TW201729907A - Method for manufacturing organic coating, method for manufacturing conductive substrate, and device for manufacturing organic coating - Google Patents

Abstract

The present invention provides a method for manufacturing an organic coating in which an organic solution is supplied to the surface of a sheet-shaped base and an organic coating is formed, wherein the method for manufacturing an organic coating comprises supplying the organic solution to the surface of the base, the base being conveyed so that the width direction of the base is set as height direction, and the organic solution being supplied from a spray nozzle in which a plurality of nozzle holes are arranged so as to face the surface of the base, and from a liquid film formation means having a supply port arranged in the top part of the base in the height direction, the organic solution being supplied from the supply port so that the organic solution flows in the form of a film and that there is contact between the surface of the base and the film-shaped flow of the organic solution.

Description

Method for producing organic film, method for producing conductive substrate, and organic film manufacturing device

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

The capacitive touch panel converts position information of an object approaching on the surface of the panel into an electrical signal by detecting a change in capacitance caused by an object approaching the surface of the panel. Since the conductive substrate 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 a low reflectance and is difficult to visually confirm.

Therefore, as a material for the conductive layer of the capacitive touch panel, wiring is formed on a transparent substrate or a transparent film using a material having a low reflectance and being difficult to visually recognize.

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

However, in recent years, a large screen of a display having a touch panel has been developed, and correspondingly, a conductive substrate for a touch panel has been required to have a large area. However, ITO has a problem that a conductive substrate using ITO is not suitable for a large panel because its resistance value is high and signal degradation is likely to occur.

Therefore, as a material of the conductive layer, it is being studied to use a metal such as copper instead of ITO. However, since the metal has a metallic luster, the visibility of the display is lowered due to reflection. However, a conductive substrate in which a metal layer made of a metal such as copper and a blackened layer made of a black material are formed is being studied.

For example, Patent Document 2 discloses a film-shaped touch panel sensor having strip-shaped copper wirings on portions of the film surface and the back surface to be seen, and black oxidation on the visible sides of the copper wirings on the front and back surfaces. Copper film.

In addition, according to the method for manufacturing a film-shaped touch panel sensor disclosed in Patent Document 2, the method has the following steps: forming a resist layer on a copper film supported by the film, using photolithography at least a step of processing the resist layer into a strip wiring pattern and a lead wiring pattern, a step of removing the exposed copper thin film by etching to form a strip copper wiring and a copper wiring for extraction, and a step of blackening the copper wiring .

However, in the method of blackening the surface after forming the copper wiring shown in Patent Document 2, the number of steps is increased. Therefore, a method is being studied in which a metal layer and a blackened layer whose surface is subjected to blackening treatment are formed on a substrate, and then the metal layer and the blackened layer are patterned by etching or the like to form a conductive substrate.

Further, in order to make the metal wiring for patterning the metal layer less conspicuous, it is effective to perform fine wiring processing of the metal layer and the blackened layer formed on the upper surface thereof. However, the blackening layer has low reactivity with respect to the etching liquid, and when the metal layer and the blackening layer are etched for fine wiring processing, the blackening layer may peel off.

Therefore, a method of improving the etching property of the blackened layer by providing an organic film between the metal layer and the blackened layer is being studied.

The organic film can be formed by coating an organic solution as a raw material of the organic film on the surface of the metal layer of the substrate formed to the metal layer, after forming the organic film A blackening layer is formed on the organic film, so that a structure in which an organic film is provided between the metal layer and the blackening layer can be formed.

Conventionally, the inventors of the present invention performed the formation of an organic film by the following method.

First, the liquid flow and the metal of the film-like organic solution formed by supplying the organic solution from the upper portion in the height direction of the substrate while transporting the substrate in the height direction of the substrate formed in the metal layer The layer surface is in contact to coat the organic solution on the surface of the metal layer. Next, the excess organic solution was removed by washing the surface on which the organic film was applied, and then dried.

<Previous Technical Literature>

<Patent Literature>

Patent Document 1: Japanese Patent Laid-Open Publication No. 2004-213114

Patent Document 2: Japanese Patent Laid-Open Publication No. 2013-206315

However, according to the method for forming an organic film, the thickness of the organic film formed on the surface of the metal layer is not fixed, or it is likely to become a state in which a portion where the organic film is not formed is formed on a part of the surface of the metal layer. The unevenness of the organic film causes a problem that the adhesion of the blackened layer formed on the upper surface of the organic film is lowered.

In view of the above problems of the prior art, it is an object of one aspect of the present invention to provide a method for producing an organic film which is capable of forming a uniform organic film on a film formation surface.

In order to solve the above problems, an aspect of the invention provides a method for producing an organic film, which supplies an organic solution to a surface of a sheet-like substrate and forms an organic film, which is transported in a direction in which the width direction of the substrate is a height direction. The surface of the substrate is supplied from the nozzle and the liquid film forming means, and the nozzle is provided with a plurality of nozzle holes so as to face the surface of the substrate, and the liquid film forming means has a height direction of the substrate In the upper supply port, the liquid film forming means is supplied from the supply port such that the organic solution becomes a film-like liquid flow and the surface of the base material comes into contact with the film-like liquid flow of the organic solution. .

According to an aspect of the invention, it is possible to provide a method for producing an organic film which can form a uniform organic film on a film formation surface.

11‧‧‧Substrate

13‧‧‧ Liquid film formation means

21‧‧‧ nozzle

211‧‧‧ nozzle hole

50A, 50B, 60A, 60B, 70‧‧‧ conductive substrates

51‧‧‧Transparent substrate

52, 52A, 52B‧‧‧ metal layer

53, 53A, 53B, 72A, 72B‧‧‧ organic film

54, 54A, 54B, 73A, 73B‧‧‧ blackening layer

FIG. 1 is an explanatory view showing a configuration example of a conventional method for producing an organic film.

Fig. 2 is a cross-sectional view taken along line A-A' of Fig. 1;

3 is an explanatory view showing a configuration example of a method of producing an organic film according to an embodiment of the present invention.

Fig. 4 is a cross-sectional view taken along line B-B' of Fig. 3;

Fig. 5A is a cross-sectional view of a conductive substrate according to an embodiment of the present invention.

5B is a cross-sectional view of a conductive substrate according to an embodiment of the present invention.

Fig. 6A is a cross-sectional view of a conductive substrate according to an embodiment of the present invention.

Fig. 6B is a cross-sectional view of a conductive substrate according to an embodiment of the present invention.

Fig. 7 is a plan view showing a conductive substrate having a mesh-like wiring according to an embodiment of the present invention.

Fig. 8A is a cross-sectional view taken along line A-A' of Fig. 7.

Fig. 8B is a cross-sectional view taken along line A-A' of Fig. 7.

FIG. 9 is an explanatory view of a cutting line formed when the adhesion test is performed in the examples and the comparative examples.

Hereinafter, an embodiment of the method for producing an organic film of the present invention, a method for producing a conductive substrate, and an apparatus for producing an organic film will be described.

(Manufacturing method of organic film)

In the method for producing an organic film of the present embodiment, an organic solution can be supplied to the surface of the sheet-like substrate to form an organic film.

Further, the organic solution can be supplied to the surface of the substrate which is transported in the height direction of the substrate in the height direction by the nozzle and the liquid film forming means.

Here, the nozzle can have a structure in which a plurality of nozzle holes are provided in such a manner as to face the surface of the substrate. Further, the liquid film forming means has a supply port provided in an upper portion of the base material in the height direction, and the liquid film forming means can be formed such that the organic solution becomes a film-like liquid flow and the surface of the base material and the organic solution are film-like. The way in which the liquid stream contacts is supplied from the supply port.

A configuration example of a conventional method for producing an organic film which is studied when an organic film is formed on a substrate will be described with reference to FIGS. 1 and 2 .

FIG. 1 is a view showing a step of forming an organic film on the substrate 11 in a direction perpendicular to the one surface 11a of the substrate 11 on which the organic film is formed. 2 is a cross-sectional view taken along line A-A' of FIG. 1.

In Fig. 1, the substrate 11 is in the form of a long sheet, and is conveyed in the direction indicated by the arrow 1 of the square shown in Fig. 1 in the X-axis direction in the drawing. At this time, the sheet-like base material 11 is in the height direction of the width direction, that is, in a state in which the width direction of the base material 11 is set along the height direction. Hold and be transported. Further, the height direction refers to the Z-axis direction shown in the drawing, and the X-axis direction is the horizontal direction.

On the upstream side in the transport direction of the substrate 11, a first water washing means 12 for washing the one surface 11a which is a surface on which the organic film is formed of the substrate 11 may be provided. The first water washing means 12 can be washed by, for example, spraying water onto one surface 11a of the base material 11 by a nozzle. Further, the first washing means 12 may have a plurality of nozzles in advance so as to be able to clean the entire surface 11a of the substrate 11 to be conveyed. The first water washing means 12 can be configured, for example, in a height direction, that is, a plurality of nozzles arranged along the Z axis in the drawing.

In addition, an organic solution which is a raw material of the organic film can be supplied from the supply port of the liquid film forming means 13 provided in the upper portion in the height direction of the substrate 11 to be conveyed in the downward direction in the drawing. At this time, as shown in FIG. 2, the liquid film forming means 13 can form the liquid film flow 14 as a film-like liquid flow from the supply port 131 of the liquid film forming means 13, and the liquid film flow 14 and the substrate 11 can be formed. The organic solution is supplied in a surface contact manner. The liquid film flow 14 is formed from above the substrate 11, and the organic film is supplied from the liquid film forming means 13 so that the liquid film flow 14 comes into contact with the surface of the substrate 11, so that it can be on one surface 11a of the substrate 11. The organic solution was applied.

Next, the second water washing means 15 may be further provided on the downstream side of the liquid film forming means 13. The excess organic solution coated on the substrate 11 can be washed with water and removed by the second water washing means 15. The second washing means 15 is a means capable of washing the surface of the base material 11 to which the organic solution has been applied, and the structure thereof is not particularly limited, and for example, the same configuration as that of the first washing means 12 described above can be employed.

The configuration example of the method for producing the organic film described above has been described. However, according to the method for producing the organic film, it is easy to form an organic film formed on the surface of the metal layer. Uneven state. The unevenness of the organic film causes a decrease in the adhesion of the blackened layer formed on the upper surface of the organic film, which is a problem.

The inventors of the present invention have conducted intensive studies on the reason why the organic film is not uniform when the organic solution is applied to the substrate by the conventional method for producing an organic film.

According to the conventional method for producing an organic film, as described above, the organic solution is applied only by bringing the liquid film flow of the organic solution into contact with the surface of the substrate, wherein the liquid film flow of the organic solution is by the width The organic solution is supplied from the upper direction to the lower side of the substrate conveyed in the state in which the direction is the height direction. According to the coating method of the organic solution, since the organic solution flows from the upper portion to the lower portion along the surface of the substrate to be conveyed, the impact against the substrate is smooth when the organic solution comes into contact with the surface of the substrate. Further, the treatment time for treating the surface of the substrate with the organic solution is limited by the transport speed of the substrate. Therefore, the inventors of the present invention have found that the treatment of coating the organic solution on the surface of the substrate is not completely completed, and the formed organic film tends to be uneven. Further, the inventors of the present invention have completed the present invention based on the problems of the conventional method for producing an organic film.

A method of producing the organic film of the present embodiment will be described with reference to FIGS. 3 and 4 . The same components as those in FIGS. 1 and 2 are denoted by the same reference numerals.

FIG. 3 is a view showing a step of forming an organic film on the substrate 11 in a direction perpendicular to the one surface 11a of the substrate 11 which is a film formation surface on which the organic film is formed. 4 is a cross-sectional view taken along line B-B' of FIG. 3.

In Fig. 3, the substrate 11 is in the form of a long sheet, and is conveyed in the direction indicated by the arrow 1 shown in the figure in the X-axis direction in the drawing.

In addition, although an example of using a long sheet-shaped base material is shown in FIG. 3, it is not limited to this aspect. However, since it is possible to continuously carry out production, it is preferably a long piece. Further, the type of the substrate is not particularly limited, and a substrate on which an organic film is formed on at least one surface can be used. For example, as described below, in order to produce a conductive substrate in which a metal layer, an organic film, and a blackened layer are laminated on a transparent substrate, a substrate on which a metal layer is formed on a transparent substrate can be used as an organic film. Substrate 11 here.

At this time, the sheet-like base material 11 is held in the height direction, that is, in a state in which the width direction of the base material 11 is provided along the height direction, and is conveyed. Further, the height direction refers to the Z-axis direction shown in the drawing, and the X-axis direction is the horizontal direction.

In addition, the liquid film flow 14 can be formed in the downward direction in the drawing from the supply port of the liquid film forming means 13 disposed in the upper portion in the height direction of the substrate 11 to be transported. The organic solution is supplied in such a manner that the liquid film stream 14 is in contact with the surface of the substrate 11. Since the liquid film forming means 13 can be configured in the same manner as in the case of the conventional method for producing an organic film, the description thereof will be omitted.

As described above, when the organic solution is supplied to one surface 11a of the substrate 11 by the liquid film forming means 13, the organic film formed may become uneven. Therefore, in the apparatus for producing an organic film of the present embodiment, in addition to the liquid film forming means described above, the organic solution can be supplied to the one surface 11a which is the surface on which the organic film is formed on the substrate 11 by the nozzle 21.

As shown in FIG. 4, the nozzle 21 may have a structure in which a plurality of nozzle holes 211 are provided to face the surface of the substrate 11, that is, the one surface 11a. Further, the organic solution can be supplied to one surface 11a of the substrate 11 from a plurality of nozzle holes 211 of the nozzle 21, thereby One surface 11a of the material 11 is coated with an organic film.

As described above, when the organic solution is applied to the surface of the substrate on which the organic film is formed by the liquid film forming means, the impact on the substrate when the organic solution comes into contact with the substrate is stable. Therefore, when the organic solution is applied to the surface of the substrate 11 on which the organic film is formed by the liquid film forming means, and the organic film is formed, the organic film may become uneven. On the other hand, when an organic solution is applied to the surface of the base material on which the organic film is formed by the nozzle, the impact on the substrate when the organic solution comes into contact with the substrate can be enhanced. Therefore, by coating the surface of the substrate with the liquid film forming means and the nozzle, an organic solution is formed and an organic film is formed, whereby a uniform organic film can be formed.

As shown in FIG. 4, the nozzle 21 may have a plurality of nozzle holes 211. The arrangement of the nozzle holes 211 is not particularly limited, and it is preferable to apply an organic solution to the entire surface 11a of the substrate 11 which is conveyed in the X-axis direction which is a direction perpendicular to the paper surface in FIG. 4, and FIG. 4 The Z-axis direction in the middle, that is, the height direction.

It is particularly preferable that the organic solution supplied from the nozzle 211 and applied onto the substrate 11 is a coating film of a continuous organic solution. Therefore, it is preferable to form a spray pattern connection by coating an organic solution on the substrate 11 from the nozzle holes 211 adjacent in the height direction, and it is more preferable to partially overlap.

The shape of the nozzle hole 211 of the nozzle 21 is not particularly limited. For example, it is preferable to use a nozzle in which a spray pattern formed on the surface of the substrate by the organic solution supplied from the nozzle hole of the nozzle is a circular or elliptical shape.

Among them, from the viewpoint of improving the uniformity of the formed organic film, it is preferable to apply a stronger impact to the substrate when the organic solution is applied onto the substrate 11 by the nozzle 21 . Further, according to the study by the inventors of the present invention, the spray pattern formed on the substrate by the organic solution supplied from the nozzle hole, that is, the pattern formed on the substrate when the organic solution is supplied from the nozzle hole to the substrate is used. A particularly strong impact is given in the case where the shape of the case is elliptical.

Therefore, in the nozzle, it is preferable that the spray pattern formed on the surface of the substrate by the organic solution supplied from the nozzle hole has an elliptical shape.

Further, the nozzle may have a plurality of nozzle holes, and the shape of the ejection pattern herein refers to a shape when the organic solution is supplied from the nozzle holes to the substrate.

Further, when the ejection pattern has an elliptical shape, the ratio of the major axis to the minor axis is not particularly limited, and for example, the major axis/minor axis is preferably 5 or more and 20 or less.

In the example shown in FIG. 3, the nozzle 21 and the liquid film forming means 13 are provided in this order from the upstream side in the transport direction of the substrate 11. However, the order of the coating means when the organic solution is applied to the substrate 11 is not particularly limited. For example, after the organic solution is applied onto the substrate 11 by the liquid film forming means 13, the organic solution may be applied onto the substrate 11 by the nozzle 21. Further, the organic solution can be simultaneously applied onto the substrate 11 by the liquid film forming means 13 and the nozzle 21.

In addition, FIG. 3 shows an example in which the organic solution is applied once by the liquid film forming means when the organic solution is applied to the substrate 11, and the organic solution is applied once by the nozzle, but the embodiment is not limited thereto. For example, a plurality of liquid film forming means and/or nozzles may be provided on the transport path of the substrate 11, and a plurality of organic solutions may be applied to the substrate 11 by a liquid film forming means and/or a nozzle.

The type of the organic solution to be used in the production of the organic film is not particularly limited, and may be arbitrarily selected depending on the type of the organic film to be produced and the like. For example, when an organic film of a conductive substrate described below is formed, an organic solution corresponding to the organic film can be used.

Further, on the upstream side in the transport direction of the substrate 11, a first water washing means 12 for washing one surface 11a of the substrate 11 may be provided.

Further, the second water washing means 15 may be provided on the downstream side in the transport direction of the liquid film forming means 13 and the substrate 11 of the nozzle 21. Since the first water washing means 12 and the second water washing means 15 can be configured in the same manner as in the conventional method for producing an organic film, the description thereof will be omitted.

Thus, the case where the organic film is formed only on one surface 11a of the substrate 11 in FIGS. 3 and 4 has been described. However, the surface facing the one surface 11a, that is, the other surface shown in FIG. 4 may be used. One face 11b simultaneously forms an organic film.

Specifically, for example, an organic film can be formed on the other surface 11b by providing the liquid film forming means and the nozzle on the other surface 11b side of the substrate 11 to be conveyed.

In the case where the organic film is also formed on the other surface 11b, it is particularly preferable that the nozzle provided on one surface 11a side and the nozzle provided on the other surface side are opposed to each other with the nozzle hole interposed therebetween, that is, disposed on the substrate. The same position when viewed in the conveying direction. This is because it is possible to suppress the occurrence of warpage or the like on the substrate 11 by supplying the organic solution at the same pressure from both surfaces of the substrate 11.

It is preferable that the liquid film forming means, the first water washing means, the second water washing means, and the like are disposed at the same position when viewed in the conveying direction of the base material 11 not only for the nozzle.

According to the method for producing an organic film of the present embodiment as described above, it is possible to form a uniform organic film on the surface of the substrate on which the organic film is formed. Therefore, when forming an organic film of a conductive substrate in which a metal layer, an organic film, or a blackened layer is laminated, for example, the adhesion of the blackened layer can be improved.

Further, heretofore, an example in which an organic film is formed on a substrate has been described. By supplying a liquid from a liquid film forming means and a nozzle to a substrate, it is possible to form a substrate. A uniform liquid film. Therefore, for example, a cleaning liquid such as water can be used instead of the organic solution, and the cleaning liquid can be supplied from the liquid film forming means and the nozzle, and can also be used as a method of cleaning the surface of the substrate. Moreover, it can also be used as a manufacturing method of various film other than an organic film.

(Organic film manufacturing device)

Next, a configuration example of the organic film production apparatus of the present embodiment will be described.

In addition, since the organic film production apparatus of the present embodiment can be suitably applied to the above-described method for producing an organic film, a part of the description of the organic film production method will be omitted.

According to the organic film production apparatus of the present embodiment, the organic solution can be supplied to the surface of the sheet-like substrate to form an organic film, and the following structure can be obtained.

The conveying means conveys in the height direction of the width direction of the base material.

A nozzle is provided with a plurality of nozzle holes in a manner opposite to a surface of the substrate.

The liquid film forming means has a supply port provided in an upper portion of the base material in the height direction, and the organic solution is formed into a film shape, and the surface of the base material is in contact with the film-like liquid flow of the organic solution from the supply port. Supply.

The organic film production apparatus of the present embodiment will be described with reference to Figs. 3 and 4 .

According to the organic film production apparatus of the present embodiment, an organic solution can be supplied and applied to the substrate to be conveyed, and an organic film can be formed.

Therefore, the organic film production apparatus of the present embodiment can have a transport means for transporting the substrate. The structure of the transport means is not particularly limited. For example, when a long sheet-like base material shown in FIG. 3 is used as the base material, a transport means for transporting the base material by a roll-to-roll method can be used. Furthermore, the means of conveying by means of a roll-to-roll method means that the substrate is previously used. A winding means for winding a substrate into a coil-like winding roller, and winding a substrate on which an organic film is formed by a winding roller to transport the substrate.

Further, the means for supplying the organic solution to the surface on which the organic film is formed by the transport means may be provided with a nozzle and a liquid film forming means.

As shown in FIGS. 3 and 4, the nozzle 21 may have a plurality of nozzle holes 211, and the organic solution may be supplied and coated from the nozzle holes 211 with respect to the surface of the substrate 11 on which the organic film is formed.

The shape of the nozzle hole of the nozzle is not particularly limited. For example, in the nozzle, it is preferable that the spray pattern formed on the surface of the substrate by the organic solution supplied from the nozzle hole has an elliptical shape.

Since the other points of the nozzle have been described in the method of manufacturing the organic film, the description thereof will be omitted.

In addition, since the structural example of the liquid film formation means has also been described, description is abbreviate|omitted here.

In addition, in FIG. 3, the structure example of the organic film manufacturing apparatus which has one nozzle 21 and the liquid film formation means 13 respectively is shown, It is not limited to this. For example, a plurality of nozzles and/or a plurality of liquid film forming means may be provided on the transport path of the substrate 11.

In addition, an example in which the nozzle 21 and the liquid film forming means 13 are provided in this order from the upstream side in the transport direction of the substrate 11 is shown in FIG. 3, but the present invention is not limited to this. For example, the liquid film forming means 13 and the nozzle 21 may be provided in this order from the upstream side in the transport direction of the substrate 11. Further, the nozzle 21 and the liquid film forming means may be disposed at positions which are repeated when viewed in the conveying direction of the substrate 11.

The organic film production apparatus of the present embodiment is not limited to the above-described members, and may have any various means. For example, it may have a first water washing means 12 and/or a second water washing means 15. Since the first water washing means 12 and the second water washing means 15 have been described, the description thereof is omitted here.

In addition, a water removing means for removing water adhering to the surface of the substrate 11 or a drying means for drying the surface of the substrate may be further provided on the downstream side of the second washing means 15 in the transport direction of the substrate 11. .

Further, although the case where the organic film is formed only on one surface 11a of the substrate 11 in FIGS. 3 and 4 has been described as an example, the surface facing the one surface 11a, that is, the surface shown in FIG. 4 may be used. The other surface 11b is formed by simultaneously forming an organic film.

Specifically, for example, an organic film can be formed on the other surface 11b by providing the liquid film forming means and the nozzle on the other surface 11b side of the substrate 11 to be conveyed. It is particularly preferable that the nozzle provided on one surface 11a side and the nozzle provided on the other surface side are opposed to each other with the nozzle hole facing the substrate 11, that is, the same position as viewed in the conveying direction of the substrate. This is because it is possible to suppress the occurrence of warpage or the like on the substrate 11 by supplying the organic solution at the same pressure from both surfaces of the substrate 11.

It is preferable that the liquid film forming means, the first water washing means, the second water washing means, and the like are disposed at the same position when viewed in the conveying direction of the base material 11 not only for the nozzle. In other words, it is preferable that various means are provided symmetrically on the cross section perpendicular to the one surface 11a of the base material 11 with the base material 11 interposed therebetween.

According to the organic film production apparatus of the present embodiment as described above, it is possible to form a uniform organic film on the surface of the substrate on which the organic film is formed. Therefore, when used for example, there is a laminate When the organic film of the conductive layer of the metal layer, the organic film, or the blackened layer is formed, the adhesion of the blackened layer can be improved.

Furthermore, the case where the organic film is formed on the substrate has been described as an example. By supplying the liquid from the liquid film forming means and the nozzle to the substrate, a uniform liquid film can be formed on the substrate. Therefore, for example, a cleaning liquid such as water can be used instead of the organic solution, and the cleaning liquid can be supplied from the liquid film forming means and the nozzle, and can also be used as a cleaning device for the surface of the substrate. Moreover, it can also be used as a manufacturing apparatus of various film other than an organic film.

(Method of Manufacturing Conductive Substrate)

Next, a configuration example of a method of manufacturing a conductive substrate of the present embodiment will be described.

The method for producing a conductive substrate of the present embodiment may have the following steps.

A metal layer forming step of forming a metal layer on at least one side of the transparent substrate.

An organic film forming step of forming an organic film on the upper surface of the metal layer.

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

Further, in the organic film forming step, the organic film can be formed on the upper surface of the metal layer by the above-described method for producing an organic film.

Here, a configuration example of a conductive substrate obtained by the method for producing a conductive substrate of the present embodiment will be described.

The conductive substrate may have a transparent substrate, a metal layer formed on at least one surface of the transparent substrate, an organic film formed on the metal layer, and a blackened layer formed on the organic film.

In addition, the conductive substrate of the present embodiment includes a substrate having a metal layer, an organic film, and a blackened layer on the surface of the transparent substrate before patterning the metal layer or the like, and A substrate on which a metal layer or the like is patterned, that is, a wiring substrate.

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

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

As a material of the resin substrate that transmits visible light, for example, polyamine resin, polyethylene terephthalate resin, polyethylene naphthalate resin, cycloolefin resin, polyimine resin, poly Resin such as carbonate. In particular, as a material of the resin substrate that transmits visible light, PET (polyethylene terephthalate), COP (cycloolefin polymer), PEN (polyethylene naphthalate), and poly are more preferably used. Guanamine, polyimine, polycarbonate, and the like.

The thickness of the transparent substrate is not particularly limited, and can be arbitrarily selected depending on the strength, capacitance, or transmittance of light required for the conductive substrate. The thickness of the transparent substrate can be, for example, 10 μm or more and 200 μm or less. In particular, when used for a touch panel, the thickness of the transparent substrate is preferably 20 μm or more and 120 μm or less, and more preferably 20 μm or more and 100 μm or less. In the case of use for a touch panel, for example, when the thickness of the entire display is required to be thinned, the thickness of the transparent substrate is preferably 20 μm or more and 50 μm or less.

The total light transmittance of the transparent substrate is preferably higher, for example, the total light transmittance is preferably 30% or more, and more preferably 60% or more. By making the total light transmittance of the transparent substrate into the above range, it is possible to sufficiently ensure the visibility of the display when used for, for example, a touch panel.

Further, the total light transmittance of the transparent 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 use may be selected. For example, the material constituting the metal layer is preferably Cu and selected from the group consisting of Ni, Mo, Ta, Ti, V, Cr, Fe. a copper alloy of at least one metal of Mn, Co, or W, or a material containing copper. Further, the metal layer may be a copper layer made of copper.

The method of forming the metal layer on the transparent substrate is not particularly limited, and in order to reduce the transmittance of light, it is preferred not to arrange an adhesive between the transparent substrate and the metal layer. In other words, it is preferred that the metal layer be formed directly on at least one side of the transparent substrate. Further, when the adhesion layer is disposed between the transparent substrate and the metal layer as described below, it is preferable that the metal layer is directly formed on the upper surface of the adhesion layer.

In order to form a metal layer directly on the upper surface of the transparent substrate, it is preferred that the metal layer 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 a transparent substrate by dry plating, and the metal thin film layer is a metal layer. Thereby, the metal layer can be formed directly on the transparent substrate without passing through the adhesive. Further, as a dry plating method, a detailed description will be given later, and for example, a sputtering method, a vapor deposition method, an ion plating method, or the like can be preferably used.

Further, when the thickness of the metal layer is increased, the metal plating layer may be formed by using a metal thin film layer as a power supply layer by a plating method which is a wet plating method, thereby forming a metal thin film layer and a metal. The metal layer of the coating. By having the metal layer with a metal thin film layer and a metal plating layer, it is also possible in this case to form the metal layer directly on the transparent substrate without passing through the adhesive.

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

However, when the metal layer is thick, there is a problem in that it is easy to cause side etching and it is difficult to form a thin line or the like due to the time required for etching when etching is performed to form a wiring pattern. Therefore, the thickness of the metal layer is preferably 5 μm or less, and more preferably 3 μm or less.

In addition, 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 from the viewpoint of particularly reducing the impedance value of the conductive substrate and sufficiently supplying the current.

Further, when the metal layer has a metal thin film layer and a metal plating layer as described above, the total thickness of the metal thin film layer and the thickness of the metal plating layer are preferably in the above range.

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

The metal layer can be patterned into a desired wiring pattern for use as a wiring, for example, as described below. Further, since the metal layer can further reduce the resistance value than the conventional ITO used as the transparent conductive film, the metal layer can be provided to reduce the resistance value of the conductive substrate.

Next, the organic film will be described.

The organic film may be formed on a face of the metal layer opposite to the blackened layer to be described below. Therefore, when it is a conductive substrate, it can be arrange|positioned between a metal layer and a blackening layer. The organic film preferably contains a nitrogen-based organic material. The reason for this is that the organic film is contained in the organic film, and the adhesion between the blackened layer and the lower metal layer and the organic film as the blackened layer can be particularly improved, and the peeling of the blackened layer can be suppressed. Therefore, the etching property of the blackening layer can be improved. Further, according to the study by the inventors of the present invention, the reflectance of the conductive substrate can be reduced by including the nitrogen-based organic material in the organic film.

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

For example, OPC DEFENSER (trade name, Okuno Pharmaceutical Co., Ltd.) can be preferably used as a commercially available chemical solution, for example, an organic solution containing a nitrogen-based organic material which can be preferably used for an organic film. )Wait.

The content of the nitrogen-based organic substance of the organic film is preferably 0.2 μg/cm ² or more, and more preferably 0.3 μg/cm ² or more. This is because, according to the study by the inventors of the present invention, the content of the nitrogen-based organic material of the organic film is 0.2 μg/cm ² or more, whereby the reflectance of the conductive substrate can be greatly suppressed. In addition, when the content of the nitrogen-based organic material of the organic film is increased, the a* value and the b* value when converting the color of the blackened layer into the CIE (L*a*b*) color system can be reduced, and in particular, the conductive can be made conductive. The wiring of the substrate is not obvious, so it is preferable.

The upper limit of the content of the nitrogen-based organic substance of the organic film is not particularly limited. However, in order to increase the content of the nitrogen-based organic substance of the organic film, it is necessary to increase the concentration of the organic solution containing the nitrogen-based organic substance used in forming the organic film or to extend the supply time of the organic solution containing the nitrogen-based organic substance. Therefore, if the content of the nitrogen-based organic material of the organic film is excessively increased, the workability of the organic solution containing the nitrogen-based organic material may be lowered, the time required for forming the organic film may be long, and the productivity may be lowered. Therefore, the content of the nitrogen-based organic material of the organic film is, for example, preferably 10 μg/cm ² or less. Further, since the adhesion of the blackened layer is good when the content is low, it is more preferably 1 μg/cm ² or less, and further preferably It is 0.5 μg/cm ² or less.

The concentration of the nitrogen-based organic substance in the organic solution to be used in the formation of the organic film is not particularly limited, and may be arbitrarily selected in consideration of the content or workability of the nitrogen-based organic substance in the target organic film. For example, the lower limit of the concentration of the nitrogen-based organic substance in the organic solution is preferably 1 mL/L or more, and more preferably 2 mL/L or more. Further, the upper limit is preferably 4 mL/L or less.

The temperature of the organic solution when the 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, workability, reactivity, and the like of the solution. For example, it is preferably 10 ° C or higher, and more preferably 20 ° C or higher. However, from the viewpoint that the organic solution may react with other substances if the temperature is raised, it is preferably 40 ° C or lower.

The pH of the organic solution is not particularly limited, and may be selected in consideration of the type of the organic solution to be used or the reactivity of the solution. For example, the pH of the organic solution is preferably 2 or more, and more preferably 3 or more. However, from the viewpoint of lowering the content of the nitrogen-based organic substance in the film when the pH is increased, the pH of the organic solution is preferably 4 or less.

The length of the treatment time for supplying and reacting the organic solution on the surface of the metal layer is not particularly limited, and may be arbitrarily selected depending on the type of the organic solution to be used, the thickness of the organic film to be formed, and the like. For example, the treatment time is preferably 3 seconds or longer, and more preferably 4 seconds or longer. However, from the viewpoint that the processing time may become too long if the processing time is too long, it is preferably 10 seconds or less. Further, in the method for producing an organic film, the processing time can be set to a desired time by adjusting the conveying speed of the substrate or the like. In addition, the processing time in the manufacturing method of the above-mentioned organic film is the sum total of the time which supplied the organic solution by the nozzle and the liquid-film formation means at arbitrary point of the surface of the base material which forms an organic film.

Next, the blackening layer will be described.

A blackening layer may be formed on the upper surface of the organic film.

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

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

Further, the blackening layer may include a metal alloy containing at least two or more metals selected from the group consisting of Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. . In this case, the blackening layer may further contain one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen. In this case, as the metal alloy containing at least two or more metals selected from the group consisting of Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn, for example, 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, Ni-Cu-Cr alloy. In particular, a Ni-Cu alloy can be further preferably used.

The film formation method of the blackening layer is not particularly limited, and the film formation can be carried out by any method. For example, the film formation can be carried out by a dry method or a wet method.

When the blackening layer is formed by a dry method, the specific method is not particularly limited. For example, a dry plating method such as a sputtering method, an ion plating method, or a vapor deposition method can be preferably used. From the viewpoint of easily controlling the film thickness when forming the blackened layer by the dry method, it is more preferable to use a sputtering method. Further, one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen as described above may be added to the blackening layer, and in this case, a reactive sputtering method is more preferably used.

When the blackening layer is formed by a reactive sputtering method, a target containing a metal species constituting the blackening layer can be used as the target. When the blackening layer contains an alloy, The target may be used for each metal form contained in the blackening layer, and an alloy may be formed on the surface of the film formation body such as a substrate, or a target in which a metal contained in the blackening layer is alloyed in advance may be used.

In addition, when one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen are contained in the blackening layer, it may be added to the blackening layer by adding it in advance in an atmosphere in which the blackening layer is formed. in. For example, when carbon is added to the blackening layer, carbon monoxide gas and/or carbon dioxide gas may be previously added to the atmosphere during sputtering, and when oxygen is added to the blackening layer, oxygen may be added in advance for sputtering. In the atmosphere, when hydrogen is added to the blackening layer, hydrogen and/or water may be previously added to the atmosphere during sputtering, and when nitrogen is added to the blackening layer, nitrogen may be added in advance for sputtering. In the atmosphere. One or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen may be added to the blackened layer by adding the gases to the inert gas at the time of forming the blackened film. Further, as the inert gas, argon can be preferably used.

When the blackened layer is formed by a wet method, the plating solution can be used depending on the material of the blackened layer, and for example, it can be formed by a plating method.

The blackening layer can be formed by any method of the dry method or the wet method as described above, but since the material constituting the organic film is dissolved in the plating solution and enters the blackening layer when the blackening layer is formed, It is possible to affect the color tone or other characteristics of the blackening layer, and therefore it is preferable to form the film by a dry method.

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

The upper limit of the thickness of the blackened layer is not particularly limited, even if it is thickened to the necessity The thickness above, the time required for film formation, or the time required for etching when wiring is formed, also becomes long, resulting in an increase in cost. Therefore, the thickness of the blackening layer is preferably 70 nm or less, and more preferably 50 nm or less.

Further, the conductive substrate may be provided with any layer other than the transparent substrate, the metal layer, the organic film, and the blackened layer described above. For example, an adhesive layer can be provided.

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

Although the metal layer can be formed on the transparent substrate as described above, when the metal layer is directly formed on the transparent substrate, the adhesion between the transparent substrate and the metal layer may not be sufficient. Therefore, when a metal layer is directly formed on the upper surface of the transparent substrate, the metal layer sometimes peels off from the transparent substrate during or during use.

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

By providing the adhesion layer between the transparent substrate and the metal layer, the adhesion between the transparent substrate and the metal layer can be improved, and peeling of the metal layer from the transparent substrate can be suppressed.

In addition, the adhesion layer can also function as a blackening layer. Therefore, it is also possible to suppress reflection of light from the metal layer caused by light on the lower surface side of the metal layer, that is, from the transparent substrate side.

The material constituting the adhesion layer is not particularly limited, and may be based on the adhesion of the transparent substrate to the metal layer or the degree of suppression of the reflection of light on the surface of the metal layer, and the environment in which the conductive substrate is used (for example, humidity). The degree of stability of the temperature or the temperature is arbitrarily selected.

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

Further, the adhesion layer may include a metal alloy containing at least two or more metals selected from the group consisting of 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 the group consisting of carbon, oxygen, hydrogen, and nitrogen. In this case, as the metal alloy containing at least two or more metals selected from the group consisting of Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn, for example, 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, Ni-Cu-Cr alloy. It is particularly preferable to use a Ni-Cu alloy.

The film formation 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, a vapor deposition method, or the like can be preferably used. From the viewpoint of easily controlling the film thickness when forming the film in the adhesion layer by the dry method, it is more preferable to use a sputtering method. Further, one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen as described above may be added to the adhesion layer. In this case, a reactive sputtering method can be more preferably used.

When the adhesion layer contains one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen, one or more selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen may be added in advance in an atmosphere in which the adhesion layer is formed. The element of the gas is thus added to the adhesion layer. For example, when carbon is added to the adhesion layer, carbon monoxide gas and/or carbon dioxide gas may be added to the atmosphere during dry plating in advance, and when oxygen is added to the adhesion layer, oxygen may be added to the atmosphere in advance. When hydrogen is added to the adhesion layer, hydrogen gas and/or water may be added to the atmosphere in advance, and when nitrogen is added to the adhesion layer, nitrogen gas may be added to the atmosphere in advance.

The gas containing one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen is preferably added to an inert gas to make it an atmosphere gas during dry plating. As an inert gas It is not particularly limited, and for example, argon can be preferably used.

By forming the adhesion layer by the dry plating method as described above, the adhesion between the transparent substrate and the adhesion layer can be improved. Further, since the adhesion layer may contain, for example, a metal as a main component, the adhesion to the metal layer is high. Therefore, by disposing the adhesion layer between the transparent substrate and the metal layer, peeling of the metal layer can be suppressed.

The thickness of the adhesion layer is not particularly limited, and is, for example, 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, to suppress reflection of light on the metal layer, the thickness of the adhesion layer is preferably set to 3 nm or more as described above.

The upper limit of the thickness of the adhesion layer is not particularly limited, and even if the thickness is increased to a required thickness or more, the time required for film formation or the time required for etching at the time of wiring formation is also prolonged, resulting in 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 configuration example of the conductive substrate will be described.

As described above, the conductive substrate of the present embodiment may have a transparent substrate, a metal layer, an organic film, and a blackened layer. Further, a layer such as an adhesion layer may be arbitrarily provided.

Specific structural examples will be described below using FIGS. 5A, 5B, 6A, and 6B. 5A, 5B, 6A, and 6B show an example of a cross-sectional view of a surface of the conductive substrate of the present embodiment which is parallel to the lamination direction of the transparent substrate, the metal layer, the organic film, and the blackened layer.

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

Specifically, for example, as shown in the conductive substrate 50A shown in FIG. 5A, the metal layer 52, the organic film 53, and the blackening layer 54 may be sequentially layered on the one surface 51a side of the transparent substrate 51. Further, as shown in the conductive substrate 50B shown in FIG. 5B, the metal layers 52A and 52B, the organic film 53A, 53B, and the black may be respectively formed on the one surface 51a side and the other surface (other surface) 51b side of the transparent substrate 51. The layers 54A, 54B are layered in layers.

Further, as an arbitrary layer, for example, an adhesion layer may be provided. In this case, for example, a structure in which an adhesion layer, a metal layer, an organic film, and a blackening layer are formed in order from the transparent substrate side on at least one surface of the transparent substrate may be employed.

Specifically, for example, as shown in the conductive substrate 60A shown in FIG. 6A, the adhesion layer 55, the metal layer 52, the organic film 53, and the blackening layer 54 may be sequentially laminated on the one surface 51a side of the transparent substrate 51.

In this case, a structure in which an adhesion layer, a metal layer, an organic film, and a blackening layer are laminated on both surfaces of the transparent substrate 51 may be employed. Specifically, as shown in the conductive substrate 60B shown in FIG. 6B, the adhesion layers 55A and 55B, the metal layers 52A and 52B, and the organic film can be sequentially laminated on the one surface 51a side and the other surface 51b side of the transparent substrate 51. 53A, 53B and blackening layers 54A, 54B.

Further, in FIGS. 5B and 6B, when a metal layer, an organic film, and a blackened layer are laminated on both surfaces of a transparent substrate, the transparent substrate 51 is used as a plane of symmetry to be above and below the transparent substrate 51. An example in which the layers of the layers are arranged symmetrically is not limited to this configuration. For example, in FIG. 6B, the structure of one surface 51a side of the transparent substrate 51 can be similarly to the structure of FIG. 5B, and the metal layer 52A, the organic film 53A, and the blackening layer 54A are sequentially laminated without providing the adhesion layer 55A. In the form, the layer laminated on the upper and lower sides of the transparent substrate 51 has an asymmetrical structure.

On the other hand, in the conductive substrate of the present embodiment, the metal layer, the organic film, and the blackened layer are provided on the transparent substrate, so that reflection of light due to the metal layer can be suppressed, and the conductive substrate can be suppressed. Reflectivity.

The degree of reflectance of the conductive substrate of the present embodiment is not particularly limited. For example, in order to improve the visibility of the display when used as a conductive substrate for a liquid crystal 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.

For the measurement of the reflectance, the blackened layer of the conductive substrate can be irradiated with light for measurement. Specifically, for example, when the metal layer 52, the organic film 53, and the blackening layer 54 are sequentially laminated on one surface 51a side of the transparent substrate 51 as shown in FIG. 5A, blackening is performed by irradiating the blackening layer 54 with light. The surface A of the layer 54 was irradiated with light and measured. In the measurement, the blackening layer 54 of the conductive substrate may be irradiated with light having a wavelength of 400 nm or more and 700 nm or less as described above at intervals of, for example, a wavelength of 1 nm, and the average value of the measured values may be used as the reflectance of the conductive substrate.

The conductive substrate of the present embodiment can be preferably used as a conductive substrate for a liquid crystal touch panel. At this time, the conductive substrate may have a structure having a mesh-like wiring.

The conductive substrate having the mesh wiring can be obtained by etching the metal layer, the organic film, and the blackened layer of the conductive substrate of the above-described embodiment.

For example, a two-layer wiring can be used to form a mesh-like wiring. The specific structure is shown in FIG. 7, for example. FIG. 7 is a view showing the conductive substrate 70 having the mesh wiring viewed from the upper surface side in the stacking direction of the metal layer or the like. The wiring substrate is omitted, and the transparent substrate 51 and the wiring formed by patterning the metal layer are omitted. Description of layers other than 71A and 72B. In addition, the wiring 71B which can be seen through the transparent substrate 51 is also shown.

The conductive substrate 70 shown in FIG. 7 has a transparent substrate 51, a plurality of wires 71A parallel to the Y-axis direction in the drawing, and a wire 71B parallel to the X-axis direction. Further, the wirings 71A and 71B are formed by etching a metal layer, and an organic film and a blackened layer (not shown) are formed on the upper surface and/or the lower surface of the wirings 71A and 71B. Further, the organic film and the blackened layer are etched into the same shape as the wirings 71A and 71B.

The arrangement of the transparent substrate 51 and the wirings 71A and 71B is not particularly limited. An example of the configuration of the arrangement of the transparent substrate 51 and the wiring is shown in FIGS. 8A and 8B. 8A and 8B correspond to a cross-sectional view taken along line A-A' of Fig. 7.

First, as shown in FIG. 8A, wirings 71A and 71B may be disposed on the upper and lower surfaces of the transparent substrate 51, respectively. In addition, in FIG. 8A, organic coatings 72A and 72B and blackening layers 73A and 73B which are etched into the same shape as the wiring are disposed on the upper surface of the wiring 71A and the lower surface of the 71B.

Further, as shown in FIG. 8B, one set of the transparent substrate 51 may be used, and one transparent substrate 51 may be interposed, and the wirings 71A and 71B may be disposed on the upper and lower surfaces, and one wiring 71B may be disposed between the transparent substrates 51. At this time, the organic films 72A and 72B and the blackening layers 73A and 73B which are etched into the same shape as the wiring are also disposed on the upper surfaces of the wirings 71A and 71B. Further, as described above, an adhesion layer may be provided in addition to the metal layer, the organic film, and the blackened layer. Therefore, in any of FIGS. 8A and 8B, for example, an adhesion layer may be provided between the wiring 71A and/or the wiring 71B and the transparent substrate 51. When the adhesion layer is provided, it is preferable that the adhesion layer is also etched into the same shape as the wirings 71A and 71B.

The conductive substrate having the mesh wiring shown in FIG. 7 and FIG. 8A can have, for example, metal layers 52A and 52B and an organic film 53A on both surfaces of the transparent substrate 51 as shown in FIG. 5B. 53B and the conductive substrate of the blackening layers 54A and 54B are formed.

If the case of using the conductive substrate of FIG. 5B is described as an example, first, a plurality of linear patterns parallel to the Y-axis direction in FIG. 5B are arranged at a predetermined interval in the X-axis direction, and The metal layer 52A, the organic film 53A, and the blackening layer 54A on one surface 51a side of the transparent substrate 51 are etched. In addition, the X-axis direction in FIG. 5B means the direction parallel to the width direction of each layer. In addition, the Y-axis direction in FIG. 5B means a direction perpendicular to the paper surface in FIG. 5B.

Then, the metal layer 52B and the organic film 53B on the other surface 51b side of the transparent substrate 51 are disposed so as to be arranged in the Y-axis direction at a predetermined interval in a plurality of linear patterns parallel to the X-axis direction in FIG. 5B. The blackening layer 54B is etched.

By the above operation, a conductive substrate having a mesh wiring as shown in FIGS. 7 and 8A can be formed. Further, both surfaces of the transparent substrate 51 may be simultaneously etched. In other words, the etching of the metal layers 52A, 52B, the organic films 53A, 53B, and the blackening layers 54A, 54B can be performed simultaneously. In addition, in FIG. 8A, a conductive substrate having an adhesion layer which is further patterned into the same shape as the wirings 71A and 71B between the wirings 71A and 71B and the transparent substrate 51 can be used by using the same as shown in FIG. 6B. The conductive substrate is also produced by etching.

The conductive substrate having the mesh wiring shown in FIG. 7 can also be formed by using two conductive substrates shown in FIG. 5A or FIG. 6A. When the case where two conductive substrates of FIG. 5A are used is described as an example, two sheets of the conductive substrate shown in FIG. 5A are vacated in a plurality of linear patterns parallel to the X-axis direction. The metal layer 52, the organic film 53, and the blackening layer 54 are etched so as to be spaced apart in the Y-axis direction. Then, it is possible to cross each other by a linear pattern formed on each of the conductive substrates by the etching treatment described above. In the alignment direction, two conductive substrates are bonded together to form a conductive substrate having mesh wiring. The bonding surface when the two conductive substrates are bonded together is not particularly limited. For example, the surface A in FIG. 5A in which the metal layer 52 or the like is laminated may be bonded to the other surface 51b in FIG. 5A in which the metal layer 52 is not laminated, thereby forming the structure shown in FIG. 8B.

Further, for example, the other surface 51b of FIG. 5A in which the metal layer 52 or the like of the transparent base material 51 is not laminated may be bonded to each other to have a cross section of the structure shown in FIG. 8A.

In addition, in FIGS. 8A and 8B, a conductive substrate having an adhesion layer patterned in the same shape as the wirings 71A and 71B between the wirings 71A and 71B and the transparent substrate 51 can be used as shown in FIG. 6A. The conductive substrate shown is produced in place of the conductive substrate shown in FIG. 5A.

The width of the wiring or the distance between the wirings in the conductive substrate having the mesh wiring shown in FIG. 7 , FIG. 8A , and FIG. 8B is not particularly limited, and may be selected according to, for example, the amount of current flowing in the wiring.

In addition, in FIG. 7, FIG. 8A, and FIG. 8B, although the wiring of the linear shape is combined and the mesh (wiring pattern) is formed, it is not limited to this form, and the wiring which comprises a wiring pattern may be. Any shape. For example, the shape of the wiring constituting the mesh wiring pattern may be formed into a zigzag-shaped curved line (a zigzag straight line) or the like so as not to generate a moiré (interference ring) between the images of the liquid crystal panel. shape.

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

Next, a configuration example of a method of manufacturing a conductive substrate of the present embodiment will be described.

A transparent substrate for the metal layer forming step can be prepared in advance. The type of the transparent substrate to be used is not particularly limited, and as described above, a transparent substrate such as a resin substrate (resin film) or a glass substrate that transmits visible light can be preferably used. The transparent substrate can also be previously cut into any size as needed.

Further, as described above, the metal layer preferably has a metal layer 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 have, for example, a step of forming a metal thin film layer by dry plating. Further, the metal layer forming step may have a step of forming a metal thin film layer by dry plating, and a step of forming a metal plating layer by a plating method using a metal thin film layer as a power supply layer by one of wet plating methods.

The dry plating method for 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, or the like can be used. Further, as the vapor deposition method, a vacuum deposition method can be preferably used. As the dry plating method for the step of forming the metal thin film layer, in particular, from the viewpoint of easily controlling the film thickness, it is more preferable to use a sputtering method.

Next, the step of forming a metal plating layer will be described. The conditions in the step of forming the metal plating layer by the wet plating method, that is, the conditions of the plating treatment are not particularly limited, and the conditions according to the usual methods may be employed. For example, a metal plating layer can be formed by supplying a substrate on which a metal thin film layer is formed to a plating bath in which a metal plating solution is injected, and controlling the current density or the transport speed of the substrate.

The preferred thickness or the like of the preferred material or metal layer which can be used for the metal layer is as described above, and thus the description thereof is omitted here.

Next, the organic film forming step will be described.

In the organic film forming step, an organic film can be formed on the metal layer.

As described above, by providing the organic film between the metal layer and the blackening layer, the adhesion of the blackened layer can be improved, and the reflectance of the conductive substrate can be suppressed.

The organic film can be formed by the above-described method for producing an organic film. In addition, the organic solution or the like used in forming the organic film has been described above, and thus the description thereof is omitted here.

Next, the blackening layer forming step will be described.

In the blackening layer forming step, the method of forming the blackening layer is not particularly limited, and it can be formed by any method.

When the blackening layer is formed in the blackening 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, from the viewpoint of easily controlling the film thickness, it is more preferable to use a sputtering method. Further, as described above, one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen may be added to the blackening layer. In this case, a reactive sputtering method can be preferably used.

Further, as described above, the blackening layer may be formed by a wet method such as electroplating.

However, since the coloring or other characteristics of the blackening layer may be affected by dissolving the material constituting the organic film in the plating solution and entering the blackening layer when the blackening layer is formed, it is preferable to use the dry method. Film formation.

The preferred thickness or the like of the preferred material or blackening layer which can be used for the blackening layer is as described above, and thus the description thereof is omitted here.

In the method for producing a conductive substrate of the present embodiment, any step other than the above steps may be carried out.

For example, when an adhesion layer is formed between the transparent substrate and the metal layer, an adhesion layer forming step of forming an adhesion layer on the surface of the transparent substrate on which the metal layer is formed may be performed. When implementing secret In the layer forming step, the metal layer forming step may be performed after the adhesion layer forming step, in which the metal thin film layer may be formed on the substrate on which the adhesion layer is formed on the transparent substrate. .

In the adhesion layer forming step, the film formation 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, a vapor deposition method, or the like can be preferably used. When the adhesion layer is formed by a dry method, it is more preferable to use a sputtering method from the viewpoint of easy control of the film thickness. Further, as described above, one or more elements selected from the group consisting of carbon, oxygen, hydrogen, and nitrogen may be added to the adhesion layer, and in this case, a reactive sputtering method may be further preferably used.

The preferred thickness or the like of the preferred material or the adhesive layer which can be used for the adhesive layer is as described above, and thus the description thereof is omitted here.

The conductive substrate obtained by the method for producing a conductive substrate of the present embodiment can be used for various applications such as a touch panel. Further, when used in various applications, it is preferable to pattern the metal layer, the organic film, and the blackened layer contained in the conductive substrate of the present embodiment. Further, when the adhesion layer is provided, it is preferable to pattern the adhesion layer. The metal layer, the organic film, the blackened layer, and the adhesion layer may be patterned in accordance with a desired wiring pattern, for example, preferably a metal layer, an organic film, a blackened layer, or sometimes a dense layer. The layered pattern is patterned into the same shape.

Therefore, the method for producing a conductive substrate of the present embodiment may have a patterning step of patterning the metal layer, the organic film, and the blackened layer. Further, when the adhesion layer is formed, the patterning step may be a step of patterning the adhesion layer, the metal layer, the organic film, and the blackening layer.

The specific procedure for the patterning step is not particularly limited, and any program can be utilized. To implement. For example, when the conductive substrate 50A in which the metal layer 52, the organic film 53 and the blackening layer 54 are laminated on the transparent substrate 51 as shown in FIG. 5A, firstly, the surface A on the blackening layer 54 may be disposed on the surface A. The mask configuration step of the mask of the pattern to be used. Next, an etching step of supplying an etching liquid to the upper surface of the blackening layer 54, that is, the one side on which the mask is disposed, may be performed.

The etching liquid used in the etching step is not particularly limited, and can be arbitrarily selected depending on the material of the layer constituting the etching. For example, the etching liquid may be changed for each layer, or the same etching liquid may be used to simultaneously etch the metal layer, the organic film, the blackening layer, and sometimes the adhesion layer.

Further, as shown in FIG. 5B, the conductive substrate 50B in which the metal layers 52A and 52B, the organic films 53A and 53B, and the blackening layers 54A and 54B are laminated on one surface 51a and the other surface 51b of the transparent substrate 51 can be also performed. Patterned patterning step. At this time, for example, a mask disposing step of arranging a mask having a predetermined pattern on the surface A and the surface B on the blackening layers 54A and 54B can be performed. Next, an etching step of supplying the etching liquid to the surface A and the surface B on the blackening layers 54A and 54B, that is, the surface side on which the mask is disposed, may be performed.

The pattern formed in the etching step is not particularly limited, and it may be any shape. For example, in the case of the conductive substrate 50A shown in FIG. 5A, the metal layer 52, the organic film 53, and the blackening layer may be applied in such a manner as to include a plurality of straight lines or zigzag curved lines (zigzag straight lines) as described above. 54 forms a pattern.

Further, in the case of the conductive substrate 50B shown in FIG. 5B, a pattern may be formed on the metal layer 52A and the metal layer 52B so as to be a mesh wiring. In this case, it is preferable that the organic film 53A and the blackening layer 54A have the same shape as the metal layer 52A, and the organic film 53B and the blackening layer 54B are patterned in the same shape as the metal layer 52B.

Further, for example, in the patterning step, the metal layer 52 of the conductive substrate 50A or the like may be patterned, and then a lamination step of laminating two or more patterned conductive substrates may be performed. In the case of laminating, for example, a laminated conductive substrate having a mesh wiring may be obtained by laminating the patterns of the metal layers of the respective conductive substrates.

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

The conductive substrate obtained by the method for producing a conductive substrate of the present embodiment has a structure in which an organic film and a blackened layer are laminated on a metal layer formed on at least one surface of the transparent substrate. Further, since the organic film is produced by the above-described method for producing an organic film, a uniform film can be formed.

Therefore, since the adhesion between the blackened layer and the underlying metal layer and the organic film as the blackened layer can be particularly improved, and the peeling of the blackened layer can be suppressed, the etching property of the blackened layer can be improved. In addition, since the fine wiring processing can be easily performed on the metal layer or the blackening layer or the like, it is possible to suppress the reflection of light on the surface of the metal layer and to form a conductive substrate that suppresses the reflectance.

Further, the visibility of the display can be improved when used for, for example, a touch panel or the like.

<Example>

Hereinafter, specific examples and comparative examples will be described, but the present invention is not limited to these examples.

(evaluation method)

First, a method of evaluating the adhesion of the blackened layer of the obtained conductive substrate will be described.

As shown in FIG. 9 , a blackening layer formed on the conductive substrate to the blackened layer was formed into a length of 11 lengths at intervals of 1.0 mm using a cutting tool (Cross Cut Kit 1.0MM manufactured by Precision Gate & Tool Company). 20 mm longitudinal cutting line 91a.

Next, using the same cutting tool, 11 transverse cutting lines 91b having a length of 20 mm were formed so as to be orthogonal to each other at a distance of 1.0 mm so as to be orthogonal to the previously formed longitudinal cutting line 91a.

By the above steps, as shown in FIG. 9, 11 cut lines in the longitudinal direction and the lateral direction are used to form a lattice-like cut on the blackened layer.

Then, the tape for adhesion evaluation (Elcometer 99 tape manufactured by Elcometer Co., Ltd.) was adhered to cover the lattice-shaped cuts, and then adhered sufficiently.

After 30 seconds passed after the adhesion evaluation tape was applied, the tape for adhesion evaluation was quickly peeled off in the direction as long as 180° with respect to the measurement surface.

After the adhesive tape for adhesion evaluation is peeled off, a metal layer (organic layer) is formed under the blackening layer in the evaluation region 92 in FIG. 9 surrounded by the lattice-shaped vertical cutting line 91a and the horizontal cutting line 91b. The area is evaluated 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% is less than 5%, it is evaluated as 4B, when 5% or more is less than 15%, it is evaluated as 3B, and when 15% or more is less than 35%. The evaluation was 2B, and when it was 35% or more and less than 65%, it was evaluated as 1B, and when it was 65% or more, it was evaluated as 0B. Regarding this evaluation, 0B is the lowest adhesion of the blackened layer, and 5B is the highest adhesion of the blackened layer.

As a result of the adhesion test, when it is 4B and 5B, it can evaluate that the adhesiveness of a blackening layer is sufficient.

(production conditions of the sample)

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

[Example 1]

(Adhesion layer forming step)

An adhesive layer was formed on one surface of a transparent substrate made of a polyethylene terephthalate resin (PET) having a width of 570 mm and a thickness of 50 μm. Further, the transparent substrate made of a polyethylene terephthalate resin used as a transparent substrate was 97% after the total light transmittance was evaluated by the method specified in JIS K 7361-1.

In the adhesion layer forming step, a Ni-Cu alloy layer containing oxygen was formed as an adhesion layer by a roll-to-roll sputtering apparatus to which a target of Ni-17 wt% Cu alloy was attached. The film formation step of the adhesion layer will be described below.

The above transparent substrate which was previously heated to 60 ° C and removed moisture was placed in the chamber of the sputtering apparatus.

Next, after evacuating the chamber to 1 × 10 ^-3 Pa, argon gas and oxygen gas were introduced to bring the pressure in the chamber to 1.3 Pa. Further, at this time, the atmosphere in the chamber was made up of oxygen at a volume ratio of 30%, and the rest was argon.

Next, electric power was supplied to the target in this atmosphere, and while the transparent substrate was conveyed, the adhesion layer was formed to have a thickness of 20 nm on one surface of the transparent substrate.

(metal layer forming step)

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

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

In the metal thin film layer forming step, a base material having an adhesion layer formed on a transparent substrate in the adhesion layer forming step is used as a base material, and a copper thin film layer as a metal thin film layer is formed on the adhesion layer.

The roll-to-roll sputtering apparatus is used in the same manner as in the case of the adhesion layer, except that a copper target is used and a argon gas is supplied to the inside of the chamber in which the substrate is provided, and an argon atmosphere is formed. A metal thin film layer is formed.

Film formation was performed so that the thickness of the copper thin film layer which is a metal thin film layer was 150 nm.

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

(organic film forming step)

In the organic film forming step, an organic film is formed on the metal layer of the substrate on which the adhesion layer and the metal layer are formed on the transparent substrate. In the organic film forming step, the organic film forming apparatus described with reference to FIGS. 3 and 4 is used to form an organic film.

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

As the conveying device, the above-mentioned base material was placed on a winding roller of an organic film manufacturing apparatus having a conveying method of a roll-to-roll type (not shown), and was wound at a conveying speed of 3.5 m/min by winding with a winding roller. Start feeding the substrate.

The first water washing means 12 is provided on the upstream side in the transport direction of the substrate, and the surface of the metal layer is cleaned on the one surface 11a which is the surface on which the organic film is formed.

Further, a nozzle 21 is provided on the downstream side in the transport direction of the first water washing means 12, and the organic solution is supplied and applied to the substrate 11 from a plurality of nozzle holes included in the nozzle 21. In addition, an injection pattern formed on the surface of the substrate 11 by using the organic solution supplied from the nozzle hole 211 is an elliptical nozzle having a short diameter of 5 mm and a long diameter of 70 mm (model: INVV11550, manufactured by Kirinoikeuchi). At this time, each nozzle hole is provided so that the long diameter of the ejection pattern is parallel to the height direction.

Further, seven nozzle holes 211 are provided at equal intervals in the height direction, and the pitch between the nozzle holes 211 is 70 mm. The organic solution was supplied from the nozzle 21 at a flow rate of 19 L/min.

Further, the liquid film forming means 13 is provided on the downstream side of the nozzle 21 in the transport direction, and the organic solution is a film-like liquid flow having a width of 320 mm, and the surface of the base material is brought into contact with the film-like liquid flow of the organic solution. The organic solution is supplied from the supply port of the liquid film forming means 13 provided in the upper portion in the height direction of the substrate. The organic solution was supplied from the liquid film forming means 13 at a flow rate of 54 L/min.

After that, the excess organic solution adhering to the surface of the substrate 11 is washed with water and removed by the second water washing means 15 provided on the downstream side in the transport direction of the substrate, and then dried by a drying means not shown. A winding roller not shown entangles the substrate on which the organic film is formed.

(blackening layer forming step)

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

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

First, a laminate in which an adhesion layer, a metal layer, and an organic film are laminated on a transparent substrate is placed in a chamber of a sputtering apparatus.

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

Next, electric power was supplied to the target in this atmosphere, and a blackened layer having a thickness of 30 nm was formed on the organic film while transporting the substrate.

According to the above steps, it is obtained that the organic film is formed on the upper surface of the metal layer, that is, the surface opposite to the surface of the metal layer opposite to the adhesion layer, and the blackened layer is formed on the surface of the metal substrate, and the layer is densely laminated on the transparent substrate. A conductive substrate having a layer, a metal layer, an organic film, and a blackened layer.

The obtained conductive substrate was 5B after the adhesion test.

[Embodiment 2]

In the organic film forming step, a circular nozzle having a diameter of 70 mm formed on the surface of the substrate 11 by the organic solution supplied from the nozzle hole 211 using the organic film forming apparatus shown in FIGS. 1 and 2 is used. A conductive substrate was produced in the same manner as in Example 1 except for this point.

The obtained conductive substrate was subjected to the above adhesion test and was 4B.

[Comparative Example 1]

A conductive substrate was produced in the same manner as in Example 1 except that the organic film production apparatus shown in FIG. 1 and FIG. 2 was not used to supply the organic solution from the nozzle to the substrate 11 in the organic film formation step.

The obtained conductive substrate was 3B after the adhesion test described above.

According to the results of the first embodiment, the second embodiment, and the comparative example 1, it was confirmed that the organic solution was supplied to the substrate by using the nozzle and the liquid film forming means in combination, and the organic film was formed, whereby the adhesion of the blackened layer can be improved. In other words, the reason is that the organic film is uniformly formed on the surface of the metal layer.

Further, according to the results of the first embodiment and the second embodiment, it was confirmed that the nozzle can be particularly improved by using a nozzle having a nozzle hole having an elliptical shape in which the ejection pattern formed on the surface of the substrate is formed. Adhesion.

From these results, it was confirmed that a uniform organic film can be formed on the substrate by using the nozzle and the liquid film forming means in combination.

The method for producing an organic film, the method for producing a conductive substrate, and the organic film production device have been described above by way of the embodiments and the examples, but the present invention is not limited to the above-described embodiments and examples. Various modifications and changes can be made without departing from the spirit and scope of the invention.

The present application claims the priority of Japanese Patent Application No. 2015-195190, filed on Sep. 30, 2015, to the Japan Patent Office, the entire contents of in.

11‧‧‧Substrate

11a‧‧‧One side

12‧‧‧First washing method

13‧‧‧ Liquid film formation means

14‧‧‧ liquid film flow

15‧‧‧Second washing means

21‧‧‧ nozzle

Claims (5)

A method for producing an organic film, which comprises supplying an organic solution to a surface of a sheet-like substrate to form an organic film, and forming a surface of the substrate which is transported in a height direction of the substrate in a direction from a nozzle and a liquid film Providing the organic solution, the nozzle is provided with a plurality of nozzle holes so as to face the surface of the substrate, and the liquid film forming means has a supply port provided at an upper portion in the height direction of the substrate, and the liquid film forming means The organic solution is supplied from the supply port so as to be in a film-like liquid flow, and the surface of the substrate is brought into contact with the film-like liquid flow of the organic solution. The method for producing an organic film according to the first aspect of the invention, wherein the nozzle has an elliptical shape formed on the surface of the substrate by the organic solution supplied from the nozzle hole. A method for producing a conductive substrate, comprising: a metal layer forming step of forming a metal layer on at least one surface of the transparent substrate; an organic film forming step of forming an organic film on the upper surface of the metal layer; and the organic film forming step a blackening layer forming step of forming a blackening layer on the upper surface; wherein, in the organic film forming step, an organic film is formed on the upper surface of the metal layer by the method for producing an organic film according to claim 1 or 2 . An organic film manufacturing apparatus which supplies an organic solution to a surface of a sheet-like substrate and forms an organic film, the organic film manufacturing apparatus including: a conveying means that conveys in a height direction of the base material; a plurality of nozzles Providing a nozzle hole in a manner opposite to a surface of the substrate; The liquid film forming means has a supply port provided in an upper portion of the base material in a height direction, and the organic solution is in a film form, and the surface of the base material is in contact with the film-like liquid flow of the organic solution. The method is supplied from the supply port. The organic film production apparatus according to claim 4, wherein the nozzle has an elliptical shape formed on the surface of the substrate by the organic solution supplied from the nozzle hole.