JP2014047402A - Etchant, method of producing conductive element, and method of producing processed body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an etchant suitably used for a printing method.SOLUTION: An etchant includes iodine, an iodine compound, and a solvent. The solvent includes a solvent having a boiling point of 170°C or more.

Description

  The present technology relates to an etching solution, a method for manufacturing a conductive element using the same, and a method for manufacturing a processed body. Specifically, the present invention relates to an etching solution suitable for use in a printing method.

  Conventionally, acid and alkali solutions are often used in silver etching (see, for example, Patent Documents 1 and 2). However, these etching solutions are not easy to handle, and in particular, the acid requires some contrivance in the container and the etching tank. Cyanide compounds and iodine solutions are known as gold etching solutions. Cyanide compounds are highly toxic, but iodine solutions are neutral and easy to handle (see Non-Patent Document 1). Patent Document 3 describes that this iodine solution can also be used for dissolving silver.

JP 2004-238656 A

JP 2004-315887 A

JP 2003-109949 A

Chemical Times 2004 No.3 P.10-16

  However, the iodine solution can be used in so-called wet etching in an etching tank, but there is a problem that when ethanol or the like is a main solvent and drying is performed quickly and directly printed, it is dried before being etched.

  Accordingly, an object of the present technology is to provide an etching solution suitable for use in a printing method, a method for manufacturing a conductive element using the same, and a method for manufacturing a processed body.

In order to solve the above-mentioned problem, the first technique is:
Containing iodine, an iodine compound, and a solvent,
The solvent is an etching solution containing a high boiling point solvent having a boiling point of 170 ° C. or higher.

The second technology is
Forming an electrically conductive portion and an insulating portion on the surface of the substrate by printing an etching solution on the conductive layer provided on the surface of the substrate, and forming a pattern of insulating elements on the surface of the substrate;
Etching solution
Containing iodine, an iodine compound, and a solvent,
A solvent is a manufacturing method of the electroconductive element containing the high boiling point solvent whose boiling point is 170 degreeC or more.

The third technology is
Printing an etchant on the thin film, and forming a plurality of hole elements in the thin film,
Etching solution
Containing iodine, an iodine compound, and a solvent,
The solvent is a method for patterning a thin film containing a high boiling point solvent having a boiling point of 170 ° C. or higher.

  According to the present technology, the etching solution contains a solvent, and this solvent contains a high-boiling point solvent having a boiling point of 170 ° C. or higher, so that drying of the etching solution can be suppressed during printing of the etching solution.

  As described above, according to the present technology, an etching solution suitable for use in a printing method can be provided.

FIG. 1 is a cross-sectional view illustrating a configuration example of an information input device. FIG. 2A is a plan view showing a configuration example of the first transparent conductive element. 2B is a cross-sectional view taken along line AA shown in FIG. 2A. FIG. 3A is a plan view illustrating a configuration example of the transparent electrode portion of the first transparent conductive element. 3B is a cross-sectional view taken along line AA shown in FIG. 3A. FIG. 3C is a plan view illustrating a configuration example of the transparent insulating portion of the first transparent conductive element. 3D is a cross-sectional view taken along the line AA shown in FIG. 3C. FIG. 4A is a schematic diagram illustrating a first arrangement example of hole elements in a transparent electrode portion. FIG. 4B is a schematic diagram illustrating a second arrangement example of the hole elements in the transparent electrode portion. FIG. 5A is a schematic diagram illustrating a first arrangement example of hole elements in the transparent insulating portion. FIG. 5B is a schematic diagram illustrating a second arrangement example of the hole elements in the transparent insulating portion. FIG. 6A is a plan view illustrating an example of a shape pattern of a boundary portion. 6B is a cross-sectional view taken along line AA shown in FIG. 6A. FIG. 7A is a schematic diagram illustrating a first arrangement example of hole elements in a boundary portion. FIG. 7B is a schematic diagram illustrating a second arrangement example of the hole elements in the boundary portion. FIG. 8A is a plan view showing a configuration example of the second transparent conductive element. 8B is a cross-sectional view taken along the line AA shown in FIG. 8A. 9A to 9C are process diagrams for explaining an example of the method for manufacturing the first transparent conductive element according to the second embodiment of the present technology. FIG. 10A is an enlarged sectional view showing a part of the patterned transparent electrode portion. FIG. 10B is a cross-sectional view illustrating another configuration example of the insulating element. FIG. 11 is a flowchart for explaining a random pattern generation algorithm. 12A to 12D are schematic diagrams for explaining a random pattern generation algorithm. FIG. 13A and FIG. 13B are schematic diagrams showing the relationship between the size of dots (squares) constituting the grid and the hole elements. FIG. 14 is a cross-sectional view illustrating a modified example of the first transparent conductive element according to the first embodiment of the present technology. FIG. 15A is a schematic diagram illustrating an example of a grid having two types of dot sizes. FIG. 15B is a schematic diagram illustrating an example of a transparent electrode portion formed using a grid having two types of dot sizes. FIG. 15C is a schematic diagram illustrating an example of a transparent insulating portion formed using a grid having two types of dot sizes. FIG. 16A is a schematic diagram illustrating an example of a grid having three types of dot sizes. FIG. 16B is a schematic diagram illustrating an example of a transparent electrode portion formed using a grid having three types of dot sizes. FIG. 16C is a schematic diagram illustrating an example of a transparent insulating portion formed using a grid having three types of dot sizes. FIG. 17A is a schematic diagram illustrating an example of a grid in which the dot shape is a parallelogram shape. FIG. 17B is a schematic diagram illustrating an example of a transparent electrode portion formed using a grid in which the dot shape is a parallelogram shape. FIG. 17C is a schematic diagram illustrating an example of a transparent insulating portion formed using a grid in which the dot shape is a parallelogram shape. FIG. 18 is a plan view showing a configuration example of wiring formed by the wiring forming method according to the fifth embodiment. FIG. 19A is a plan view showing a first configuration example of the region R shown in FIG. 18A. FIG. 19B is a plan view showing a second configuration example of the region R shown in FIG. 18A.

Embodiments of the present technology will be described in the following order with reference to the drawings.
1. First embodiment (example of etching solution)
2. Second Embodiment (Example of Method for Manufacturing Conductive Element)
3. Third Embodiment (Example of Transparent Electrode Part and Transparent Insulating Part Having Multiple Size Hole Element)
4). Fourth embodiment (example in which the arrangement direction of the hole elements is in an oblique crossing relationship)
5. Fifth Embodiment (Example of Wiring Formation Method)

<1. First Embodiment>
[Etching solution]
The etching solution contains iodine, an iodine compound, and a solvent. The solvent is a single solvent or a mixed solvent containing two or more solvents, and includes a high boiling point solvent. From the viewpoint of suppressing the drying of the etching solution, the solvent is preferably composed of a high-boiling solvent or contains a high-boiling solvent as a main component. Here, the main component means that it is within the range of 50 parts by mass or more and less than 100 parts by mass with respect to 100 parts by mass of the whole solvent (the whole mixed solvent).

  The boiling point of the high boiling point solvent is 170 ° C or higher, preferably 170 ° C or higher and 310 ° C or lower. When the boiling point of the high-boiling solvent is 170 ° C. or higher, drying of the etching solution can be suppressed during printing of the etching solution. On the other hand, when the boiling point of the high boiling point solvent is 310 ° C. or lower, the high boiling point solvent can be easily obtained as a commercial product.

  When the solvent contains a high-boiling solvent as a main component, a low-boiling solvent is used as a sub-component solvent. In particular, in the case of a solution containing an iodine compound, since inexpensive water can be used and the amount of the organic solvent can be reduced, the etching solution can be reduced in price.

  The etching solution is suitable for application to a printing method. Among the printing methods, it is particularly suitable when applied to the ink jet method. In the ink jet method, since the printing droplets are as small as several pL or less, the specific surface area is increased and the drying speed is increased. However, in the etching solution according to the present embodiment, since the solvent contains a high boiling point solvent as described above, an increase in the drying speed is suppressed even when printing droplets are as small as several pL or less. Can do. Therefore, the insulating element having a desired shape can be patterned into the conductive layer. That is, an arbitrary etching pattern can be formed by direct printing without complicated processes such as resist film formation and exposure.

  The etchant is preferably neutral. This is because the etching liquid can be easily handled. Here, neutral means that the hydrogen ion index (Ph) is in the range of 6 to 8. The etching solution is suitable for use as a metal etching solution for etching metal, and is particularly suitable for use in etching silver among metals.

(Iodine compound)
The iodine compound is not particularly limited as long as it can supply I ⁻ ions, and a known material can be used. For example, potassium iodide, tetrabutylammonium iodide, ammonium iodide or the like can be used alone or in combination of two or more. When an aqueous solvent is used as the solvent, it is preferable to prepare a potassium iodide solution and dissolve iodine therein. This is because iodine is difficult to dissolve in water, but dissolves well in an aqueous lithium iodide solution, so that iodine can be dissolved to a predetermined concentration.

(High boiling point solvent)
A high boiling point solvent will not be specifically limited if it has a boiling point of 170 degreeC or more, A well-known solvent can be used. For example, diethylene glycol, propylene glycol, triethylene glycol, ethylene glycol, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, Dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, ethylene glycol monobutyl ether acetate The , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 3-methoxy butanol, dimethyl sulfoxide, butyl carbitol, N- such methylpyrrolidone may be used alone or in combination of two or more. In particular, glycol-based and ether-based compounds have good compatibility with water and can be easily mixed with an aqueous potassium iodide solution.

(Other solvents)
The other solvent mixed with the high boiling point solvent is, for example, a low boiling point solvent at 170 ° C. or lower. A low boiling point solvent will not be specifically limited if it has a boiling point of 170 degrees C or less, A well-known solvent can be used. For example, pure water, ethanol, isopropyl alcohol (IPA), methyl ethyl ketone (MEK), toluene (TOL), cyclohexanone, acetonitrile and the like can be used alone or in combination of two or more.

(Thickener)
From the viewpoint of increasing the viscosity, the etching solution preferably further contains a thickener. The thickener is not particularly limited, and a known thickener can be used. For example, cellulose, ethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, higher fatty acid amide, carbon black, montmorillonite and other clay minerals, silica, acrylic resin, urethane resin, epoxy resin, polyester resin, gelatin, albumin, casein, polyamide compound, polyether A compound, a polyglycol compound, a polyvinyl compound, a polyalkylene oxide compound, a polyacrylic acid compound and the like can be used alone or in combination of two or more.

(Object to be etched)
Examples of the shape of the object to be etched (corroded) by the etchant include a thin film shape, a plate shape, a block shape, a flake shape, a predetermined pattern shape, and the like, but are not limited to these shapes. The predetermined pattern shape may be either a random shape or a regular shape, and examples thereof include a linear shape such as a mesh shape and a stripe shape, but are not limited thereto. Examples of the member obtained by etching the object to be etched include conductive portions such as electrodes and wirings. Specific objects to be etched include what is printed in a mesh, nanowires are produced and applied to a substrate, so-called transparent conductive layers, plated films, nanoparticle layers, and metal layers by sputtering or vapor deposition. Examples of wiring using a nanoparticle paste are not limited thereto.

  Examples of the material to be etched (corroded material) include metals, metal alloys, and metal compounds. As a metal compound, a metal oxide is mentioned, for example. Examples of the metal and metal alloy include silver, gold, copper, nickel, and alloys thereof. Particularly, the etching performance to silver is good. Moreover, if it is a protective layer which can permeate | etch an etching liquid, you may be provided in the surface of the transparent conductive layer. As a material for the protective layer, for example, UV curable resin, thermosetting resin, or the like can be used.

(Printing method)
A known method can be used as the printing method. For example, an inkjet method, a relief printing method, an intaglio printing method, a stencil printing method, and the like can be used, and among these printing methods, the inkjet method is preferable. This is because a low-viscosity solution having good fluidity can be directly printed, so that the etching speed can be increased. When using a relief printing method, an intaglio printing method, a stencil printing method, etc. as a printing method, it is preferable that the etching liquid contains the thickener. This is because these printing methods require the etchant to have a high viscosity.

[effect]
According to the first embodiment, the etching solution contains a solvent, and this solvent contains a solvent having a boiling point of 170 ° C. or higher. For this reason, drying of an etching liquid can be suppressed at the time of printing of an etching liquid. Therefore, a desired etching pattern can be formed on the object to be etched.

  Etching by direct printing eliminates the need for auxiliary materials such as a photoresist and a dry film, so that steps such as exposure and development can be omitted. Therefore, the productivity of conductive elements (for example, electrode substrates and circuit boards) can be improved. Moreover, since the etching liquid which concerns on 1st Embodiment is neutral, handling of an etching liquid is easy.

<2. Second Embodiment>
In the second embodiment, a method for manufacturing a transparent conductive element using the etching solution according to the first embodiment will be described. The transparent conductive element obtained by this production method is suitable for use in information input devices and display devices. Hereinafter, a conductive element obtained by this manufacturing method and an information input device using the same will be described.

[Configuration of information input device]
FIG. 1 is a cross-sectional view illustrating a configuration example of an information input device. As shown in FIG. 1, the information input device 10 is provided on the display surface of a display device 4 which is an example of an electronic device. The information input device 10 is bonded to the display surface of the display device 4 by, for example, a bonding layer 5.

(Display device)
The display device 4 to which the information input device 10 is applied is not particularly limited. For example, a liquid crystal display, a CRT (Cathode Ray Tube) display, a plasma display panel (PDP), electroluminescence ( Various display devices such as an electro luminescence (EL) display and a surface-conduction electron-emitter display (SED) can be used.

(Information input device)
The information input device 10 is a so-called projected capacitive touch panel, and includes a first transparent conductive element 1 and a second transparent conductive element provided on the surface of the first transparent conductive element 1. 2, and the first transparent conductive element 1 and the second transparent conductive element 2 are bonded together via a bonding layer 6. Moreover, you may make it further provide the optical layer 3 on the surface of the 2nd transparent conductive element 2 as needed.

(First transparent conductive element)
FIG. 2A is a plan view showing a configuration example of the first transparent conductive element. 2B is a cross-sectional view taken along line AA shown in FIG. 2A. As shown in FIGS. 2A and 2B, the first transparent conductive element 1 includes a substrate 11 having a surface and a transparent conductive layer 12 provided on the surface. Here, two directions that are orthogonally crossed in the plane of the substrate 11 are defined as an X-axis direction (first direction) and a Y-axis direction (second direction).

The transparent conductive layer 12 includes a transparent electrode part (transparent conductive part) 13 and a transparent insulating part 14. The transparent electrode portion 13 is an X electrode portion that extends in the X-axis direction. The transparent insulating portion 14 is a so-called dummy electrode portion, is an insulating portion that extends in the X-axis direction and is interposed between the transparent electrode portions 13 to insulate between the adjacent transparent electrode portions 13. These transparent electrode portions 13 and transparent insulating portions 14 are provided on the surface of the base material 11 so as to be alternately adjacent in a plane in the Y-axis direction. 2A and 2B, the first region R ₁ indicates a formation region of the transparent electrode portion 13, and the second region R ₂ indicates a formation region of the transparent insulating portion 14.

(Transparent electrode part, transparent insulation part)
The shape of the transparent electrode portion 13 is preferably appropriately selected according to the screen shape, the drive circuit, and the like, and examples thereof include a linear shape and a shape in which a plurality of rhombus shapes (diamond shapes) are linearly connected. In particular, it is not limited to these shapes. 2A and 2B illustrate a configuration in which the shape of the transparent electrode portion 13 is a linear shape.

  FIG. 3A is a plan view illustrating a configuration example of the transparent electrode portion of the first transparent conductive element. 3B is a cross-sectional view taken along line AA shown in FIG. 3A. The transparent electrode portion 13 is a transparent conductive layer 12 formed so that a plurality of hole elements (insulating elements) 13 a are randomly arranged two-dimensionally in the X-axis direction and the Y-axis direction on the surface of the substrate 11. . In this way, the formation of moire can be suppressed by forming the plurality of hole elements 13a at random. In adjacent rows, hole elements adjacent in the X-axis direction and hole elements adjacent in the Y-axis direction are connected.

  The plurality of hole elements 13a are formed, for example, connected or separated from each other in the X-axis direction. The plurality of hole elements 13a are formed, for example, connected in the Y-axis direction or separated from each other. The hole 13b of the transparent electrode portion 13 is formed by the hole elements 13a formed so as to be connected or separated from each other. That is, the hole 13b is formed by one or a plurality of hole elements 13a. In adjacent rows, it is preferable that the hole elements 13a in the oblique direction with respect to the X-axis direction or the Y-axis direction are separated from each other. Thereby, in order to reduce the difference in coverage of the transparent conductive material between the transparent electrode portion 13 and the transparent insulating portion 14, even when the ratio of the hole element 13a of the transparent electrode portion 13 is increased, the X-axis direction Alternatively, a conductive path oblique to the Y-axis direction can be ensured. That is, a low surface resistance can be maintained.

  More specifically, the transparent electrode portion 13 is a transparent conductive layer 12 formed by randomly separating a plurality of hole portions 13b, and a transparent conductive portion 13c is interposed between adjacent hole portions 13b. Yes. The hole 13b is formed by one hole element 13a or a plurality of connected hole elements 13a. The shape of the hole 13b changes randomly on the surface of the substrate 11. The transparent conductive portion 13c has, for example, a transparent conductive material as a main component. The conductivity of the transparent electrode portion 13 is obtained by the transparent conductive portion 13c.

  FIG. 4A is a schematic diagram illustrating a first arrangement example of hole elements in a transparent electrode portion. In the first arrangement example shown in FIG. 4A, the hole elements 13a adjacent to each other in the X-axis direction in the adjacent row and the hole elements 13a adjacent to each other in the Y-axis direction are connected to each other. Alternatively, the hole elements 13a adjacent to each other in an oblique direction with respect to the Y-axis direction are also connected. Here, the oblique directions with respect to the X-axis direction or the Y-axis direction are specifically directions of 45 degrees, 135 degrees, 225 degrees, and 315 degrees.

  FIG. 4B is a schematic diagram illustrating a second arrangement example of the hole elements in the transparent electrode portion. In the second arrangement example shown in FIG. 4B, the hole elements 13a adjacent to each other in the X axis direction and the hole elements 13a adjacent to each other in the Y axis direction are connected to each other in the adjacent line. The hole elements 13a adjacent in the oblique direction with respect to the X-axis direction or the Y-axis direction are separated from each other by the transparent conductive portion 13c.

  In the first arrangement example, the hole elements 13a adjacent in the oblique direction are connected to each other, and the conductive path in the oblique direction is cut, whereas in the second arrangement example, the hole elements adjacent in the oblique direction are cut. 13a are separated from each other, and an oblique conductive path is secured. Therefore, in the second arrangement example, the transparent electrode has a higher ratio of the hole elements 13a than in the first arrangement example (that is, a low coverage ratio of the transparent conductive material as compared with the first arrangement example). The part 13 can function as an electrode part. Accordingly, when the second arrangement example is adopted as the configuration of the transparent electrode portion 13, the transparent conductive material of the transparent electrode portion 13 and the transparent insulating portion 14 is suppressed while suppressing the increase in the surface resistance of the transparent electrode portion 13. It is possible to reduce the coverage difference and suppress the pattern appearance of the transparent electrode portion 13.

  FIG. 3C is a plan view illustrating a configuration example of the transparent insulating portion of the first transparent conductive element. 3D is a cross-sectional view taken along the line AA shown in FIG. 3C. The transparent insulating part 14 is a transparent conductive layer formed such that a plurality of hole elements (insulating elements) 14a are randomly arranged two-dimensionally in the X-axis direction and the Y-axis direction on the substrate surface. In this way, the formation of moire can be suppressed by forming the plurality of hole elements 14a at random. In adjacent rows, hole elements adjacent in the X-axis direction and hole elements adjacent in the Y-axis direction are connected.

  The plurality of hole elements 14a are formed, for example, connected in the X-axis direction or separated from each other. The plurality of hole elements 14a are formed, for example, connected to or separated from each other in the Y-axis direction. The gap portion 14c of the transparent insulating portion 14 is formed by the hole elements 14a formed so as to be connected or separated from each other. In adjacent rows, it is preferable that the hole elements 14a in the oblique direction with respect to the X-axis direction or the Y-axis direction are connected to each other. Thereby, in order to reduce the coverage difference of the transparent conductive material between the transparent electrode portion 13 and the transparent insulating portion 14, even when the ratio of the hole element 14a of the transparent insulating portion 14 is reduced, the X-axis direction Alternatively, the conductive paths oblique to the Y axis direction can be reduced. That is, high surface resistance can be maintained.

  More specifically, the transparent insulating portion 14 is composed of a plurality of island portions 14b separated by a separation portion 14c. The plurality of island portions 14b are formed on the surface of the base material 11 in a random pattern. The spacing portion 14c is formed by one hole element 14a or a plurality of connected hole elements 14a. The islands 14b are electrically insulated by the spacing part 14c. The shape of the island part 14 b changes randomly on the surface of the base material 11. The island part 14a has, for example, a transparent conductive material as a main component.

  FIG. 5A is a schematic diagram illustrating a second arrangement example of hole elements in the transparent insulating portion. In the first arrangement example shown in FIG. 5A, the hole elements 14a adjacent to each other in the X-axis direction in the adjacent row and the hole elements 14a adjacent to each other in the Y-axis direction are connected to each other, and the X-axis direction in the adjacent row Alternatively, the hole elements 14a adjacent to each other in the oblique direction with respect to the Y-axis direction are also connected. Here, the oblique directions with respect to the X-axis direction or the Y-axis direction are specifically directions of 45 degrees, 135 degrees, 225 degrees, and 315 degrees.

  FIG. 5B is a schematic diagram illustrating a first arrangement example of hole elements in the transparent insulating portion. In the second arrangement example shown in FIG. 5B, the hole elements 14a adjacent in the X-axis direction or the Y-axis direction are connected to each other in the adjacent row, whereas in the adjacent row, the hole elements 14a are connected to the X-axis direction or the Y-axis direction. The hole elements 14a adjacent to each other in an oblique direction are separated from each other by an island part 14b.

  In the first arrangement example, the island portions 14b adjacent in the oblique direction are separated from each other and the conductive path in the oblique direction is cut, whereas in the second arrangement example, the island portions 14b adjacent in the oblique direction are cut. They are connected, and a conductive path in an oblique direction is secured. Therefore, in the first arrangement example, the transparent insulating layer has a lower ratio of the hole elements 14a than in the second arrangement example (that is, even in the high coverage ratio of the transparent conductive layer as compared with the second arrangement example). The part 14 can function as an insulating part. Therefore, when the first arrangement example is adopted as the configuration of the transparent insulating portion 14, the transparent conductive material of the transparent electrode portion 13 and the transparent insulating portion 14 is prevented from decreasing the surface resistance of the transparent electrode portion 13. It is possible to reduce the coverage difference and suppress the pattern appearance of the transparent electrode portion 13.

  4A to 5B show examples of the transparent electrode portion 13 and the transparent insulating portion 14 when the hole elements 13a and 14a are formed by the ink jet printing method. When the hole elements 13a and 14a are formed by the ink jet printing method, the hole elements 13a and 14a have a circular shape, a substantially circular shape, an elliptical shape, a substantially elliptical shape, or the like.

  Whether or not the ink jet printing method is used to form the hole elements 13a and 14a can be confirmed as follows. That is, the transparent electrode portion 13 and the transparent insulating portion 14 are observed with a microscope or the like, and whether or not the shape of the hole element 13a and the hole element 14a includes a shape such as a circular arc, a substantially circular arc, an elliptical arc, or a substantially elliptical arc shape. Determine. If any of these shapes is included in the shapes of the hole element 13a and the hole element 14a, it can be assumed that the ink jet printing method is used to form the hole element 13a and the hole element 14a.

  As the shape of the hole elements 13a and 14a, for example, a dot shape can be used. As the dot shape, for example, a circular shape, a substantially circular shape, an elliptical shape, or a substantially elliptical shape can be used. Different shapes may be adopted for the hole element 13a and the hole element 14a. Here, the substantially circular shape means a circle in which some distortion is given to a perfect circle (perfect circle) defined mathematically. The almost elliptical shape means an ellipse in which some distortion is given to a mathematically defined complete ellipse, and the elliptical shape includes, for example, an ellipse and an egg shape.

  It is preferable that the hole element 13a and the hole element 14a have a size that cannot be visually recognized. Moreover, you may make it employ | adopt a different magnitude | size with the hole element 13a and the hole element 14a.

  It is preferable that the hole 13b and the island part 14b have a size that cannot be recognized visually. Specifically, the size of the hole 13b and the island 14b is preferably 100 μm or less, more preferably 60 μm or less. Here, the size (diameter) means the maximum one of the passing lengths of the hole portion 13b and the island portion 14b. When the size of the hole 13b and the island 14b is 100 μm or less, the visual recognition of the hole 13b and the island 14b can be suppressed.

In the first region R ₁ , for example, the plurality of hole portions 13b are exposed regions on the substrate surface, whereas the transparent conductive portion 13c interposed between the adjacent hole portions 13b is a covered region on the substrate surface. It becomes. On the other hand, in the second region R ₂ , the plurality of island portions 14b serve as the covering region of the base material surface, whereas the separated portions 14c interposed between the adjacent island portions 14b are separated from the exposed region of the base material surface. Become.

  The average ratio P1 of the hole elements 13a per unit section of the transparent electrode part 13 is preferably P1 ≦ 50 [%], more preferably P1 ≦ 40 [%], and further preferably P1 ≦ 30 [%]. Satisfies. This is because by satisfying the relationship of P1 ≦ 50 [%], an increase in electrical resistance of the transparent electrode portion 13 can be suppressed and the function of the transparent electrode portion 13 as an electrode can be improved.

  The average ratio P2 of the hole elements 14a per unit section of the transparent insulating portion 14 preferably satisfies the relationship of 50 [%] <P2, more preferably 60 [%] <P2. This is because by satisfying the relationship of 50 [%] <P2, it is possible to suppress a decrease in the electrical resistance of the transparent insulating portion 14 and improve the function of the transparent insulating portion 14 as an insulating portion.

The difference ΔP (= P2−P1) between the average ratio P1 of the hole elements 13a per unit section of the transparent electrode section 13 and the average ratio P2 of the hole elements 14a per unit section of the transparent insulating section 14 is preferably ΔP ≦ 30 [%], more preferably ΔP ≦ 20 [%], and still more preferably ΔP ≦ 10 [%]. By satisfying this relationship, when the transparent electrode portion 13 and the transparent insulating portion 14 are visually compared, the transparent conductive layer 12 is covered in the same manner in the first region R ₁ and the second region R _2. Therefore, the visual recognition of the transparent electrode portion 13 and the transparent insulating portion 14 can be suppressed.

The average ratio P1 of the hole elements 13a per unit section of the transparent electrode part 13 can be obtained as follows.
First, an image of the transparent electrode portion 13 is taken with a microscope. Next, a 100 × 100 grid (unit section) is set in the photographed image, and it is determined whether or not the hole element 13a is formed at each dot (square) position constituting the grid. The number n of dots on which 13a is formed is counted. Here, a section in which a 100 × 100 grid is set is referred to as a unit section. Next, the ratio p of the hole element 13a is obtained using the following equation.
p = (n / N) × 100
n: Number of dots in which the hole element 13a is formed among the dots constituting the grid of 100 × 100 N: Sum of dots constituting the grid of 100 × 100

This process is performed at 10 locations arbitrarily selected from the transparent electrode portion 13, and the ratios p1, p2,..., P10 of the hole element 13a per unit section of the transparent electrode portion 13 are obtained. Next, the average number P1 of the hole elements 13a per unit section of the transparent electrode portion 13 is obtained by simply averaging (arithmetic average) the number of dots obtained as described above.
The average ratio P2 of the hole elements 14a per unit section of the transparent insulating portion 14 can also be obtained in the same manner as the average ratio P1 of the hole elements 13a per unit section of the transparent electrode section 13 described above.

(Boundary part)
FIG. 6A is a plan view illustrating an example of a shape pattern of a boundary portion. 6B is a cross-sectional view taken along line AA shown in FIG. 6A. A random shape pattern is preferably provided at the boundary between the transparent electrode portion 13 and the transparent insulating portion 14. Thus, by providing a random shape pattern at the boundary part, the visual recognition of the boundary part can be suppressed. Here, the boundary portion indicates a region between the transparent electrode portion 13 and the transparent insulating portion 14, and the boundary L indicates a boundary line that separates the transparent electrode portion 13 and the transparent insulating portion 14. . Depending on the shape pattern of the boundary portion, the boundary L may be a virtual line instead of a solid line.

  FIG. 7A is a schematic diagram illustrating a first arrangement example of hole elements in a boundary portion. It is preferable that the hole element 13a and the hole element 14a are randomly arranged in the boundary part between the transparent electrode part 13 and the transparent insulating part 14 in the extending direction of the boundary part. When such an arrangement is adopted, the hole elements 13a are arranged so as to be in contact with or overlap the boundary L on the transparent electrode part 13 side, for example. The hole elements 14a are arranged so as to be in contact with or overlap the boundary L on the transparent insulating portion 14 side, for example.

  The arrangement of the hole elements 13a and the hole elements 14a at the boundary is not limited to a random arrangement, and the hole elements 13a and the hole elements 14a are regularly arranged only at the boundary. Also good.

  As shown in FIG. 7B, the holes 13 b and the islands 14 b may be arranged at the boundary L in synchronization with the extending direction of the boundary L. Moreover, the hole element 13a and the hole element 14a, or the hole 13b and the island part 14b may be arranged at the boundary L in synchronization with the extending direction of the boundary L.

(Base material)
As the substrate 11, for example, a transparent inorganic substrate or plastic substrate can be used. As the shape of the base material 11, for example, a transparent film, sheet, substrate or the like can be used. Examples of the inorganic base material include quartz, sapphire, glass, and clay film. As a material for the plastic substrate, for example, a known polymer material can be used. Specific examples of known polymer materials include triacetyl cellulose (TAC), polyester (TPEE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polyamide (PA), and aramid. , Polyethylene (PE), polyacrylate, polyether sulfone, polysulfone, polypropylene (PP), diacetyl cellulose, polyvinyl chloride, acrylic resin (PMMA), polycarbonate (PC), epoxy resin, urea resin, urethane resin, melamine resin , Cycloolefin polymer (COP), cycloolefin copolymer (COC) and the like. The thickness of the plastic substrate is preferably 3 to 500 μm from the viewpoint of productivity, but is not particularly limited to this range.

(Transparent conductive layer)
As the material of the transparent conductive layer 12, for example, one or more selected from the group consisting of a metal oxide material having electrical conductivity, a metal material, and the like can be used. Examples of the metal oxide material include indium tin oxide (ITO), zinc oxide, indium oxide, antimony-added tin oxide, fluorine-added tin oxide, aluminum-added zinc oxide, gallium-added zinc oxide, silicon-added zinc oxide, and zinc oxide. -Tin oxide system, indium oxide-tin oxide system, zinc oxide-indium oxide-magnesium oxide system, etc. are mentioned. As the metal material, for example, metal nanoparticles, metal wires, and the like can be used. Specific examples of such materials include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, Examples thereof include metals such as antimony and lead, and alloys thereof.

(Second transparent conductive element)
FIG. 8A is a plan view showing a configuration example of the second transparent conductive element. 8B is a cross-sectional view taken along the line AA shown in FIG. 8A. As shown in FIGS. 8A and 8B, the second transparent conductive element 2 includes a base material 21 having a surface and a transparent conductive layer 22 provided on the surface. Here, two directions orthogonal to each other in the plane of the substrate 21 are defined as an X-axis direction and a Y-axis direction.

The transparent conductive layer 22 includes a transparent electrode part (transparent conductive part) 23 and a transparent insulating part 24. The transparent electrode portion 23 is a Y electrode portion that extends in the Y-axis direction. The transparent insulating portion 24 is a so-called dummy electrode portion, is an insulating portion that extends in the Y-axis direction and is interposed between the transparent electrode portions 23 to insulate between the adjacent transparent electrode portions 23. These transparent electrode portions 23 and transparent insulating portions 24 are provided on the surface of the base material 21 so as to be alternately adjacent in a plane in the X-axis direction. The transparent electrode portion 13 and the transparent insulating portion 14 included in the first transparent conductive element 1 and the transparent electrode portion 23 and the transparent insulating portion 24 included in the second transparent conductive element 2 are, for example, orthogonal to each other. . 8A and 8B, the first region R ₁ indicates a region for forming the transparent electrode portion 23, and the second region R ₂ indicates a region for forming the transparent insulating portion 24.
The second transparent conductive element 2 is the same as the first transparent conductive element 1 except for the above.

(Optical layer)
The optical layer 3 is, for example, a protective layer for suppressing change with time. The material of the optical layer 3 is not particularly limited as long as it is transparent, but examples thereof include UV (ultraviolet) curable resins, thermosetting resins, and thermoplastic resins. Specifically, acrylic resin, urethane resin, polyester resin, polyester polyurethane resin, epoxy resin, urea resin, melamine fat, cycloolefin polymer (COP), cycloolefin copolymer (COC), ethyl cellulose, polyvinyl alcohol (PVA), silicone Well-known materials, such as resin, are mentioned.

[Method for producing transparent conductive element]
Next, an example of a method for manufacturing the first transparent conductive element 1 configured as described above will be described with reference to FIGS. 9A to 9C. Note that the second transparent conductive element 2 can be manufactured in substantially the same manner as the first transparent conductive element 1, and therefore the description of the method for manufacturing the second transparent conductive element 2 is omitted.

(Film formation process)
First, as shown to FIG. 9A, the transparent conductive base material 1a is produced by forming the transparent conductive layer 12 as a thin film on the surface of the base material 11. As shown in FIG. As a method for forming the transparent conductive layer 12, any of dry and wet film forming methods can be used.

  Examples of dry film forming methods include CVD (Chemical Vapor Deposition): chemical reaction such as thermal CVD, plasma CVD, photo-CVD, and ALD (Atomic Layer Disposition). In addition to PVD methods (Physical Vapor Deposition) such as vacuum deposition, plasma-assisted deposition, sputtering, and ion plating: materials vaporized physically in vacuum Can be used on the substrate to form a thin film.

  In the case of using a dry film forming method, after the transparent conductive layer 12 is formed, the transparent conductive layer 12 may be annealed as necessary. Thereby, the transparent conductive layer 12 becomes, for example, a mixed state of amorphous and polycrystalline or a polycrystalline state, and the conductivity of the transparent conductive layer 12 is improved.

  As a wet film forming method, for example, a transparent conductive paint containing a conductive filler is applied or printed on the surface of the base material 11 to form a coating film on the surface of the base material 11, and then dried and / or baked. The method can be used. Examples of the coating method include a micro gravure coating method, a wire bar coating method, a direct gravure coating method, a die coating method, a dip method, a spray coating method, a reverse roll coating method, a curtain coating method, a comma coating method, a knife coating method, and a spin coating method. A coating method or the like can be used, but is not particularly limited thereto. Further, as the printing method, for example, a relief printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, a screen printing method and the like can be used, but not particularly limited thereto. . Moreover, as the transparent conductive substrate 1, a commercially available material can be used.

(Etching process)
Next, as shown in FIG. 9B, an etching solution is printed (drawn) on the first region R ₁ of the transparent conductive layer 12, and the transparent conductive layer 12 is dissolved by this etching solution. Thereby, the hole elements 13a are formed so as to be randomly arranged two-dimensionally in the X-axis direction (first direction) and the Y-axis direction (second direction) of the surface of the base material 11. Next, the progress of etching is stopped by cleaning the transparent conductive layer 12 as necessary. Thus, the first region R ₁ of the transparent conductive layer 12 is patterned, a transparent electrode 13 is obtained.

Next, as shown in FIG. 9C, an etching solution is printed (drawn) on the second region R ₂ of the transparent conductive layer 12, and the transparent conductive layer 12 is dissolved by this etching solution. Thereby, the hole elements 14a are formed so as to be randomly arranged two-dimensionally in the X-axis direction (first direction) and the Y-axis direction (second direction) of the surface of the substrate 11. Next, the progress of etching is stopped by cleaning the transparent conductive layer 12 as necessary. Thus, the second region R ₂ of the transparent conductive layer 12 is patterned, a transparent insulating portion 14 is obtained.

By repeating the etching process of the first region R ₁ and the second region R ₂ described above, the transparent electrode portions 13 and the transparent insulating portions 14 that are alternately provided in a plane on the surface of the base material 11 are formed.

  As the etchant, the etchant according to the first embodiment described above is used. As the printing method, for example, a relief printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, an ink jet printing method, a micro contact printing method, a screen printing method, or the like can be used. Among the methods, it is preferable to use an ink jet printing method. This is because there is no need to produce a plate and printing on demand is possible. 9B and 9C show an example in which the etching solution is printed (drawn) on the transparent conductive layer 12 by applying the etching solution from the nozzle 33 by the ink jet printing method.

  The etching liquid is printed (drawn) based on, for example, a random pattern generated in advance. Specifically, the random pattern is stored in advance in the storage unit as a raster image in which white dots and black dots are arranged in a random pattern, and the etching liquid is printed (drawn) based on the raster image. The details of the algorithm for creating a raster image in which white dots and black dots are arranged in a random pattern will be described later.

  It is preferable to select the printing resolution appropriately depending on the printing method. For example, in the inkjet printing method, it is necessary to determine the resolution (Dots Per Inch (dpi)) from the size of one dot depending on the performance and to draw.

以上により、図２Ａおよび図２Ｂに示す第１の透明導電性素子１が得られる。 Table 1 shows an example of the relationship between the size of one dot and the resolution.

Thus, the first transparent conductive element 1 shown in FIGS. 2A and 2B is obtained.

  FIG. 10A is an enlarged sectional view showing a part of the patterned transparent electrode portion 13. In FIG. 10A, an example of the transparent conductive layer 12 including the metal wire 101 and the binder 102 is shown. In the etching step, the portion of the transparent conductive layer 12 where the etching solution is dropped is removed, and a hole element 13a as an insulating element is formed. That is, in the etching process, the metal wire 101 and the binder 102 which are members constituting the transparent conductive layer 12 are removed. 10A, it is preferable that a part of the metal nanowire 101 included in the transparent conductive layer 12 protrudes from the surface of the transparent conductive layer 12. This is because the transparent electrode portion 13 and an external FPC (Flexible Printed Circuit), a drive circuit, and the like can be electrically connected through the protruding portion of the metal nanowire 101. Here, the hole element 13 a of the transparent electrode portion 13 has been described, but the same applies to the hole element 14 a of the transparent insulating portion 14.

  FIG. 10B is a cross-sectional view illustrating another configuration example of the insulating element. The insulating element is not limited to the above-described hole element 13a. As shown in FIG. 10B, in the etching process, the metal wire 101 included in the transparent conductive layer 12 where the etching solution is dropped is divided. Thus, the insulating element 13d may be formed by being in an insulated state. In this case, the film also remains in the portion of the transparent conductive layer 12 that becomes the insulating element 13d. Although the insulating part element of the transparent electrode part 13 has been described here, the same applies to the insulating part element of the transparent insulating part 14.

[Raster image creation algorithm]
Hereinafter, a raster image creation algorithm will be described with reference to FIG.
First, when the dot size and the overall size are set in step S1, a grid in which the overall size is divided in units of the set dot size is created in step S2 as shown in FIG. 12A. In the above-described etching process, the etching solution is printed (drawn) at the positions of the dots of the grid to form the hole elements 13a and 14a. The dots constituting the grid are rectangular, but when the etching solution is printed (drawn) by the ink jet printing method, the hole elements 13a and 14a are circular, almost circular, or elliptical as described above. Or since it becomes a substantially elliptical shape, both shapes differ.

Next, in step S3, as shown in FIG. 12B, an address (n ₁ , n ₂ ) is set to each dot of the created grid. Here, n ₁ is an address in the row direction (X-axis direction (first direction)), and n ₂ is an address in the column direction (Y-axis direction (second direction)). Next, when the dot ratio p forming the hole element is set in step S4, the address (n ₁ , n ₂ ) is set to the initial address (1, 1) in step S5. Here, the dot ratio p is a numerical value of 0 or more and 100 or less. In the following description, “%” may be added to the dot ratio p.

  Here, the ratio p of the dots forming the hole elements indicates the ratio of the dots forming the hole elements among all the dots constituting the entire size (that is, the ratio of the dots for printing (drawing) the etching solution). . The ratio p of the dots forming the hole element corresponds to the average ratio P1 of the hole elements 13a and the average ratio P2 of the hole elements 14a. When generating a random pattern for forming the transparent electrode portion 13, the dot ratio p is preferably p ≦ 50 [%], more preferably p ≦ 40 [%], and still more preferably p ≦ 30 [%]. %] Is preferable. On the other hand, when generating a random pattern for forming the transparent insulating portion 14, the dot ratio p is preferably set within a range of 50 [%] <p, more preferably 60 [%] <p. It is preferable.

  The difference Δp (= p2−p1) between the dot ratio p1 of the random pattern for forming the transparent electrode portion 13 and the dot ratio p2 of the random pattern for forming the transparent insulating portion 14 is preferably Δp ≦ It is preferable to set within a range of 30 [%], more preferably Δp ≦ 20 [%], and still more preferably Δp ≦ 10 [%].

Next, in step S6, the dot of the address (n ₁ , n ₂ ) (hereinafter referred to as “set address”) set in step S5, step S12 or step S13 is 0 or more and 100 or less. A random number Nr is generated. As an algorithm for generating the random number Nr, for example, Mersenne twister (MT) can be used. Next, in step S7, it is determined whether or not the random number Nr generated in step 6 is equal to or less than the dot ratio p set in step S4 (Nr ≦ p).

Table 2 shows the relationship between the random number Nr and the print information (binary information).

If the random number Nr is equal to or less than the dot ratio p, in step S8, as shown in FIG. 12C, the dot at the set address (n ₁ , n ₂ ) is set for printing. On the other hand, when the random number Nr is larger than the hole element ratio P, in step S8, as shown in FIG. 12C, the dot at the set address (n ₁ , n ₂ ) is not printed (hereinafter referred to as “non-printing”). )).

  FIG. 12C shows an example in which dots set for printing are represented by “black dots” and dots set for non-printing are represented by “white dots”. FIG. 12C shows an example in which one of print information (binary information “print” and “non-print”) is set for each dot in the order indicated by the arrows. Is an example, and the order of setting print information is not limited to this example.

Next, in step S10, it is determined whether or not the address n ₁ is the maximum address value N ₁ in the row direction. If the address n ₁ is the maximum value N ₁ , the process proceeds to step S11. On the other hand, if the address n ₁ is not the maximum value N ₁ , the address n ₁ is incremented in step S12, and the process returns to step S6.

In step S11, it is determined whether or not the address n ₂ is the maximum address value N ₂ in the column direction. If the address n ₂ is not the maximum value N ₂ , the address n ₂ is incremented in step S13, and the process returns to step S6. On the other hand, when the address n ₂ is the maximum value N ₂ , as shown in FIG. 12D, print information (binary information) is set for all the dots constituting the grid, and white dots 32 and black A raster image in which dots 31 are arranged in a random pattern is completed, and the process proceeds to step S14. Next, in step S14, the raster image (binary image) may be stored in the storage unit.

  In the above-described etching process, the raster image is read from the storage unit, and the inkjet head nozzle is sequentially moved to the position on the transparent conductive layer 12 corresponding to each dot of the raster image, based on the printing information of the raster image. Etch the etchant.

  Specifically, the etching liquid is applied from the inkjet head at a position on the transparent conductive layer 12 corresponding to a dot (for example, “black dot 31”) set for raster image printing. On the other hand, the etching liquid is not applied from the inkjet head at a position on the transparent conductive layer 12 corresponding to a dot (for example, “white dot 32”) set to non-printing of the raster image. Thereby, an etching pattern corresponding to the random pattern of the white dots 32 and the black dots 31 of the raster image is formed in the transparent conductive layer 12. In the above description of the operation control of the inkjet head, the example in which the inkjet head is moved to all of the printing position and the non-printing position has been described. However, the operation control of the inkjet head is not limited to this example. For example, the operation control of the ink jet head may be performed so that the ink jet head sequentially moves only to the printing position.

  FIG. 13A and FIG. 13B are schematic diagrams showing the relationship between the size of dots (squares) constituting the grid and the hole elements. As shown in FIG. 13A, when the circumference (for example, the circumference) of the hole element is located outside the corner of the square dot, the hole element 13a adjacent in the X axis direction or the Y axis direction in the adjacent example. In addition, in the adjacent example, the hole elements 13a adjacent to each other in an oblique direction with respect to the X-axis direction or the Y-axis direction are also connected to form one hole 13b. On the other hand, as shown in FIG. 13B, when the circumference (for example, the circumference) of the hole element is located on the inner side than the corner of the square dot, in the adjacent example, it is oblique to the X axis direction or the Y axis direction. The hole elements 13a adjacent to each other in the direction are not connected to each other, and a hole 13b that is spaced apart is formed.

[effect]
In the second embodiment, a plurality of hole elements (insulating part elements) 13a and hole elements (insulating part elements) 14a are two-dimensionally formed on the transparent conductive layer 12 in the X-axis direction and the Y-axis direction of the substrate surface. Since they are arranged at random, the hole elements 13a and 14a can be easily produced by a printing method, particularly an ink jet printing method.

  By connecting the hole elements 14a adjacent in the X-axis direction and the hole elements 14a adjacent in the Y-axis direction, the electrical path of the transparent conductive layer 12 is cut, and the transparent conductive layer 12 is replaced with the transparent insulating part 14 Can function as.

Since the transparent electrode portions 13 and the transparent insulating portions 14 are alternately provided on the substrate surface in a plane, the first region R ₁ where the transparent electrode portion 13 is provided and the transparent electrode portion 13 where the transparent electrode portion 13 is not provided. Thus, the difference in reflectance from the region R ₂ can be reduced. Further, since the provided hole elements 13a to the transparent electrode 13, the first region R ₁ and the reflectance difference between the second region R ₂ can be further reduced. Therefore, the visual recognition of the pattern of the transparent electrode part 13 can be suppressed.

  When a random pattern is created using a raster image, a random pattern matched with a printing method, particularly an ink jet printing method can be formed. Inkjet printing is on-demand printing, so there is no need to produce a plate, and feedback such as trial design becomes easy. Further, the ink jet printing method is suitable for use in a small amount and a variety of products, and is suitable for use as a touch panel of a mobile device in which product changes are remarkable.

[Modification]
(Protective layer)
As shown in FIG. 14, a protective layer 61 may be further provided on the surface of the transparent conductive layer 12. When the protective layer 61 includes metal nanowires, it is preferable that part of the metal nanowires protrude from the surface of the protective layer 61. This is because the transparent electrode portion 13 and an external FPC (Flexible Printed Circuit) 83, a drive circuit, and the like can be electrically connected through the protruding portion of the metal nanowire.

  The protective layer 61 protects the transparent conductive layer 12 and may have a function as a hard coat layer. As the material of the protective layer 61, for example, an ionizing radiation curable resin that is cured by light or an electron beam or a thermosetting resin that is cured by heat is preferably used, and a photosensitive resin that is cured by ultraviolet rays is most preferable. As such a photosensitive resin, for example, acrylate resins such as urethane acrylate, epoxy acrylate, polyester acrylate, polyol acrylate, polyether acrylate, and melamine acrylate can be used. For example, a urethane acrylate resin is obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and reacting the resulting product with an acrylate or methacrylate monomer having a hydroxyl group.

  The formation process of the protective layer 61 is provided between the film-forming process and the etching process of the transparent conductive layer 12, or after the etching process of the transparent conductive layer 12, for example. That is, the protective layer 61 is formed on the surface of the transparent conductive layer 12 before or after patterning. When the protective layer 61 is formed on the transparent conductive layer 12 before patterning, the transparent conductive layer 12 is etched as follows. First, when an etching solution is dropped on the surface of the protective layer 61, the dropped etching solution penetrates the protective layer 61 and reaches the transparent conductive layer 12. Thereafter, the transparent conductive layer 12 is etched by the reached etching solution.

  As a method for forming the protective layer, for example, a coating method or a printing method can be used. Examples of the coating method include a micro gravure coating method, a wire bar coating method, a direct gravure coating method, a die coating method, a dip method, a spray coating method, a reverse roll coating method, a curtain coating method, a comma coating method, a knife coating method, or a spin coating method. A coating method or the like can be used. As a printing method, for example, a relief printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, an ink jet printing, a micro contact printing or a screen printing method can be used.

(Pole element pattern)
In the second embodiment described above, an example in which a plurality of hole elements 13a and 14a are randomly formed and arranged two-dimensionally in the X-axis direction and the Y-axis direction on the surface of the base material 11 has been described. The formation pattern of the hole elements 13a and 14a is not limited to this example. For example, the plurality of hole elements 13 a and 14 a can be regularly formed and arranged two-dimensionally in the X-axis direction and the Y-axis direction on the surface of the base material 11. In addition, one of the plurality of hole elements 13a and 14a is two-dimensionally randomly arranged in the X-axis direction and the Y-axis direction on the surface of the substrate 11, and the other is ruled two-dimensionally. They may be formed and arranged as desired. Further, a hole element 14a on the surface of the substrate 11 only the second region in the (insulating region) R ₂ form, the first region (electrode region) hole elements 13a on the surface of the substrate 11 in R ₁ The transparent conductive layer (continuous film) 12 may be provided continuously without forming the film.

<3. Third Embodiment>
The third embodiment is different from the first embodiment in that the hole elements 13a and 14a have two or more kinds of sizes. In order to form the hole elements 13a and 14a having two or more types of sizes, for example, the dot size of the grid may be set to two or more types.

  FIG. 15A shows an example of a grid having two types of dot sizes. FIGS. 15B and 15C show examples of the transparent electrode portion 13 and the transparent insulating portion 14 formed using this grid, respectively. The transparent electrode portion 13 and the transparent insulating portion 14 have two types of hole elements 13a and 14a.

  FIG. 16A shows an example of a grid having three types of dot sizes. FIGS. 16B and 16C show examples of the transparent electrode portion 13 and the transparent insulating portion 14 formed using this grid, respectively. The transparent electrode portion 13 and the transparent insulating portion 14 have hole elements 13a and 14a having three kinds of sizes.

<4. Fourth Embodiment>
In the fourth embodiment, the X-axis direction (first direction) and the Y-axis direction (second direction) are in a diagonally intersecting relationship, and the hole elements 13a in the X-axis direction and the Y-axis direction in this relationship, 14a is different from the first embodiment in that it is formed so as to be randomly arranged two-dimensionally. In order to form the hole elements 13a and 14a in the X-axis direction (first direction) and the Y-axis direction (second direction) that are in an oblique intersection relationship, for example, the grid dot shape is a shape such as a parallelogram shape. You can do it.

  FIG. 17A shows an example of a grid in which the dot shape is a parallelogram shape. FIGS. 17B and 17C show examples of the transparent electrode portion 13 and the transparent insulating portion 14 formed using this grid, respectively.

<5. Fifth Embodiment>
In the fifth embodiment, a wiring forming method using the etching solution according to the first embodiment will be described.

  FIG. 18 shows a configuration example of wiring formed by the wiring forming method according to the fifth embodiment. Note that in the fifth embodiment, the same portions as those in the first embodiment are denoted by the same reference numerals, and description thereof is omitted.

  A wiring 82 is electrically connected to one end of the transparent electrode portion 13, and the wiring 82 and a drive circuit (not shown) are connected via an FPC (Flexible Printed Circuit) 83. Between the wirings 82, an insulating part 84 having a long and narrow shape such as a linear shape is provided, and adjacent wirings 82 are electrically insulated from each other through the insulating part 84. In addition, in FIG. 18, the example in which the transparent electrode part 13 has a rhombus (diamond shape) is shown.

  FIG. 19A is a plan view illustrating a part of the wiring 82 and the insulating portion 84 in an enlarged manner. As shown in FIG. 19A, the wiring 82 is a linear conductive layer (continuous film) provided continuously without exposing the surface of the base material 11 by the hole element. The conductive layer, which is a continuous film, preferably has a substantially uniform film thickness. The conductive layer contains a metal material or a transparent conductive material as a main component. The insulating portion 84 between the wirings 82 has the same configuration as that of the transparent insulating portion 14 in the above-described second embodiment except that the island portion 14b has a metal material or a transparent conductive material as a main component. The hole element 14a of the insulating portion 84 can also be formed by a printing method such as an ink jet printing method as in the second embodiment.

  As illustrated in FIG. 19B, an insulating portion 84 formed of one row or two or more rows of hole element 14 a extending in the extending direction of the wiring 82 may be formed between the wirings 82. At this time, the adjacent hole elements 14a are connected in the extending direction and the direction perpendicular to the extending direction. Thereby, the wiring 82 is insulated by the hole element 14a. It is preferable that adjacent hole elements 14a are also connected in an oblique direction with respect to the extending direction and the direction perpendicular to the extending direction. This hole element 14a can also be formed by a printing method such as an ink jet printing method as in the second embodiment.

  Hereinafter, the present technology will be specifically described by way of examples. However, the present technology is not limited only to these examples.

(Examples 1-8)
First, iodine, potassium iodide (iodine compound), diethylene glycol monoethyl ether (high boiling point solvent) and pure water (low boiling point solvent) were mixed in the formulation shown in Table 4, and then dissolved by ultrasound. A mixture was prepared. Next, this mixed solution was heated in an oven at 80 ° C. for 30 minutes to obtain a uniform etching solution.

Example 9
Etching solution in the same manner as in Examples 1 to 8, except that iodine, potassium iodide (iodine compound), diethylene glycol monoethyl ether (high boiling point solvent) and pure water (low boiling point solvent) are mixed in the formulation shown in Table 5. Got.

(Example 10)
Etching solution was obtained in the same manner as in Examples 1 to 8, except that iodine, potassium iodide (iodine compound), propylene glycol (high boiling point solvent) and pure water (low boiling point solvent) were mixed in the formulation shown in Table 5. It was.

(Example 11)
Etching solution in the same manner as in Examples 1 to 8, except that iodine, potassium iodide (iodine compound), ethylene glycol monomethyl ether (high boiling point solvent) and pure water (low boiling point solvent) are mixed in the formulation shown in Table 5. Got.

(Example 12)
Etching solution was obtained in the same manner as in Examples 1 to 8, except that iodine, potassium iodide (iodine compound), dimethyl sulfoxide (high boiling point solvent) and pure water (low boiling point solvent) were mixed in the formulation shown in Table 5. It was.

(Examples 13 to 15)
After mixing iodine, potassium iodide (iodine compound), diethylene glycol monoethyl ether (high boiling point solvent) and pure water (low boiling point solvent) with the composition shown in Table 5, the mixture is dissolved by ultrasonic waves. A liquid was prepared. Next, after adding the addition amount of hydroxypropylmethylcellulose (thickening agent) shown in Table 2 to this mixed solution, it was heated in an oven at 80 ° C. for 30 minutes to obtain a uniform etching solution.

(Example 16)
Etching solutions were obtained in the same manner as in Examples 1 to 8, except that iodine, tetrabutylammonium iodide (iodine compound), and dimethyl sulfoxide (high boiling point solvent) were mixed in the formulation shown in Table 5.

(Comparative Example 1)
Etching solution was obtained in the same manner as in Examples 1 to 8, except that iodine, potassium iodide (iodine compound), ethanol (low boiling point solvent) and pure water (low boiling point solvent) were mixed in the formulation shown in Table 6. It was.

(Comparative Example 2)
Etching solution was prepared in the same manner as in Examples 1 to 8, except that iodine, potassium iodide (iodine compound), isopropyl alcohol (low boiling point solvent) and pure water (low boiling point solvent) were mixed in the formulation shown in Table 6. Obtained.

(Comparative Example 3)
Etching solutions were obtained in the same manner as in Examples 1 to 8, except that iodine, potassium iodide (iodine compound), and methyl ethyl ketone (low boiling point solvent) were mixed in the formulation shown in Table 6.

(Comparative Example 4)
Etching liquids were obtained in the same manner as in Examples 1 to 8, except that iodine, potassium iodide (iodine compound), and toluene (low boiling point solvent) were mixed in the formulation shown in Table 6.

(Comparative Example 5)
Etching liquids were obtained in the same manner as in Examples 1 to 8, except that iodine, potassium iodide (iodine compound), and cyclohexane (low boiling point solvent) were mixed in the formulation shown in Table 6.

(Comparative Example 6)
Etching solutions were obtained in the same manner as in Examples 1 to 8, except that iodine, potassium iodide (iodine compound), and acetonitrile (low boiling point solvent) were mixed in the formulation shown in Table 6.

<Etching performance>
Etching performance was evaluated as follows using the etching solutions of Examples 1 to 16 and Comparative Examples 1 to 6 obtained as described above. 1 microliter of etching liquid was dripped at the silver nanowire layer without a protective film, the silver nanowire layer after several seconds passed from the dripping under normal temperature environment was observed with the optical microscope, and the etching performance was evaluated on the following references | standards. The results are shown in Table 8.
○: The silver nanowire layer where the etching solution was dropped completely dissolved Δ: The silver nanowire layer where the etching solution was dropped partially dissolved ×: The silver nanowire layer where the etching solution was dropped Z

  1 μL of an etching solution is dropped on a silver nanowire layer with a protective film, and the silver nanowire layer after the lapse of 2 minutes and after the lapse of 3 minutes has been observed with an optical microscope in an environment at a temperature of 60 ° C. or 80 ° C. The etching performance was evaluated based on the above criteria. The results are shown in Table 8.

In addition, the silver nanowire layer without the above-mentioned protective film was produced as follows.
First, silver nanowire paint (manufactured by Blue nano), hydroxypropylmethylcellulose as a binder, and isocyanate were charged into a solvent and dispersed to prepare a silver nanowire paint. The mass ratio of the silver wire and the binder was 1: 1. The ratio of hydroxypropylmethylcellulose to isocyanate was 20 parts by mass of isocyanate with respect to 100 parts by mass of hydroxypropylmethylcellulose. As the solvent, a mixed solvent in which water and ethanol were mixed at a mass ratio of 1: 1 was used. The solid content of the silver nanowire paint was adjusted to 2% by mass. Next, the prepared silver nanowire coating was applied to the surface of a PET (polyethylene terephthalate) substrate (thickness: 100 μm) with a bar coater at 10 μm and dried to form a silver nanowire layer.

The silver nanowire layer with a protective film was produced as follows.
First, a silver nanowire layer was formed on the surface of a PET substrate in the same manner as the silver nanowire layer without the protective film described above. Next, an ultraviolet curable resin composition having the following composition was prepared, applied to the surface of the silver nanowire layer with a bar coater to a thickness of 3 μm, and cured by irradiating UV light from a UV lamp. Thereby, the protective layer was formed on the surface of the silver nanowire layer.

(Formulation of UV curable resin composition)
Urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UV1700B): 28.5% by mass
Polymerization initiator (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184D): 1.5% by mass
Butyl acetate: 70% by mass

<Viscosity measurement>
The viscosities of the etching solutions of Examples 5 and 13 to 15 obtained as described above were measured. An E-type viscometer was used for the measurement, and the measurement temperature was 25 ° C.

<Drawing test>
Using the etching solution of Example 5 obtained as described above, a drawing test using an industrial inkjet was actually performed. As a result, etching failure due to drying did not occur and arbitrary drawing was possible.

Table 3 shows the boiling points of the solvents contained in the etching solutions of Examples 1 to 16 and Comparative Examples 1 to 6.

Table 4 shows the compositions of the etching solutions of Examples 1-8. In addition, the unit of the numerical value of each component in Table 2 is “mass%”.

Table 5 shows the compositions of the etching solutions of Examples 9-16. In addition, the unit of the numerical value of each component in Table 3 is “mass%”.

Table 6 shows the compositions of the etching solutions of Comparative Examples 1-6. In addition, the unit of the numerical value of each component in Table 4 is “mass%”.

Table 7 shows the viscosities of the etching solutions of Examples 5 and 13-15.

Table 8 shows the evaluation results of the etching solutions of Examples 1 to 16 and Comparative Examples 1 to 6.

The following can be seen from the above evaluation results.
Examples 1 to 15: As a solvent for an etching solution, a mixed solvent containing a solvent having a boiling point of 170 ° C. or higher (high boiling point solvent) as a main component can be used to etch even a minute droplet.
Example 16: By using a single solvent composed of a solvent having a boiling point of 170 ° C. or higher as a solvent for an etching solution, etching can be performed even when a small droplet is dropped. Further, when tetrabutylammonium iodide is used as the iodine compound instead of potassium iodide, the same etching performance as that obtained when potassium iodide is used as the iodine compound can be obtained.
Examples 1 to 8: Good etching performance is obtained regardless of the mixing ratio of iodine and iodine compound.
Examples 13 to 15: When the etching solution contains a thickener, the etching rate tends to decrease.
Examples 9 to 12: If the main solvent has a boiling point of 170 ° C. or higher, good etching performance can be obtained regardless of the type.
Comparative Examples 1 and 2: Since a mixed solvent containing a low-boiling solvent having a boiling point of less than 170 ° C. is used, etching cannot be performed by dropping fine droplets.
Comparative Examples 3 to 6: Since a single solvent composed of a low-boiling solvent having a boiling point of less than 170 ° C. is used, etching cannot be performed by dropping fine droplets.

As described above, when the etching solution contains a high boiling point solvent having a boiling point of 170 ° C. or higher as the solvent, an etching solution suitable for use in the printing method can be provided.
The solvent for the etching solution is preferably a single solvent composed of a high boiling point solvent having a boiling point of 170 ° C. or higher, or a mixed solvent containing a high boiling point solvent having a boiling point of 170 ° C. or higher as a main component.

  The embodiments and examples of the present technology have been specifically described above. However, the present technology is not limited to the above-described embodiments and examples, and various modifications based on the technical idea of the present technology are possible. It is.

  For example, the configurations, methods, steps, shapes, materials, numerical values, and the like given in the above-described embodiments and examples are merely examples, and different configurations, methods, steps, shapes, materials, numerical values, and the like are necessary as necessary. May be used.

  The configurations, methods, steps, shapes, materials, numerical values, and the like of the above-described embodiments and examples can be combined with each other without departing from the gist of the present technology.

The present technology can also employ the following configurations.
(1)
Containing iodine, an iodine compound, and a solvent,
The said solvent is an etching liquid containing the high boiling point solvent whose boiling point is 170 degreeC or more.
(2)
The said solvent consists of a high boiling point solvent with a boiling point of 170 degreeC or more, or the etching liquid as described in (1) which has a high boiling point solvent with a boiling point of 170 degreeC or more as a main component.
(3)
The etching solution according to any one of (1) to (2), further containing a thickener.
(4)
The etching solution according to any one of (1) to (3), wherein the hydrogen ion index is 6 or more and 8 or less.
(5)
Forming an electrically conductive portion and an insulating portion on the surface of the base material by printing an etching solution on the conductive layer provided on the surface of the base material, and forming a pattern of an insulating element on the surface of the base material.
The etchant is
Containing iodine, an iodine compound, and a solvent,
The said solvent is a manufacturing method of the electroconductive element containing the high boiling point solvent whose boiling point is 170 degreeC or more.
(6)
The insulating element is two-dimensionally formed in a first direction and a second direction of the substrate surface,
The said electroconductive part and an insulating part are the manufacturing methods of the electroconductive element as described in (5) by which the said base-material surface is alternately provided planarly.
(7)
The method for producing a conductive element according to (6), wherein the insulating elements adjacent in the first direction and the insulating elements adjacent in the second direction are connected to each other.
(8)
The said printing is a manufacturing method of the electroconductive element in any one of (5) to (7) which is printing by the inkjet method.
(9)
The method for manufacturing a conductive element according to any one of (5) to (8), wherein a virtual grid is set on the substrate surface, and the etching solution is printed based on the set grid.
(10)
The method for manufacturing a conductive element according to any one of (5) to (9), wherein the insulating element is a hole element.
(11)
The said conductive layer is a manufacturing method of the electroconductive element in any one of (5) to (10) containing the metal filler.
(12)
The said metal filler is a manufacturing method of the electroconductive element as described in (11) which is metal nanowire.
(13)
The method for producing a conductive element according to (12), wherein the metal nanowires included in the conductive layer are divided by printing the etchant.
(14)
The method for producing a conductive element according to any one of (5) to (13), wherein the conductive layer is a transparent conductive layer or a metal layer.
(15)
The conductive layer manufacturing method according to any one of (5) to (14), wherein the conductive layer contains silver.
(16)
The conductive part according to any one of (5) to (15), wherein the conductive part is an electrode or a wiring.
(17)
Printing an etchant on the object to be etched, and forming a plurality of insulating elements on the object to be etched,
The etchant is
Containing iodine, an iodine compound, and a solvent,
The said solvent is a manufacturing method of the processed body containing the high boiling point solvent whose boiling point is 170 degreeC or more.
(18)
The method for manufacturing a processed body according to (17), wherein the object to be etched is a thin film.

DESCRIPTION OF SYMBOLS 1 1st transparent conductive element 2 2nd transparent conductive element 3 Optical layer 4 Display apparatus 5, 6 Bonding layer 10 Information input device 11, 21 Base material 12, 22 Transparent conductive layer 13, 23 Transparent electrode part 14 , 24 Transparent insulating part 13a Hole element 13b Hole part 13c Transparent conductive part 14a Island part 14b Island part 14c Gap part L Boundary R ₁ First area R ₂ Second area

Claims (18)

Containing iodine, an iodine compound, and a solvent,
The said solvent is an etching liquid containing the high boiling point solvent whose boiling point is 170 degreeC or more.   The etching solution according to claim 1, wherein the solvent comprises a high-boiling solvent having a boiling point of 170 ° C. or higher, or a high-boiling solvent having a boiling point of 170 ° C. or higher as a main component.   The etching solution according to claim 1, further comprising a thickener.   The etching solution according to claim 1, wherein the hydrogen ion index is 6 or more and 8 or less. Forming an electrically conductive portion and an insulating portion on the surface of the base material by printing an etching solution on the conductive layer provided on the surface of the base material, and forming a pattern of an insulating element on the surface of the base material.
The etchant is
Containing iodine, an iodine compound, and a solvent,
The said solvent is a manufacturing method of the electroconductive element containing the high boiling point solvent whose boiling point is 170 degreeC or more. The insulating element is two-dimensionally formed in a first direction and a second direction of the substrate surface,
The method for manufacturing a conductive element according to claim 5, wherein the conductive portion and the insulating portion are alternately provided in a planar manner on the surface of the base material.   The method for manufacturing a conductive element according to claim 6, wherein insulating elements adjacent in the first direction and insulating elements adjacent in the second direction are connected to each other.   The method for producing a conductive element according to claim 5, wherein the printing is printing by an inkjet method.   The method for manufacturing a conductive element according to claim 5, wherein a virtual grid is set on the substrate surface, and the etching solution is printed based on the set grid.   The method for manufacturing a conductive element according to claim 5, wherein the insulating element is a hole element.   The method for producing a conductive element according to claim 5, wherein the conductive layer contains a metal filler.   The method for producing a conductive element according to claim 11, wherein the metal filler is a metal nanowire.   The method for producing a conductive element according to claim 12, wherein the metal nanowires included in the conductive layer are divided by printing the etching solution.   The method for manufacturing a conductive element according to claim 5, wherein the conductive layer is a transparent conductive layer or a metal layer.   The method for manufacturing a conductive element according to claim 5, wherein the conductive layer contains silver.   The method for manufacturing a conductive element according to claim 5, wherein the conductive portion is an electrode or a wiring. Printing an etchant on the object to be etched, and forming a plurality of insulating elements on the object to be etched,
The etchant is
Containing iodine, an iodine compound, and a solvent,
The said solvent is a manufacturing method of the processed body containing the high boiling point solvent whose boiling point is 170 degreeC or more.   The method for manufacturing a workpiece according to claim 17, wherein the object to be etched is a thin film.

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