CN108027689B - Method for producing organic film, method for producing conductive substrate, and apparatus for producing organic film - Google Patents

Method for producing organic film, method for producing conductive substrate, and apparatus for producing organic film Download PDF

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Publication number
CN108027689B
CN108027689B CN201680055845.8A CN201680055845A CN108027689B CN 108027689 B CN108027689 B CN 108027689B CN 201680055845 A CN201680055845 A CN 201680055845A CN 108027689 B CN108027689 B CN 108027689B
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substrate
layer
organic
film
organic film
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CN108027689A (en
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须田贵广
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B1/00—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means
    • B05B1/14—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means with multiple outlet openings; with strainers in or outside the outlet opening
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C13/00—Means for manipulating or holding work, e.g. for separate articles
    • B05C13/02—Means for manipulating or holding work, e.g. for separate articles for particular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
    • B05C5/005—Curtain coaters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C9/00—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
    • B05C9/06—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying two different liquids or other fluent materials, or the same liquid or other fluent material twice, to the same side of the work
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Abstract

A method for producing an organic film by supplying an organic solution to a surface of a sheet-like substrate to form the organic film, wherein the organic solution is supplied from a nozzle provided with a plurality of nozzle holes so as to face the surface of the substrate and a liquid film forming unit having a supply port provided at an upper portion of the substrate in a height direction, and the organic solution is supplied from the supply port so that the organic solution becomes a film-like liquid flow and the surface of the substrate comes into contact with the film-like liquid flow of the organic solution.

Description

Method for producing organic film, method for producing conductive substrate, and apparatus for producing organic film
Technical Field
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.
Background
The capacitive touch panel converts position information of an object approaching on a panel surface into an electrical signal by detecting a change in capacitance caused by the object approaching the panel surface. 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 to be difficult to visually confirm.
Therefore, as a material for the conductive layer of the capacitive touch panel, a material having a low reflectance and being difficult to visually confirm is used, and the wiring is formed on the transparent substrate or the transparent thin film.
For example, patent document 1 discloses a capacitive digital touch panel in which a touch panel portion is formed of a plurality of transparent sheet electrodes on which a signal pattern and a GND pattern are printed on a PET film by an ITO film.
However, in recent years, the screen size of a display having a touch panel has been increased, and accordingly, a conductive substrate for a touch panel is also required to have a large area. However, ITO has a high resistance value and is likely to cause signal degradation, and thus a conductive substrate using ITO is not suitable for a large panel.
Therefore, as a material of the conductive layer, use of a metal such as copper instead of ITO is being studied. However, since metals have metallic luster and cause a problem that visibility of a display is reduced by reflection, conductive substrates on which a blackened layer composed of a metal such as copper and a black material is formed have been studied.
For example, patent document 2 discloses a film-like touch panel sensor including stripe-like copper wirings on portions of a front surface and a back surface of the film, which portions need to be seen through, and black copper oxide films on visible sides of the copper wirings on the front surface and the back surface.
Further, according to the method for manufacturing a thin-film touch panel sensor disclosed in patent document 2, the method includes a step of forming a resist layer on a copper thin film supported by the thin film, a step of processing at least the resist layer into a stripe-shaped wiring pattern and a lead-out wiring pattern by photolithography, a step of removing the exposed copper thin film by etching to form stripe-shaped copper wirings and lead-out copper wirings, and a step of blackening the copper wirings.
However, the method disclosed in patent document 2, in which the surface of the copper wiring is blackened after the copper wiring is formed, involves a large number of steps. Therefore, a method of forming a metal layer and a blackened layer on the surface of the metal layer on a base material, and then patterning the metal layer and the blackened layer by etching or the like to form a conductive substrate has been studied.
In addition, in order to make the metal wiring for patterning the metal layer more inconspicuous, it is effective to perform fine wiring processing of the metal layer and the black layer formed on the upper surface thereof. However, the blackened layer has low reactivity with an etching solution, and when the metal layer and the blackened layer are etched for fine wiring processing, the blackened layer may be peeled 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 has been studied.
The organic film may be formed by applying an organic solution, which is a raw material of the organic film, to the surface of the metal layer of the substrate formed up to the metal layer, and the organic film may be formed by forming a blackened layer on the organic film after the organic film is formed, thereby forming a structure in which the organic film is provided between the metal layer and the blackened layer.
The present inventors have conventionally performed the formation of an organic film by the following method.
First, while the substrate is conveyed with the width direction of the substrate formed to the metal layer as the height direction, a liquid flow of a film-like organic solution formed by supplying the organic solution from the upper portion of the substrate in the height direction is brought into contact with the surface of the metal layer to coat the surface of the metal layer with the organic solution. Subsequently, the surface coated with the organic film is washed with water to remove excess organic solution, and then dried.
< Prior Art document >
< patent document >
Patent document 1: japanese laid-open patent application No. 2004-213114
Patent document 2: japanese unexamined patent publication No. 2013-206315
Disclosure of Invention
< problems to be solved by the present invention >
However, according to the above-described method for forming an organic film, the thickness of the organic film formed on the surface of the metal layer is not constant, or unevenness such as a portion where no organic film is formed is likely to occur on a part of the surface of the metal layer. The non-uniformity of the organic film causes a problem that the adhesion of the black layer formed on the upper surface of the organic film is reduced.
In view of the above-described problems of the prior art, an object of one aspect of the present invention is to provide a method for producing an organic film, which can form a uniform organic film on a film formation surface.
< solution to problem >
In order to solve the above problems, an aspect of the present invention provides a method for producing an organic film by supplying an organic solution to a surface of a sheet-shaped substrate to form the organic film, wherein the organic solution is supplied from a nozzle provided with a plurality of nozzle holes so as to face the surface of the substrate and a liquid film forming unit having a supply port provided at an upper portion of the substrate in a height direction, and the organic solution is supplied from the supply port so that the organic solution becomes a film-like liquid flow and the surface of the substrate comes into contact with the film-like liquid flow of the organic solution.
< effects of the invention >
According to one aspect of the present invention, a method for producing an organic film capable of forming a uniform organic film on a film to be formed can be provided.
Drawings
Fig. 1 is an explanatory diagram of 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.
Fig. 3 is an explanatory diagram of a configuration example of the method for producing an organic film according to the 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 the conductive substrate according to the embodiment of the present invention.
Fig. 5B is a sectional view of the conductive substrate according to the embodiment of the present invention.
Fig. 6A is a cross-sectional view of the conductive substrate according to the embodiment of the present invention.
Fig. 6B is a sectional view of the conductive substrate according to the embodiment of the present invention.
Fig. 7 is a plan view of a conductive substrate having mesh-shaped 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 scribe line formed when the adhesion test is performed in examples and comparative examples.
Detailed Description
Hereinafter, one embodiment of a method for producing an organic film, a method for producing a conductive substrate, and an apparatus for producing an organic film according to the present invention will be described.
(method for producing organic coating film)
In the method for producing an organic film according to the present embodiment, an organic solution can be supplied to the surface of a sheet-like substrate to form an organic film.
The organic solution can be supplied to the surface of the substrate conveyed with the width direction of the substrate as the height direction by the nozzle and the liquid film forming unit.
Here, the nozzle may have a structure in which a plurality of nozzle holes are provided so as to face the surface of the base material. The liquid film forming unit has a supply port provided at an upper portion of the substrate in the height direction, and the organic solution can be supplied from the supply port so that the organic solution becomes a film-like liquid flow and so that the surface of the substrate comes into contact with the film-like liquid flow of the organic solution.
One configuration example of a conventional method for producing an organic film, which is being studied when forming an organic film on a substrate, will be described with reference to fig. 1 and 2.
Fig. 1 is a view showing a step of forming an organic film on a substrate 11, as viewed from a direction perpendicular to one surface 11a of the substrate 11, which is a surface to be film-formed on which the organic film is formed. Fig. 2 is a cross-sectional view taken along line a-a' of fig. 1.
In fig. 1, the base material 11 is a long sheet and is conveyed in the direction indicated by a block arrow 1 shown in fig. 1 along the X-axis direction in the figure. At this time, the sheet-like base material 11 is held and conveyed with the width direction being the height direction, that is, with the width direction of the base material 11 being set along the height direction. The height direction means the Z-axis direction shown in the figure, and the X-axis direction is the horizontal direction.
A first washing unit 12 for washing one surface 11a of the substrate 11, which is a surface on which the organic film is formed, may be provided on the upstream side of the substrate 11 in the transport direction. The first washing unit 12 may wash the one surface 11a of the substrate 11 by spraying water through a nozzle, for example. The first washing unit 12 may be provided with a plurality of nozzles so that the entire surface 11a of the substrate 11 to be conveyed can be washed. The first washing unit 12 may have a structure in which a plurality of nozzles are arranged along the height direction, that is, along the Z axis in the figure, for example.
Further, an organic solution as a raw material of the organic film may be supplied downward in the drawing from a supply port of the liquid film forming unit 13 provided at an upper portion in the height direction of the substrate 11 to be conveyed. At this time, as shown in fig. 2, the liquid film forming unit 13 may form a liquid film flow 14 as a film-like liquid flow from a supply port 131 of the liquid film forming unit 13, and supply the organic solution so that the liquid film flow 14 contacts the surface of the substrate 11. The organic solution can be applied to the one surface 11a of the substrate 11 by forming the liquid film flow 14 from above the substrate 11 and supplying the organic solution from the liquid film forming unit 13 so that the liquid film flow 14 comes into contact with the surface of the substrate 11.
Next, a second water washing unit 15 may be further provided on the downstream side of the liquid film forming unit 13. The second washing unit 15 can wash and remove the excess organic solution applied to the substrate 11 with water. The second washing unit 15 is not particularly limited as long as it can wash the surface of the substrate 11 coated with the organic solution with water, and may have a similar configuration to the first washing unit 12.
However, according to this method for producing an organic film, the organic film formed on the surface of the metal layer tends to be uneven. The non-uniformity of the organic film causes a problem in that the adhesion of the black layer formed on the upper surface of the organic film is reduced.
The present inventors have made intensive studies on the reason why the organic film becomes uneven when the organic solution is applied to the substrate and the organic film is formed 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 so that the liquid film flow of the organic solution formed by supplying the organic solution from above to below the substrate conveyed in a state in which the substrate is in the height direction is brought into contact with the surface of the substrate. According to the organic solution coating method, since the organic solution flows from the upper portion to the lower portion along the surface of the substrate to be conveyed, the impact on the substrate when the organic solution is in contact with the surface of the substrate is smooth. In addition, 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 applying the organic solution to the surface of the substrate is not completely completed, and the formed organic film is likely to become uneven. The present inventors have completed the present invention based on the problems of the conventional method for producing an organic coating.
A method for producing an organic film according to the present embodiment will be described with reference to fig. 3 and 4. The same components as those in fig. 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, as viewed from a direction perpendicular to one surface 11a of the substrate 11, which is a surface to be film-formed on which the organic film is formed. Fig. 4 is a cross-sectional view taken along line B-B' of fig. 3.
In fig. 3, the base material 11 is in the form of a long sheet and is conveyed in the direction indicated by a block arrow 1 in the figure along the X-axis direction in the figure.
Fig. 3 shows an example in which a long sheet-like base material is used, but the present invention is not limited to this embodiment. However, since continuous production is possible, a long sheet is preferable. The type of the substrate is not particularly limited, and a substrate having an organic film formed on at least one surface thereof may be used. For example, as described below, in order to manufacture a conductive substrate in which a metal layer, an organic film, and a black layer are laminated on a transparent substrate, a substrate in which a metal layer is formed on a transparent substrate may be used as the substrate 11 in this case when forming an organic film.
At this time, the sheet-like base material 11 is held and conveyed with the width direction being the height direction, that is, with the width direction of the base material 11 being set along the height direction. The height direction means the Z-axis direction shown in the figure, and the X-axis direction is the horizontal direction.
The organic solution may be supplied so that the organic solution as a raw material of the organic film is directed downward in the drawing from a supply port of the liquid film forming unit 13 disposed at an upper portion in the height direction of the substrate 11 to be conveyed to form a liquid film flow 14, and so that the liquid film flow 14 comes into contact with the surface of the substrate 11. 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, and therefore, the description thereof is omitted here.
As described above, when the organic solution is supplied and applied to only one surface 11a of the substrate 11 by the liquid film forming unit 13, the formed organic film may become uneven. Therefore, in the apparatus for producing an organic film according to the present embodiment, in addition to the liquid film forming unit, the organic solution may be supplied to the one surface 11a of the substrate 11, which is a surface on which the organic film is formed, 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 so as to face the surface, i.e., one surface 11a, of the substrate 11. The organic solution is supplied from the plurality of nozzle holes 211 of the nozzle 21 to the one surface 11a of the substrate 11, whereby the organic film can be applied to the one surface 11a of the substrate 11.
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 contacts the substrate is smooth. Therefore, when an organic solution is applied to the surface of the substrate 11 on which the organic film is formed only by the liquid film forming means and the organic film is formed, the organic film may become uneven. In contrast, when the organic solution is applied to the surface of the substrate on which the organic film is formed by the nozzle, the impact on the substrate when the organic solution contacts the substrate can be increased. Therefore, by applying an organic solution to the surface of the substrate by the liquid film forming means and the nozzle to form an organic film, 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 that the organic solution be arranged in the Z-axis direction in fig. 4, that is, in the height direction so that the organic solution can be applied to the entire one surface 11a of the base material 11 conveyed in the X-axis direction which is a direction perpendicular to the paper surface in fig. 4.
The organic solution supplied from the nozzle hole 211 and applied to the substrate 11 is particularly preferably a continuous coating film of the organic solution. Therefore, the ejection patterns formed by applying the organic solution to the substrate 11 through the nozzle holes 211 adjacent to each other in the height direction are preferably connected to each other, and more preferably partially overlap each other.
The shape of the nozzle hole 211 of the nozzle 21 is not particularly limited. For example, a nozzle having a circular or elliptical spray pattern formed on the surface of the base material by the organic solution supplied from a nozzle hole of the nozzle can be preferably used.
However, from the viewpoint of improving the uniformity of the organic film to be formed, it is preferable to give a stronger impact to the substrate when the organic solution is applied to the substrate 11 by the nozzle 21. Further, according to the study of the inventors of the present invention, a particularly strong impact is given to a spray pattern formed on a base material by an organic solution supplied from a nozzle hole, that is, a case where the shape of the pattern formed on the base material when the organic solution is supplied from the nozzle hole to the base material is an ellipse.
Therefore, the nozzle preferably has an elliptical spray pattern formed on the surface of the base material by the organic solution supplied from the nozzle hole.
The nozzle may have a plurality of nozzle holes, and the shape of the spray pattern herein refers to the shape when the organic solution is supplied onto the substrate from each nozzle hole.
In the case where the spray 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 to 20.
Fig. 3 shows an example in which the nozzle 21 and the liquid film forming unit 13 are provided in this order from the upstream side in the transport direction of the substrate 11, but the order of the coating units when the organic solution is coated on the substrate 11 is not particularly limited. For example, the organic solution may be applied to the substrate 11 by the nozzle 21 after the organic solution is applied to the substrate 11 by the liquid film forming unit 13. In addition, the organic solution may be simultaneously applied on the substrate 11 by the liquid film forming unit 13 and the nozzle 21.
Fig. 3 shows an example in which the organic solution is applied 1 time by the liquid film forming means and the organic solution is applied 1 time by the nozzle when the organic solution is applied to the substrate 11, but the present invention is not limited to this embodiment. For example, a plurality of liquid film forming units and/or nozzles may be provided in the transport path of the substrate 11, and the organic solution may be applied to the substrate 11a plurality of times by the liquid film forming units and/or nozzles.
The type of the organic solution 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.
A first washing unit 12 for washing the one surface 11a of the substrate 11 may be provided on the upstream side in the transport direction of the substrate 11.
Further, the second washing unit 15 may be provided downstream of the liquid film forming unit 13 and the nozzle 21 in the transport direction of the substrate 11. The first washing unit 12 and the second washing unit 15 can be configured in the same manner as in the case of the conventional organic film production method, and therefore, the description thereof is omitted here.
Although fig. 3 and 4 illustrate the case where the organic film is formed only on one surface 11a of the substrate 11, the organic film may be formed simultaneously on a surface facing the one surface 11a, that is, the other surface 11b shown in fig. 4.
Specifically, for example, a liquid film forming unit and a nozzle may be similarly provided on the other surface 11b side of the substrate 11 to be conveyed, whereby the organic film may be formed on the other surface 11 b.
When the organic film is formed also on the other surface 11b, it is particularly preferable that the nozzle provided on the one surface 11a side and the nozzle provided on the other surface side are provided at the same position as seen in the conveyance direction of the substrate so that the nozzle holes face each other with the substrate 11 interposed therebetween. This is because the organic solution is supplied from both surfaces of the substrate 11 at the same pressure, and thereby occurrence of warpage or the like on the substrate 11 can be suppressed.
It is preferable that the liquid film forming unit, the first water washing unit, the second water washing unit, and the like are disposed at the same position as the nozzles as viewed in the transport direction of the substrate 11.
According to the method for producing an organic film of the present embodiment, as described above, a uniform organic film can be formed on the surface of the substrate on which the organic film is formed. Therefore, when the organic film is used for forming a conductive substrate in which a metal layer, an organic film, and a black layer are laminated, for example, the adhesion of the black layer can be improved.
In addition, the case where the organic film is formed on the substrate has been described above by way of example, and a uniform liquid film can be formed on the substrate by supplying a liquid onto the substrate from a liquid film forming unit and a nozzle. Therefore, for example, a cleaning liquid such as water is used instead of the organic solution, and the cleaning liquid is supplied from the liquid film forming unit and the nozzle, whereby the method of cleaning the surface of the substrate can be used. In addition, the method can be used as a method for producing various coatings other than organic coatings.
(apparatus for producing organic coating)
Next, a description will be given of a configuration example of the organic film manufacturing apparatus of the present embodiment.
Note that, since the organic film production apparatus of the present embodiment can be suitably applied to the above-described organic film production method, some of the matters already described in the organic film production method will be omitted.
According to the organic film manufacturing apparatus of the present embodiment, the organic film can be formed by supplying the organic solution to the surface of the sheet-like base material, and the following configuration can be provided.
And a conveying unit which conveys the substrate with the width direction of the substrate as the height direction.
And a nozzle provided with a plurality of nozzle holes so as to face the surface of the base material.
And a liquid film forming unit having a supply port provided at an upper portion of the substrate in a height direction, the liquid film forming unit supplying the organic solution from the supply port so that the organic solution is in a film shape and so that a surface of the substrate is in contact with a film-shaped liquid flow of the organic solution.
An organic film production apparatus according to the present embodiment will be described with reference to fig. 3 and 4.
According to the organic film manufacturing apparatus of the present embodiment, the organic film can be formed by supplying and applying the organic solution to the conveyed substrate.
Therefore, the organic film manufacturing apparatus of the present embodiment may include a conveying unit that conveys the substrate. The structure of the conveying unit is not particularly limited, and for example, when a long sheet-like base material shown in fig. 3 is used as the base material, a conveying unit that conveys the base material by a roll-to-roll method may be used. The transport unit using the roll-to-roll system is a transport unit that feeds a substrate from a take-off roll, around which the substrate is wound in a coil shape in advance, and transports the substrate by winding the substrate on which the organic film is formed around the take-off roll.
The unit for supplying the organic solution to the surface of the substrate conveyed by the conveying unit on which the organic film is formed may include a nozzle and a liquid film forming unit.
As shown in fig. 3 and 4, the nozzle 21 may have a plurality of nozzle holes 211, and the organic solution may be supplied from the nozzle holes 211 to the surface of the substrate 11 to be conveyed on which the organic film is formed, and applied.
The shape of the nozzle hole of the nozzle is not particularly limited, and for example, it is preferable that the nozzle has an elliptical spray pattern formed on the surface of the base material by the organic solution supplied from the nozzle hole.
The other points of the nozzle are not described because the method for producing the organic coating has already been described.
Further, since a structural example of the liquid film forming unit has already been described, the description thereof is omitted here.
Fig. 3 shows an example of the configuration of an organic film manufacturing apparatus having one nozzle 21 and one liquid film forming unit 13, respectively, but the present invention is not limited to this embodiment. For example, a plurality of nozzles and/or a plurality of liquid film forming units may be provided in the transport path of the substrate 11.
Fig. 3 shows an example in which the nozzle 21 and the liquid film forming unit 13 are provided in this order from the upstream side in the transport direction of the substrate 11, but the present invention is not limited to this. For example, the liquid film forming unit 13 and the nozzle 21 may be provided in this order from the upstream side in the transport direction of the substrate 11. In addition, the nozzle 21 and the liquid film forming unit may be provided on a position on the substrate 11 on which the cutting is superimposed as viewed in the conveying direction.
The organic film production apparatus of the present embodiment is not limited to the above-described components, and may include any of various units. For example, the first water washing unit 12 and/or the second water washing unit 15 may be provided. Since the first and second water washing units 12 and 15 have already been described, the description thereof is omitted here.
Further, a water removal unit for removing water adhering to the surface of the substrate 11, a drying unit for drying the surface of the substrate, or the like may be further provided on the downstream side of the second water washing unit 15 in the transport direction of the substrate 11.
In fig. 3 and 4, the case where the organic film is formed only on one surface 11a of the substrate 11 has been described as an example, but the apparatus may be configured so that the organic film is formed simultaneously on a surface facing the one surface 11a, that is, the other surface 11b shown in fig. 4.
Specifically, for example, a liquid film forming unit and a nozzle may be similarly provided on the other surface 11b side of the substrate 11 to be conveyed, whereby the organic film may be formed on the other surface 11 b. In particular, it is preferable that the nozzle provided on the one surface 11a side and the nozzle provided on the other surface side are provided at the same position as viewed in the conveyance direction of the substrate so that the nozzle holes face each other with the substrate 11 interposed therebetween. This is because the organic solution is supplied from both surfaces of the substrate 11 at the same pressure, and thereby occurrence of warpage or the like on the substrate 11 can be suppressed.
It is preferable that the liquid film forming unit, the first water washing unit, the second water washing unit, and the like are disposed at the same position as the nozzles as viewed in the transport direction of the substrate 11. In other words, it is preferable that the various units are provided symmetrically with respect to the substrate 11 on a cross section on a plane perpendicular to the one surface 11a of the substrate 11.
According to the organic film production apparatus of the present embodiment as described above, a uniform organic film can be formed on the surface of the substrate on which the organic film is formed. Therefore, when the organic film is used for forming a conductive substrate in which a metal layer, an organic film, and a black layer are laminated, for example, the adhesion of the black layer can be improved.
In the case where the organic film is formed on the substrate, the liquid film forming unit and the nozzle supply the liquid onto the substrate, thereby forming a uniform liquid film on the substrate. Therefore, for example, by using a cleaning liquid such as water instead of the organic solution and supplying the cleaning liquid from the liquid film forming unit and the nozzle, it is also possible to use the cleaning apparatus for the substrate surface. Further, the present invention can be used as an apparatus for producing various coatings other than organic coatings.
(method for producing conductive substrate)
Next, a description will be given of a configuration example of the method for manufacturing a conductive substrate according to the present embodiment.
The method for manufacturing a conductive substrate of the present embodiment may include the following steps.
A metal layer forming step of forming a metal layer on at least one surface of the transparent substrate.
And an organic film forming step of forming an organic film on the upper surface of the metal layer.
And a blackening layer forming step of forming a blackening layer on the upper surface of the organic film.
In the organic film forming step, the organic film may be formed on the upper surface of the metal layer by the above-described method for producing an organic film.
First, a configuration example of the conductive substrate obtained by the method for manufacturing a conductive substrate according to the present embodiment will be described.
The conductive substrate may have a transparent base, a metal layer formed on at least one surface of the transparent base, an organic film formed on the metal layer, and a blackened layer formed on the organic film.
The conductive substrate of the present embodiment includes a substrate having a metal layer, an organic film, and a black layer on the surface of a transparent base material before patterning the metal layer and the like, and a wiring substrate that is a substrate having a patterned metal layer and the like.
Here, first, each member included in the conductive substrate will be described below.
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 is preferably used.
As a material of the resin substrate that transmits visible light, for example, a resin such as a polyamide resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, a cycloolefin resin, a polyimide resin, or a polycarbonate resin can be preferably used. In particular, as a material of the resin substrate that transmits visible light, PET (polyethylene terephthalate), COP (cycloolefin polymer), PEN (polyethylene naphthalate), polyimide, polyamide, polycarbonate, or the like can be more preferably used.
The thickness of the transparent base is not particularly limited, and may be arbitrarily selected depending on the intensity, capacitance, light transmittance, and the like required for the conductive substrate. The thickness of the transparent substrate may be, for example, 10 μm or more and 200 μm or less. In particular, when the transparent substrate is used for a touch panel, the thickness of the transparent substrate is preferably 20 μm to 120 μm, more preferably 20 μm to 100 μm. In the case of use in a touch panel, for example, when the thickness of the entire display is particularly required to be reduced, the thickness of the transparent substrate is preferably 20 μm or more and 50 μm or less.
The transparent substrate preferably has a high total light transmittance, and for example, the total light transmittance is preferably 30% or more, more preferably 60% or more. By setting the total light transmittance of the transparent base material to the above range, it is possible to sufficiently ensure the visibility of the display when used for a touch panel, for example.
The total light transmittance of the transparent substrate can be evaluated by the method defined in JIS K7361-1.
Next, the metal layer will be explained.
The material constituting the metal layer is not particularly limited, and a material having electrical conductivity depending on the application may be selected, and for example, the material constituting the metal layer is preferably a copper alloy containing Cu and at least one or more metals selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Mn, Co, and W, or a material containing copper. The metal layer may be a copper layer made of copper.
The method for forming the metal layer on the transparent substrate is not particularly limited, and it is preferable not to dispose an adhesive between the transparent substrate and the metal layer in order not to decrease the light transmittance. In other words, it is preferable that the metal layer is directly formed on at least one side of the transparent substrate. When an adhesion layer is disposed between the transparent substrate and the metal layer as described below, the metal layer is preferably formed directly on the upper surface of the adhesion layer.
In order to directly form the metal layer on the upper surface of the transparent substrate, the metal layer preferably has a metal thin film layer. In addition, the metal layer may have a metal thin film layer and a metal plating layer.
For example, a metal thin film layer can be formed on a transparent substrate by a dry plating method, and the metal thin film layer can be used as a metal layer. Thus, the metal layer can be directly formed on the transparent substrate without using an adhesive. As a dry plating method, which will be described in detail later, for example, a sputtering method, a vapor deposition method, an ion plating method, or the like can be preferably used.
In addition, when the thickness of the metal layer is increased, the metal layer having the metal thin film layer and the metal plating layer may be formed by forming the metal plating layer by an electroplating method, which is one of wet plating methods, using the metal thin film layer as a power supply layer. By providing the metal layer with the metal thin film layer and the metal plating layer, the metal layer can be directly formed on the transparent substrate without an adhesive in this case as well.
The thickness of the metal layer is not particularly limited, and when the metal layer is used as a wiring, the thickness can be arbitrarily selected according to the magnitude of current supplied to the wiring, the width of the wiring, or the like.
However, when the metal layer is thick, there may be a problem that etching takes time when etching is performed to form a wiring pattern, and therefore, side etching is likely to occur, and it is difficult to form a fine line. Therefore, the thickness of the metal layer is preferably 5 μm or less, and more preferably 3 μm or less.
In addition, from the viewpoint of reducing the resistance value of the conductive substrate in particular and sufficiently supplying current, for example, the thickness of the metal layer is preferably 50nm or more, more preferably 60nm or more, and still more preferably 150nm or more.
When the metal layer has the metal thin film layer and the metal plating layer as described above, the sum of the thickness of the metal thin film layer and the thickness of the metal plating layer is preferably in the above range.
Even in the case where the metal layer is composed of a metal thin film layer or in the case where the metal thin film layer and the metal plating layer are provided, the thickness of the metal thin film layer is not particularly limited, and is preferably 50nm or more and 500nm or less, for example.
The metal layer may be patterned into a desired wiring pattern to be used as a wiring, for example, as described below. Further, since the metal layer can further reduce the resistance value as compared with ITO which is conventionally used as a transparent conductive film, the resistance value of the conductive substrate can be reduced by providing the metal layer.
Next, the organic film will be described.
The organic film may be formed on a surface of the metal layer opposite to a blackening layer which will be described below. Therefore, the conductive substrate can be disposed between the metal layer and the blackened layer. The organic coating preferably contains a nitrogen-containing organic substance. This is because, by containing a nitrogen-containing organic substance in the organic film, the adhesion between the blackened layer and the metal layer and the organic film which are the lower layer of the blackened layer can be particularly improved, and the peeling of the blackened layer can be suppressed, so that the etching property of the blackened layer can be improved. Further, according to the study of the present inventors, the reflectance of the conductive substrate can be reduced by making the organic film contain a nitrogen-containing organic substance.
The nitrogen-containing organic substance used for the organic film is not particularly limited, and can be arbitrarily selected from nitrogen-containing organic compounds. The nitrogen-containing organic material for the organic coating film preferably contains, for example, 1,2, 3-benzotriazole or a derivative thereof. Specific examples of the nitrogen-containing organic compound used for the organic coating film include 1,2, 3-benzotriazole and 5-methyl-1H-benzotriazole.
As the organic solution containing a nitrogen-containing organic substance that can be preferably used for the organic coating, for example, a rust-proofing agent for copper can be preferably used, and as a commercially available chemical, for example, OPC-DEFENSER (trade name, ohne pharmaceutical industry co.) or the like can be preferably used.
The content of the nitrogen-containing organic substance in the organic coating is preferably 0.2. mu.g/cm2Above, more preferably 0.3. mu.g/cm2The above. This is because, according to the study of the inventors of the present invention, the content of the nitrogen-containing organic substance in the organic coating film is set to 0.2 μ g/cm2As described above, the reflectance of the conductive substrate can be greatly suppressed. In addition, when the content of the nitrogen-containing organic substance in the organic coating film is increased, the values a and b can be reduced when the color of the blackened layer is converted into the CIE (L × a × b) color system, and particularly, the wiring of the conductive substrate can be made inconspicuous, which is preferable.
The upper limit of the content of the nitrogen-containing organic substance in the organic coating is not particularly limited. However, in order to increase the content of the nitrogen-containing organic substance in the organic coating, it is necessary to increase the concentration of the organic solution containing the nitrogen-containing organic substance used for forming the organic coating or to extend the supply time of the organic solution containing the nitrogen-containing organic substance. Therefore, if the content of the nitrogen-containing organic substance in the organic coating is excessively increased, the organic solution containing the nitrogen-containing organic substance may be degraded in workability, and the time required for forming the organic coating may be increased, resulting in a decrease in productivity. Therefore, the content of the nitrogen-containing organic substance in the organic coating is preferably 10 μ g/cm, for example2In addition, since the adhesion of the blackened layer is good when the content is low,therefore, it is more preferable to set the concentration to 1. mu.g/cm2It is more preferably set to 0.5. mu.g/cm2The following.
The concentration of the nitrogen-containing organic substance in the organic solution used for forming the organic film is not particularly limited, and may be arbitrarily selected in consideration of the content of the nitrogen-containing organic substance in the target organic film, the workability, and the like. For example, the lower limit of the concentration of the nitrogen-containing organic substance in the organic solution is preferably 1mL/L or more, and more preferably 2mL/L or more. The upper limit is preferably 4mL/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 may be arbitrarily selected in consideration of the viscosity, handling properties, reactivity, and the like of the solution. For example, it is preferably 10 ℃ or higher, and more preferably 20 ℃ or higher. However, from the viewpoint that the organic solution may react with other substances when the temperature is increased, it is preferably 40 ℃ or lower.
The pH of the organic solution is not particularly limited, and may be selected in consideration of the kind of the organic solution to be used, the reactivity of the solution, and the like, and for example, the pH of the organic solution is preferably 2 or more, and more preferably 3 or more. However, the pH of the organic solution is preferably 4 or less from the viewpoint that the content of the nitrogen-containing organic substance in the coating film decreases when the pH increases.
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 kind of the organic solution used, the thickness of the organic film to be formed, and the like. For example, the treatment time is preferably 3 seconds or more, and more preferably 4 seconds or more. However, from the viewpoint that productivity may be reduced if the treatment time is too long, it is preferably 10 seconds or less. In the method for producing an organic film, the processing time can be set to a desired time by adjusting the transport speed of the substrate and the like. The treatment time in the method for producing an organic film is the sum of the times of supplying the organic solution to an arbitrary point on the surface of the substrate on which the organic film is formed by the nozzle and the liquid film forming means.
Next, the blackened layer will be explained.
The black layer may be formed on an upper surface of the organic film.
The material of the blackened layer is not particularly limited, and any material that can suppress reflection of light on the surface of the metal layer can be preferably used.
The blackened layer preferably contains at least 1 or more metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn, for example. The blackened layer may further contain 1 or more elements selected from carbon, oxygen, hydrogen, and nitrogen.
The blackened layer may include a metal alloy containing at least 2 or more metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. In this case, the blackened layer may further contain 1 or more elements selected from carbon, oxygen, hydrogen, and nitrogen. In this case, as the metal alloy containing at least 2 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, a Cu-Ti-Fe alloy, a Cu-Ni-Fe alloy, a Ni-Cu alloy, a Ni-Zn alloy, a Ni-Ti alloy, a Ni-W alloy, a Ni-Cr alloy, and a Ni-Cu-Cr alloy can be preferably used. In particular, a Ni-Cu alloy can be more preferably used.
The method for forming the black layer is not particularly limited, and the film can be formed by any method, for example, a dry method or a wet method.
When the blackened layer is formed by a dry method, a specific method thereof is not particularly limited, and for example, a dry plating method such as a sputtering method, an ion plating method, or a vapor deposition method can be preferably used. The sputtering method is more preferably used from the viewpoint of easy control of the film thickness when the black layer is formed by the dry method. In addition, 1 or more elements selected from carbon, oxygen, hydrogen, and nitrogen as described above may be added to the blackened layer, and in this case, the reactive sputtering method is more preferably used.
When the blackened layer is formed by the reactive sputtering method, a target including a metal species (metal species) constituting the blackened layer can be used as the target. When the blackened layer contains an alloy, the alloy may be formed on the surface of a film-formed body such as a substrate by using a target in each form of a metal contained in the blackened layer, or a target obtained by alloying a metal contained in the blackened layer in advance may be used.
In addition, when 1 or more elements selected from carbon, oxygen, hydrogen, and nitrogen are contained in the blackened layer, they may be added to the blackened layer by previously adding them to the atmosphere at the time of forming the blackened layer. For example, when carbon is added to the blackened layer, carbon monoxide gas and/or carbon dioxide gas may be previously added to the atmosphere during sputtering, when oxygen is added to the blackened layer, oxygen may be previously added to the atmosphere during sputtering, when hydrogen is added to the blackened layer, hydrogen gas and/or water may be previously added to the atmosphere during sputtering, and when nitrogen is added to the blackened layer, nitrogen may be previously added to the atmosphere during sputtering. These gases may be added to an inert gas used in forming the black layer, so that 1 or more elements selected from carbon, oxygen, hydrogen, and nitrogen may be added to the black layer. Argon is preferably used as the inert gas.
When the blackened layer is formed by a wet method, a plating solution may be used depending on the material of the blackened layer, and the film may be formed by, for example, an electroplating method.
As described above, the blackened layer can be formed by any of the dry method and the wet method, but when the blackened layer is formed, the material constituting the organic film is dissolved in the plating solution and enters the blackened layer, which may affect the color tone and other characteristics of the blackened layer.
The thickness of the black layer is not particularly limited, and is, for example, preferably 15nm or more, and more preferably 25nm or more. This is because, when the thickness of the blackened layer is small, reflection of light on the surface of the metal layer may not be sufficiently suppressed, and therefore, it is preferable to configure the blackened layer to have a thickness of 15nm or more as described above so that reflection of light on the surface of the metal layer can be particularly suppressed.
The upper limit of the thickness of the blackened layer is not particularly limited, and even if the thickness is increased to a value not less than necessary, the time required for film formation and the time required for etching at the time of wiring formation become long, which leads to an increase in cost. Therefore, the thickness of the blackened layer is preferably 70nm or less, more preferably 50nm or less.
The conductive substrate may be provided with any layer other than the transparent base material, the metal layer, the organic film, and the blackening layer. For example, an adhesion layer may be provided.
An example of the structure of the adhesion layer will be described.
As described above, the metal layer can be formed on the transparent substrate, but when the metal layer is formed directly on the transparent substrate, the adhesion between the transparent substrate and the metal layer may be insufficient. Therefore, when the metal layer is directly formed on the upper surface of the transparent substrate, the metal layer may be peeled off from the transparent substrate during the manufacturing process or in use.
Therefore, in the conductive substrate of the present embodiment, an adhesion layer may be disposed on the transparent base material in order to improve adhesion between the transparent base material and the metal layer.
By disposing the adhesion layer between the transparent base material and the metal layer, adhesion between the transparent base material and the metal layer can be improved, and peeling of the metal layer from the transparent base material can be suppressed.
In addition, the adhesion layer can also function as a blackening layer. Therefore, reflection of light at the metal layer due to light from the lower surface side of the metal layer, that is, from the transparent base material side can also be suppressed.
The material constituting the adhesion layer is not particularly limited, and may be arbitrarily selected depending on the adhesion between the transparent base material and the metal layer, the degree of suppression of light reflection on the surface of the metal layer, the degree of stability against the use environment (for example, humidity or temperature) of the conductive substrate, and the like.
The adhesion layer preferably contains at least 1 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. The adhesion layer may further contain 1 or more elements selected from carbon, oxygen, hydrogen, and nitrogen.
The adhesion layer may contain a metal alloy containing at least 2 or more metals selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. In this case, the adhesion layer may further contain 1 or more elements selected from carbon, oxygen, hydrogen, and nitrogen. In this case, as the metal alloy containing at least 2 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, a Cu-Ti-Fe alloy, a Cu-Ni-Fe alloy, a Ni-Cu alloy, a Ni-Zn alloy, a Ni-Ti alloy, a Ni-W alloy, a Ni-Cr alloy, and a Ni-Cu-Cr alloy can be preferably used. Particularly, a Ni-Cu alloy can be more preferably used.
The method for forming the adhesion layer is not particularly limited, and the film is preferably formed 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. The sputtering method is more preferably used from the viewpoint of easy control of the film thickness when the adhesion layer is formed by the dry method. In addition, 1 or more elements selected from carbon, oxygen, hydrogen, and nitrogen as described above may be added to the adhesion layer, and in this case, the reactive sputtering method may be more preferably used.
When the adhesion layer contains 1 or more elements selected from carbon, oxygen, hydrogen, and nitrogen, a gas containing 1 or more elements selected from carbon, oxygen, hydrogen, and nitrogen may be added to the adhesion layer by previously adding the gas to the atmosphere in the process of forming the adhesion layer. For example, when carbon is added to the adhesion layer, carbon monoxide gas and/or carbon dioxide gas may be added in advance to the atmosphere in which dry plating is performed, when oxygen is added to the adhesion layer, oxygen may be added in advance to the atmosphere, when hydrogen is added to the adhesion layer, hydrogen gas and/or water may be added in advance to the atmosphere, and when nitrogen is added to the adhesion layer, nitrogen may be added in advance to the atmosphere.
The gas containing 1 or more elements selected from carbon, oxygen, hydrogen and nitrogen is preferably added to an inert gas to be an atmosphere gas in the case of dry plating. The inert gas is not particularly limited, and argon can be preferably used, for example.
By forming the adhesion layer by the dry plating method as described above, the adhesion between the transparent base material and the adhesion layer can be improved. Further, the adhesion layer may contain a metal as a main component, and thus has high adhesion to the metal layer. Therefore, by disposing the adhesion layer between the transparent base material 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 3nm to 50nm, more preferably 3nm to 35nm, and still more preferably 3nm to 33 nm.
When the adhesion layer also functions as a blackening layer, that is, when reflection of light on the metal layer is suppressed by the adhesion layer, the thickness of the adhesion layer is preferably 3nm 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 value more than necessary, the time required for film formation and the time required for etching at the time of wiring formation become long, which leads to an increase in cost. Therefore, the thickness of the adhesion layer is preferably 50nm or less, more preferably 35nm or less, and still more preferably 33nm or less, as described above.
Next, a description will be given of a structural example of the conductive substrate.
As described above, the conductive substrate of the present embodiment may have a transparent base material, a metal layer, an organic film, and a blackened layer. Further, a layer such as an adhesion layer may be optionally provided.
Specific configuration examples will be described below with reference to fig. 5A, 5B, 6A, and 6B. Fig. 5A, 5B, 6A, and 6B show examples of cross-sectional views of the conductive substrate according to the present embodiment on a plane parallel to the stacking direction of the transparent base material, the metal layer, the organic coating, and the black layer.
The conductive substrate of the present embodiment may have, for example, a structure in which a metal layer, an organic film, and a black layer are laminated in this order from the transparent base material side on at least one surface of a transparent base material.
Specifically, for example, as in the conductive substrate 50A shown in fig. 5A, a metal layer 52, an organic film 53, and a blackened layer 54 may be sequentially laminated in a layer-by-layer manner on the one surface 51a side of the transparent base 51. As shown in fig. 5B, in the conductive substrate 50B, the metal layers 52A and 52B, the organic films 53A and 53B, and the blackened layers 54A and 54B may be sequentially stacked on one surface 51a side and the other surface (the other surface) 51B side of the transparent base 51.
Further, as an arbitrary layer, for example, an adhesion layer may be provided. In this case, for example, an adhesive layer, a metal layer, an organic coating film, and a black layer may be formed on at least one surface of the transparent substrate in this order from the transparent substrate side.
Specifically, for example, as shown in fig. 6A, in the conductive substrate 60A, an adhesion layer 55, a metal layer 52, an organic film 53, and a blackening layer 54 may be sequentially stacked on one surface 51a side of the transparent base 51.
In this case, an adhesion layer, a metal layer, an organic coating film, and a black layer may be laminated on both surfaces of the transparent base 51. Specifically, as shown in fig. 6B, in the conductive substrate 60B, the adhesion layers 55A and 55B, the metal layers 52A and 52B, the organic films 53A and 53B, and the black layers 54A and 54B may be sequentially stacked on one surface 51a and the other surface 51B of the transparent base 51.
Fig. 5B and 6B show an example in which, when a metal layer, an organic coating film, and a black layer are laminated on both surfaces of a transparent base, the transparent base 51 is disposed symmetrically with respect to the layers laminated above and below the transparent base 51, but the present invention is not limited to this embodiment. For example, in fig. 6B, the structure of the one surface 51a side of the transparent substrate 51 is made to be the same as that of fig. 5B, and the metal layer 52A, the organic film 53A, and the blackened layer 54A are sequentially stacked without providing the adhesion layer 55A, and the layers stacked above and below the transparent substrate 51 may be made to be asymmetric.
On the other hand, in the conductive substrate of the present embodiment, since the metal layer, the organic film, and the black layer are provided on the transparent base material, reflection of light by the metal layer can be suppressed, and the reflectance of the conductive substrate can be suppressed.
The degree of the reflectance of the conductive substrate of the present embodiment is not particularly limited, and is preferably low, for example, in order to improve the visibility of a display when used as a conductive substrate for a liquid crystal touch panel. For example, the average reflectance of light having a wavelength of 400nm to 700nm is preferably 20% or less, more preferably 17% or less, and particularly preferably 15% or less.
The measurement of the reflectance can be performed by irradiating the blackened layer of the conductive substrate with light. Specifically, for example, as shown in fig. 5A, when the metal layer 52, the organic film 53, and the blackened layer 54 are laminated in this order on the side of the one surface 51a of the transparent substrate 51, the surface a of the blackened layer 54 is irradiated with light so as to irradiate the blackened layer 54 with light, and measurement is performed. In the measurement, the blackened layer 54 of the conductive substrate may be irradiated with light having a wavelength of 400nm or more and 700nm or less at intervals of 1nm, for example, 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. In this case, the conductive substrate may have a mesh-like wiring structure.
The conductive substrate having mesh wiring can be obtained by etching the metal layer, the organic film, and the blackened layer of the conductive substrate of the present embodiment.
For example, a mesh-like wiring may be formed by using two layers of wirings. The specific structure is shown in fig. 7, for example. Fig. 7 shows a view of the conductive substrate 70 having mesh-like wiring viewed from the upper surface side in the laminating direction of the metal layers and the like, and the transparent base 51 and layers other than the wirings 71A and 71B formed by patterning the metal layers are omitted for easy understanding of the wiring pattern. Further, the wiring 71B is also shown to be visible through the transparent base material 51.
The conductive substrate 70 shown in fig. 7 has a transparent base 51, a plurality of wirings 71A parallel to the Y-axis direction in the figure, and wirings 71B parallel to the X-axis direction. The wirings 71A and 71B are formed by etching a metal layer, and an organic coating and a black layer, not shown, are formed on the upper surface and/or the lower surface of the wirings 71A and 71B. The organic film and the black 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. Fig. 8A and 8B show examples of the arrangement of the transparent substrate 51 and the wiring. Fig. 8A and 8B correspond to cross-sectional views taken along line a-a' of fig. 7.
First, as shown in fig. 8A, the wires 71A and 71B may be disposed on the upper and lower surfaces of the transparent base 51, respectively. In fig. 8A, organic films 72A and 72B and black layers 73A and 73B etched to have the same shape as the wiring are disposed on the upper surface of the wiring 71A and the lower surface of the wiring 71B.
As shown in fig. 8B, 1 set of transparent substrates 51A and 51B may be used, and the wirings 71A and 71B may be arranged on the upper and lower surfaces of one transparent substrate 51A, and one wiring 71B may be arranged between the transparent substrates 51. At this time, organic films 72A and 72B and black layers 73A and 73B etched in the same shape as the wirings are also disposed on the upper surfaces of the wirings 71A and 71B. As described above, an adhesion layer may be provided in addition to the metal layer, the organic film, and the blackening layer. Therefore, in either case of fig. 8A and 8B, for example, an adhesion layer may be provided between the wiring 71A and/or the wiring 71B and the transparent base material 51. When the adhesion layer is provided, the adhesion layer may be etched into the same shape as the wirings 71A and 71B.
The conductive substrate having mesh wiring shown in fig. 7 and 8A can be formed, for example, by a conductive substrate having metal layers 52A and 52B, organic films 53A and 53B, and blackened layers 54A and 54B on both surfaces of a transparent base 51 as shown in fig. 5B.
To explain the case of using the conductive substrate of fig. 5B as an example, first, the metal layer 52A, the organic film 53A, and the blackened layer 54A on the side of the one surface 51a of the transparent base material 51 are etched so that a plurality of linear patterns parallel to the Y-axis direction in fig. 5B are arranged at predetermined intervals in the X-axis direction. The X-axis direction in fig. 5B means a 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.
Next, the metal layer 52B, the organic film 53B, and the black layer 54B on the other surface 51B side of the transparent substrate 51 are etched so as to be arranged in the Y-axis direction with a predetermined interval in a plurality of linear patterns parallel to the X-axis direction in fig. 5B.
By the above operation, a conductive substrate having mesh-like wiring as shown in fig. 7 and 8A can be formed. Both surfaces of the transparent base material 51 may be etched at the same time. In other words, the metal layers 52A and 52B, the organic films 53A and 53B, and the blackened layers 54A and 54B can be etched at the same time. In fig. 8A, a conductive substrate having an adhesion layer, which is patterned between the wirings 71A and 71B and the transparent base material 51 and has the same shape as the wirings 71A and 71B, can be manufactured by etching in the same manner as the conductive substrate shown in fig. 6B.
The conductive substrate having mesh wiring shown in fig. 7 may be formed using 2 conductive substrates shown in fig. 5A or 6A. To explain the case of using the conductive substrate of fig. 5A as an example, the metal layer 52, the organic film 53, and the blackened layer 54 are etched on 2 conductive substrates shown in fig. 5A, respectively, so that a plurality of linear patterns parallel to the X-axis direction are arranged in the Y-axis direction with predetermined intervals therebetween. Next, 2 conductive substrates were bonded to each other so that the linear patterns formed on the respective conductive substrates by the etching treatment were aligned in directions intersecting each other, thereby forming a conductive substrate having mesh wiring. The bonding surface when 2 sheets of conductive substrates are bonded is not particularly limited. For example, the structure shown in fig. 8B may be formed by bonding the surface a in fig. 5A on which the metal layer 52 and the like are laminated and the other surface 51B in fig. 5A on which the metal layer 52 and the like are not laminated.
For example, the other surfaces 51b of the transparent base material 51 in fig. 5A, on which the metal layer 52 and the like are not laminated, may be bonded to each other so that the cross section thereof has the structure shown in fig. 8A.
In fig. 8A and 8B, a conductive substrate having an adhesion layer patterned in the same shape as the lines 71A and 71B between the lines 71A and 71B and the transparent base material 51 can be produced by using the conductive substrate shown in fig. 6A instead of the conductive substrate shown in fig. 5A.
The width of the wires and the distance between the wires in the conductive substrate having mesh-shaped wires shown in fig. 7, 8A, and 8B are not particularly limited, and may be selected according to the amount of current flowing through the wires, for example.
In fig. 7, 8A, and 8B, an example in which linear wires 71A and 71B are combined to form a mesh-shaped wire (wiring pattern) is shown, but the present invention is not limited to this form, and the wire constituting the wiring pattern may have any shape. For example, the wires constituting the mesh-like wiring pattern may be formed in various shapes such as zigzag-bent lines (zigzag lines) so that no moire (interference ring) is generated between the wires and the image of the liquid crystal panel.
The conductive substrate having mesh-like wiring formed of 2-layer wiring as described above can be preferably used as a conductive substrate for a projected capacitive touch panel, for example.
Next, a description will be given of a configuration example of the method for manufacturing a conductive substrate according to the present embodiment.
A transparent substrate for the metal layer forming step may 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 may be cut into an arbitrary size in advance as needed.
As described above, the metal layer preferably has a metal layer thin film layer. In addition, the metal layer may have a metal thin film layer and a metal plating layer. Therefore, the metal layer forming step may include, for example, a step of forming a metal thin film layer by dry plating. The metal layer forming step may include a step of forming a metal thin film layer by a dry plating method and a step of forming a metal plating layer by an electroplating method which is one of wet plating methods using the metal thin film layer as a power supply layer.
The dry plating method used in the step of forming the metal thin film layer is not particularly limited, and for example, a vapor deposition method, a sputtering method, an ion plating method, or the like can be used. As the vapor deposition method, a vacuum vapor deposition method can be preferably used. As the dry plating method used for the step of forming the metal thin film layer, a sputtering method is more preferably used particularly from the viewpoint of controlling the film thickness.
Next, the step of forming the metal plating layer will be described. The conditions in the step of forming the metal plating layer by the wet plating method, that is, the conditions of the plating treatment are not particularly limited, and various conditions according to the conventional method may be adopted. For example, the metal plating layer can be formed by supplying a substrate on which a metal thin film layer is formed into a plating tank into which a metal plating solution is injected, and controlling the current density or the transport speed of the substrate.
The preferable material that can be used for the metal layer or the preferable thickness of the metal layer, etc. are as described above, and therefore, the description thereof is omitted here.
Next, the organic film forming step will be described.
In the organic film forming step, an organic film may be formed on the metal layer.
As described above, by providing the organic film between the metal layer and the blackened 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 method for producing an organic film. The organic solution and the like used for forming the organic film have already been described above, and therefore the description thereof is omitted here.
Next, a blackening layer forming step will be described.
In the blackening layer forming step, a method for forming the blackening layer is not particularly limited, and the blackening layer can be formed by any method.
In the case where the blackened layer is formed in the blackened layer forming step, for example, a dry plating method such as a sputtering method, an ion plating method, or a vapor deposition method can be preferably used. In particular, the sputtering method is more preferably used from the viewpoint of easy control of the film thickness. As described above, 1 or more elements selected from carbon, oxygen, hydrogen, and nitrogen may be added to the black layer, and in this case, the reactive sputtering method may be preferably used.
As described above, the blackened layer may be formed by a wet method such as a plating method.
However, when the blackened layer is formed, the material constituting the organic film is dissolved in the plating solution and then enters the blackened layer, which may affect the color tone and other characteristics of the blackened layer.
The preferable material that can be used for the blackening layer, the preferable thickness of the blackening layer, and the like are as described above, and thus, the description thereof is omitted here.
In the method for manufacturing a conductive substrate of the present embodiment, any steps may be performed in addition to the above steps.
For example, when the 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 the adhesion layer forming step is performed, the metal layer forming step may be performed after the adhesion layer forming step, and in the metal layer forming step, the metal thin film layer may be formed on the substrate on which the adhesion layer is formed on the transparent substrate in this step.
In the step of forming the adhesion layer, the method of forming the adhesion layer is not particularly limited, and the adhesion layer is preferably formed 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, a sputtering method is more preferably used from the viewpoint of easy control of the film thickness. As described above, 1 or more elements selected from carbon, oxygen, hydrogen, and nitrogen may be added to the adhesion layer, and in this case, the reactive sputtering method is more preferably used.
The preferable material or the preferable thickness of the adhesion layer, etc. that can be used for the adhesion layer are as described above, and therefore, the description thereof is omitted here.
The conductive substrate obtained by the method for manufacturing a conductive substrate according to the present embodiment can be used for various applications such as a touch panel. In addition, when used for various applications, it is preferable to pattern the metal layer, the organic film, and the blackened layer included in the conductive substrate of the present embodiment. When an adhesion layer is provided, the adhesion layer is preferably also patterned. The metal layer, the organic film, the black layer, and the adhesion layer may be patterned in accordance with a desired wiring pattern, and the metal layer, the organic film, the black layer, and the adhesion layer may be patterned in the same shape.
Therefore, the method for manufacturing a conductive substrate according to the present embodiment may include a patterning step of patterning the metal layer, the organic film, and the blackened layer. In the case where an adhesion layer is formed, the patterning step may be a step of patterning the adhesion layer, the metal layer, the organic film, and the black layer.
The specific procedure of the patterning step is not particularly limited, and may be performed by any procedure. For example, as shown in fig. 5A, in the case of a conductive substrate 50A in which a metal layer 52, an organic film 53, and a blackened layer 54 are laminated on a transparent base 51, a mask arrangement step of arranging a mask having a desired pattern on a surface a on the blackened layer 54 may be first performed. Next, an etching step of supplying an etching solution to the upper surface of the blackened layer 54, that is, the side on which the mask is disposed, may be performed.
The etching solution used in the etching step is not particularly limited, and may be arbitrarily selected depending on the material constituting the layer to be etched. For example, the etching solution may be changed for each layer, or the metal layer, the organic coating, the black layer, and the adhesion layer may be etched simultaneously using the same etching solution.
As shown in fig. 5B, a patterning step of patterning the conductive substrate 50B in which the metal layers 52A and 52B, the organic films 53A and 53B, and the blackened layers 54A and 54B are also stacked on the one surface 51a and the other surface 51B of the transparent base 51 may be performed. At this time, for example, a mask arrangement step of arranging masks having a predetermined pattern on the surfaces a and B of the blackened layers 54A and 54B may be performed. Next, an etching step of supplying an etching solution to the surface a and the surface B on the blackened 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 may have 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 blackened layer 54 may be patterned so as to include a plurality of straight lines or lines bent in a zigzag shape (zigzag lines) as described above.
In the case of the conductive substrate 50B shown in fig. 5B, the metal layer 52A and the metal layer 52B may be patterned to form mesh-shaped wiring. In this case, it is preferable to pattern the organic film 5A and the blackened layer 54A so as to have the same shape as the metal layer 52A, and to pattern the organic film 53B and the blackened layer 54B so as to have the same shape as the metal layer 52B.
For example, the metal layer 52 of the conductive substrate 50A may be patterned in a patterning step, and then a lamination step of laminating 2 or more patterned conductive substrates may be performed. In the case of lamination, for example, a laminated conductive substrate having mesh wiring may be obtained by laminating the conductive substrates so that the patterns of the metal layers of the conductive substrates intersect with each other.
The method for fixing the conductive substrates laminated with 2 or more sheets is not particularly limited, and for example, the conductive substrates can be fixed by an adhesive or the like.
The conductive substrate obtained by the method for manufacturing a conductive substrate according to 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 a transparent base material. 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 black layer and the metal layer and the organic film which are the lower layer of the black layer can be particularly improved and the peeling of the black layer can be suppressed, the etching property of the black layer can be improved. Further, since fine wiring processing can be easily performed on the metal layer, the blackened layer, or the like, reflection of light on the surface of the metal layer can be suppressed, and a conductive substrate with suppressed reflectance can be formed.
Further, when used in a touch panel or the like, for example, the visibility of the display can be improved.
< example >
The following description will be given by way of specific examples and comparative examples, but the present invention is not limited to these examples.
(evaluation method)
First, a method for evaluating the adhesion of the blackened layer of the obtained conductive substrate will be described.
As shown in fig. 9, 11 longitudinal cutting lines 91a having a length of 20MM were formed in parallel with each other at intervals of 1.0MM by using a dicing Tool (Cross Cut Kit 1.0MM manufactured by Precision Gate & Tool Company).
Next, 11 transverse cutting lines 91b having a length of 20mm were formed in parallel with each other at intervals of 1.0mm so as to be orthogonal to the previously formed longitudinal cutting lines 91a using the same cutting tool.
Through the above steps, as shown in fig. 9, 11 cutting lines in the vertical and horizontal directions form lattice-shaped cuts in the blackened layer.
Next, an adhesion evaluation tape (Elcometer 99 tape manufactured by Elcometer corporation) was attached so as to cover the lattice-shaped cuts, and then sufficiently attached.
After 30 seconds after the adhesion evaluation tape was attached, the adhesion evaluation tape was quickly peeled off in a direction as 180 ° as possible from the measurement surface.
After the adhesive tape for evaluation of adhesion was peeled off, the adhesion was evaluated based on the area of the metal layer (organic layer) formed under the blackened layer in the evaluation region 92 in fig. 9 surrounded by the grid-like vertical cut line 91a and the cross cut line 91 b.
The metal layer in the evaluation region was evaluated as 5B when the exposed area was 0%, 4B when more than 0% and less than 5%, 3B when 5% or more and less than 15%, 2B when 15% or more and less than 35%, 1B when 35% or more and less than 65%, and 0B when 65% or more. For this evaluation, 0B is the lowest adhesion of the black layer, and 5B is the highest adhesion of the black layer.
As a result of the adhesion test, in the case of 4B and 5B, the adhesion of the blackened layer can be evaluated to be sufficient.
(conditions for preparing sample)
As examples and comparative examples, conductive substrates were produced under the following conditions, and evaluated by the above-described evaluation method.
[ example 1]
(step of Forming an adhesion layer)
An adhesive layer was formed on one surface of a transparent substrate made of polyethylene terephthalate (PET) resin having a width of 570mm and a thickness of 50 μm in the form of a strip. The total light transmittance of a transparent substrate made of a polyethylene terephthalate resin used as a transparent substrate was 97% when evaluated by the method defined in JIS K7361-1.
In the adhesion layer forming step, an oxygen-containing Ni — Cu alloy layer is formed as an adhesion layer by a roll-to-roll sputtering apparatus equipped with a target of Ni — 17 wt% Cu alloy. The following describes a process for forming the adhesion layer.
The transparent substrate heated to 60 ℃ in advance and removed of moisture was set in a chamber of a sputtering apparatus.
Then, the chamber was evacuated to 1 × 10-3After Pa, argon gas and oxygen gas were introduced so that the pressure in the chamber became 1.3 Pa. In this case, the atmosphere in the chamber is 30% by volume of oxygen and the remainder is argon.
Then, an adhesion layer was formed on one surface of the transparent substrate to a thickness of 20nm while supplying electric power to the target in the atmosphere and conveying 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, a metal thin film layer forming step will be described.
In the metal thin film layer forming step, a substrate having an adhesion layer formed on a transparent substrate in the adhesion layer forming step is used as a substrate, and a copper thin film layer as a metal thin film layer is formed on the adhesion layer.
The metal thin film layer was formed by a roll-to-roll sputtering apparatus in the same manner as in the case of the adhesion layer, except that a copper target was used, and argon gas was supplied after the inside of the chamber provided with the base material was exhausted to form an argon atmosphere.
The copper thin film layer as the metal thin film layer was formed to a thickness of 150 nm.
Next, in the metal plating layer forming step, a copper plating layer is formed as the metal plating layer. The copper plating layer was formed to have a thickness of 0.5 μm by an electroplating method.
(organic film Forming step)
In the organic coating forming step, an organic coating 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 is formed using the organic film manufacturing apparatus described with reference to fig. 3 and 4.
In the organic film-forming step, OPC-DEFENSER (manufactured by osma pharmaceutical industries, ltd.) containing 1,2, 3-benzotriazole as a nitrogen-containing organic substance was used as an organic solution. The organic solution was adjusted in advance so that the concentration of 1,2, 3-benzotriazole was 3mL/L, the bath temperature was 30 ℃ and the pH was 3.
As a conveying device, the substrate was set on a take-off roll of an organic film manufacturing apparatus having a not-shown roll-to-roll conveying unit, and the substrate was wound by the take-off roll to start conveying the substrate at a conveying speed of 3.5 m/min.
On the upstream side in the substrate transport direction, a first washing unit 12 is provided to wash the surface of the metal layer with respect to one surface 11a of the substrate 11, which is a surface on which the organic film is formed.
A nozzle 21 is provided on the downstream side in the transport direction of the first washing unit 12, and the organic solution is supplied and applied to the substrate 11 from a plurality of nozzle holes provided in the nozzle 21. In addition, a nozzle (model InVV11550) having an elliptical spray pattern with a short diameter of 5mm and a long diameter of 70mm formed on the surface of the base material 11 by the organic solution supplied from the nozzle hole 211 was used. At this time, the nozzle holes are arranged so that the long diameter of the ejection pattern is parallel to the height direction.
Further, 7 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 a nozzle 21 at a flow rate of 19L/min.
Further, a liquid film forming unit 13 was provided on the downstream side in the transport direction of the nozzle 21, and the organic solution was supplied from a supply port of the liquid film forming unit 13 provided on the upper portion in the height direction of the substrate so that the organic solution was a film-like liquid flow having a width of 320mm and the surface of the substrate was in contact with the film-like liquid flow of the organic solution. The organic solution was supplied from the liquid film-forming unit 13 at a flow rate of 54L/min.
Thereafter, the excess organic solution adhering to the surface of the substrate 11 is further washed with water and removed by a second washing unit 15 provided on the downstream side in the substrate conveying direction, and then dried by a drying unit, not shown, and the substrate on which the organic film is formed is wound by a winding roller, not shown.
(blackened layer formation step)
In the blackening layer forming step, a Ni — Cu layer is formed as a blackening layer on the organic film formed in the organic film forming step by a sputtering method.
In the blackening layer forming step, a Ni — Cu alloy layer is formed as a blackening layer by a roll-to-roll sputtering apparatus equipped with a target of Ni — 35 wt% Cu alloy. The following describes a procedure for forming the black layer.
First, a laminate in which an adhesion layer, a metal layer, and an organic film are laminated on a transparent substrate is set in a chamber of a sputtering apparatus.
Then, the chamber was evacuated to 1 × 10-3After Pa, argon gas was introduced so that the pressure in the chamber became 1.3 Pa.
Then, in this atmosphere, power was supplied to the target, and a blackened layer having a thickness of 30nm was formed on the organic film while the substrate was conveyed.
In the above procedure, a conductive substrate was obtained in which a blackened layer was formed on the upper surface of the metal layer, that is, the surface of the metal layer opposite to the surface facing the adhesion layer, via the organic film, and the adhesion layer, the metal layer, the organic film, and the blackened layer were sequentially laminated on the transparent base material.
The obtained conductive substrate was subjected to an adhesion test and found to be 5B.
[ example 2]
A conductive substrate was produced in the same manner as in example 1, except that a nozzle having a circular spray pattern with a diameter of 70mm, which was formed on the surface of the base material 11 by the organic solution supplied from the nozzle hole 211 in the organic film production apparatus shown in fig. 1 and 2, was used in the organic film formation step.
The obtained conductive substrate was subjected to the adhesion test and found to be 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 2 was used in the organic film formation step, and the organic solution was not supplied from the nozzle to the substrate 11.
The obtained conductive substrate was subjected to the adhesion test and found to be 3B.
From the results of example 1, example 2, and comparative example 1, it was confirmed that the adhesion of the blackened layer can be improved by supplying the organic solution to the substrate and forming the organic film by using the nozzle and the liquid film forming unit in combination. In other words, the reason for this is that the organic coating is uniformly formed on the surface of the metal layer.
Further, according to the configurations of embodiment 1 and embodiment 2, it was confirmed that the nozzle having the nozzle hole in which the ejection pattern formed on the surface of the base material is elliptical can be used as the nozzle, and the adhesion of the black layer can be particularly improved.
From these results, it was confirmed that a uniform organic coating film could be formed on the substrate by using the nozzle and the liquid film forming unit in combination.
The method for producing an organic film, the method for producing a conductive substrate, and the apparatus for producing an organic film have been described above with reference to the embodiments, examples, and the like, but the present invention is not limited to the embodiments, examples, and the like. Various modifications and changes can be made within the scope of the present invention described in the claims.
This application is based on the priority claim of Japanese patent application No. 2015-195190, which was filed on the patent office on 30.9.2015, which is hereby incorporated by this international application for its entirety.
Description of the symbols
11 base material
13 liquid film forming unit
21 nozzle
211 nozzle hole
50A, 50B, 60A, 60B, 70 conductive substrate
51 transparent substrate
52. 52A, 52B metal layer
53. 53A, 53B, 72A, 72B organic coating
54. 54A, 54B, 73A, 73B blackened layer

Claims (5)

1. A method for producing an organic film by supplying an organic solution to the surface of a sheet-like substrate to form an organic film,
supplying the organic solution from a nozzle and a liquid film forming unit to a surface of the substrate conveyed with a width direction of the substrate as a height direction,
the nozzle is provided with a plurality of nozzle holes in a manner to oppose the surface of the base material,
the liquid film forming unit has a supply port provided at an upper portion of the substrate in a height direction, and the liquid film forming unit supplies the organic solution from the supply port so that the organic solution becomes a film-like liquid flow and so that a surface of the substrate comes into contact with the film-like liquid flow of the organic solution.
2. The method for producing an organic coating according to claim 1, wherein an ejection pattern of the nozzle formed on the surface of the base material by the organic solution supplied from the nozzle hole has an elliptical shape.
3. A method for manufacturing a conductive substrate includes:
a metal layer forming step of forming a metal layer on at least one surface of a transparent substrate;
an organic film forming step of forming an organic film on the upper surface of the metal layer; and
a blackening layer forming step of forming a blackening layer on an upper surface of the organic film,
in the organic film forming step, an organic film is formed on the upper surface of the metal layer by the method for manufacturing an organic film according to claim 1 or 2.
4. An organic film manufacturing apparatus for forming an organic film by supplying an organic solution to a surface of a sheet-like substrate, the apparatus comprising:
a conveying unit for conveying the base material with the width direction of the base material as the height direction;
a plurality of nozzles provided with nozzle holes so as to face the surface of the base material; and
a liquid film forming unit having a supply port provided at an upper portion of the substrate in a height direction, the liquid film forming unit supplying the organic solution from the supply port so that the organic solution is in a film shape and a surface of the substrate is in contact with a film-shaped liquid flow of the organic solution.
5. The apparatus for manufacturing an organic coating according to claim 4, wherein an ejection pattern of the nozzle formed on the surface of the base material by the organic solution supplied from the nozzle hole has an elliptical shape.
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