrate with high adhesion of the blackened layer. In addition, since the blackened layer is arranged on the organic layer, the visibility of the display can be improved when used in applications such as touch panels.

<Example>

Hereinafter, specific examples and comparative examples will be described, 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) Contact angle

When the produced conductive substrates were produced in each of the following Examples and Comparative Examples, after the formation of the organic layer and before the formation of the blackened layer, the contact angle of the surface of the organic layer with respect to pure water was measured.

Automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., type No.: DM-301) to proceed.

After the organic substance layer was formed, 1.0 μL of pure water was supplied to the surface of the organic substance layer where the blackened layer was formed, and the contact angle was measured.

(Adhesion test)

As shown in Figure 5, for the blackened layer of the conductive substrate formed to the blackened layer, using a cutting tool (manufactured by Precision Gate & Tool Company, Cross Cut Kit 1.0MM), 11 strips were formed parallel to each other at 1.0 mm intervals. A longitudinal cutting line 51a with a length of 20 mm.

Next, using the same cutting tool, 11 horizontal cutting lines 51b with a length of 20 mm were formed so as to be orthogonal to the longitudinal cutting line 51a formed earlier and parallel to each other at 1.0 mm intervals.

Through the above steps, as shown in FIG. 5, 11 cutting lines in the vertical and horizontal directions are used to form grid-like cuts in the blackened layer.

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

After 30 seconds have passed after the adhesiveness evaluation tape is attached, the adhesiveness evaluation tape is quickly torn off in a direction as close as possible to 180° with respect to the measurement surface.

After tearing off the adhesiveness evaluation tape, the metal layer (organic layer) is formed under the blackened layer in the evaluation area 52 in FIG. 5 surrounded by the grid-shaped vertical cutting line 51a and the horizontal cutting line 51b. ) Area to evaluate the adhesion.

When the exposed area of the metal layer in the evaluation area is 0%, it is evaluated as 5B, when more than 0% and less than 5%, it is evaluated as 4B, when it is greater than or equal to 5% and less than 15%, it is evaluated as 3B, and when it is greater than or equal to 15% and less than 35 % Is evaluated as 2B, when it is greater than or equal to 35% and less than 65%, it is evaluated as 1B. It is evaluated as 0B when it is equal to 65%. Regarding this 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, it can be evaluated that the adhesion of the blackened layer is sufficient when it is 5B.

(Conditions for sample production)

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

[Example 1]

(Adhesive layer formation step)

The adhesion layer was formed into a film on one surface of an insulating substrate made of polyethylene terephthalate resin (PET) with a length of 500 mm × a width of 500 mm and a thickness of 50 μm. In addition, for an insulating substrate made of polyethylene terephthalate resin used as an insulating substrate, the total light transmittance was 97% when evaluated by the method specified in JIS K 7361-1.

In the adhesion layer forming step, a sputtering device equipped with a target of Ni-17 wt% Cu alloy is used to form a Ni-Cu alloy layer containing oxygen as the adhesion layer. The film forming step of the adhesion layer will be described below.

The above-mentioned insulating base material previously heated to 60° C. to remove moisture was set in the chamber of the sputtering device.

Then, after exhausting the chamber to 1×10 ^-3 Pa, argon and oxygen are introduced to make the pressure in the chamber 1.3 Pa. In addition, at this time, the environment in the chamber is calculated by volume ratio, 30% is oxygen, and the rest is argon.

Next, power was supplied to the target in this environment, and the insulating substrate The adhesion layer was formed into a film so that the thickness became 20 nm.

(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 copper thin film layer as a metal thin film layer is formed on the adhesive layer by forming an adhesive layer on the insulating substrate in the adhesive layer forming step as the substrate.

For the metal thin film layer, except for the use of a copper target and the fact that argon gas is supplied to form an argon atmosphere after exhausting the chamber in which the substrate is provided, the film is formed by a sputtering apparatus in the same manner as in the case of the adhesion layer.

The film formation was performed so that the thickness of the copper thin film layer as the metal thin film layer was 150 nm.

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

(Organic layer formation step)

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

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

Next, the solution adhered to the upper surface of the metal layer, that is, the surface opposite to the surface of the metal layer facing the adhesion layer, is removed by washing with water, and then dried to form an organic layer on the metal layer.

In addition, after the organic substance layer formation step, a part of the substrate was cut off for the evaluation of the above-mentioned contact angle.

(Blackening layer formation step)

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

In the blackening layer forming step, a sputtering device equipped with a target of Ni-35% by weight Cu alloy is used to form a Ni-Cu alloy layer as a blackening layer. The film forming step of the blackened layer will be described below.

First, a laminate in which an adhesive layer, a metal layer, and an organic layer are laminated on an insulating base material is set in a chamber of a sputtering device.

Next, after evacuating the chamber to 1×10 ^-3 Pa, argon gas is introduced to make the pressure in the chamber 1.3 Pa.

Next, power was supplied to the target under this environment, and a blackened layer having a thickness of 30 nm was formed on the organic layer.

Through the above steps, a blackened layer is formed on the top of the metal layer, that is, on the side opposite to the side of the metal layer facing the adhesion layer, through the organic layer, and the adhesion layer and the metal layer are sequentially laminated on the insulating substrate , Organic layer, blackened layer of conductive substrate.

With respect to the obtained conductive substrate, an adhesion test was performed.

The results are shown in Table 1.

[Example 2, Example 3]

A conductive substrate was produced in the same manner as in Example 1, except that the contact angle of the surface of the organic layer was changed by changing the concentration, bath temperature, or pH of the OPC-DEFENSER solution when forming the organic layer.

With respect to the obtained conductive substrate, the aforementioned adhesion test was carried out.

The results are shown in Table 1.

[Comparative Example 1]

A conductive substrate was produced in the same manner as in Example 1, except that the contact angle of the surface of the organic layer was changed by changing the concentration, bath temperature, or pH of the OPC-DEFENSER solution when forming the organic layer.

With respect to the obtained conductive substrate, the aforementioned adhesion test was carried out.

The results are shown in Table 1.

Figure 6 shows the relationship between the contact angle of the organic layer shown in Table 1 and the adhesion evaluation result of the blackened layer.

It can be clearly confirmed from the results of Table 1 and FIG. 6 that for Examples 1 to 3 in which the contact angle on the surface of the organic layer is 60° or less, the result of the adhesion test is 5B. In contrast, in Comparative Examples 1 to 3 in which the contact angle of the organic layer surface exceeded 60°, the result of the adhesion test was 3B or 4B, and the peeling of the blackened layer was confirmed.

Based on the above results, it can be confirmed that, for a conductive substrate with an organic layer formed between the metal layer and the blackened layer, by setting the contact angle of the organic layer surface to 60° or less, the adhesion of the blackened layer can be achieved High conductivity substrate.

The conductive substrate and the method of manufacturing the conductive substrate have been described above with the embodiment and the examples. However, the present invention is not limited to the above-mentioned embodiment and examples. Various modifications and changes can be made within the scope of the gist of the present invention described in the scope of the patent application.

This application claims priority based on the application No. 2015-152896 filed with the Japan Patent Office on July 31, 2015, and the entire content of the application No. 2015-152896 is cited in this international application.

Claims (4)

A conductive substrate having: an insulating base material; a metal layer formed on at least one surface of the insulating base material; an organic layer containing nitrogen-based organics formed on the metal layer; and formed on the organic layer For the blackened layer, the contact angle of pure water on the surface of the organic layer facing the blackened layer is 60° or less. Such as the conductive substrate of the first item in the scope of patent application, wherein the nitrogen-based organic substance contains 1,2,3-benzotriazole or its derivatives. A method for manufacturing a conductive substrate, which has the following steps: a metal layer forming step: forming a metal layer on at least one surface of an insulating substrate; an organic layer forming step: forming an organic substance containing a nitrogen-based organic substance on the metal layer And a blackening layer forming step: forming a blackening layer on the organic layer, in the organic layer forming step, the contact angle of the pure water of the surface of the organic layer facing the blackening layer is 60° or less The organic layer is formed. For example, the manufacturing method of the conductive substrate of the third item of the scope of patent application, wherein the nitrogen-based organic substance contains 1,2,3-benzotriazole or its derivatives.

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