JP2018181677A - Transparent conductive wiring pattern, transparent conductive wiring substrate and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fine transparent conductive wiring pattern using a metal nanowire as a conductive material, to provide a transparent conductive wiring board having the transparent conductive wiring pattern formed thereon and to provide a method for manufacturing the transparent conductive wiring board.SOLUTION: The method for manufacturing a transparent conductive wiring board includes: a first step of forming a liquid repellent layer to a suspension including metal nanowires on the whole or a part of at least one main surface of a transparent base material; a second step of performing a lyophilization treatment for converting a predetermined region for wiring pattern formation on the surface of the liquid repellent layer into a lyophilic region to the suspension so that the difference in a contact angle of the liquid repellent layer before and after the lyophilization treatment to the suspension is 10 to 35°; a third step of applying a suspension including metal nanowires to the surface of the liquid repellent layer including the predetermined region subjected to lyophilization treatment; and a fourth step of drying and removing a dispersion medium in the suspension after the application of the suspension and selectively deposing the metal nanowires in the suspension on the predetermined region for wiring pattern formation to form a wiring pattern. Preferably, a metal constituting metal nanowires in a transparent conductive wiring pattern is silver or copper.SELECTED DRAWING: Figure 5

Description

  The present invention relates to a transparent conductive wiring pattern using metal nanowires, a transparent conductive wiring substrate on which the transparent conductive wiring pattern is formed, and a method of manufacturing the same.

  Metal nanowires are not only materials that can form transparent conductors that are superior in transparency and conductivity compared to transparent conductive film materials represented by conventional ITO, but also for mechanical durability such as bending and stretching. Since it is excellent, it is used for formation of the transparent conductive film using the film base material etc. which have flexibility.

Non-Patent Document 1 describes the following steps as an example of a method of forming a pattern using a conductive material containing metal nanowires.
(1) A step of applying a conductive ink containing metal nanowires to a substrate.
(2) A step of baking to form a transparent conductive layer.
(3) A step of forming a photosensitive resist on the transparent conductive layer.
(4) applying light energy to the resist through a suitable light shielding mask corresponding to a fine pattern;
(5) Developing the latent image of the obtained resist by elution with an appropriate developing solution.
(6) removing the exposed patterned film (transparent conductive layer) using an appropriate etching method.
(7) removing the remaining resist using an appropriate method.

  The patterning using subtractive photolithography as disclosed in the above-mentioned Non-Patent Document 1 requires a complicated process for patterning, including exposure, development, and cleaning, and metal of the area to be removed In addition to wasting the nanowires in some cases, it may be necessary to treat the developer waste solution. Further, there is a problem that the occurrence of a defect that collapses the conductive network of the nanowire formed on the substrate at the time of development, cleaning, etc. can not be avoided, and it is difficult to maintain the low resistance value expected as the conductive layer.

  As an additive manufacturing method that does not have the above-mentioned problems in the pattern formation method using the subtractive method, establishment of a technique for directly forming a fine pattern by a printing method such as inkjet printing, screen printing, or gravure printing which is a wet process It is desired.

  For example, in Non-Patent Document 2 below, a technique for forming a silver nanowire wiring pattern having a wiring width of about 1 mm is disclosed using inkjet printing as a patterning method.

  Further, in Non-Patent Document 3 below, a wiring pattern of silver nanowires is formed using a screen printing technique, with a wiring width of about 50 μm, and a distance between adjacent wirings (inter-wiring distance) of about 50 μm. Forming techniques are disclosed.

  Further, Non-Patent Document 4 discloses a technique for forming a silver nanowire wiring pattern having a wiring width of about 450 μm and a wiring distance of about 100 μm using a gravure printing method.

  Further, in Patent Document 1 below, a functional liquid containing a conductive material mainly based on a nonpolar solvent is coated and formed on a substrate partially pretreated with energy such as ultraviolet light irradiation and ozone treatment, It is disclosed that a wiring pattern having a line width of 41 μm and a line interval (inter-wiring distance) of 39 μm is possible as a conductive polymer-based wiring by a technology for forming a wiring on a processing portion. Similarly, in the wiring formation using organic silver as a toluene solvent, a wiring pattern having a line width of 10.4 μm and a line interval of 9.6 μm is formed.

JP, 2008-6565, A

Shih-Hsiang Lai, Chun-Yao Ou, Chia-Hao Tsai, Bor-Chuan Chuang, Ming-Ying Ma, and Shuo-Wei Liang; SID Symposium Digest of Technical Papers, Vol. 39, Issue 1, pp. 1200-1202 (2008) ACS Appl. Mater. Interfaces 7, 9254 (2015) Adv. Mater. 28 (28), 5986 (2016) Thin Solid Films 586, 70 (2015)

  However, in any of the additive methods shown in Non-Patent Documents 2 to 4, it is not possible to achieve both the transparency with a total light transmittance of 50% or more and the fineness with a wiring width of 50 μm or less. Further, in the technique of Patent Document 1, although a pattern of about 10 μm is formed for both the line width (wiring width) of the wiring and the line interval, the process for forming the wiring pattern is the high water repellency of the liquid repellent layer. The process is complicated because it is necessary to apply energy to the entire surface of the substrate with an excimer lamp for the purpose of conversion, and there is no mention of a wiring pattern using a highly anisotropic conductive material such as silver nanowires.

  In view of the above problems of the prior art, the present invention requires fine patterning such as industrially useful flexible displays, touch panels, electrodes for flexible transistors, wearable sensors, implant sensors, microchannels, MEMS, electrodes for electrochemical measurement, etc. It is an object of the present invention to provide a fine transparent conductive wiring pattern using metal nanowires as a conductive material, a transparent conductive wiring substrate on which a transparent conductive wiring pattern is formed, and a method of manufacturing the same.

  In order to achieve the above object, the present invention has the following embodiments.

  [1] The absolute value of the degree of orientation of the central portion of the wire with respect to the longitudinal direction of the wire is 35 ° or more and 65 ° or less of the metal nanowire constituting the wire including the metal nanowire as the conductive material; The transparent conductive wiring pattern characterized in that the absolute value of the degree of orientation is 20 ° or more and 45 ° or less.

  [2] The transparent conductive wiring pattern according to the above [1], wherein the metal constituting the metal nanowire is silver or copper.

  [3] The transparent conductive wiring pattern according to [1] or [2], wherein the width of the wiring is 20 to 50 μm.

  [4] Any one or a combination of one or more selected from the group consisting of glass, polyurethane, silicone, saturated polyester, polycarbonate, polyparaxylylene, thermoplastic polyimide, polyether sulfone, acrylic resin, polyolefin and polyvinyl chloride The transparent conductive wiring board provided with the transparent conductive wiring pattern as described in any one of said [1]-[3] formed in the surface of the said transparent base material comprised by these, and the said base material.

  [5] A first step of forming a liquid repellent layer for a suspension containing metal nanowires on all or part of at least one main surface of a transparent substrate, forming a predetermined wiring pattern on the surface of the liquid repellent layer Lyophilic treatment is performed to change the suspension area to lyophilic with respect to the suspension, and the difference in contact angle between the liquid repellent layer and the suspension before and after the lyophilic treatment is 10 ° or more and 35 ° or less A second step of applying a suspension containing the metal nanowires to the surface of a liquid repellent layer containing the predetermined region for forming a wiring pattern subjected to the lyophilic treatment, a suspension containing the metal nanowires After the application of the liquid, the dispersion medium in the suspension is dried and removed, and the metal nanowires in the suspension are selectively deposited on the predetermined wiring pattern forming region to form a wiring pattern. Manufacturing the transparent conductive wiring substrate according to the above [4] including How to make.

  [6] The method for producing a transparent conductive wiring board according to [5], wherein the lyophilic treatment is irradiation with ultraviolet light.

  [7] The method for producing a transparent conductive wiring substrate according to the above [5] or [6], wherein the viscosity of the suspension containing the metal nanowires at 25 ° C. is 0.5 to 50 mPa · s.

  [8] The method for producing a transparent conductive wiring substrate according to any one of the above [5] to [7], wherein the suspension containing the metal nanowires does not contain a binder resin.

  According to the present invention, it is possible to form a fine wiring pattern having transparency by the industrially useful and simple additive method, and the industrially useful flexible display, touch panel, electrode for flexible transistor, wearable sensor, implant sensor The present invention is applicable to devices requiring fine patterning, such as micro-channels, MEMS, and electrodes for electrochemical measurement.

It is explanatory drawing of the edge part (edge) part and center part in the transparent conductive wiring pattern concerning embodiment. It is a figure which shows the definition of the orientation degree of the transparent conductive wiring pattern concerning embodiment, the Gaussian fitting calculated from image process data, and its calculation conditions. They are an image-processed photograph (a) of the wiring in the transparent conductive wiring pattern concerning embodiment, and a figure (b) which shows angle distribution of metal nanowire obtained from image processing data based on this. It is a figure which shows the orientation degree of the metal nanowire in wiring from which wiring width differs in the transparent conductive wiring pattern concerning embodiment. It is a figure which shows the difference in the orientation degree of metal nanowire in the wiring end (edge) part in the transparent conductive wiring pattern concerning embodiment, a wiring center part, and the whole wiring. It is a figure which shows the measurement result by X-ray-photoelectron spectroscopy (XPS) of the liquid-repellent layer surface before and behind vacuum-ultraviolet light irradiation in Example 1. FIG. It is a figure which shows the scanning electron micrograph of wiring of the linear pattern containing silver nanowire obtained in Examples 1-4.

  Hereinafter, modes for carrying out the present invention (hereinafter, referred to as embodiments) will be described according to the drawings.

  The explanatory view of the end (edge) part and the central part in the transparent conductive wiring pattern concerning an embodiment is shown in Drawing 1 (a) and (b). FIG. 1 (a) shows the case of the wiring of the straight line pattern, and FIG. 1 (b) shows the case of the wiring of the curved line pattern.

  Here, the transparent conductive wiring pattern according to the embodiment is formed of the wiring including the metal nanowire as the conductive material, and the degree of orientation of the metal nanowire constituting the wiring in the longitudinal direction of the wiring is closer to the wiring end It is characterized in that it is small at the edge).

  In the present specification, “transparent” means that in the transparent conductive wiring pattern, the area not occupied by the metal nanowires in the wiring pattern area is 60% or more, and the transparent conductive wiring substrate is all It means that the said transparent conductive wiring pattern is formed in the base-material surface whose light transmittance is 80% or more.

  In addition, the wiring end (edge) portion E (hereinafter sometimes referred to as a wiring end E) means an end portion (the length of the wiring when the entire wiring width is A, as shown in FIG. 1A). 10 μm from the end of the wire in the direction orthogonal to the direction, and the wire central portion C is a region up to ± 5 μm from the center in the width direction of the wire, and the degree of orientation of the metal nanowire It is an area to evaluate. For this reason, when the wiring width is smaller than 30 μm, a state in which parts of the wiring end (edge) portion E and the wiring central portion C overlap with each other occurs. The present embodiment can be applied to a wiring pattern having a wiring width of 20 μm or more.

  As the shape of the wiring, in addition to the straight line pattern shown in FIG. 1A and the curve pattern shown in FIG. 1B, a broken line pattern (having a bent portion), a honeycomb pattern, a ring pattern, etc. may be mentioned. The wiring pattern may have any shape as long as it has a resistance value required for various applications as a conductive material. In the case of a curved pattern, as shown in FIG. 1 (b), the wiring end (edge) portion E is a region from the outer peripheral end and the inner peripheral end to 10 μm when the entire wiring width is A. It is possible to evaluate the orientation by defining the central portion C of the wiring as a region up to ± 5 μm from the middle in the width direction of the wiring. The wiring end (edge) portion E means both side portions in the case of a straight wiring and both the inner and outer circumferences in the case of a curved wiring.

  For the orientation of metal nanowires, specify the image of wiring edge E, wiring central part C and entire wiring from the magnified image of wiring, and use commercially available image analysis software, such as the orientation J Distribution of the open source and public domain ImageJ. The angle of the metal nanowires with respect to the longitudinal direction of the wiring using software (the angle between the longitudinal direction of the wiring and the metal nanowires, which is not larger than the absolute value, in the range of -90 ° to + 90 °) It is possible to obtain a distribution of values). Furthermore, Gaussian fitting (for example, using Origin commercially available as a data analysis tool manufactured by Light Stone (registered trademark), using angular distribution data of metal nanowires with respect to the longitudinal direction of the wiring obtained by the above image analysis Full-width at half maximum (FWHM) that defines the degree of orientation by using Gaussian fitting) and using the value of the standard deviation σ obtained from the approximate expression according to the basic equation (1) and definition shown in FIG. You can ask for

Here, the counts (denoted as Y-axis Counts) in FIG. 2 are values substantially corresponding to the number of metal nanowires having a predetermined degree of orientation, and are based on the metal nanowires in the predetermined wiring pattern area subjected to image analysis. One connection between two adjacent pixels having the same brightness is regarded as one count. The horizontal axis (X axis) in FIG. 2 is the angle of the metal nanowire with respect to the longitudinal direction of the wiring. As an image analysis method for obtaining the angular distribution, the background is processed to dark and the metal nanowires are processed to light gray (gray to white) gray scale, and adjacent pixels of the same level of brightness centering on light pixels are processed. The angle between the direction and the base axis (longitudinal direction of the wiring) is calculated at two points found, and the frequency at each angle is integrated. For example, if the pixel direction of the adjacent bright color is 10 °, the count of 10 ° becomes one. In the basic formula (1), A indicates the baseline of the distribution curve of FIG. 2, and B indicates the peak top. σ is a standard deviation obtained by Gaussian fitting of the angular distribution (X-axis: angle, Y-axis: count), and FWHM represented by the following formula (2) The length (unit: "°") of the angle range (X-axis value) corresponding to the Y-axis value), which is an absolute half of the "orientation degree definition" diagram described in FIG. The value (FWHM / 2) is defined as the degree of orientation.
FWHM = 2 × σ × (2 × ln 2) ^0.5 2.32.35482 × σ (2)
The smaller the degree of orientation (FWHM / 2), the higher the orientation of the metal nanowires, which means that the directions of the metal nanowires are aligned (close to parallel to the longitudinal direction of the wiring).

  FIGS. 3A and 3B show an example of an image-processed photograph of the wiring in the transparent conductive wiring pattern according to the embodiment and the angular distribution of the metal nanowire obtained from the image processing data based thereon. FIG. 3 (a) is an image-processed photograph, and FIG. 3 (b) is an angular distribution of the metal nanowires over the entire width of the wiring.

  From the angular distribution of the metal nanowires shown in FIG. 3 (b), the degree of orientation of the metal nanowires in the wiring shown in the image processing photograph of FIG. 3 (a) is, as described above, using the algorithm shown in FIG. Can be calculated. FIG. 4 shows the degree of orientation (FWHM / 2) of the metal nanowires in the wirings having different wiring widths in the transparent conductive wiring pattern according to the embodiment. The orientation of the metal nanowires determined by the method shown in FIGS. 2 (a), (b) and FIGS. 3 (a) and 3 (b) when the wirings are formed with the wiring width set to 20 μm, 50 μm, 100 μm and 150 μm Degrees. It can be seen that the smaller the wire width, the smaller the value of the degree of orientation, and the more the metal nanowires in the entire wire are oriented (the directions are more uniform).

  As the wiring including the metal nanowires, it is desirable that the metal nanowires cross each other and that the intersections are connected in order to maintain the conductivity. The degree of orientation (FWHM / 2) of the metal nanowires when the longitudinal direction of the entire wiring including the metal nanowires is 0 ° C. has an absolute value of 30 ° to 60 ° (30 ° to 60 °, or -60 °) It is preferable that it is --30 degrees, and 35 degrees or more and 55 degrees or less are more preferable. If the absolute value of the degree of orientation is less than 30 °, it becomes difficult to form an intersection between metal nanowires necessary for the development of conductivity. Also, if it exceeds 60 °, it means that the proportion of metal nanowires oriented in a direction close to the direction perpendicular to the longitudinal direction of the wiring increases, and an efficient conductive path utilizing the anisotropy of metal nanowires Formation of

  In FIG. 5, the wiring edge (edge) portion E in the transparent conductive wiring pattern in which the wiring width is set to 20 μm, 50 μm, 100 μm and 150 μm, the central part C of the wiring and the degree of metal nanowire orientation in the entire wiring (FWHM / 2 Is shown. In the transparent conductive wiring pattern of any wiring width, the degree of orientation of the wiring end (edge) portion E is smaller than the degree of orientation of the wiring central portion C. This indicates that the degree of orientation of the end portion E of the wire is aligned in the longitudinal direction of the wire, and that the central portion C of the wire has a favorable orientation for forming the intersection (intersection) of the metal nanowires. There is. Thus, by aligning the degree of orientation at the end portion E of the wire in the longitudinal direction of the wire, a structure advantageous for preventing a short circuit between wires is obtained, and the absolute value of the degree of orientation of the entire wire with respect to the longitudinal direction of the wire By setting the angle to 30 ° or more and less than 60 °, the probability of forming the intersections (intersections) of the metal nanowires is improved, which is a structure useful for forming a conductive path.

  20 degrees or more and 45 degrees or less are preferable, and, as for the absolute value of the orientation degree of the wiring edge part E, 25 degrees or more and 40 degrees or less are more preferable. When the absolute value of the degree of orientation of the wiring end E is less than 20 °, the degree of contribution to the reduction of the resistance value due to the connection of the intersections (intersections) of the metal nanowires present at the wiring end E decreases. Also, if the absolute value of the degree of orientation of the end portion E of the wire is more than 45 °, this means that there are many metal nanowire wires facing in the direction perpendicular to the wire direction, and perpendicular to the longitudinal direction The probability of metal nanowires pointing in a direction close to the normal direction is high, which induces undesirable phenomena such as migration.

  35 degrees or more and 65 degrees or less are preferable, and, as for the absolute value of the orientation degree of wiring center part C, 40 degrees or more and 60 degrees or less are more preferable. If the absolute value of the degree of orientation of the central portion C of the wiring is less than 35 °, the probability of forming intersections (intersections) decreases, and if it exceeds 65 °, the conductivity in the longitudinal direction of the wiring is reduced.

  Further, by using the manufacturing method described later, the degree of orientation and the occupancy rate of the metal nanowires occupied in the wiring become higher at the wiring end E than at the wiring center C.

  A transparent conductive wiring substrate according to another embodiment of the present invention includes a transparent base and the above-mentioned transparent conductive wiring pattern formed on the surface of the base. The base on which the transparent conductive wiring pattern is formed may be any base that does not interfere with the function of the transparent conductive wiring pattern, but a base having better adhesion to the wiring including metal nanowires is preferable, and heat is preferable. Further preferred is a film made of a plastic resin material. By using a film made of a thermoplastic resin material and performing heat treatment at or above its softening point, metal nanowires can be embedded in a substrate, and adhesion can be further improved. In addition, transparent base materials, such as thermosetting resin and glass, can also be used.

  The transparent substrate may be colored, but the total light transmittance (the transparency of visible light) is preferably high, and the total light transmittance is preferably 80% or more. For example, glass, polyurethane, silicone, polyparaxylylene (parylene (registered trademark)), saturated polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.), polycarbonate, thermoplastic polyimide, polyether sulfone, acrylic resin ( A film made of a thermoplastic resin such as PMMA or the like), polyolefin, polyvinyl chloride or the like is mentioned as a suitable example, and a substrate composed of any one or a combination of two or more selected from these may be used. Among them, a substrate containing glass, polyurethane, silicone, polyparaxylylene (parylene (registered trademark)) is preferable in view of industrial versatility, heat resistance, adhesion with metal nanowires, and stretchability of the substrate. .

  In the transparent conductive wiring substrate, a step of forming a liquid repellent layer having liquid repellency against a suspension containing metal nanowires on all or part of at least one main surface of a substrate (hereinafter, first step) A lyophilic treatment is carried out to change the predetermined wiring pattern forming area on the surface of the liquid repellent layer to a lyophilic property with respect to the suspension containing the metal nanowires, and the liquid repellent layer before and after the lyophilic treatment. The step of setting the difference between the contact angle with the suspension to 10 ° or more and 35 ° or less (hereinafter referred to as the second step) and the surface of the liquid repellent layer including the predetermined area for forming a wiring pattern subjected to the lyophilic treatment A step of applying a suspension containing metal nanowires (hereinafter referred to as the third step) and drying of the dispersion medium in the suspension after the application of the suspension containing the metal nanowires Selective deposition of metal nanowires on specified wiring pattern formation areas And forming a wiring pattern (hereinafter referred to as the fourth step). That is, the wettability (contact angle) of the suspension containing the metal nanowires to the substrate is formed on the surface of the substrate, and the wettability (contact angle) of the suspension containing the metal nanowires to the substrate is good The metal nanowires are deposited by selectively depositing a suspension containing the metal nanowires in the region and drying off the dispersion medium.

  The first step is a step of forming a liquid repellent layer having liquid repellency to a suspension containing metal nanowires on all or part of at least one main surface of the substrate. The liquid repellent layer has a property of repelling when the suspension containing the metal nanowires is applied on the liquid repellent layer because the wettability of the suspension containing the metal nanowires is small (the contact angle is large). The liquid repellent layer may be a material capable of causing a chemical reaction on the surface of the liquid repellent layer in the second step described later to convert the liquid repellent region into a lyophilic region, preferably a fluorine-based coating A membrane is mentioned.

  The second step is a step of changing part of the liquid repellent layer formed in the first step to lyophilic with respect to the suspension. A part of the lyophilic area (lyophilic area) is an area for forming a wiring pattern in which metal nanowires are selectively deposited in a fourth step described later to form a wiring pattern. In the present embodiment, by lyophilizing a part of the lyophobic layer (lyophilic treatment), the difference in the contact angle of the lyophobic layer before and after the lyophilic treatment is treated to be 10 ° or more and 35 ° or less. Process the predetermined wiring pattern formation area on the liquid repellent layer so that the contact angle of the liquid repellent layer after the lyophilic treatment is smaller than the contact angle of the liquid repellent layer before the lyophilic treatment by 10 ° or more and 35 ° or less As a method, a method of irradiating ultraviolet light is preferable. As the ultraviolet light, vacuum ultraviolet light (wavelength: 10 to 200 nm) is suitably used. When the ultraviolet light is irradiated, the liquid repellent layer is decomposed, and the base material of the base is exposed to be lyophilic. Plasma treatment is another effective means. By performing the oxygen plasma treatment, a hydrophilic functional group is formed on the surface of the substrate, and along with that, it can be made lyophilic.

  About the contact angle after irradiation of an ultraviolet light etc., the difference of the contact angle of a liquid-repellent area (non-wiring area) and a lyophilic area (wiring pattern formation area) should just be 10 degrees or more and 35 degrees or less. The preferred contact angle difference depends on the substrate to be used and the liquid repellent layer formed on the surface of the substrate, and therefore it is determined by experiments. For example, a fluorine-based coating agent was used as the liquid repellent layer. In the case, it is preferably 10 ° or more and 35 ° or less, and more preferably 15 ° or more and less than 30 °. If the difference in contact angle is less than 10 °, the difference in contact angle between the liquid repellent area and the lyophilic area is small, and the boundary area of the pattern becomes unclear. Also, if it exceeds 35 °, the difference in boundary area between the liquid repellent area and the lyophilic area becomes large, the difference in wettability with the suspension containing the metal nanowires becomes large, and the wiring having appropriate orientation of the metal nanowires Formation of

  Moreover, although the said ultraviolet light is irradiated through the photomask which has a light transmission part between an ultraviolet light source and a base material, the transparent conductive wiring obtained in the 4th process mentioned later by the width | variety of this light transmission part The wiring width of the wiring including the metal nanowires formed on the substrate is determined. In the present invention, it is possible to produce a wiring including metal nanowires having a wiring width of 20 μm or more, and the wiring width can be changed according to the application to be used. A wire with a wire width of less than 20 μm is excellent in various properties such as transparency, but depending on the degree of orientation, there is a problem that the conductivity decreases due to the decrease in the frequency of intersection of metal nanowires. is there.

  The third step is a step of applying a suspension containing the metal nanowires onto the liquid repellent layer surface including the predetermined wiring pattern forming region subjected to the lyophilic treatment in the second step. When the suspension containing the metal nanowires is applied to the entire surface of the liquid repellent layer after the second step, the suspension containing the metal nanowires applied to the surface of the liquid repellent layer not subjected to the lyophilic treatment is repelled, It moves to the predetermined wiring pattern formation area subjected to the lyophilic treatment. The metal nanowires in the suspension containing the metal nanowires coated on the surface of the liquid repellent layer not subjected to the lyophilic treatment by this movement are the edge (edge) portion (wiring of the region for forming the predetermined wiring pattern subjected to the lyophilic treatment) It is swept away to the end E). As a result, the density (occupied area ratio) of the metal nanowires at the end (edge) of the predetermined wiring pattern forming area is the density (occupied area) of the metal nanowires at the central part (wiring central part C) of the wiring pattern forming area. And the degree of orientation of the metal nanowires in the longitudinal direction of the wiring at the edge portion becomes relatively high.

  The metal nanowire is a metal having a diameter of nanometer order size, and is a conductive material having a wire-like shape. In the present embodiment, metal nanotubes which are conductive materials having a porous or non-porous tube shape may be used together with (mixed with) the metal nanowires or in place of the metal nanowires. In the present specification, "wire-like" and "tube-like" are both linear, but the former is intended not to be hollow in the center and the latter to be hollow in the center. The properties may be flexible or rigid. Hereinafter, when "metal nanowire" and "metal nanotube" are not described in succession in the present specification, "metal nanowire" is used to mean including metal nanowire and metal nanotube.

  1 to 500 nm is preferable, 5 to 200 nm is more preferable, 5 to 100 nm is more preferable, and 10 to 100 nm is particularly preferable. Moreover, 1-100 micrometers is preferable, as for the average of the length of the major axis of a metal nanowire and a metal nanotube, 1-80 micrometers is more preferable, 2-70 micrometers is more preferable, and 5-50 micrometers is especially preferable. The metal nanowires and metal nanotubes preferably have an average aspect ratio of 5 or more, more preferably 10 or more, and an average aspect ratio of at least 5 and preferably at least 10, while the average of the thickness of the diameter and the average of the lengths of the major axes satisfy the above ranges. It is more preferable that it is the above, and it is especially preferable that it is 200 or more. Here, the aspect ratio is a value obtained by a / b when the average diameter of the metal nanowires and metal nanotubes is b and the average length of the major axis is a. a and b can be measured using a scanning electron microscope (SEM) and an optical microscope. Specifically, the diameter of 10 or more of the metal nanowires is measured by SEM (FE-SEM S-5200 manufactured by Hitachi High-Tech Co., Ltd.), and the length of 100 or more of the metal nanowires is measured with an optical microscope (Keyence Corporation) Each of the lengths is measured using VHX-600 manufactured by H.K.

  The material of such metal nanowires is not particularly limited as long as the material itself is a conductive metal, but silver, copper and the like are preferable in terms of high conductivity.

  A well-known manufacturing method can be used as a manufacturing method of metal nanowire or a metal nanotube. For example, silver nanowires can be synthesized by reducing silver nitrate in the presence of polyvinyl pyrrolidone using the Polyol (Poly-ol) method (see Chem. Mater., 2002, 14, 4736). Gold nanowires can also be synthesized by reduction of chloroauric acid hydrate in the presence of polyvinyl pyrrolidone (see J. Am. Chem. Soc., 2007, 129, 1733). WO 2008/073143 pamphlet and WO 2008/046058 pamphlet have detailed description about the technology of large-scale synthesis and purification of silver nanowires and gold nanowires. Gold nanotubes having a porous structure can be synthesized by using a silver nanowire as a template and reducing a chlorauric acid solution. Here, the silver nanowires used as the template are dissolved in the solution by the redox reaction with chloroauric acid, and as a result, gold nanotubes having a porous structure can be formed (J. Am. Chem. Soc., 2004, 126, 3892 -3901).

  The suspension containing the metal nanowires is a dispersion mainly composed of the metal nanowires and the hydrophilic organic solvent, and the suspension containing the metal nanowires applied to the liquid repellent surface in the third step. The viscosity is preferably low from the viewpoint of ease of movement to the lyophilic processed wiring pattern forming area, and the viscosity at 25 ° C. is preferably 0.5 to 50 mPa · s, and 0.8 It is more preferable that it is -30 mPa * s. Therefore, it is preferable that the content of the binder resin having a function of adjusting the viscosity to improve the leveling property and to obtain a uniform coating is small, and it is more preferable that the binder resin is not contained. Since the wiring after applying the suspension containing the metal nanowire which does not contain the binder resin and performing the predetermined drying process is formed only of the metal nanowire, it is possible to suppress the increase in resistance due to the binder resin. It becomes possible. The viscosity can be measured, for example, using a common B-type viscometer.

  The dispersion medium of the suspension containing the metal nanowires is preferably selected from hydrophilic organic solvents having high volatility and low viscosity, with emphasis on the simplicity of the industrial process, and alcohols are preferable. is there. More preferably, the monovalent saturated alcohol having 1 to 4 carbon atoms, specifically, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butanol, isobutanol, sec-butanol, tert-butanol or the like Among these, methanol, ethanol and isopropyl alcohol may be used alone or in combination of two or more thereof, and industrial availability is easily obtained. More preferable in terms of sex.

  The method of applying the suspension containing the metal nanowires to the substrate may be any method as long as it can uniformly apply the lyophilic treated area for forming a wiring pattern, preferably spin coating application, bar coating application, application Examples of the method include casting methods such as tar coating, screen printing, gravure printing, and gravure offset printing methods, but casting methods which are industrially easy methods are preferable.

  The fourth step is a step of leaving the substrate after the third step and selectively depositing metal nanowires in a suspension containing the metal nanowires in a predetermined wiring pattern formation region. By holding the substrate after the third step in a predetermined atmosphere, the dispersion medium of the suspension containing the metal nanowires held on the region for forming the wiring pattern is dried and removed, whereby the metal nanowires are made of wiring. A transparent conductive wiring substrate is obtained in which the wiring selectively deposited in the pattern shape is formed. At this time, as described above, the degree of orientation of the metal nanowires in the longitudinal direction is smaller at the end of the wiring than at the center of the wiring. The manufacturing method of the transparent conductive wiring substrate of the present embodiment is effective for manufacturing a wiring pattern having a narrow wiring width, and is suitable for manufacturing a wiring pattern having a wiring width of 20 to 50 μm.

  The metal nanowires may be partially embedded in the substrate. The part of the metal nanowires refers to any part of the metal nanowires in the longitudinal direction, and includes one or both of the ends, a part between the ends, and the like. When a part of the metal nanowires is embedded in the substrate, the metal nanowire layer formed on the substrate can obtain high mechanical strength against bending and stretching of the substrate. Preferably, 5 to 95% of the surface area of the metal nanowires embedded in the substrate is exposed. In addition, metal nanowires completely buried in the substrate may be present. It may also contain metal nanowires that do not have embedded portions in the substrate. In that case, it is preferable to set it as 5% or more and 95% or less of the metal nanowire which does not have the part embedded in the base material, It is more preferable to set it as 10% or more and 85% or less, and 15% or more 75% It is more preferable to set it as the following. The drying in the fourth step is performed at a temperature above the temperature at which the substrate softens (glass transition temperature or softening point) or at a temperature above the temperature at which the substrate softens separately after the fourth step (glass transition temperature or softening point) By heat-treating at a temperature, and by pressurizing the substrate if necessary, it is possible to form a state in which a part of the metal nanowires is embedded in the substrate.

  In addition, the metal nanowires may be plated on a part or the whole of a portion exposed from the substrate, that is, a portion not embedded in the substrate. In particular, in the electroless plating step, the plating layer formed on the metal nanowires is stabilized by performing heat treatment after being immersed in the catalyst solution, and a plating layer having excellent durability such as improvement in peeling resistance can be obtained. As a result, it is possible to suppress the occurrence of migration and deterioration due to sulfidation, oxidation and the like. The heat treatment conditions depend on the heat resistance temperature of the substrate, and thus can not be determined generally, but may be within the heat resistance temperature range of the substrate, preferably 30 ° C. to 180 ° C., more preferably 40 ° C. It is in the range of 150 ° C. Further, the treatment time is not limited as long as the solvent of the catalyst solution is volatilized within a range not to damage the substrate, but preferably 1 second to 1 hour, more preferably 30 seconds to 30 minutes Range.

  The transparent conductive wiring substrate in which the transparent conductive wiring pattern including the metal nanowire according to the present embodiment described above is formed on the transparent substrate surface contacts, for example, a solution (such as water or saline solution) that promotes metal migration. The present invention is applicable to conductive members that require reliability in and out of the members. For example, a transparent conductive film formed on a flexible substrate in a device in contact with moisture, water, etc., a wearable device or embedded sensor in contact with sweat or biological fluid, a chemical sensor, a microchannel device It can be used as a sensor member such as an infrastructure exposed to rain or seawater or a sensor for agriculture and forestry. It can be used for conductive members of functional devices that require migration resistance other than sensors, for example, conductive members such as solar cells using organic or inorganic semiconductors, LEDs, and transistors.

  In addition to the first to fourth steps, a step of connecting at least a part of the metal nanowires constituting the wiring including the metal nanowires may be provided. Here, the step of connecting at least a portion of the metal nanowires means the step of melting and integrating at least a portion of the plurality of intersections of the metal nanowires present on the substrate surface. There is no limitation as long as it is a method that can give the energy required to connect the metal nanowires without melting and cutting as a method of connecting them, and heating such as an oven, microwave irradiation, and pulsed light irradiation are preferable. .

  The pulsed light irradiation is irradiation of light with a short light irradiation time (irradiation time), and when light irradiation is repeated multiple times, light is irradiated between the first irradiation time and the second irradiation time. It means light irradiation having a period that is not The light intensity may change within the light irradiation time. The pulsed light is emitted from a light source provided with a flash lamp such as a xenon flash lamp.

  As the pulsed light, an electromagnetic wave in a wavelength range of 1 pm to 1 m can be used, preferably an electromagnetic wave in a wavelength range of 10 nm to 1000 μm, more preferably an electromagnetic wave in a wavelength range of 100 nm to 2000 nm. Examples of such electromagnetic waves include gamma rays, X rays, ultraviolet rays, visible light, infrared rays, microwaves, electromagnetic waves having a longer wavelength than microwaves, and the like. When conversion to thermal energy is considered, when the wavelength is too short, damage to the resin substrate is large, which is not preferable. In addition, when the wavelength is too long, it is not preferable because efficient absorption and heat generation can not be performed. Among the wavelengths described above, the wavelength range is preferably in the range of ultraviolet to infrared, and more preferably in the range of 100 nm to 2000 nm. There is no particular limitation on the atmosphere in which the pulsed light is emitted. It can be carried out under the atmosphere. It can also be carried out under an inert atmosphere if necessary.

  Although the irradiation time of one pulse light depends on the light intensity, the range of 20 microseconds to 50 milliseconds is preferable. If it is shorter than 20 microseconds, sintering of the metal nanowires is difficult to progress, and if it is longer than 50 milliseconds, the substrate may have an adverse effect on the substrate due to photodegradation and thermal degradation. More preferably, it is 40 microseconds to 10 milliseconds.

  Although the pulsed light irradiation may be effective even if it is carried out in a single shot, it may be carried out repeatedly as described above. In the case of repetitive implementation, the irradiation interval is preferably in the range of 20 microseconds to 5 seconds in consideration of productivity, and more preferably in the range of 2 milliseconds to 2 seconds. If it is shorter than 20 microseconds, it will be close to continuous light, and since it will be irradiated soon after being cooled after one irradiation, the substrate may be heated and the temperature may be increased to deteriorate. Also, if it is longer than 5 seconds, the process time will be long.

  The microwave used in microwave heating is an electromagnetic wave having a wavelength range of 1 m to 1 mm (frequency of 300 MHz to 300 GHz). The microwave irradiation is performed in a state in which the surface of the substrate on which the metal nanowire layer is formed is maintained substantially parallel to the direction of the electric force line of the microwave (the direction of the electric field). Here, “substantially parallel” refers to a state in which the plane of the substrate and the electric force line direction of the microwaves are parallel or maintain an angle within 30 degrees with respect to the electric force line direction. The above-mentioned angle within 30 degrees means a state in which the normal to the surface of the substrate and the electric force line direction form an angle of 60 degrees or more. Thereby, the number of electric lines of force passing through the wiring including the metal nanowire formed on the substrate is limited, and the generation of the spark can be suppressed. There is no particular limitation on the atmosphere for the microwave irradiation. It can be carried out under the atmosphere. It can also be carried out under an inert atmosphere if necessary.

  Examples of the present invention will be specifically described below. The following examples are for the purpose of facilitating the understanding of the present invention, and the present invention is not limited to these examples.

Example 1
{Method for manufacturing photomask used for patterning}
A photomask for substrate surface lyophilic treatment was prepared to apply a suspension containing metal nanowires on a substrate in a predetermined wiring pattern shape. The devices used are listed below.

  The apparatus uses PLS-1000 (LED drawing device PLS-1000, manufactured by PMT), and as mask blanks, CS HARDMASK BLANKS (Clean surface technology Co., Ltd. manufactured synthetic quartz / CrO (8 nm) / Cr (62 nm) / CrO (30 nm), board thickness 1.5 mm), and the size of 2.5 inch to 4 inch was appropriately used according to the example.

  First, set the mask blanks on the spin coater (MS-A100, manufactured by Mikasa Corporation) so that the surface on which CrO (thickness 8 nm) / Cr (thickness 62 nm) / CrO (thickness 30 nm) layer is formed is the upper side. 1 to 10 ml of AZ promoter (manufactured by Merck Performance Materials) is dropped on the approximate center of a (thickness 8 nm) / Cr (thickness 62 nm) / CrO (thickness 30 nm) layer, spin-coated at 3000 rpm for 10 seconds, A resist material (AZ5206E, manufactured by Merck Performance Materials, Inc.) was spin-coated at 4000 rpm for 60 seconds, and heated on a hot plate at 95 ° C. for 3 minutes to form a resist film.

  This mask blank was set to PLS-1000, exposure was carried out, and linear patterns of 20 μm, 50 μm, 100 μm, and 150 μm in width were drawn, respectively. After completion, development was performed by immersion for 2 to 5 minutes in 10 to 50 ml of a developing solution (NMD-W 2.38%, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for development to form openings corresponding to a linear pattern in the resist layer.

  The developed mask blank is immersed in ultra pure water and washed, dried on a hot plate, and then CrO (thickness 8 nm) located at the opening of the resist layer for 10 seconds or more with a mixed acid etching solution (manufactured by Kanto Chemical Co., Ltd.) The Cr (thickness 62 nm) / CrO (thickness 30 nm) layer is etched and further dipped in ultra pure water and washed, then impregnated with 10 to 50 ml of a resist remover (AZ remover 200, manufactured by Merck Performance Materials) for 30 minutes or more Then, the resist was removed to obtain a mask blank (photomask) having openings corresponding to a linear pattern on a CrO (thickness 8 nm) / Cr (thickness 62 nm) / CrO (thickness 30 nm) layer.

{Synthesis of metal nanowires and preparation of metal nanowire suspension}
100 g of propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) is weighed in a 200 mL glass container, and 2.3 g (13 mmol) of silver nitrate (manufactured by Toyo Chemical Industries, Ltd.) is added as a metal salt and stirred at room temperature for 2 hours. A second solution was prepared.

  In a nitrogen gas atmosphere, 600 g of propylene glycol, 0.052 g (0.32 mmol) of tetraethylammonium chloride as an ionic derivative in a 1 L four-necked flask (mechanical stirrer, dropping funnel, reflux tube, thermometer, nitrogen gas inlet tube) (Lion Specialty Chemicals Co., Ltd.) and sodium bromide 0.008 g (0.08 mmol) (Manuc Co., Ltd.), 7.2 g of polyvinyl pyrrolidone K-90 (PVP) as a structure defining agent (Wako Pure Chemical Industries, Ltd., weight average) The molecular weight was 350,000, and the mixture was completely dissolved by stirring at 150 ° C. for 1 hour at a rotational speed of 200 rpm to obtain a first solution. The silver nitrate solution (second solution) prepared above is added to the dropping funnel, and the first solution is added dropwise over 2.5 hours at a temperature of 150 ° C. (the feed mole number of silver nitrate is 0.087 mmol / min). Silver nanowires were synthesized. In this case, the molar ratio (metal salt) calculated from the total number of moles (0.40 mmol) of halogen atoms of the ionic derivative in the first solution and the number of moles of silver atoms (0.087 mmol) of silver nitrate supplied in 1 minute / Ionic derivative) is 0.22. In addition, when the silver ion concentration in the first solution was measured during the reaction, the molar ratio of the halogen atom of the ionic derivative to the metal atom of the metal salt (the number of moles of the metal atom of the metal salt / the halogen atom of the ionic derivative) The total number of moles of) was in the range of 0.2 to 6.7. After completion of the dropwise addition, heating and stirring were continued for 1 hour to complete the reaction.

  The reaction mixture was diluted 5-fold with ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), and the silver nanowires were sedimented by applying a centrifugal force at a rotational speed of 6000 rpm for 5 minutes using a centrifuge. After removing the supernatant, fresh ethanol substantially equivalent to the supernatant removed was added, and the mixture was treated with 6000 rpm for 5 minutes twice more to wash the PVP and the solvent remaining in the system.

  IPA (manufactured by Wako Pure Chemical Industries, Ltd.) having the same volume as that of the dispersion is added to the purified silver nanowire / ethanol dispersion after purification and diluted (ethanol / IPA = 50/50 [volume]) to obtain a dispersion liquid. A metal nanowire suspension (suspension containing metal nanowires) was prepared such that the composition of silver nanowires was 1.5% by mass.

{Viscosity of suspension}
The viscosity at 25 degrees C of the metal nanowire suspension produced as mentioned above was calculated | required by VISCOMETER DV-II + Pro (made by BROOKFIELD, CPE-40 use). As a result, it was 1.6 mPa · s.

{Patterning}
Chemical vapor deposition film formation of diX (registered trademark)-SR (made by KISCO) on a glass substrate of 2 to 3 cm square and 1 mm in thickness with a laboratory coater (PDS-2010, made by Parylene Japan), and 3 μm thick parylene (registered) The coating film of trademark was obtained. 0.1 to 1 ml of a fluorine-based coating agent (WP-100, manufactured by Daikin Industries, Ltd.) was dropped thereon, and film formation was performed using a spin coater at 6000 rpm for 20 seconds to form a liquid repellent layer. The contact angle of the suspension containing the metal nanowires in the liquid repellent layer was 43 °.

  Next, using an excimer lamp (FLAT EXIMER EX-min, manufactured by Hamamatsu Photonics K.K.), vacuum ultraviolet light (172 nm) is applied under a nitrogen atmosphere through the photomask prepared for the above-mentioned 20 .mu.m linear pattern. The fluorine-based coating film (liquid repellent layer) was irradiated for 2 seconds to form a lyophilic region (a region for forming a wiring pattern). The contact angle of the suspension containing metal nanowires in the lyophilic region was 26 °. The contact angle is a measured value (five-point average value) before and after lyophilic treatment in a lyophilic area (solid pattern area) provided separately from the lyophilic area (area for forming wiring pattern), and DM It measured using -500 (made by Kyowa Interface Chemical Co., Ltd.).

  The results of X-ray photoelectron spectroscopy (XPS) measurement of the surface before and after irradiation with vacuum ultraviolet light, that is, before and after the lyophilic treatment of the fluorine-based coating film are shown in FIG.

From this result, it is understood that the F _1s peak of the fluorine atom bonded to the alkylene group of the fluorine-based coating film disappears in the region irradiated with the vacuum ultraviolet light of 172 nm, and the vacuum ultraviolet light irradiation for a short time It can be seen that the surface liquid repellency can be effectively changed (the liquid repellent layer is removed).

{Silver nanowire suspension application}
6 to 9 μL of the 1.5 mass% silver nanowire suspension prepared by the above method is dropped on the substrate on which the lyophilic region is formed in part of the liquid repellent layer, and the dropped ink is on the substrate A stepper motor (OSMS (CS) 26-100 (X), manufactured by Sigma Koki Co., Ltd.) is placed along the surface of the substrate with a glass rod with a diameter of 8 mm placed at the upper end of the substrate so that A substrate with a silver nanowire suspension applied on the surface of a liquid repellent layer in which a lyophilic area is formed, by moving the speed horizontally at 1 mm / sec (the gap between the substrate and the glass rod is adjusted to 30 μm) Was produced. After producing the above substrate, vacuum drying is carried out with a vacuum drier (AVD-200 NS, manufactured by As One Corporation) at 120 ° C. for 1 hour to volatilize the solvent (dispersion medium) of the silver nanowire suspension to dry and remove it. A linear pattern of wiring (transparent conductive wiring pattern) was obtained.

{Calculation of transparency of transparent conductive wiring pattern}
The area occupied by the wire in the wiring was calculated from the gray scale processed image obtained using the above-mentioned Orientation J Distribution software, and the transparency of the transparent conductive wiring pattern was calculated from the following calculation formula (3).
Dark part / (light part + dark part) = (S-S _AgNW ) / S (3)
S _AgNW means an area occupied by silver nanowires in the wiring, and S indicates the area of the wiring used for image analysis. The calculation results are shown in Table 1.

{Measurement of total light transmittance of substrate}
The total light transmittance of the substrate (liquid repellent layer / coating layer (parylene) / glass substrate) on which the liquid repellent layer prepared in the example was formed was measured using Haze Meter NDH 2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) The total light transmittance was 93%.

{Measurement of resistance value}
The resistance value of the wiring of the linear pattern containing the produced silver nanowire was measured by B2900A (made by Keysight). The measurement results (five-point average value) are shown in Table 1.

{SEM observation of sample}
The wiring of the linear pattern containing the produced silver nanowire was observed with the scanning electron microscope (FE-SEM SU8020, Hitachi High-Technologies company make). The electron micrograph of the wiring of the linear pattern containing silver nanowire with a line | wire width of 20 micrometers obtained by FIG. 7 (a) is shown.

{Calculating degree of orientation}
The degree of orientation of the silver nanowires constituting the produced wiring was determined by the method described above. The degree of orientation of the wiring end E is calculated by image processing of an area of 10 μm from the end of the wiring width, and the degree of orientation of the wiring center C is image processing of an area of ± 5 μm from the center of the wiring width. The degree of orientation of the whole wiring was not defined as it was, but the degree of orientation of the whole was determined. The results are shown in Table 1. In Table 1, the wiring end E is described as an edge, and the wiring center C is described as a center.

Example 2
A wiring of a linear pattern including silver nanowires was obtained as in Example 1 except that a photomask with a line width of 50 μm was used as a photomask. The measurement result is shown in Table 1, and the electron micrograph is shown in FIG. 7 (b).

Example 3
A wiring of a linear pattern including silver nanowires was obtained as in Example 1 except that a photomask with a line width of 100 μm was used as a photomask. The measurement result is shown in Table 1, and the electron micrograph is shown in FIG. 7 (c).

Example 4
A wiring of a linear pattern including silver nanowires was obtained as in Example 1 except that a photomask with a line width of 150 μm was used as a photomask. The measurement result is shown in Table 1, and the electron micrograph is shown in FIG. 7 (d).

Comparative Example 1
A fluorine-based coating layer in which a fluorine-based coating layer was formed on the coating film of the parylene (registered trademark) -coated film-forming substrate used in Example 1 using the suspension containing the metal nanowires used in Example 1 Gravure printing of a linear wiring pattern having a wiring width of 20 μm was tried without the liquefaction treatment, but in each case there was a problem that metal nanowires were deposited between adjacent wirings.

Claims (8)

  The absolute value of the degree of orientation of the central portion of the wire with respect to the longitudinal direction of the wire is 35 ° or more and 65 ° or less, and the degree of orientation of the edge portion of the wire is The transparent conductive wiring pattern characterized by absolute value being 20 degrees or more and 45 degrees or less.   The transparent conductive wiring pattern according to claim 1, wherein a metal constituting the metal nanowire is silver or copper.   The transparent conductive wiring pattern according to claim 1, wherein a width of the wiring is 20 to 50 μm. Glass, polyurethane, silicone, saturated polyester, polycarbonate, polyparaxylylene, thermoplastic polyimide, polyether sulfone, acrylic resin, polyolefin, polyvinyl chloride and any one or more combinations selected from the group consisting of Transparent base material,
The transparent conductive wiring pattern according to any one of claims 1 to 3, formed on the surface of the substrate.
A transparent conductive wiring substrate comprising: A first step of forming a liquid repellent layer against a suspension containing metal nanowires on all or part of at least one major surface of a transparent substrate,
A lyophilic treatment is performed to change the predetermined wiring pattern forming area on the surface of the lyophobic layer to be lyophilic with respect to the suspension, and the lyophobic layer before and after the lyophilic treatment and the suspension The second step of setting the contact angle difference to 10 ° or more and 35 ° or less,
A third step of applying a suspension containing the metal nanowires on the surface of a liquid repellent layer including the predetermined region for forming a wiring pattern subjected to the lyophilic treatment,
After applying the suspension containing the metal nanowires, the dispersion medium of the suspension is dried and removed, and the metal nanowires in the suspension are selectively deposited on the predetermined wiring pattern forming region to form a wiring pattern. The fourth step to form
The manufacturing method of the transparent conductive wiring board of Claim 4 containing B.   The method for producing a transparent conductive wiring substrate according to claim 5, wherein the lyophilic treatment is ultraviolet light irradiation.   The method for producing a transparent conductive wiring substrate according to claim 5 or 6, wherein the viscosity at 25 ° C of the suspension containing the metal nanowires is 0.5 to 50 mPa · s. The manufacturing method of the transparent conductive wiring board as described in any one of Claims 5-7 in which the suspension containing the said metal nanowire does not contain binder resin.