Method for manufacturing a conductive substrate and conductive substrate

Abstract

To provide a manufacturing method for a conductive substrate that has a conductive thin wire with low electric resistance and high invisibility, and provide a conductive substrate.SOLUTION: A conductive substrate manufacturing method is designed to manufacture a conductive substrate including a substrate and a conductive thin wire on the substrate, the method including, in the following order, a step 1 of forming a thin wire containing a metal on the substrate; a step 2 of bringing the thin wire into contact with a solution containing an organic acid; and a step 3 of subjecting the thin wire to a plating treatment to form a conductive thin wire.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a conductive substrate having conductive fine wires and a conductive substrate.

Background Art

[0002] Conductive substrates having conductive fine wires (fine wire-shaped wirings exhibiting conductivity) are widely used in various applications such as touch panels. For example, as shown in Patent Document 1, the conductive fine wires of a conductive substrate are formed by sequentially performing exposure processing, development processing, etc. on a photosensitive layer containing silver halide to form conductive fine wires containing metallic silver.

[0003] Patent Document 1 describes a method for manufacturing a conductive material using a conductive material precursor containing at least one layer of a silver halide emulsion layer on a support. In the method for manufacturing the conductive material of Patent Document 1, the conductive material precursor is treated with an enzyme-containing treatment liquid containing an enzyme that acts on the binder constituting the silver halide emulsion layer, and then electroplated.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] When a conductive substrate having conductive fine wires is used for a touch panel, the conductive fine wires are required to have conductivity, that is, low electrical resistance, and to be difficult to visually recognize. However, in Patent Document 1, both of the above characteristics could not be achieved.

[0006] An object of the present invention is to provide a method for manufacturing a conductive substrate having a conductive fine wire with low electrical resistance and being difficult to visually recognize, and a conductive substrate.

Means for Solving the Problems

[0007] In order to achieve the above object, one aspect of the present invention is a method for manufacturing a conductive substrate including a substrate and a conductive fine wire disposed on the substrate, the method including: Step 1 of forming a fine wire containing a metal on the substrate; Step 2 of bringing the fine wire into contact with a solution containing an organic acid; and Step 3 of performing a plating treatment on the fine wire to form a conductive fine wire, in this order.

[0008] Preferably, a Step 4 of performing a plating treatment on the fine wire is further included between Step 1 and Step 2. Preferably, the pH value of the solution containing an organic acid is in the range of 1.5 to 6.0 at a temperature of 25°C. Preferably, the solution containing an organic acid contains a carboxylic acid. Preferably, the carboxylic acid is a divalent or higher carboxylic acid. Preferably, the carboxylic acid is any one selected from the group consisting of glutaric acid and citric acid. Preferably, the solution containing an organic acid further contains a quaternary ammonium salt. Preferably, the quaternary ammonium salt is selected from the group consisting of a compound represented by general formula (X), a compound represented by general formula (Y), and a compound represented by general formula (Z).

[0009]

Chemical Formula

[0010] In general formula (X), R a1 and R a2 each independently represent an alkyl group having 4 or less carbon atoms which may have a substituent, and R a3 and R a4Each independently represents an alkyl group having 8 or more carbon atoms which may have a substituent. In general formula (Y), R b1 ~R b3 Each independently represents an alkyl group having 4 or less carbon atoms which may have a substituent, and R b4 represents an alkyl group having 8 or more carbon atoms which may have a substituent. In general formula (Z), R c1 represents an alkyl group having 8 or more carbon atoms which may have a substituent.

[0011] The solution containing an organic acid preferably contains a dicarboxylic acid having 2 or more carboxyl groups and a compound selected from the group consisting of the compound represented by general formula (X), the compound represented by general formula (Y), and the compound represented by general formula (Z).

[0012]

Chemical formula

[0013] In general formula (X), R a1 and R a2 Each independently represents an alkyl group having 4 or less carbon atoms which may have a substituent, and R a3 and R a4 Each independently represents an alkyl group having 8 or more carbon atoms which may have a substituent. In general formula (Y), R b1 ~R b3 Each independently represents an alkyl group having 4 or less carbon atoms which may have a substituent, and R b4 represents an alkyl group having 8 or more carbon atoms which may have a substituent. In general formula (Z), R c1 represents an alkyl group having 8 or more carbon atoms which may have a substituent.

[0014] In step 2, the contact time between the fine wire and the solution containing an organic acid is preferably 5 to 180 seconds. It is preferable to further include a step 5 of bringing a solution containing a quaternary ammonium salt into contact with the fine wire between step 1 and step 2, or between step 2 and step 3. It is preferable that step 3 or step 4 has a neutralization washing step of bringing the fine wire into contact with an acidic solution having a pH of 3 to 7 to stop the plating reaction by plating treatment. The acidic solution preferably has a buffering action. The fine wire preferably contains a polymer.

[0015] One aspect of the present invention is a conductive substrate including a substrate and a conductive fine wire disposed on the substrate and containing a metal. In a vertical cross-section of the conductive fine wire in a direction perpendicular to the direction in which the conductive fine wire extends, the ratio of the area showing the metal within the maximum inscribed circle of the observation region where the metal is observed is 81 to 99%, and the gray value obtained by imaging the conductive fine wire using reflected light is 150 or less in terms of the luminance value represented by 256 gradations. The present invention provides a conductive substrate. In a circumscribed rectangle that circumscribes the observation region where the metal is observed, and in which the angles of the four corners are each 90° and one side is parallel to the surface of the substrate, among the contact points between the side perpendicular to the surface of the substrate of the circumscribed rectangle and the observation region, taking the upper contact point at the position farthest from the surface of the substrate as one corner, the rectangular region on the opposite side of the surface of the substrate from the upper contact point of the circumscribed rectangle is defined as the upper circumscribed rectangle. The upper circumscribed rectangle has angles of the four corners each being 90° and one side being parallel to the surface of the substrate. In the upper circumscribed rectangle, when the length of the contour of the region where the metal exists is denoted as Lm and the total length of the four sides of the upper circumscribed rectangle is denoted as Ls, and the ratio represented by Lm / Ls is denoted as γ, it is preferable that 1.3 ≤ γ ≤ 2.0.

[0016] The line width of the conductive fine wire is preferably 0.1 μm or more and less than 5.0 μm. In a vertical cross-section of the conductive fine wire in a direction perpendicular to the direction in which the conductive fine wire extends, the ratio of the height of the conductive fine wire to the line width of the conductive fine wire is preferably 0.6 or more and less than 1.5. The substrate is preferably composed of a flexible film. The flexible film preferably contains polyethylene terephthalate, cycloolefin polymer, cycloolefin copolymer, or polycarbonate. The metal contained in the conductive fine wire preferably contains silver. The metal contained in the conductive fine wire is preferably silver. The metal contained in the conductive fine wire is preferably in particulate form. The conductive fine wire preferably contains a polymer.

Advantages of the Invention

[0017] According to the present invention, it is possible to provide a method for manufacturing a conductive substrate having conductive fine wires with low electrical resistance and being difficult to visually recognize, and a conductive substrate.

Brief Description of the Drawings

[0018]

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Embodiments for Carrying Out the Invention

[0019] Hereinafter, based on the preferred embodiments shown in the accompanying drawings, the manufacturing method of the conductive substrate and the conductive substrate of the present invention will be described in detail. Note that the drawings described below are exemplary for explaining the present invention, and the present invention is not limited to the drawings shown below. Note that in the following, "~" indicating a numerical range includes the numerical values described on both sides. For example, when ε is a numerical value ε α ~ numerical value ε β it means that the range of ε is the numerical value ε α and the numerical value ε βis a range that, in mathematical notation, is ε α ≦ ε ≦ ε β is true. Angles such as "angles represented by specific numerical values", "parallel", "perpendicular", and "orthogonal" include the error ranges generally acceptable in the relevant technical field unless otherwise specified.

[0020] <Conductive substrate> FIG. 1 is a schematic perspective view showing an example of a conductive substrate according to an embodiment of the present invention, and FIG. 2 is a schematic diagram showing an example of a conductive substrate according to an embodiment of the present invention. The conductive substrate 10 has a substrate 12 and conductive fine lines 14 disposed on the surface 12a of the substrate 12 and containing metal. In FIG. 1, two conductive fine lines 14 extending in one direction are shown, but the arrangement form and the number of the conductive fine lines 14 are not particularly limited. The conductive fine lines 14 contain metal as described above, but preferably contain a metal 15 and a polymer 16 as shown in FIG. 2, for example. In the conductive fine line 14 shown in FIG. 2, the metal 15 is present in the polymer 16. The metal 15 is, for example, in a particulate form, but is not limited to a particulate form and may be in a form such as being fused and bonded partially or entirely, for example.

[0021] FIGS. 1 and 2 show a vertical cross-section Ac of the conductive fine line 14 in a direction DW orthogonal to the direction DL in which the conductive fine line 14 extends. The vertical cross-section Ac of the conductive fine line 14 is the cross-section when cut along a plane orthogonal to the direction DL in which the conductive fine line 14 extends. That is, the vertical cross-section Ac of the conductive fine line 14 is the cross-section when cut along a plane perpendicular to the surface 14a of the conductive fine line 14 along the direction DW orthogonal to the direction DL in which the conductive fine line 14 extends. In the vertical cross-section Ac of the conductive fine line 14, the ratio of the area showing the metal 15 within the maximum inscribed circle S of the observation region R where the metal 15 is observed is 81 - 99%. Among them, preferably, it is 86% or more, and more preferably, it is 88% or more. The upper limit is preferably 96% or less, and more preferably, it is 94% or less. If the ratio of the area indicating the above metal is 81 to 99%, the electrical resistance can be reduced to obtain conductivity, and the visibility of the conductive fine wire 14 can be prevented. In the conductive fine wire 14, if the ratio of the area indicating the metal 15 is less than 81%, sufficient conductivity cannot be obtained. On the other hand, in the conductive fine wire 14, if the ratio of the area indicating the metal 15 exceeds 99%, the bendability deteriorates.

[0022] The gray value obtained by imaging the conductive fine wire 14 using reflected light is 150 or less in terms of the luminance value represented by 256 gradations. The value of 256 gradations is the value corrected with a standard white plate conforming to JIS (Japanese Industrial Standards) K 5602 each time. The gray value is preferably 0 to 150 in terms of the luminance value, and more preferably 0 to 130. If the above gray value is 150 or less in terms of the luminance value, the visibility of the conductive fine wire 14 can be prevented without performing a blackening process. The gray value is obtained by observing and photographing the conductive fine wire 14 using reflected light as follows, using a digital microscope (VH - 5000) manufactured by KEYENCE CORPORATION, at a lens magnification of ×5000 times and an illumination luminance of 70%. Draw a line corresponding to a length of 20 μm on the photographed image of the conductive fine wire 14. Next, using the image processing software ImageJ, calculate the gray value of the line corresponding to the above length of 20 μm. Calculate the gray value 3 times for each image and obtain the average value. This average value is taken as the gray value of the conductive fine wire 14. Note that the measurement of the gray value was carried out after calibration using a standard calibration plate each time before photographing.

[0023] In the conductive substrate 10, select one extending conductive fine wire, and select an arbitrary location on the selected one conductive fine wire to obtain a vertical cross - section Ac. Observe the vertical cross - section Ac with a scanning electron microscope, and obtain the maximum inscribed circle S, the ratio indicating the metal, and the ratio γ as follows.

[0024] In the measurement method using a scanning electron microscope, in order to impart conductivity to the surface of the conductive fine wire 14, Pt is coated using an ion sputtering apparatus (E-1030 type ion sputtering apparatus manufactured by Hitachi High-Technologies Corporation). In this state, the vertical cross-section Ac of the conductive fine wire 14 is processed by the ion beam processing function of a scanning electron microscope with a focused ion beam processing function (Helios 600i manufactured by Thermo Fisher Scientific Inc.), and by observing the exposed cross-sectional form, the region where the metal 15 exists inside the conductive fine wire 14 can be observed, and an observation image of the vertical cross-section Ac is obtained. The observation conditions are carried out in the backscattered electron mode at an acceleration voltage of 1 kV.

[0025] As shown in FIG. 2, the metal 15 exists in the vertical cross-section Ac of the conductive fine wire 14. The maximum inscribed circle S is the largest among the inscribed circles in the observation region R where the metal 15 is observed in the vertical cross-section Ac. Here, FIGS. 3 to 6 are schematic diagrams showing the measurement method of the ratio of the region indicating the metal in the conductive fine wire of the embodiment of the present invention in the order of steps. First, an observation image (not shown) of the vertical cross-section Ac (see FIG. 2) of the conductive fine wire 14 is obtained. The observation image is acquired in a format of image data that can be analyzed by a computer. The image data may be binary data, grayscale data, or RGB data. For example, the image data of the observation region R shown in FIG. 3 is obtained from the observation image.

[0026] Next, from the observation region R, the contour line R shown in FIG. 4 is obtained. L The contour line R indicates the contour of the observation region R where the metal is observed in the vertical cross-section Ac (see FIG. 2). In the vertical cross-section Ac (see FIG. 2), the metal 15 exists inside the contour line R. L The contour line R is extracted from the image of the observation region R using, for example, image analysis software ImageJ. Note that the image analysis software is not particularly limited to ImageJ as long as the contour line R can be extracted. L The contour line R is, for example, extracted from the image of the observation region R using image analysis software ImageJ. Note that the image analysis software is not particularly limited to ImageJ as long as the contour line R can be extracted. The contour line R L is extracted from the image of the observation region R using, for example, image analysis software ImageJ. Note that the image analysis software is not particularly limited to ImageJ as long as the contour line R can be extracted. L is not particularly limited to ImageJ as long as the contour line R can be extracted. Next, the contour line R LFor this, a maximum inscribed circle S is set. The maximum inscribed circle S is, for example, the contour line R L Inside, an inscribed circle is randomly generated, and among the generated inscribed circles, the one with the maximum radius is set as the maximum inscribed circle S. When there are multiple inscribed circles with the maximum radius, the one with the center position closer to the centroid in the image data of the observation region R is set as the maximum inscribed circle S. For this reason, when there are multiple inscribed circles with the maximum radius, the mass center in the image data of the observation region R is obtained, and the position information of the position of the mass center is stored. The position of the mass center is obtained using a known method such as using image processing software. The position information of the position of the mass center is, for example, the position coordinates in the image data. Note that the center position of the inscribed circle and the center position of the maximum inscribed circle S are not particularly limited as long as they are inside the contour line R L Inside, it is not particularly limited. The position information of the center position of the maximum inscribed circle S is stored. The position information of the center position is, for example, the position coordinates in the image data.

[0027] Next, as shown in FIG. 6, the maximum inscribed circle S is aligned with the observation region R obtained in FIG. 3 using the position information of the center position of the maximum inscribed circle S. Next, the area of the region indicating the metal 15 inside the maximum inscribed circle S is measured. Let the area of the region indicating the metal 15 inside the maximum inscribed circle S be Sm. Let the area of the maximum inscribed circle S be Ss. The area Sm of the region indicating the metal 15 inside the maximum inscribed circle S with respect to the area Ss of the maximum inscribed circle S is obtained. That is, (Sm / Ss)×100 (%) is obtained. Thereby, the ratio (%) of the region indicating the metal inside the maximum inscribed circle of the observation region where the metal is observed can be obtained.

[0028] Here, FIG. 7 is a schematic diagram showing the circumscribed rectangle of the region indicating the metal in the conductive fine line of the conductive substrate according to the embodiment of the present invention, FIG. 8 is a schematic diagram showing the circumscribed rectangle of the region indicating the metal in the conductive fine line of the conductive substrate according to the embodiment of the present invention, and FIG. 9 is a schematic diagram showing the circumscribed rectangle of the region indicating the metal in the conductive fine line of the conductive substrate according to the embodiment of the present invention.

[0029] In the conductive fine wire 14, in a circumscribed rectangle 20 whose four corner angles are each 90° and one side 20a is parallel to the surface 12a of the substrate 12 and that circumscribes the observation region R where the metal 15 is observed, among the contact points 21 and 22 between the sides 20b and 20c perpendicular to the surface 12a of the substrate 12 of the circumscribed rectangle 20 and the observation region R, an upper contact point 22a (see FIG. 8) that is at the position farthest from the surface 12a of the substrate 12 is taken as one corner, and a rectangular region on the opposite side of the substrate 12 from the upper contact point 22a of the circumscribed rectangle 20 is defined as an upper circumscribed rectangle 23 (see FIGS. 8 and 9). The upper circumscribed rectangle 23 has four corner angles each of 90°, and one side 23a is parallel to the surface 12a (see FIG. 7) of the substrate 12 (see FIG. 7).

[0030] In the upper circumscribed rectangle 23, when the length of the contour line Rm (see FIG. 8) of the region Rb (see FIG. 8) where the metal 15 exists is Lm, the total length of the four sides of the upper circumscribed rectangle 23 (see FIG. 9) is Ls, and the ratio represented by Lm / Ls is γ, it is preferable that 1.3 ≤ γ ≤ 2.0. The ratio γ represented by Lm / Ls is a parameter that reflects the unevenness on the surface 14a side of the conductive fine wire 14. When the value of the ratio γ is large, the length Lm of the contour line Rm (see FIG. 8) of the region Rb (see FIG. 8) where the metal 15 exists is long, and the difference between the length Lm and the total length Ls of the four sides of the upper circumscribed rectangle 23 (see FIG. 9) is large. That is, when the value of the ratio γ is large, the surface area of the conductive fine wire 14 is large, indicating that the surface 14a of the conductive fine wire 14 is uneven. When the value of the ratio γ is within 2.0, the unevenness of the surface 14a of the conductive fine wire 14 is of a preferable magnitude, the diffuse reflected light becomes small, and the conductive fine wire 14 becomes difficult to see. When the value of the ratio γ is small, the length Lm is short. That is, when the value of the ratio γ is small, the surface area of the conductive fine wire 14 is small, indicating that the unevenness of the surface 14a of the conductive fine wire 14 is small. When the value of the ratio γ is 1.3 or more, the unevenness of the surface 14a of the conductive fine wire 14 is of a preferable magnitude, the specular reflected light becomes small, and the conductive fine wire 14 becomes difficult to see. When the value of the ratio γ is 1.3 ≤ γ ≤ 2.0, the reflectance of the conductive fine wire 14 decreases and the luminance decreases.

[0031] First, as shown in FIG. 7, image data of the observation region R where the metal 15 is observed is obtained. The image data is data that can be analyzed by a computer as described above. Next, a circumscribed rectangle 20 that circumscribes the observation region R where the metal 15 is observed is set. The circumscribed rectangle 20 has angles of 90° at each of its four corners, and one side 20a is parallel to the surface 12a of the substrate 12. A circumscribed rectangle with angles of 90° at each of its four corners and one side parallel to the surface 12a of the substrate 12 is randomly generated, and among the generated circumscribed rectangles, the one with the largest area is the circumscribed rectangle 20. Next, the contact points 21 and 22 between the sides 20b and 20c perpendicular to the surface 12a of the substrate 12 of the circumscribed rectangle 20 and the observation region R are obtained. Among the contact points 21 and 22, the contact point 22 at the position farthest from the surface 12a (see FIG. 7) of the substrate 12 (see FIG. 1) is defined as the upper contact point 22a (see FIG. 8). A rectangular region on the opposite side of the substrate 12 from the upper contact point 22a of the circumscribed rectangle 20 with this upper contact point 22a as one corner is defined as the upper circumscribed rectangle 23 (see FIG. 8). The upper circumscribed rectangle 23 can be obtained, for example, by trimming the circumscribed rectangle 20. As described above, the upper circumscribed rectangle 23 has angles of 90° at each of its four corners, and one side 23a is parallel to the surface 12a (see FIG. 7) of the substrate 12 (see FIG. 7). Within the upper circumscribed rectangle 23, a contour line Rm (see FIG. 9) is obtained for the region Rb (see FIG. 8) where the metal 15 exists. The contour line Rm shown in FIG. 9 can be obtained in the same manner as the above-mentioned contour line R L (see FIG. 4). Next, the length Lm of the contour line Rm is obtained. Also, the total length Ls of the four sides of the upper circumscribed rectangle 23 is obtained. Next, the ratio γ represented by Lm / Ls is obtained. Note that the ratio γ is obtained for the three conductive thin wires 14, and the average value thereof is taken as the final value of the ratio γ.

[0032] The conductive thin wire contains metal. The metal is the part that ensures the conductivity of the conductive thin wire. As the metal, silver (metallic silver), copper (metallic copper), gold (metallic gold), nickel (metallic nickel), palladium (metallic palladium), or a mixture of two or more of these is preferable in terms of better conductivity, silver, copper, or a mixture thereof is more preferable, and silver is even more preferable. The conductive fine wire may contain only silver as the metal, and it is preferable that all the metals are composed of silver. By making all the metals composed of silver, the occurrence of disconnection failure of the conductive fine wire is reduced. Note that the metal exists in a particulate form in the conductive fine wire 14, but it is not limited to this form. For example, the metal may be in a layered form and dispersed in the conductive fine wire. Also, the conductive fine wire may contain a polymer. In this case, the metal particles may be discretely present in the polymer, or the metal particles may aggregate and exist as an aggregate in the polymer. The type of the polymer is not particularly limited, and known polymers can be used. Examples of the polymer include the polymers contained in the fine wires described in the explanation of the method for manufacturing the conductive fine wire described later, and specific polymers described later are preferable.

[0033] The substrate 12 is composed of, for example, a flexible film. The flexible film is composed of, for example, polyethylene terephthalate (PET), cycloolefin polymer (COP), cycloolefin copolymer (COC), or polycarbonate (PC).

[0034] The line width Wa of the conductive fine wire 14 (see FIG. 2) is the maximum length of the region where the metal 15 of the conductive fine wire 14 exists in the direction DW (see FIG. 2) orthogonal to the direction DL (see FIG. 1) in which the conductive fine wire 14 extends. The line width Wa of the conductive fine wire 14 is preferably 0.1 μm or more and less than 5.0 μm from the viewpoint of the balance between bendability and difficulty of visual recognition. Among them, from the point that the conductive fine wire 14 is difficult to be visually recognized, the line width Wa is preferably 2.5 μm or less, and more preferably 2.0 μm or less. The lower limit is not particularly limited, but from the point that the conductivity of the conductive fine wire is more excellent, 0.5 μm or more is preferable, and 1.2 μm or more is more preferable. The height T of the conductive fine wire (see FIG. 2) is the maximum length of the region where the metal 15 of the conductive fine wire 14 exists in the direction perpendicular to the surface 12a of the substrate 12. The height T of the conductive fine wire 14 is not particularly limited, but from the viewpoint of the balance between conductivity and bendability, it is preferably 0.06 μm or more and less than 7.5 μm, and more preferably the height T is 0.3 or more and 3 μm or less.

[0035] Regarding the line width Wa of the above-mentioned conductive fine wire 14, using a scanning electron microscope, five arbitrary positions corresponding to the line width of one conductive fine wire are selected, and the arithmetic average value of the line widths corresponding to the five positions is defined as the line width Wa. Also, regarding the height T of the above-mentioned conductive fine wire 14, using a scanning electron microscope, five arbitrary positions corresponding to the height of one conductive fine wire are selected, and the arithmetic average value of the portions corresponding to the heights of the five positions is defined as the height T. In order to ensure the conductivity of the conductive fine wire 14, a certain aspect ratio (for example, aspect ratio: 0.3 to 2.5) is required. However, the lower the aspect ratio to some extent, the less likely it is to receive the surface pressure of the roll and the less likely it is to cause wire breakage or the like. For this reason, in the vertical cross-section Ac of the conductive fine wire 14, it is preferable that the ratio of the height T of the conductive fine wire 14 to the line width Wa of the conductive fine wire 14 is 0.6 or more and less than 1.5.

[0036] The line resistance value of the conductive fine wire is preferably less than 200 Ω / mm. Among them, from the viewpoint of operability when used as a touch panel, it is more preferably less than 100 Ω / mm, and even more preferably less than 60 Ω / mm. The linear resistance value is the resistance value measured by the four-terminal method divided by the distance between the measurement terminals. More specifically, after disconnecting both ends of any one conductive thin wire constituting the mesh pattern and separating it from the mesh pattern, four (A, B, C, D) microprobes (tungsten probes (diameter 0.5 μm) manufactured by Micro Support Co., Ltd.) are brought into contact with the separated conductive thin wire, and a constant current I is applied using a source meter (KEITHLEY source meter 2400 type general-purpose source meter) to the outermost probes A and D so that the voltage V between the internal probes B and C becomes 5 mV. The resistance value Ri = V / I is measured, and the obtained resistance value Ri is divided by the distance between B and C to obtain the linear resistance value.

[0037] The conductive thin wires may form a predetermined pattern. For example, the pattern is not particularly limited, and is preferably a geometric figure combined with triangles such as equilateral triangles, isosceles triangles, and right triangles, quadrilaterals such as squares, rectangles, rhombuses, parallelograms, and trapezoids, (regular) n-gons such as (regular) hexagons and (regular) octagons, circles, ellipses, and stars, and more preferably a mesh shape (mesh pattern). The mesh shape is intended to be a shape including a plurality of openings (lattices) 18 formed by intersecting conductive thin wires 14B as shown in FIG. 10. The conductive thin wire 14B has the same configuration as the above-described conductive thin wire 14. In FIG. 10, the opening 18 has a diamond (square) shape, but may have other shapes. For example, it may be a polygonal shape (for example, a triangle, a quadrilateral, a hexagon, and a random polygon). Also, the shape of one side may be linear, curved, or arcuate. In the case of an arcuate shape, for example, for two opposing sides, it may be an arcuate shape convex outward, and for the other two opposing sides, it may be an arcuate shape convex inward. Also, the shape of each side may be a wavy shape in which an arcuate shape convex outward and an arcuate shape convex inward are continuous. Of course, the shape of each side may be a sine curve. Here, FIG. 10 is a plan view showing an example of a mesh pattern formed by conductive thin wires of a conductive substrate according to an embodiment of the present invention.

[0038] The length L of one side of the opening 18 is not particularly limited, but is preferably 1500 μm or less, more preferably 1300 μm or less, still more preferably 1000 μm or less, preferably 5 μm or more, more preferably 30 μm or more, and still more preferably 80 μm or more. When the length of the side of the opening is within the above range, it is possible to further maintain good transparency, and when the conductive substrate is attached to the front surface of the display device, the display can be visually recognized without a sense of incongruity. From the viewpoint of visible light transmittance, the aperture ratio of the mesh pattern is preferably 90.00% or more, more preferably 95.00% or more, and still more preferably 99.50% or more. The upper limit is not particularly limited, but is less than 100%. The aperture ratio corresponds to the ratio of the area on the substrate excluding the area where the conductive fine wires are present in the mesh pattern region to the entire area.

[0039] <Touch panel sensor> FIG. 11 is a schematic plan view showing an example of a touch panel sensor using the conductive substrate of the embodiment of the present invention. The touch panel sensor 30 is a part that functions as a touch sensor of a touch panel (not shown), and is a detection region E where an input operation can be performed by a user 1 and a detection unit 32, and a peripheral region E 1 located outside the detection region E 2 and a peripheral wiring portion 33. The detection unit 32 has, for example, a first detection electrode layer 34A and a second detection electrode layer 34B. The first detection electrode layer 34A and the second detection electrode layer 34B are arranged, for example, via the substrate 12. The first detection electrode layer 34A and the second detection electrode layer 34B are electrically insulated by the substrate. The substrate functions as an electrical insulating layer. As shown in FIG. 11, the first detection electrode layer 34A has a plurality of first dummy electrodes 36a disposed between adjacent first detection electrodes 35 and insulated from the first detection electrodes 35.

[0040] The plurality of first detection electrodes 35 are strip-shaped electrodes extending in the X direction parallel to each other, and are provided on the surface 12a of the substrate 12 at intervals in the Y direction orthogonal to the X direction, and are electrically insulated from each other in the Y direction. Further, the plurality of first dummy electrodes 36a are arranged between the first detection electrodes 35 and are provided on the surface 12a of the substrate 12 in a state of being electrically insulated from the first detection electrodes 35. The first detection electrodes 35 are each provided with a first electrode terminal 38 at at least one end in the X direction. The second detection electrode layer 34B has a plurality of second dummy electrodes 36b arranged between and adjacent to the plurality of second detection electrodes 37 and insulated from the second detection electrodes 37. The plurality of second detection electrodes 37 are strip-shaped electrodes extending in the Y direction parallel to each other, and are provided on the back surface 12b of the substrate 12 at intervals in the X direction and are electrically insulated from each other in the X direction. Further, the plurality of second dummy electrodes 36b are arranged between the second detection electrodes 37 and are provided on the back surface 12b of the substrate 12 in a state of being electrically insulated from the second detection electrodes 37. The second detection electrodes 37 are each provided with a second electrode terminal 39 at one end in the Y direction.

[0041] The plurality of first detection electrodes 35 and the plurality of second detection electrodes 37 are provided orthogonally, but are electrically insulated from each other by the substrate 12 as described above. Note that the first dummy electrodes 36a and the second dummy electrodes 36b in the first detection electrodes 35 and the second detection electrodes 37 are regions that are separated from the first detection electrodes 35 or the second detection electrodes 37 by disconnection portions and are not electrically connected. Therefore, as described above, the plurality of first detection electrodes 35 are electrically insulated from each other in the Y direction, and the plurality of second detection electrodes 37 are electrically insulated from each other in the X direction. As shown in FIG. 11, in the detection unit 32, six first detection electrodes 35 and five second detection electrodes 37 are provided, but the number is not particularly limited as long as there are a plurality of them. The first detection electrode layer 34A and the second detection electrode layer 34B are composed of conductive fine wires 14 (see FIG. 1). When the first detection electrode 35 and the second detection electrode 37 are metal meshes having a mesh pattern formed by the conductive fine wires 14, the first dummy electrode 36a and the second dummy electrode 36b are also metal meshes having a mesh pattern formed by the conductive fine wires 14. The electrode width of the first detection electrode 35 and the electrode width of the second detection electrode 37 are not particularly limited, but are, for example, 1 to 5 mm, and the pitch between the electrodes is 1 to 6 mm. The electrode width of the first detection electrode 35 is the maximum length in the Y direction, and the electrode width of the second detection electrode 37 is the maximum length in the X direction.

[0042] The peripheral wiring portion 33 is a region in which peripheral wirings (first peripheral wiring 40a, second peripheral wiring 40b), which are wirings for transmitting or relaying a touch drive signal and a touch detection signal from a controller (not shown) to the first detection electrode 35 and the second detection electrode 37, are arranged. The peripheral wiring portion 33 has a plurality of first peripheral wirings 40a and a plurality of second peripheral wirings 40b. One end of the first peripheral wiring 40a is electrically connected to the first detection electrode 35 via the first electrode terminal 38, and the other end is electrically connected to the first external connection terminal 41a. Also, one end of the second peripheral wiring 40b is electrically connected to the second detection electrode 37 via the second electrode terminal 39, and the other end is electrically connected to the second external connection terminal 41b. A flexible circuit board 42 is electrically connected to the first external connection terminal 41a and the second external connection terminal 41b and is connected to a controller (not shown). Note that the first electrode terminal 38 and the second electrode terminal 39 may be in a solid film shape or may be in a mesh shape as shown in Japanese Patent Application Laid-Open No. 2013-127658. The preferable range of the width of the first electrode terminal 38 and the second electrode terminal 39 is respectively 1 / 3 times or more and 1.2 times or less of the electrode width of the first detection electrode 35 and the second detection electrode 37.

[0043] The first detection electrode 35, the first dummy electrode 36a, the first electrode terminal 38, and the first peripheral wiring 40a are preferably integrally formed from the viewpoints of electrical resistance and the difficulty of occurrence of disconnection, and more preferably formed of the same metal material. Similarly, the second detection electrode 37, the second dummy electrode 36b, the second electrode terminal 39, and the second peripheral wiring 40b are preferably integrally formed from the viewpoints of electrical resistance and resistance to disconnection, and more preferably formed of the same metal material.

[0044] FIG. 12 is a schematic diagram showing a first example of the first peripheral wiring of a touch panel sensor using the conductive substrate of the embodiment of the present invention, and FIG. 13 is a schematic diagram showing a second example of the first peripheral wiring of a touch panel sensor using the conductive substrate of the embodiment of the present invention. FIG. 14 is a schematic diagram showing a third example of the first peripheral wiring of a touch panel sensor using the conductive substrate of the embodiment of the present invention, and FIG. 15 is a schematic diagram showing a fourth example of the first peripheral wiring of a touch panel sensor using the conductive substrate of the embodiment of the present invention. FIG. 16 is a schematic diagram showing a fifth example of the first peripheral wiring of a touch panel sensor using the conductive substrate of the embodiment of the present invention. In FIGS. 12 to 16, the same components as those of the touch panel sensor 30 shown in FIG. 11 are denoted by the same reference numerals, and detailed description thereof is omitted.

[0045] As shown in FIG. 12, the first peripheral wiring 40a has, for example, the same line width configuration. That is, the first peripheral wiring 40a is configured with a constant line width. Further, as shown in FIG. 13, the first peripheral wiring 40a may have a configuration in which the line width is partially different. In FIG. 13, the first peripheral wiring 40a has a first wiring portion 43a with a narrow line width and a second wiring portion 43b with a wider line width than the first wiring portion 43a. The first wiring portion 43a is connected to the first detection electrode 35. Further, the first peripheral wiring 40a is not limited to being configured by a single line, and as shown in FIGS. 14 to 16, a part thereof may be configured by a plurality of lines. Disconnection can be suppressed by the configuration of the first peripheral wiring 40a shown in FIGS. 14 to 16. In the first peripheral wiring 40a shown in FIGS. 14 to 16, the portion connected to the first detection electrode 35 is configured by a plurality of lines.

[0046] The first peripheral wiring 40a shown in FIG. 14 has a third wiring portion 43c with a narrower line width than the second wiring portion 43b and a fourth wiring portion 43d on the side of the first detection electrode 35 (not shown). The third wiring portion 43c and the fourth wiring portion 43d are arranged in parallel. The fourth wiring portion 43d has a narrower line width than the third wiring portion 43c. The fourth wiring portion 43d is preferable because it has the same line width as the conductive fine wire 14, which can improve plating uniformity and reduce the probability of disconnection. The first peripheral wiring 40a shown in FIG. 15 has a third wiring portion 43c with a narrower line width than the second wiring portion 43b and a fourth wiring portion 43d on the side of the first detection electrode 35 (not shown). The third wiring portion 43c is arranged on both sides of the fourth wiring portion 43d, and a part of the first peripheral wiring 40a is composed of three wiring portions. The fourth wiring portion 43d is preferable because it has the same line width as the conductive fine wire 14, which can improve plating uniformity and reduce the probability of disconnection. The first peripheral wiring 40a shown in FIG. 16 has a third wiring portion 43c with a narrower line width than the second wiring portion 43b on the side of the first detection electrode 35 (not shown). Two third wiring portions 43c are arranged in parallel, and a part of the first peripheral wiring 40a is composed of two wiring portions. Although the first peripheral wiring 40a of the touch panel sensor 30 has been described, the second peripheral wiring 40b can also have the same configuration as the first peripheral wiring 40a.

[0047] FIG. 17 is a schematic plan view showing another example of a touch panel sensor using a conductive substrate according to an embodiment of the present invention. In FIG. 17, the same components as those of the touch panel sensor 30 shown in FIG. 11 are denoted by the same reference numerals, and detailed description thereof is omitted. The touch panel sensor 30a shown in FIG. 17 is different from the touch panel sensor 30 shown in FIG. 11 in that it has a shield electrode 43, and other configurations are the same as those of the touch panel sensor 30 shown in FIG. 11. The shield electrode 43 is provided on the back surface 12b of the substrate 12 so as to surround the detection region E 1 The shield electrode 43 is in the peripheral region E on the back surface 12b of the substrate 12 2It is provided in a region corresponding to The shield electrode 43 shields electromagnetic waves from the detection unit 32. The influence of electromagnetic waves on the detection unit 32 is suppressed by the shield electrode 43. Note that the shield electrode 43 may be a solid film, for example, a mesh pattern similar to the first detection electrode 35. Also, the shield electrode 43 can be used as a ground electrode.

[0048] The conductive fine wire preferably contains more carbon atoms and preferably more polymers in the metal part. By containing a polymer, durability, bendability, and handling suitability can be improved. As the polymer, gelatin and polymers different from the gelatin described later are preferable, and a water-soluble polymer such as gelatin is more preferable. The content of the polymer in the conductive fine wire is preferably 200 mg / m per area of the conductive fine wire 2 or more, more preferably 400 mg / m 2 or more, and even more preferably 500 mg / m 2 or more. When the polymer is, for example, gelatin, the content of the polymer can be quantified by the BCA method (bicinchoninic acid method) for a range of about 4 cm × 4 cm only at the site where the metal solid film is formed. For other polymers, it can be quantified by appropriately selecting a known method such as an extraction method. Also, it is preferable that the pattern portion (hereinafter also simply referred to as "peripheral pattern") located in the peripheral wiring portion contains more polymer with respect to the detection unit by the conductive fine wire. In a region where the ratio of the number of metal atoms inside the peripheral pattern is 50% or more, the ratio of the number of carbon atoms / metal atoms is preferably 0.2 or more. The atomic ratio can be calculated by analyzing the atomic composition of the peripheral pattern by Ar sputtering (2 kV, Ar ions, 2 mm × 2 mm) and XPS (X-ray source: Al Kα, Quantera SXM manufactured by ULVAC-PHI, Inc.) in the depth direction from the surface on the side opposite to the substrate of the conductive fine wire. The side closer to the substrate than the position where the ratio of the number of metal atoms becomes 50% or more is defined as the inside, and the atomic number ratio (carbon atoms / metal atoms) of carbon atoms and metal atoms in the internal region can be obtained. As a method for obtaining the atomic composition, for example, in the case of a conductive thin wire or pattern with a width of 100 μm or more, the above-described sputtering and XPS (X-ray Photoelectron Spectroscopy) methods can be used. When the size of the pattern is smaller, for example, 100 μm or less, the cross-section of the pattern is taken, and the atomic composition inside the pattern can be obtained by the SEM-EDX (Scanning Electron Microscope-Energy Dispersive X-ray Spectrometry) method using the center as a representative value.

[0049] It is also preferable when there are not only the conductive thin wires of the detection unit, but also peripheral wiring parts connected to the detection unit, a ground electrode located outside the detection unit, a shield electrode, etc., and the effect of plating uniformity can be obtained. There are no particular restrictions on the relative position, configuration, area, etc. of the peripheral wiring parts, ground wiring, shield electrodes, etc. with respect to the detection unit, and they can be preferably adjusted according to the application of each application. Regarding the shapes of the first peripheral wiring 40a and the plurality of second peripheral wirings 40b, they can be appropriately selected. However, in the case of the plating method, in order to improve the plating uniformity, it is preferable that the line widths of the first peripheral wiring 40a and the plurality of second peripheral wirings 40b are approximately the same as the line width of the conductive thin wire 14. Also, as shown in FIG. 13 described above, it is preferable that the first peripheral wiring 40a and the plurality of second peripheral wirings 40b have a configuration in which the first wiring part 43a connected to the first detection electrode 35 is thin. Since the risk of disconnection increases during handling or processing when the line width of the first wiring part 43a is made thin, it is also preferable that the first peripheral wiring 40a and the plurality of second peripheral wirings 40b are partially configured with a plurality of lines, as shown in FIGS. 14 to 16. When configured with a plurality of lines, in order to improve the plating uniformity, it is preferable that the line width is equal to or approximately the same as the line width of the conductive thin wire.

[0050] The heights of the first peripheral wiring 40a and the second peripheral wiring 40b can be defined and measured in the same manner as the conductive fine wires as shown in FIG. 2. The height of the peripheral wiring is not particularly limited, but from the viewpoint of the balance between conductivity and bendability, it is preferably 0.06 μm or more and less than 7.5 μm, and more preferably 0.3 or more and 3 μm or less.

[0051] The line widths of the first peripheral wiring 40a and the second peripheral wiring 40b can be defined and measured in the same manner as the conductive fine wires as shown in FIG. 2. There is no particular limitation on the line width of the peripheral wiring, but a larger line width is preferable for improving conductivity, and a smaller line width is preferable for reducing the area of the frame portion of the touch sensor and enhancing the design. Specifically, it is preferably 1 μm or more and less than 50 μm, more preferably 1.5 μm or more and less than 30 μm, and most preferably 3 μm or more and less than 25 μm. The aspect ratio of the first peripheral wiring 40a and the second peripheral wiring 40b is preferably lower to some extent so that it is less likely to receive the surface pressure of the roll and less likely to cause disconnection or the like. Therefore, in the vertical cross-section of the first peripheral wiring 40a and the second peripheral wiring 40b, the ratio of the height of the peripheral wiring to the line width of the peripheral wiring is preferably 0.01 or more and less than 1, and more preferably 0.03 or more and less than 0.6.

[0052] <Method for manufacturing a conductive substrate> Next, a method for manufacturing a conductive substrate will be described. The method for manufacturing a conductive substrate is not particularly limited as long as a conductive substrate having the above-described configuration can be manufactured. However, from the viewpoint of productively manufacturing a conductive substrate having the above-described predetermined characteristics, a manufacturing method having the following steps 1 to 3 in this order is preferable. Step 1: A step of forming fine wires containing a metal on a substrate Step 2: A step of bringing the above-mentioned fine wires into contact with a solution containing an organic acid Step 3: A step of performing a plating process on the above-mentioned fine wires to form conductive fine wires Hereinafter, each step will be described in detail.

[0053] [Step 1] Step 1 is a step of forming fine wires containing a metal on a substrate.

[0054] Examples of the type of metal include those exemplified as the metal contained in the above-described conductive fine wire, and silver is preferred. The metal may be in the form of particles. In that case, the average particle diameter of the metal particles is preferably 10 to 1000 nm, more preferably 10 to 200 nm, and even more preferably 50 to 150 nm in terms of the equivalent spherical diameter. Note that the equivalent spherical diameter is the diameter of a spherical particle having the same volume. Also, the "equivalent spherical diameter" used as the average particle diameter of the above metal particles is an average value, which is obtained by measuring the equivalent spherical diameters of 100 objects and calculating their arithmetic mean.

[0055] The shape of the metal particles is not particularly limited, and examples thereof include spherical, cubic, flat plate (hexagonal flat plate, triangular flat plate, quadrangular flat plate, etc.), octahedral, and tetrakaidecahedral shapes. The content of the metal in the fine wire is not particularly limited, and 3.0 to 20.0 g / m is preferred in terms of better conductivity of the conductive substrate. 2 is preferred.

[0056] The above fine wire preferably contains a polymer. That is, in the fine wire, it is preferable that the metal is dispersed in the polymer with the polymer as a binder. The type of the polymer is not particularly limited, but a polymer different from gelatin (hereinafter also referred to as "specific polymer") is preferred in terms of forming a conductive fine wire with better strength. The type of the specific polymer is not particularly limited as long as it is different from gelatin, and a polymer that is not decomposed by a proteolytic enzyme or an oxidizing agent that decomposes gelatin described later is preferred. Examples of the specific polymer include hydrophobic polymers (water-insoluble polymers), such as at least one resin selected from the group consisting of (meth)acrylic resins, styrene resins, vinyl resins, polyolefin resins, polyester resins, polyurethane resins, polyamide resins, polycarbonate resins, polydiene resins, epoxy resins, silicone resins, cellulose-based polymers, and chitosan-based polymers, or copolymers composed of monomers constituting these resins. Further, the specific polymer preferably has a reactive group that reacts with a crosslinking agent described later. The specific polymer is preferably in a particulate form. That is, the photosensitive layer preferably contains particles of the specific polymer. Among them, as the specific polymer, a polymer (copolymer) represented by the general formula (1) described later is preferable.

[0057] The content of the polymer in the fine line is not particularly limited, and at least one of the effects that the electric resistance of the conductive fine line is lower and the conductive fine line is less difficult to visually recognize (hereinafter, also simply referred to as "the point where the effects of the present invention are more excellent") is obtained. In terms of this, 0.005 to 2.0 g / m 2 is preferable, and 0.01 to 1.0 g / m is preferable.

[0058] The fine line may form a predetermined pattern, and examples of the pattern that the above-described conductive fine line can form are given. The description of the substrate is as described above.

[0059] The method for forming a fine line containing a metal on a substrate is not particularly limited, and a known method is adopted. For example, a method of performing exposure and development using silver halide, a method of forming a layer containing a metal on the entire surface of the substrate and then removing a part of the layer using a resist pattern to form the above-described fine line, and a method of forming a fine line by discharging a composition containing metal particles and a polymer onto a substrate by a known printing method such as inkjet are given. Among them, in terms of the point where the effects of the present invention are more excellent, a method of performing exposure and development using silver halide is preferable. Hereinafter, this method will be described in detail.

[0060] The method of performing exposure and development using silver halide preferably has the following steps. Step A: A step of forming a silver halide-containing photosensitive layer containing silver halide, gelatin, and a specific polymer on a substrate Process B: A process of exposing a silver halide-containing photosensitive layer and then performing development processing to form a fine linear silver-containing layer containing metallic silver, gelatin, and a polymer different from gelatin Process C: A process of subjecting the silver-containing layer obtained in Process B to a heat treatment Process D: A process of removing the gelatin in the silver-containing layer obtained in Process C to form the above-mentioned fine lines Hereinafter, the procedures of each process will be described in detail.

[0061] [Process A] Process A is a process of forming a silver halide-containing photosensitive layer (hereinafter, also referred to as "photosensitive layer") containing silver halide, gelatin, and a specific polymer on a substrate. By this process, a substrate with a photosensitive layer to which an exposure treatment described later will be applied is manufactured. First, the materials and substrate used in Process A will be described in detail, and then the procedure of Process A will be described in detail.

[0062] (Silver Halide) The halogen atom contained in the silver halide may be any of a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, or a combination thereof. For example, silver halide mainly composed of silver chloride, silver bromide, or silver iodide is preferable, and silver halide mainly composed of silver chloride or silver bromide is more preferable. Note that silver chlorobromide, silver iodochlorobromide, or silver iodobromide is also preferably used. Here, for example, "silver halide mainly composed of silver chloride" means silver halide in which the molar fraction of chloride ions in the total halide ions in the silver halide composition is 50% or more. This silver halide mainly composed of silver chloride may contain bromide ions and / or iodide ions in addition to chloride ions.

[0063] The silver halide is usually in the form of solid particles, and the average particle diameter of the silver halide is preferably 10 to 1000 nm, more preferably 10 to 200 nm, and still more preferably 50 to 150 nm in terms of the equivalent spherical diameter. The shape of the silver halide grains is not particularly limited, and examples thereof include spherical, cubic, tabular (hexagonal tabular, triangular tabular, quadrangular tabular, etc.), octahedral, and tetradecahedral shapes.

[0064] (Gelatin) The type of gelatin is not particularly limited, and examples thereof include lime-treated gelatin and acid-treated gelatin. Further, a hydrolyzate of gelatin, an enzymatically decomposed product of gelatin, and gelatin modified with an amino group and / or a carboxyl group (phthalated gelatin and acetylated gelatin) may also be used.

[0065] (Specific polymer) The photosensitive layer contains a polymer different from gelatin (specific polymer). By including this specific polymer in the photosensitive layer, the strength of the silver-containing layer and the conductive fine lines formed from the photosensitive layer is more excellent. The characteristics such as the type, specific examples, and shape of the specific polymer are as described above.

[0066] Among them, as the specific polymer, a polymer (copolymer) represented by the following general formula (1) is preferable. General formula (1): -(A)x-(B)y-(C)z-(D)w- In general formula (1), A, B, C, and D each represent a repeating unit represented by the following general formulas (A) to (D).

[0067] [Chemical formula]

[0068] R 1 represents a methyl group or a halogen atom, and a methyl group, a chlorine atom, or a bromine atom is preferable. p represents an integer of 0 to 2, 0 or 1 is preferable, and 0 is more preferable. R 2 represents a methyl group or an ethyl group, and a methyl group is preferable. R 3represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred. L represents a divalent linking group, and a group represented by the following general formula (2) is preferred. General formula (2): -(CO-X 1 )r-X 2 - In general formula (2), X 1 represents an oxygen atom or NR 30 -. Here, R 30 represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group, and each may have a substituent (for example, a halogen atom, a nitro group, and a hydroxyl group). As R 30 , a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, an n-butyl group, and an n-octyl group), or an acyl group (for example, an acetyl group and a benzoyl group) is preferred. As X 1 , an oxygen atom or NH- is preferred. X 2 represents an alkylene group, an arylene group, an alkylene arylene group, an arylene alkylene group, or an alkylene arylene alkylene group, and -O-, -S-, -CO-, -COO-, -NH-, -SO 2 -, -N(R 31 )-, or -N(R 31 )SO 2 - etc. may be inserted in the middle. R 31 represents a linear or branched alkyl group having 1 to 6 carbon atoms. As X 2 , a dimethylene group, a trimethylene group, a tetramethylene group, an o-phenylene group, an m-phenylene group, a p-phenylene group, -CH 2 CH 2 OCOCH 2 CH 2 -, or -CH 2 CH 2 OCO(C 6 H 4 )- is preferred. r represents 0 or 1. q represents 0 or 1, and 0 is preferred.

[0069] R 4represents an alkyl group, an alkenyl group, or an alkynyl group, preferably an alkyl group having 5 to 50 carbon atoms, more preferably an alkyl group having 5 to 30 carbon atoms, and even more preferably an alkyl group having 5 to 20 carbon atoms. R 5 represents a hydrogen atom, a methyl group, an ethyl group, a halogen atom, or -CH 2 COOR 6 and is preferably a hydrogen atom, a methyl group, a halogen atom, or -CH 2 COOR 6 more preferably a hydrogen atom, a methyl group, or -CH 2 COOR 6 and even more preferably a hydrogen atom. R 6 represents a hydrogen atom or an alkyl group having 1 to 80 carbon atoms, and may be the same as or different from R 4 , and the number of carbon atoms of R 6 is preferably 1 to 70, and more preferably 1 to 60.

[0070] In the general formula (1), x, y, z, and w represent the molar ratios of the respective repeating units. x is 3 to 60 mol%, preferably 3 to 50 mol%, and more preferably 3 to 40 mol%. y is 30 to 96 mol%, preferably 35 to 95 mol%, and more preferably 40 to 90 mol%. z is 0.5 to 25 mol%, preferably 0.5 to 20 mol%, and more preferably 1 to 20 mol%. w is 0.5 to 40 mol%, preferably 0.5 to 30 mol%. In the general formula (1), it is preferable that x is 3 to 40 mol%, y is 40 to 90 mol%, z is 0.5 to 20 mol%, and w is 0.5 to 10 mol%.

[0071] As the polymer represented by the general formula (1), a polymer represented by the following general formula (2) is preferable.

[0072]

Chemical formula

[0073] In general formula (2), x, y, z, and w are as defined above.

[0074] The polymer represented by general formula (1) may contain repeating units other than the repeating units represented by the above general formulas (A) to (D). Examples of the monomers for forming other repeating units include acrylic esters, methacrylic esters, vinyl esters, olefins, crotonic acid esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, and unsaturated nitriles. These monomers are also described in paragraphs 0010 to 0022 of Japanese Patent No. 3754745. From the viewpoint of hydrophobicity, acrylic esters or methacrylic esters are preferable, and hydroxyalkyl methacrylate or hydroxyalkyl acrylate is more preferable. The polymer represented by general formula (1) preferably contains a repeating unit represented by general formula (E).

[0075]

Chemical formula

[0076] In the above formula, L E represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and still more preferably an alkylene group having 2 to 4 carbon atoms.

[0077] As the polymer represented by general formula (1), a polymer represented by the following general formula (3) is particularly preferable.

[0078]

Chemical formula

[0079] In the above formula, a1, b1, c1, d1, and e1 represent the molar ratios of each repeating unit, where a1 represents 3 to 60 (mol%), b1 represents 30 to 95 (mol%), c1 represents 0.5 to 25 (mol%), d1 represents 0.5 to 40 (mol%), and e1 represents 1 to 10 (mol%). The preferred range of a1 is the same as the preferred range of x above, the preferred range of b1 is the same as the preferred range of y above, the preferred range of c1 is the same as the preferred range of z above, and the preferred range of d1 is the same as the preferred range of w above. e1 is 1 to 10 mol%, preferably 2 to 9 mol%, and more preferably 2 to 8 mol%.

[0080] The specific polymer can be synthesized, for example, with reference to Japanese Patent No. 3305459 and Japanese Patent No. 3754745, etc. The weight average molecular weight of the specific polymer is not particularly limited, preferably 1000 to 1000000, more preferably 2000 to 750000, and even more preferably 3000 to 500000.

[0081] The photosensitive layer may contain other materials in addition to the materials described above, if necessary. Examples of other materials include metal compounds belonging to Groups 8 and 9 such as rhodium compounds and iridium compounds used for the stabilization and high-sensitivity of silver halides. Also, examples of other materials include antistatic agents, nucleation accelerators, spectral sensitizing dyes, surfactants, fog inhibitors, hardeners, black spot inhibitors, redox compounds, monomethine compounds, and dihydroxybenzenes as described in paragraphs 0220 to 0241 of JP-A-2009-004348. In addition, as other materials, there are viscosity modifiers (e.g., thickening polysaccharides, celluloses, water-soluble polymers, etc.), film-forming aids (e.g., glycol derivatives, diol compounds such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, etc.), preservatives, plasticizers, lubricants, fillers composed of organic or inorganic or organic-inorganic composite materials (e.g., PMMA (Poly Methyl Methacrylate), polystyrene, colloidal silica, zirconia, cellulose nanofibers, CNT (carbon nanotube), etc.), and ultraviolet absorbers, etc. The antistatic agent can prevent the adhesion of foreign substances due to the charging of the silver halide-containing light-sensitive material or the malfunction due to unintended light-sensitivity caused by discharge light emission, and is preferable. The surfactant is preferable because it can control the coatability of the light-sensitive layer, the adhesion to the substrate, and the dispersibility of silver halide, binder, and other contained components. In addition, the light-sensitive layer may contain a crosslinking agent or curing agent described in paragraphs 0146 to 0158 of JP-A No. 2009-004348, a dye described in paragraphs 0160 to 0170, and a water-soluble binder described in paragraphs 0214 to 0217. The light-sensitive layer may also contain a metal stabilizer described in paragraphs 0079 to 0081 of WO 2020 / 195622 and a specific compound described in paragraphs 0109 to 0118. Furthermore, the light-sensitive layer may contain physical development nuclei.

[0082] In addition, the light-sensitive layer may contain a crosslinking agent used for crosslinking the above specific polymers. By including the crosslinking agent, crosslinking between the specific polymers proceeds, and the connection between silver metals in the conductive fine wires is maintained even when gelatin is decomposed and removed. These materials other than gelatin and the specific polymer may be contained in the silver halide-free layer and / or the protective layer described later.

[0083] (Procedure of Step A) The method for forming the light-sensitive layer containing the above components in Step A is not particularly limited, but from the viewpoint of productivity, a method of contacting a light-sensitive layer-forming composition containing silver halide, gelatin, and a specific polymer with a substrate to form a light-sensitive layer on the substrate is preferable. The form of the composition for forming a photosensitive layer used in this method will be described in detail below, and then the procedure of the process will be described in detail.

[0084] (Materials contained in the composition for forming a photosensitive layer) The composition for forming a photosensitive layer contains the silver halide, gelatin, and specific polymer described above. Note that, if necessary, the specific polymer may be contained in the composition for forming a photosensitive layer in a particulate form. The composition for forming a photosensitive layer may contain a solvent, if necessary. Examples of the solvent include water, organic solvents (for example, alcohols, ketones, amides, sulfoxides, esters, and ethers), ionic liquids, and mixed solvents thereof.

[0085] The method of bringing the composition for forming a photosensitive layer into contact with the substrate is not particularly limited, and examples thereof include a method of applying the composition for forming a photosensitive layer onto the substrate and a method of immersing the substrate in the composition for forming a photosensitive layer. Note that, after the above treatment, a drying treatment may be performed, if necessary.

[0086] (Silver halide-containing photosensitive layer) The photosensitive layer formed by the above procedure contains silver halide, gelatin, and specific polymer. The content of silver halide in the photosensitive layer is not particularly limited, and in terms of more excellent effects of the present invention, it is preferably 3.0 to 20.0 g / m in terms of silver conversion 2 more preferably 5.0 to 15.0 g / m 2 even more preferably. The silver conversion means that it is converted to the mass of silver produced when all the silver halide is reduced. The content of the specific polymer in the photosensitive layer is not particularly limited, and in terms of more excellent effects of the present invention, it is preferably 0.04 to 2.0 g / m 2 more preferably 0.08 to 0.40 g / m 2 even more preferably.

[0087] [Process B] Step B is a step of performing development processing on the photosensitive layer after exposure to form a thin silver-containing layer containing metallic silver, gelatin, and a specific polymer.

[0088] By subjecting the photosensitive layer to an exposure process, a latent image is formed in the exposed area. The exposure may be performed in a pattern. For example, in order to obtain a mesh pattern composed of conductive thin lines described later, methods of exposure through a mask having a mesh-shaped opening pattern and a method of scanning a laser beam for mesh-shaped exposure can be mentioned. The type of light used during exposure is not particularly limited as long as it can form a latent image on silver halide. Examples include visible light, ultraviolet light, and X-rays.

[0089] When performing exposure through a mask having an opening pattern, the exposure amount may be reduced and exposure may be performed only at specific locations in the mask opening pattern to adjust the latent image formation amount. By adjusting the latent image formation amount, the amount of metal and the thickness (height) formed in the subsequent operation can be adjusted. There is no particular limitation on the means for reducing the exposure amount only at specific locations, but examples include a method of adjusting the exposure amount from the light source irradiated on the specific portion. For example, methods such as only reducing the output of the lamp or LED above this portion to lower the exposure amount, or installing a light reduction filter above the specific portion can be mentioned. Also, as another means for reducing the exposure amount only at specific locations, a method using a halftone mask with a semi-permeable membrane applied to a specific portion of the mask opening pattern can be mentioned. From the viewpoint of productivity, it is preferable to use a halftone mask.

[0090] By subjecting the exposed photosensitive layer to development processing, metallic silver is deposited in the exposed area (the area where the latent image is formed). The method of development processing is not particularly limited, and examples include known methods used for silver salt photographic films, photographic papers, films for printing plate making, and emulsion masks for photomasks. In the development process, a developer is usually used. The type of the developer is not particularly limited, and examples thereof include a PQ (phenidone hydroquinone) developer, an MQ (Metol hydroquinone) developer, and an MAA (Metol ascorbic acid) developer.

[0091] This step may further include a fixing process that is performed for the purpose of removing and stabilizing silver halide in the unexposed portion. The fixing process is carried out simultaneously with and / or after the development. The method of the fixing process is not particularly limited, and examples thereof include methods used for silver salt photographic films, photographic papers, films for printing plate making, and emulsion masks for photomasks. In the fixing process, a fixer is usually used. The type of the fixer is not particularly limited, and examples thereof include the fixer described in "Chemistry of Photography" (written by Sasai, published by Photographic Industry Co., Ltd., p321).

[0092] By carrying out the above-mentioned process, a fine linear silver-containing layer containing metallic silver, gelatin, and a specific polymer is formed. As a method for adjusting the line width of the silver-containing layer, for example, a method of adjusting the aperture width of the mask used during exposure can be mentioned. Also, when using a mask during exposure, the width of the formed silver-containing layer can be adjusted by adjusting the exposure amount. For example, when the aperture width of the mask is narrower than the width of the target silver-containing layer, the width of the region where the latent image is formed can be adjusted by increasing the exposure amount more than usual. Furthermore, when using a laser beam, the exposure region can be adjusted by adjusting the condensing range and / or scanning range of the laser beam.

[0093] In addition, in order to adjust the ratio of the number of carbon atoms to the number of metal atoms in the region where the ratio of the number of metal atoms inside the peripheral pattern is 50% or more as described above, there is a method of adjusting the size of the peripheral pattern with respect to the detection electrode. When the size of the peripheral pattern with respect to the detection electrode is large, it becomes difficult to remove gelatin from the peripheral pattern in Step D described later, and as a result, a peripheral pattern with a high ratio of carbon atoms can be formed.

[0094] [Step C] Step C is a step of performing a heat treatment on the silver-containing layer obtained in Step B. By carrying out this step, fusion between specific polymers in the silver-containing layer proceeds, and the strength of the silver-containing layer is improved.

[0095] The method of heat treatment is not particularly limited, and examples include a method of bringing the silver-containing layer into contact with superheated steam and a method of heating the silver-containing layer with a temperature control device (for example, a heater). A method of bringing the silver-containing layer into contact with superheated steam is preferred.

[0096] The superheated steam may be superheated water vapor or a mixture of superheated water vapor and other gases. The contact time between the superheated steam and the silver-containing layer is not particularly limited, and preferably ranges from 10 to 70 seconds. The supply amount of the superheated steam is preferably 500 - 600 g / m 3 and the temperature of the superheated steam is preferably 100 - 160°C (more preferably 100 - 120°C) at 1 atmosphere.

[0097] As the heating conditions in the method of heating the silver-containing layer with a temperature control device, conditions of heating at 100 - 200°C (more preferably 100 - 150°C) for 1 - 240 minutes (more preferably 60 - 150 minutes) are preferred.

[0098] [Step D] Step D is a step of removing gelatin from the silver-containing layer obtained in Step C to form the above-mentioned thin lines. By carrying out this step, gelatin is removed from the silver-containing layer, and the above-mentioned thin lines with voids formed inside are formed. The plating solution described later penetrates into these voids, and metal plating is formed. When removing gelatin, all of the gelatin in the silver-containing layer may be removed, or the removal may be performed such that a part of the gelatin remains. Among these, in terms of more excellent effects of the present invention, it is preferable to perform Step D such that a part of the gelatin remains.

[0099] The method for removing gelatin is not particularly limited, and examples thereof include a method using a proteolytic enzyme (hereinafter, also referred to as "Method 1"), and a method of decomposing and removing gelatin using an oxidizing agent (hereinafter, also referred to as "Method 2").

[0100] Examples of the proteolytic enzyme used in Method 1 include known enzymes that are plant-derived or animal-derived enzymes capable of hydrolyzing proteins such as gelatin. Examples of the proteolytic enzyme include pepsin, rennin, trypsin, chymotrypsin, cathepsin, papain, ficin, thrombin, rennin, collagenase, bromelain, and bacterial protease, and trypsin, papain, ficin, or bacterial protease is preferable. The procedure in Method 1 may be any method of bringing the silver-containing layer into contact with the above proteolytic enzyme. For example, a method of bringing the silver-containing layer into contact with a treatment liquid containing the proteolytic enzyme (hereinafter, also referred to as "enzyme solution") can be mentioned. Examples of the contact method include a method of immersing the silver-containing layer in the enzyme solution and a method of applying the enzyme solution onto the silver-containing layer. The content of the proteolytic enzyme in the enzyme solution is not particularly limited, and in terms of easy control of the degree of decomposition and removal of gelatin, 0.05 to 20% by mass is preferable, and 0.5 to 10% by mass is more preferable, based on the total amount of the enzyme solution. The enzyme solution usually contains water in addition to the above proteolytic enzyme. The enzyme solution may contain other additives (for example, a pH buffer, an antibacterial compound, a wetting agent, and a preservative) as necessary. The pH of the enzyme solution is selected so that the function of the enzyme can be maximally obtained. Generally, 5 to 9 is preferable. The temperature of the enzyme solution is preferably a temperature at which the function of the enzyme increases, specifically 20 to 45°C.

[0101] In addition, if necessary, after the treatment with the enzyme solution, a washing treatment may be performed to wash the obtained silver-containing layer with warm water. The washing method is not particularly limited, and a method of bringing the silver-containing layer into contact with warm water is preferable. Examples thereof include a method of immersing the silver-containing layer in warm water and a method of applying warm water onto the silver-containing layer. The temperature of the warm water is appropriately selected as an optimal temperature according to the type of protease used. From the viewpoint of productivity, 20 to 80°C is preferable, and 40 to 60°C is more preferable. The contact time (washing time) between the warm water and the silver-containing layer is not particularly limited. From the viewpoint of productivity, 1 to 600 seconds is preferable, and 10 to 180 seconds is more preferable.

[0102] As the oxidizing agent used in Method 2, any oxidizing agent that can decompose gelatin may be used, and an oxidizing agent having a standard electrode potential of +1.5 V or more is preferable. Here, the standard electrode potential refers to the standard electrode potential (25°C, E0) with respect to the standard hydrogen electrode in an aqueous solution of the oxidizing agent. Examples of the above oxidizing agent include persulfuric acid, percarbonic acid, perphosphoric acid, hypochlorous acid, peracetic acid, m-chloroperbenzoic acid, hydrogen peroxide solution, perchloric acid, periodic acid, potassium permanganate, ammonium persulfate, ozone, hypochlorous acid or its salts, etc. From the viewpoints of productivity and economy, hydrogen peroxide solution (standard electrode potential: 1.76 V), hypochlorous acid or its salts are preferable, and sodium hypochlorite is more preferable.

[0103] The procedure in Method 2 may be any method of bringing the silver-containing layer into contact with the above oxidizing agent. Examples thereof include a method of bringing the silver-containing layer into contact with a treatment solution containing the oxidizing agent (hereinafter also referred to as "oxidizing agent solution"). Examples of the contact method include a method of immersing the silver-containing layer in the oxidizing agent solution and a method of applying the oxidizing agent solution onto the silver-containing layer. The type of the solvent contained in the oxidizing agent solution is not particularly limited, and examples thereof include water and organic solvents.

[0104] [Step E] Step 1 may have Step E of forming a silver halide-free layer containing gelatin and a specific polymer on a substrate before Step A. By performing this step, a silver halide-free layer is formed between the substrate and the silver halide-containing photosensitive layer. This silver halide-free layer serves as a so-called antihalation layer and contributes to improving the adhesion between the conductive fine wire and the substrate. The silver halide-free layer contains the above-mentioned gelatin and specific polymer. On the other hand, the silver halide-free layer does not contain silver halide. The ratio of the mass of the specific polymer to the mass of gelatin (mass of specific polymer / mass of gelatin) in the silver halide-free layer is not particularly limited, and is preferably 0.1 to 5.0, more preferably 1.0 to 3.0. The content of the specific polymer in the silver halide-free layer is not particularly limited, and is often 0.03 g / m 2 In many cases as above, in terms of more excellent adhesion of the conductive fine wire, 1.0 g / m 2 or more is preferable. The upper limit is not particularly limited, but is often 1.63 g / m 2 or less.

[0105] The method for forming the silver halide-free layer is not particularly limited, and examples include a method of applying a composition for forming a layer containing gelatin and a specific polymer on a substrate and performing a heat treatment as necessary. The composition for forming a layer may contain a solvent as necessary. Examples of the type of solvent include the solvents used in the above-mentioned composition for forming a photosensitive layer. The thickness of the silver halide-free layer is not particularly limited, and is often 0.05 μm or more. In terms of more excellent adhesion of the conductive fine wire, more than 1.0 μm is preferable, and more than 1.5 μm is more preferable. The upper limit is not particularly limited, but it is preferably less than 3.0 μm.

[0106] [Step F] Step 1 may have Step F of forming a protective layer containing gelatin and a specific polymer on the silver halide-containing photosensitive layer after Step A and before Step B. By providing the protective layer, it is possible to prevent scratches on the photosensitive layer and improve the mechanical properties. The ratio of the mass of the specific polymer to the mass of gelatin (mass of specific polymer / mass of gelatin) in the protective layer is not particularly limited, preferably more than 0 and 2.0 or less, more preferably more than 0 and 1.0 or less. Also, the content of the specific polymer in the protective layer is not particularly limited, 0 g / m 2 more than 0.3 g / m 2 or less is preferable, and 0.005 to 0.1 g / m 2 is more preferable.

[0107] The method for forming the protective layer is not particularly limited. For example, a method of applying a protective layer-forming composition containing gelatin and a specific polymer onto a silver halide-containing photosensitive layer and performing a heat treatment as necessary can be mentioned. The protective layer-forming composition may contain a solvent as necessary. Examples of the type of solvent include the solvents used in the above-described photosensitive layer-forming composition. The thickness of the protective layer is not particularly limited, preferably 0.03 to 0.3 μm, more preferably 0.075 to 0.20 μm.

[0108] In addition, the above-described Step E, Step A, and Step F may be simultaneously performed by simultaneous multilayer coating.

[0109] [Step 2] Step 2 is a step of bringing the above-mentioned fine wire into contact with a solution containing an organic acid. By performing this step, the organic acid adheres to the surface of the fine wire, and during the plating treatment in Step 3 described later, the plating deposition on the surface of the fine wire is suppressed, and the plating solution more easily penetrates into the fine wire. As a result, it becomes easier for the metal (metal plating) to deposit inside the fine wire, and the desired effect can be obtained. Hereinafter, first, the solution used in this step will be described in detail, and then the procedure of Step 2 will be described in detail.

[0110] (Solution containing organic acid) The type of the organic acid contained in the solution containing an organic acid (hereinafter, also simply referred to as "the first solution") is not particularly limited as long as it is an acid containing a carbon atom. For example, carboxylic acids (organic compounds having a carboxy group), sulfonic acids (organic compounds having a sulfonic acid group), and phosphonic acids (organic compounds having a phosphonic acid group) can be mentioned. Among them, carboxylic acids are preferable in terms of more excellent effects of the present invention.

[0111] The molecular weight of the organic acid (for example, carboxylic acid) is not particularly limited, but in terms of more excellent effects of the present invention, 60 to 400 is preferable, and 90 to 300 is more preferable.

[0112] The carboxylic acid may be a monovalent carboxylic acid or a divalent or higher (polyvalent) carboxylic acid. In terms of more excellent effects of the present invention, polyvalent carboxylic acids are preferable. As the divalent or higher carboxylic acid, a 2- to 7-valent carboxylic acid is preferable, and a 2- to 4-valent carboxylic acid is more preferable. Note that the above valence represents the number of carboxy groups contained, and a monovalent carboxylic acid is a compound having one carboxy group.

[0113] The carboxylic acid may have other polar groups (for example, hydroxy group, amino group, carbonyl group, ether group) in addition to the carboxy group.

[0114] Examples of the carboxylic acid include monovalent carboxylic acids such as acetic acid, lactic acid, and hydroxybutyric acid; divalent carboxylic acids such as oxalic acid, malonic acid, tartaric acid, L-aspartic acid, DL-malic acid, oxaloacetic acid, succinic acid, glutamic acid, 2-oxoglutaric acid, glutaric acid, adipic acid, and pimelic acid; trivalent carboxylic acids such as citric acid, 1,2,3-propanetricarboxylic acid, and 1,3,5-pentanetricarboxylic acid; tetravalent carboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, ethylenediaminetetraacetic acid, and ethyleneglycolbis(β-aminoethyl ether)-N,N,N,N-tetraacetic acid; and pentavalent carboxylic acids such as diethylenetriaminepentaacetic acid.

[0115] The first solution contains a solvent. The type of the solvent is not particularly limited, and examples thereof include water, organic solvents (e.g., alcohols, ketones, amides, sulfoxides, esters, and ethers), ionic liquids, and mixed solvents thereof. Among them, water is preferred.

[0116] The first solution may contain other components in addition to the organic acid and the solvent. Examples of the other components include the quaternary ammonium salts contained in the second solution described later. The aspects of the quaternary ammonium salts will be described in detail in the following section.

[0117] The content of the organic acid in the first solution is not particularly limited, but in terms of more excellent effects of the present invention, it is preferably 0.2 to 5% by mass, more preferably 0.5 to 3% by mass, based on the total mass of the first solution.

[0118] The pH value of the first solution is not particularly limited, but in terms of more excellent effects of the present invention, it is preferably 1.5 to 6.0, more preferably 2.0 to 4.0, at a temperature of 25°C. As a method for measuring pH, it can be measured with a pH meter using a pH electrode.

[0119] When the first solution contains a quaternary ammonium salt, the content of the quaternary ammonium salt in the first solution is not particularly limited, but in terms of more excellent effects of the present invention, it is preferably 10 -6 ~10 -1 % by mass, more preferably 10 -5 ~10 -3 % by mass, based on the total mass of the first solution.

[0120] (Procedure of Step 2) The method for bringing the fine wire into contact with the first solution is not particularly limited, and examples thereof include a method of immersing a substrate having the fine wire in the first solution and a method of applying the first solution onto the fine wire. The contact time between the fine wire and the first solution is not particularly limited, and from the viewpoints of more excellent effects of the present invention and productivity, it is preferably 5 to 180 seconds, more preferably 20 to 120 seconds. The temperature of the first solution when it comes into contact with the thin wire is not particularly limited, but in terms of more excellent effects of the present invention, 30 to 100 °C is preferable, and 65 to 95 °C is more preferable.

[0121] After bringing the thin wire into contact with the first solution, if necessary, the thin wire may be washed with a solvent (for example, water).

[0122] [Step 3] Step 3 is a step of performing a plating treatment on the above-mentioned thin wire to form a conductive thin wire. By carrying out this step, a conductive thin wire filled with a metal (plated metal) is formed in the thin wire. In particular, in the thin wire obtained by carrying out the above-described Steps A to D, since there is a space formed by removing gelatin, the space is filled with a metal (plated metal). When Step 2 is carried out immediately before Step 3, the thin wire obtained in Step 2 is subjected to a plating treatment. As will be described later, when Step 5 is carried out between Step 2 and Step 3, the thin wire obtained in Step 5 is subjected to a plating treatment.

[0123] The type of plating treatment is not particularly limited, and examples include electroless plating (chemical reduction plating or displacement plating) and electroplating, and electroless plating is preferable. As the electroless plating, known electroless plating techniques are used. Examples of the plating treatment include silver plating treatment, copper plating treatment, nickel plating treatment, and cobalt plating treatment. In terms of the electrical resistance of the conductive thin wire being smaller, silver plating treatment or copper plating treatment is preferable, and silver plating treatment is more preferable.

[0124] The components contained in the plating solution used in the plating treatment are not particularly limited, but usually, in addition to a solvent (for example, water), 1. metal ions for plating, 2. a reducing agent, 3. an additive (stabilizer) for improving the stability of the metal ions, and 4. a pH adjuster are mainly included. In addition to these, this plating bath may contain known additives such as a stabilizer of the plating bath. The type of metal ions for plating contained in the plating solution can be appropriately selected according to the type of metal to be deposited. For example, silver ions, copper ions, nickel ions, and cobalt ions can be mentioned. The pH of the plating solution is not particularly limited, but in terms of more excellent effects of the present invention, alkalinity is preferable at a temperature of 25 °C, more preferably 8.5 to 11.0, and even more preferably 9.0 to 10.5.

[0125] The procedure of the above plating treatment is not particularly limited, and any method of bringing the fine wire into contact with the plating solution may be used. For example, a method of immersing a silver-containing layer in the plating solution and a method of applying the plating solution onto the fine wire can be mentioned. The contact time between the fine wire and the plating solution is not particularly limited, and from the viewpoints of more excellent effects of the present invention and productivity, 25 seconds to 30 minutes is preferable. After contacting the plating solution, the fine wire may be washed with water or neutralized and washed with an acidic solution having a pH of 3 to 7, and the pH of the acidic solution is more preferably 4 to 6. As long as the acidic solution has a pH of 3 to 7, sulfur and the like do not generate from sulfurous acid derived from the plating solution. In addition, an increase in the pH of the plating solution is also suppressed, and the plating reaction can be stopped. The acidic solution functions as a plating stop solution. The acidic solution preferably has a buffering action, and a solid content concentration of 0.1 mass% or more is preferable because it exhibits sufficient buffering capacity. The temperature of the plating solution is preferably 10 to 40 °C, and more preferably 15 to 30 °C. The contact time is not particularly limited, and from the viewpoints of more excellent effects of the present invention and productivity, 5 to 60 seconds is preferable.

[0126] The above Step 2 and Step 3 may be repeatedly performed. That is, after Step 3 is completed, Step 2 and Step 3 may be further performed. The number of times of repeating the procedures of Step 2 and Step 3 is not particularly limited, and 2 to 4 times is preferable.

[0127] [Step 4] The method for manufacturing a conductive substrate may further include a step 4 of plating the fine wires between step 1 and step 2. By performing step 4, the conductivity of the conductive fine wires is further improved. Since the procedure of step 4 is the same as the procedure of step 3 described above, the description thereof is omitted. It should be noted that step 4, step 2, and step 3 may be repeatedly performed. That is, after step 3 is completed, step 4, step 2, and step 3 may be further performed. The number of times of repeating the procedures from step 4 to step 3 is not particularly limited, and 2 to 4 times are preferable. Also in step 4, similar to step 3, after contacting the fine wires with the plating solution, the fine wires may be washed with water or neutralization-washed with an acidic solution having a pH of 3 to 7, and it is more preferable that the pH of the acidic solution is 4 to 6. As long as the acidic solution has a pH of 3 to 7, sulfur or the like does not generate from sulfurous acid derived from the plating solution. Further, an increase in the pH of the plating solution is suppressed, and the plating reaction can be stopped. The acidic solution preferably has a buffering action, and it is preferable that a sufficient buffering capacity is exhibited if the solid content concentration is 0.1 mass% or more. As described above, step 3 or step 4 preferably includes a neutralization washing step of bringing the fine wires into contact with an acidic solution having a pH of 3 to 7 to stop the plating reaction by the plating treatment. Further, the acidic solution preferably has a buffering action as described above. By using a buffer solution for the neutralization washing, even if the plating solution is mixed, an increase in pH can be suppressed, and the plating reaction can be uniformly stopped.

[0128] [Step 5] The method for manufacturing a conductive substrate may further include a step 5 of bringing a solution containing a quaternary ammonium salt into contact with the fine wires between step 1 and step 2, or between step 2 and step 3. By performing this step, the ions of the quaternary ammonium salt adhere to the surface of the fine wires, and during the plating treatment in step 3 described later, the plating deposition on the surface of the fine wires is suppressed, and the plating solution more easily penetrates into the fine wires. As a result, it becomes easier for metal (metal plating) to deposit inside the fine wires, and a desired effect is obtained. First, the solution used in this step 5 will be described in detail, and then the procedure of step 5 will be described in detail.

[0129] (Solution containing quaternary ammonium salt) The type of the quaternary ammonium salt contained in the solution containing a quaternary ammonium salt (hereinafter, also simply referred to as "the second solution") is not particularly limited as long as it is a compound having a quaternary nitrogen. The molecular weight of the quaternary ammonium salt is not particularly limited, but in terms of more excellent effects of the present invention, it is preferably 100 to 700, and more preferably 200 to 650.

[0130] As the quaternary ammonium salt, a compound represented by the general formula (I) or a compound represented by the general formula (II) is preferable. General formula (I) (R 1 ) 4 N + A -

[0131]

Chemical formula

[0132] In the general formula (I), R 1 each independently represents an alkyl group which may have a substituent. The four R 1 may be the same group or different groups from each other. The number of carbon atoms of the above alkyl group is not particularly limited, but is preferably 1 to 30, and more preferably 1 to 20. The type of the substituent which the alkyl group may have is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group (for example, a phenyl group), an alkoxy group, an aryloxy group, an acyl group (for example, an acetyl group), an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, and a diarylamino group.

[0133] In the general formula (II), R2 represents an alkyl group which may have a substituent. R 2 Examples and preferred ranges of the alkyl group which may have a substituent represented by are the same as those of the alkyl group which may have a substituent represented by the above-described R 1 and the examples and preferred ranges of the alkyl group which may have a substituent represented by are included.

[0134] A in the general formulas (I) and (II) - represents an anion. The type of the anion is not particularly limited, and examples thereof include halogen ions (for example, F - , Cl - , Br - , and I - ), HSO 4 - , OH - , CH 3 COO - , PF 6 - , R 3 CO 3 - , ClO 4 - , BF 4 - , SbF 6 - , and AsF 6 - . Note that R 3 represents a hydrogen atom or an alkyl group which may have a substituent. R 3 Examples and preferred ranges of the alkyl group which may have a substituent represented by are the same as those of the alkyl group which may have a substituent represented by the above-described R 1 and the examples and preferred ranges of the alkyl group which may have a substituent represented by are included.

[0135] As the quaternary ammonium salt, a compound represented by the general formula (X), a compound represented by the general formula (Y), or a compound represented by the general formula (Z) is preferable in terms of more excellent effects of the present invention.

[0136]

Chemical formula

[0137] In general formula (X), R a1 and R a2 each independently represent an alkyl group having 4 or fewer carbon atoms which may have a substituent, and R a3 and R a4 each independently represent an alkyl group having 8 or more carbon atoms which may have a substituent. R a1 and R a2 The alkyl group having 4 or fewer carbon atoms which may have a substituent represented by is preferably 1 or 2 in that the effect of the present invention is more excellent. R a3 and R a4 The alkyl group having 8 or more carbon atoms which may have a substituent represented by is preferably 8 to 30, more preferably 10 to 20, in that the effect of the present invention is more excellent. R a1 and R a2 The alkyl group represented by, and the alkyl group represented by R a3 and R a4 The types of substituents which the alkyl group may have are not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, and a diarylamino group.

[0138] In general formula (Y), R b1 ~R b3 each independently represent an alkyl group having 4 or fewer carbon atoms which may have a substituent, and R b4 represents an alkyl group having 10 or more carbon atoms which may have a substituent. R b1 ~R b3 The alkyl group having 4 or fewer carbon atoms which may have a substituent represented by is preferably 1 or 2 in that the effect of the present invention is more excellent. R b4The number of carbon atoms of the alkyl group which may have a substituent represented by is 8 or more, and in terms of more excellent effects of the present invention, 8 to 30 is preferable, and 10 to 20 is more preferable. R b1 ~R b3 The alkyl group represented by, and the substituent which the alkyl group represented by R b4 may respectively have is not particularly limited. For example, the groups exemplified as the substituent which the alkyl group represented by the above-mentioned R a1 may have are mentioned.

[0139] In general formula (Z), R c1 represents an alkyl group having 10 or more carbon atoms which may have a substituent. R c1 The number of carbon atoms of the alkyl group which may have a substituent represented by is 10 or less, and in terms of more excellent effects of the present invention, 10 to 30 is preferable, and 10 to 20 is more preferable. R c1 The substituent which the alkyl group represented by may have is not particularly limited. For example, the groups exemplified as the substituent which the alkyl group represented by the above-mentioned R a1 may have are mentioned.

[0140] In general formulas (X) to (Z), A - represents an anion. In general formulas (X) to (Z), as the anion represented by A - the anions exemplified as the anions in the above-mentioned general formulas (I) and (II) for A - are mentioned.

[0141] The second solution contains a solvent. The type of the solvent is not particularly limited, and examples include water, organic solvents (for example, alcohols, ketones, amides, sulfoxides, esters, and ethers), ionic liquids, and mixed solvents thereof. Among them, water is preferable.

[0142] The second solution may contain other components (for example, the above-mentioned organic acid) other than the quaternary ammonium salt and the solvent.

[0143] The content of the quaternary ammonium salt in the second solution is not particularly limited, but in terms of more excellent effects of the present invention, it is preferably 10 -6 to 1% by mass, more preferably 10 -6 to 0.1% by mass, based on the total mass of the second solution.

[0144] The pH value of the second solution is not particularly limited, but in terms of more excellent effects of the present invention, it is preferably 3 to 7, more preferably 4 to 6 at a temperature of 25°C.

[0145] (Procedure of Step 5) The method of bringing the fine wire into contact with the second solution is not particularly limited, and examples include a method of immersing the substrate having the fine wire in the second solution and a method of applying the second solution onto the fine wire. The contact time between the fine wire and the second solution is not particularly limited, and from the viewpoints of more excellent effects of the present invention and productivity, it is preferably 5 to 180 seconds, more preferably 20 to 120 seconds. The temperature of the second solution during the contact between the fine wire and the second solution is not particularly limited, but in terms of more excellent effects of the present invention, it is preferably 20 to 80°C, more preferably 30 to 70°C.

[0146] After bringing the fine wire into contact with the second solution, the fine wire may be washed with a solvent (for example, water) as necessary.

[0147] When Step 5 is carried out between Step 1 and Step 2, Step 5, Step 2, and Step 3 may be repeatedly carried out. That is, after Step 3 is completed, Step 5, Step 2, and Step 3 may be further carried out. The number of times of repeating the procedures from Step 5 to Step 3 is not particularly limited, and preferably 2 to 4 times.

[0148] Also, when Step 5 is carried out between Step 2 and Step 3, Step 2, Step 5, and Step 3 may be repeatedly carried out. That is, after Step 3 is completed, Step 2, Step 5, and Step 3 may be further carried out. The number of times of repeating the procedures from Step 2 to Step 5 is not particularly limited, and preferably 2 to 4 times.

[0149] [Step 6] The method for manufacturing a conductive substrate may include Step 6 of performing a heat treatment on the conductive fine wires obtained in Step 3 after Step 3. By carrying out this step, the strength of the conductive fine wires is improved. Examples of the heat treatment performed in Step 6 include the heat treatment performed in Step C described above.

[0150] [Step 7] The method for manufacturing a conductive substrate may wash the conductive fine wires with a solvent after Step 3 or after Step 6. Examples of the solvent to be used include water, organic solvents (e.g., alcohols, ketones, amides, sulfoxides, esters, and ethers), ionic liquids, and mixed solvents thereof. Several types of solvents may be used for washing. For example, after washing with an organic solvent, it may be further washed with water. As the solvent, a mixed solvent may be used. For example, a mixed solvent of alcohols or ethers and water is preferable. As the alcohols, ethanol is preferable, and as the ethers, diethylene glycol monoethyl ether or diethylene glycol monomethyl ether is preferable.

[0151] [Applications] The conductive substrate obtained as described above can be applied to various applications, such as touch panels (or touch panel sensors), semiconductor chips, various printed wiring boards, FPCs (Flexible Printed Circuits), COFs (Chip on Film), TABs (Tape Automated Bonding), antennas, multilayer wiring boards, and motherboards. Among them, the conductive substrate of the present invention is preferably used for touch panels (capacitive touch panels). When the conductive substrate of the present invention is used for a touch panel, the above-described conductive fine wires can function effectively as detection electrodes. In the conductive substrate, in addition to the conductive fine wires having the above-described predetermined characteristics, it may have a conductive portion having a configuration different from that of the conductive fine wires. This conductive portion may be electrically connected to the above-described conductive fine wires and be electrically conductive.

[0152] The present invention is basically configured as described above. As described above, the manufacturing method of the conductive substrate and the conductive substrate of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various improvements or modifications can of course be made without departing from the gist of the present invention.

Example

[0153] The features of the present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios thereof, and operations shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following examples.

[0154] <Example 1> (Preparation of silver halide emulsion) To the following Solution 1 maintained at 30°C and pH 4.5, amounts corresponding to 90% of each of the following Solution 2 and Solution 3 were added simultaneously over 20 minutes while stirring Solution 1 to form 0.16 μm core particles. Subsequently, Solution 4 and Solution 5 were added to the resulting solution over 8 minutes, and further, the remaining 10% of the amounts of the following Solution 2 and Solution 3 were added over 2 minutes to grow the core particles to 0.10 μm. Furthermore, 0.15 g of potassium iodide was added to the resulting solution and aged for 5 minutes to complete particle formation.

[0155] Solution 1: Water 750 ml Gelatin 8.6 g Potassium bromide 3 g 1,3-Dimethylimidazolidine-2-thione 20 mg Sodium benzenethiosulfonate 10 mg Citric acid 0.7 g Solution 2: Water 300 ml Silver nitrate 150 g Solution 3: Water 300 ml Sodium chloride 38 g Potassium bromide 32 g Potassium hexachloroiridate(III) (0.005% KCl 20% aqueous solution) 5 ml Ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) 7 ml Solution 4: Water 100 ml Silver nitrate 50 g Solution 5: Water 100 ml Sodium chloride 13 g Potassium bromide 11 g Potassium ferrocyanide 5 mg

[0156] Thereafter, washing with water was carried out by the flocculation method according to a conventional method. Specifically, the temperature of the above-obtained solution was lowered to 35° C., and the pH was lowered using sulfuric acid until silver halide was precipitated (the range was pH 3.6 ± 0.2). Next, about 3 liters of the supernatant was removed from the obtained solution (first water washing). Next, 3 liters of distilled water was added to the solution from which the supernatant had been removed, and then sulfuric acid was added until silver halide was precipitated. Again, 3 liters of the supernatant was removed from the obtained solution (second water washing). The same operation as the second water washing was repeated one more time (third water washing), and the water washing and desalting steps were completed. The emulsion after water washing and desalting was adjusted to pH 6.4 and pAg 7.5, and 2.5 g of gelatin, 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 15 mg of sodium thiosulfate, and 10 mg of chloroauric acid were added, and chemical sensitization was performed at 55° C. to obtain the optimum sensitivity. Thereafter, 100 mg of 1,3,3a,7-tetraazaindene as a stabilizer and 100 mg of Proxel (trade name, manufactured by ICI Co., Ltd.) as a preservative were further added to the obtained emulsion. The finally obtained emulsion contained 0.08 mol% of silver iodide, and the ratio of silver chlorobromide was 70 mol% of silver chloride and 30 mol% of silver bromide, and was a silver chlorobromide cubic particle emulsion having an average particle diameter (equivalent spherical diameter) of 100 nm and a coefficient of variation of 9%.

[0157] (Preparation of Photosensitive Layer-Forming Composition) To the above emulsion, 1,3,3a,7-tetraazaindene (1.2×10 -4 mol / mol Ag), hydroquinone (1.2×10 -2 mol / mol Ag), citric acid (3.0×10 -4 mol / mol Ag), 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt (0.90 g / mol Ag), and a trace amount of a hardening agent were added to obtain a composition. Next, the pH of the composition was adjusted to 5.6 using citric acid. To the above composition, a polymer latex containing a polymer represented by the following (P-1) (hereinafter also referred to as "polymer 1"), a dispersant composed of a dialkylphenyl PEO (PEO is an abbreviation for polyethylene oxide) sulfate ester, and water (the ratio of the mass of the dispersant to the mass of polymer 1 (mass of dispersant / mass of polymer 1, unit: g / g) is 0.02, and the solid content is 22% by mass) was added so that the ratio of the mass of polymer 1 to the total mass of gelatin in the composition (mass of polymer 1 / mass of gelatin, unit: g / g) was 0.25 / 1 to obtain a polymer latex-containing composition. Here, in the polymer latex-containing composition, the ratio of the mass of gelatin to the mass of silver derived from silver halide (mass of gelatin / mass of silver derived from silver halide, unit: g / g) was 0.11. Furthermore, EPOXY RESIN DY 022 (trade name: manufactured by Nagase ChemteX Corporation) was added as a crosslinking agent. The addition amount of the crosslinking agent was adjusted so that the amount of the crosslinking agent in the silver halide-containing photosensitive layer described later was 0.09 g / m 2 Furthermore, surfactant 1, surfactant 2, and sodium polystyrene sulfonate (molecular weight of about 1 million) as a thickening agent were added. The photosensitive layer-forming composition was prepared as described above. Note that polymer 1 was synthesized with reference to Japanese Patent No. 3305459 and Japanese Patent No. 3754745.

[0158] [Chemical Formula]

[0159] A polyethylene terephthalate film with a thickness of 40 μm (a roll-shaped long film manufactured by Fuji Film Co., Ltd.) was coated with the above-mentioned polymer latex to provide an undercoat layer with a thickness of 0.05 μm. This treatment was carried out in a roll-to-roll manner, and the following respective treatments (processes) were also carried out in the same roll-to-roll manner. At this time, the roll width was 1 m and the length was 1000 m.

[0160] (Process E-1, Process A-1, Process F-1) Next, a composition for forming a silver halide-free layer, the above-mentioned composition for forming a photosensitive layer, and a composition for forming a protective layer described later were simultaneously applied in multiple layers on the undercoat layer to form a silver halide-free layer, a silver halide-containing photosensitive layer, and a protective layer on the undercoat layer. Here, the composition for forming a silver halide-free layer consists of an aqueous solution containing the above-mentioned polymer 1, gelatin, a solid dispersion of a dye described later, surfactant 1, surfactant 2, surfactant 3, and sodium polystyrene sulfonate (molecular weight of about 1 million) as a thickener. The thickness of the silver halide-free layer is 2.0 μm, the mixing mass ratio of polymer 1 to gelatin (polymer 1 / gelatin) in the silver halide-free layer is 2 / 1, and the content of polymer 1 is 1.3 g / m 2 It was. Also, the content of the dye is 0.08 g / m 2 It is, and the contents of surfactant 1, surfactant 2, surfactant 3, and thickener are 0.02 g / m each 2 、0.02 g / m 2 、0.02 g / m 2 、0.04 g / m 2 It was. Also, the thickness of the silver halide-containing photosensitive layer is 2.5 μm, the mixing mass ratio of polymer 1 to gelatin (polymer 1 / gelatin) in the silver halide-containing photosensitive layer is 0.25 / 1, and the content of polymer 1 is 0.19 g / m 2 It was. Also, the contents of surfactant 1, surfactant 2, and thickener are 0.04 g / m each 2 、0.01 g / m 2, 0.01 g / m 2 It was.

[0161] In addition, the composition for forming the protective layer consists of an aqueous solution containing the above-mentioned polymer 1, gelatin, colloidal silica (average particle diameter 12 nm: manufactured by Nissan Chemical Industries, Ltd., Snowtex C), surfactant 1, surfactant 2, surfactant 3, surfactant 4, sodium polystyrene sulfonate (molecular weight of about 1 million) as a thickener, and N,N'-bis(vinylsulfonylacetyl)ethylenediamine ethylene bis(vinylsulfonylacetamide) as a gelatin cross-linking agent. The thickness of the protective layer is 0.15 μm, the mixing mass ratio of polymer 1 and gelatin in the protective layer (polymer 1 / gelatin) is 0.1 / 1, and the content of polymer 1 is 0.015 g / m 2 It was. Also, the content of colloidal silica is 0.1 g / m 2 , surfactant 1, surfactant 2 (average molecular weight 1368), surfactant 3, surfactant 4, and the contents of the thickener are each 0.01 g / m 2 , 0.02 g / m 2 , 0.02 g / m 2 , 0.001 g / m 2 , 0.01 g / m 2 It was. Also, the content of the gelatin cross-linking agent was an amount that was 3 mass percent with respect to the total mass of the gelatin in the entire layer.

[0162]

Chemical formula

[0163]

Chemical formula

[0164]

Chemical formula

[0165]

Chemical formula

[0166]

Chem.

[0167] (Project B) The above-prepared photosensitive layer was exposed using parallel light with a high-pressure mercury lamp as the light source through a grid-shaped photomask. As the photomask, a mask for pattern formation was used, and the line width of the unit square lattice forming the grid as shown in Fig. 10 was 1.2 μm, and the length L of one side of the grid (opening) was set to 600 μm. After exposure, the obtained sample was developed with a developer described later, and further subjected to a developing process using a fixing solution (trade name: N3X-R for CN16X, manufactured by Fujifilm Corporation), then rinsed with pure water at 25 °C, and then dried to obtain Sample A having a silver-containing layer containing metallic silver formed in a mesh pattern. In Sample A, a conductive mesh pattern region with a size of 21.0 cm × 29.7 cm was formed.

[0168] (Composition of the developer) The following compounds are contained in 1 liter (L) of the developer. Hydroquinone 0.037 mol / L N-Methylaminophenol 0.016 mol / L Sodium metaborate 0.140 mol / L Sodium hydroxide 0.360 mol / L Sodium bromide 0.031 mol / L Potassium metabisulfite 0.187 mol / L

[0169] The obtained Sample A was immersed in warm water at 50 °C for 180 seconds. After that, the water was drained with an air shower and naturally dried.

[0170] (Process C-1) Sample A obtained in Process B-1 was carried into a superheated steam treatment tank at 110 °C and left standing for 30 seconds to perform superheated steam treatment. The steam flow rate at this time was 100 kg / h.

[0171] (Process D-1) The sample A obtained in Process C-1 was immersed in an aqueous solution of proteolytic enzyme (40 °C) for 30 seconds. The sample A was taken out from the aqueous solution of proteolytic enzyme, and the sample A was immersed in warm water (liquid temperature: 50 °C) for 120 seconds for washing. After that, the water was drained with an air shower and naturally dried. Note that the aqueous solution of proteolytic enzyme used was prepared according to the following procedure. To an aqueous solution of proteolytic enzyme (Bioprase 30L manufactured by Nagase ChemteX Corporation) (concentration of proteolytic enzyme: 0.5% by mass), triethanolamine and sulfuric acid were added to adjust the pH to 8.5.

[0172] (Process 2-1) The sample A obtained in Process D-1 was immersed in a 1% by mass aqueous solution of glutaric acid (70 °C) for 2 minutes. The sample A was taken out from the aqueous solution of glutaric acid, and the sample A was immersed in water at 30 °C for 5 seconds for washing. Glutaric acid manufactured by Fujifilm Wako Pure Chemical Corporation was used.

[0173] (Process 3-1) The sample A obtained in Process 2-1 was immersed in plating solution A (30 °C) having the following composition for 5 minutes. The sample A was taken out from the plating solution A, and the sample A was immersed in a 1% by mass citric acid buffer solution (pH = 5, liquid temperature: 25 °C) for 30 seconds for washing. That is, neutralization washing was performed. The composition of the plating solution A (total amount 1200 ml) was as follows. Note that the pH of the plating solution A was 9.9, and it was adjusted by adding a predetermined amount of potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Corporation). Also, all of the following components used were manufactured by Fujifilm Wako Pure Chemical Corporation. No change in line width was observed before and after the plating process.

[0174] (Composition of plating solution A) ·AgNO 3 2.1 g ·Sodium sulfite 86 g ·Sodium thiosulfate pentahydrate 60 g · Aron T-50 (manufactured by Toagosei Co., Ltd., solid content concentration 40%) 36 g · Methylhydroquinone 13 g · Potassium carbonate in a predetermined amount · Water, the balance

[0175] (Step 7-1) The sample A obtained in Step 3-1 was immersed in a solution with a mass ratio of water / diethylene glycol monoethyl ether = 30 / 70 (liquid temperature: 50°C) for 60 seconds. Then, the obtained sample A was immersed in water (liquid temperature: 30°C) for 30 seconds for washing. (Step 6-1) The sample A obtained in Step 3-1 was carried into a superheated steam treatment tank at 110°C and left standing for 30 seconds for superheated steam treatment. At this time, the steam flow rate was 100 kg / h. The obtained conductive mesh pattern region was a mesh-like layer formed by conductive fine wires. The line width of the conductive fine wires was 1.8 μm, and the thickness (height) of the conductive fine wires was 1.8 μm.

[0176] For the obtained sample A, in order to impart conductivity to the surface of the conductive fine wires, Pt was coated using an ion sputtering apparatus (E-1030 type ion sputtering manufactured by Hitachi High-Technologies Corporation). In this state, the vertical cross-section of the conductive fine wires was processed by the ion beam processing function of a scanning electron microscope with a focused ion beam processing function (Helios600i manufactured by Thermo Fisher Scientific K.K.), and the exposed cross-sectional morphology was observed, so that the region where the metal inside the conductive fine wires existed could be observed, and an observation image of the vertical cross-section was obtained. The observation conditions were in the backscattered electron mode with an acceleration voltage of 1 kV.

[0177] The "line width" and "gray value" described in Table 1 were measured after the hot steam treatment in Step 6-1, and a microscope VHX-5000 manufactured by Keyence Corporation was used for the measurement.

[0178] [Examples 2 to 12, 18 to 22] As shown in Table 1 described later, a conductive substrate was produced according to the same procedure as in Example 1, except that the type of the first solution used, the temperature of the first solution, the type of the substrate, the line width of the conductive fine wire, and the aspect ratio of the conductive fine wire were adjusted. Note that the line width of the conductive fine wire was controlled by adjusting the exposure amount in Step B-1. Further, the aspect ratio of the conductive fine wire was controlled by adjusting the coating amount of the composition for forming a photosensitive layer.

[0179] <Example 13> A conductive substrate was produced according to the same procedure as in Example 1, except that the following Step 5-13 was carried out between Step D-1 and Step 2-1.

[0180] [Step 5-13] Sample A obtained in Step D-1 was immersed in an aqueous solution of 0.1 mass% laurylpyridinium chloride (30 °C) for 2 minutes. Sample A was taken out from the aqueous solution of laurylpyridinium chloride and immersed in water at 30 °C for 5 seconds for washing. Laurylpyridinium chloride manufactured by Fujifilm Wako Pure Chemical Corporation was used.

[0181] <Example 14> A conductive substrate was produced according to the same procedure as in Example 1, except that the following Step 5-14 was carried out between Step 2-1 and Step 3-1.

[0182] [Step 5-14] Sample A obtained in Step 2-1 was immersed in an aqueous solution of 0.1 mass% laurylpyridinium chloride (30 °C) for 2 minutes. Sample A was taken out from the aqueous solution of laurylpyridinium chloride and immersed in water at 30 °C for 5 seconds for washing. Laurylpyridinium chloride manufactured by Fujifilm Wako Pure Chemical Corporation was used.

[0183] <Examples 15 to 17> As shown in Table 1 described later, a conductive substrate was produced according to the same procedure as in Example 14, except that the type of the second solution used was changed.

[0184] <Comparative Example 1> A conductive substrate was fabricated according to the same procedure as in Example 1, except that Steps 2-1 and 3-1 were not performed.

[0185] <Comparative Example 2> A conductive substrate was fabricated according to the same procedure as in Example 1, except that Step 2-1 was not performed.

[0186] <Evaluation> Hereinafter, conductivity, bendability, and visibility, which are evaluation items, will be described.

[0187] (Conductivity) Regarding conductivity, the sheet resistance value of the conductive mesh pattern region of the obtained conductive substrate was measured and evaluated. The sheet resistance value is the resistance value measured by the four-terminal probe method divided by the distance between the measurement terminals. More specifically, after disconnecting both ends of any one conductive fine wire constituting the mesh pattern and separating it from the mesh pattern, four (A, B, C, D) microprobes (tungsten probes (diameter 0.5 μm) manufactured by Micro Support Co., Ltd.) were brought into contact with the separated conductive fine wire, and a constant current I was applied using a source meter (KEITHLEY source meter, Model 2400 general-purpose source meter) so that the voltage V between the inner probes B and C with a 250-μm interval became 5 mV. The resistance value Ri = V / I was measured, and the obtained resistance value Ri was divided by the distance between B and C to obtain the sheet resistance value. The obtained resistance value Ri was divided by the distance between B and C to obtain the sheet resistance value, and the average value of the measurement values at any 10 locations was evaluated as conductivity according to the following criteria. As an evaluation of conductivity, among the following 1 to 5, 3 or more is preferable, 4 or more is more preferable, and 5 is still more preferable. 5: The sheet resistance value is less than 60 Ω / mm. 4: The sheet resistance value is 60 Ω / mm or more and less than 80 Ω / mm. 3: The sheet resistance value is 80 Ω / mm or more and less than 100 Ω / mm. 2: The sheet resistance value is 100 Ω / mm or more and less than 200 Ω / mm. 1: The sheet resistance value is 200 Ω / mm or more.

[0188] (Flexibility) Regarding flexibility, the obtained conductive substrate was bent multiple times with a bending tester in a direction where the angle formed by the direction in which the conductive fine wires extend and the bending direction is 45°, and the change in conductivity was measured and evaluated. For the bending test, a small desktop tester TCDM111LH manufactured by Yuasa System Devices Co., Ltd. was used. The bending radius was set to 2 mm, and the evaluation was performed according to the following criteria based on the resistance change δ after 200,000 bends. The resistance change δ is represented by resistance change δ = (resistance value after bending test) / (resistance value before bending test). The "resistance value" mentioned here refers to the resistance value Ri obtained by the above-mentioned conductivity evaluation. As an evaluation of flexibility, among the following 1 to 5, 3 or more is preferable, 4 or more is more preferable, and 5 is even more preferable. 5: δ is less than 1.1. 4: δ is 1.1 or more and less than 1.15. 3: δ is 1.15 or more and less than 1.2. 2: δ is 1.2 or more and less than 1.5. 1: δ is 1.5 or more, or the conductive fine wires are broken.

[0189] (Visibility) The obtained conductive substrate was laminated in the order of glass / conductive substrate / polarizing plate / polarizing plate (in a direction where the polarization planes are perpendicular) / black PET (manufactured by Panac Co., Ltd., industrial black PET (GPH100E82A04)) to obtain a laminate. The conductive substrate was arranged so that the conductive mesh pattern was located on the glass side in the conductive substrate. Next, the obtained laminate was visually observed by 10 observers at 500 lux of ambient light from the front on the glass surface side and at an angle of 30 to 60° obliquely, and the visibility was evaluated according to the following criteria. When the mesh pattern is difficult to visually recognize, the optical properties are excellent, and moiré generated when the conductive substrate is laminated on a display is reduced. As an evaluation of visibility, among the following 1 to 5, 3 or more is preferable, 4 or more is more preferable, and 5 is even more preferable. When observing the conductive substrate from a position 5:15 cm away, the mesh pattern was not visually recognized. When observing the conductive substrate from a position 4:30 cm away, the number of observers who visually recognized the mesh pattern was 0 or 1. When observing the conductive substrate from a position 3:30 cm away, the number of observers who visually recognized the mesh pattern was 2 - 4. When observing the conductive substrate from a position 2:30 cm away, the number of observers who visually recognized the mesh pattern was 5 or more. When observing the conductive substrate from a position 1:50 cm away, the number of observers who visually recognized the mesh pattern was 5 or more.

[0190] In Table 1, "LPC", which is the compound used, represents lauryl pyridinium chloride (manufactured by Fujifilm Wako Pure Chemical Corporation), "DSAB" represents distearyldimethylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Corporation), and "EPB" represents ethyl pyridinium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0191] In Table 1, the "Compound" column in the "First Solution" column represents the type of organic acid contained in the first solution, the "Concentration" column in the "First Solution" column represents the content (mass%) of the organic acid contained in the first solution with respect to the total mass of the first solution, the "pH" column in the "First Solution" column represents the pH of the first solution, and the "Temperature" column in the "First Solution" column represents the temperature of the first solution. In Examples 11 and 12, it is shown that two types, glutaric acid and LPC, are contained in the first solution. In the "Concentration" column, the left numerical value represents the content (mass%) of glutaric acid with respect to the total mass of the first solution, and the right numerical value represents the content (mass%) of LPC with respect to the total mass of the first solution. In Table 1, the "Compound" column in the "Second Solution" column represents the type of organic acid contained in the second solution, the "Concentration" column in the "Second Solution" column represents the content (mass%) of the organic acid contained in the second solution with respect to the total mass of the second solution, the "pH" column in the "Second Solution" column represents the pH of the second solution, and the "Temperature" column in the "Second Solution" column represents the temperature of the second solution. In Table 1, the "Internal Silver Density" column represents the ratio of the area of silver (metal) within the maximum inscribed circle of the observation region where silver (metal) is observed in the vertical cross-section of the conductive fine wire in a direction perpendicular to the direction in which the conductive fine wire extends. In Table 1, the "Line Width" column represents the line width of the conductive fine wire. In Table 1, the "Thickness (Height)" column represents the thickness (height) of the conductive fine wire. In Table 1, the "Aspect Ratio" column represents the aspect ratio of the conductive fine wire (the ratio of the height of the conductive fine wire to the line width of the conductive fine wire). In Table 1, the "Gray Value" column is the gray value obtained by imaging the conductive fine wire using reflected light as described above. In Table 1, the "Ratio γ" column is the ratio γ represented by Lm / Ls as described above. As described above, in Example 13, Step 5 using the second solution was carried out before Step 2 using the first solution, and in Examples 14 to 17, Step 5 using the second solution was carried out after Step 2 using the first solution.

[0192]

Table 1

[0193] As shown in Table 1 above, the conductive substrate of the present invention exhibited a predetermined effect. From the comparison of Examples 1 to 17, it was confirmed that when the internal silver density is 86% or more, the conductivity is more excellent. Also, from the comparison of Examples 1 to 17, it was confirmed that when the gray value is 115 or less, the visibility is more excellent. Also, from the comparison of Example 20 with other examples, it was confirmed that when the line width of the conductive fine wire is 0.1 μm or more and less than 5.0 μm, the visibility is more excellent. Also, from the comparison of Examples 20 and 21 with other examples, it was confirmed that when the aspect ratio of the conductive fine wire is 0.6 or more and less than 1.5, the bendability is more excellent. Also, from the comparison of Example 22 with other examples, it was confirmed that when a flexible film is used as the substrate, the bendability is more excellent. Also, from the comparison of Examples 1, 2, 6 to 7, it was confirmed that when the temperature of the first solution was 65 to 95 °C, more excellent effects were obtained. Also, from the comparison of Examples 1, 3 to 5, it was confirmed that when the content of the organic acid in the first solution was 0.5 mass% or more (preferably, when it was 0.5 to 1.5 mass%), more excellent effects were obtained. Also, from the comparison of Examples 1, 8 to 10, it was confirmed that when a carboxylic acid having two or more valences was used as the organic acid, more excellent effects were obtained.

[0194] <Examples 23 to 28, Comparative Examples 3 to 4> As shown in Table 2 described later, a conductive substrate was manufactured according to the same procedure as in Example 1, except that the temperature of the proteolytic enzyme aqueous solution, the immersion time, and the type and immersion time of Solution X were changed. In Comparative Examples 3 and 4, the treatment with Solution X was not carried out. Also, in Examples 23 to 28, exposure was performed using a mask capable of obtaining a touch panel sensor (detection electrode layer, peripheral wiring, shield electrode) as shown in FIG. 17.

[0195] The amount of gelatin in the fine lines obtained after performing the treatment (Step D) using the proteolytic enzyme aqueous solution and the amount of gelatin in the conductive fine lines obtained after performing the plating treatment (Step 3) were quantified by the BCA method. The results are summarized in Table 2. The atomic number ratio of carbon atoms to silver atoms (carbon atom / silver atom: C / Ag ratio) in the internal region on the substrate side from the position where the metal atom number ratio in the conductive fine lines in the conductive substrate became 50% or more was analyzed by Ar sputtering (2 kV, Ar ions, 2 mm□) and XPS (X-ray source: Quantera SXM manufactured by Al Kα Albak·Phi Co., Ltd.) in the depth direction from the surface on the side opposite to the substrate side of the peripheral pattern. The column "Remaining amount 1" in Table 2 represents the amount of gelatin in the fine lines obtained after performing Step D. The column "Remaining amount 2" in Table 2 represents the amount of gelatin in the shield electrode after Step 3. The "Remaining Amount 3" column in Table 2 represents the amount of gelatin in the detection electrode after Step 3. The "Remaining Amount 4" column in Table 2 represents the amount of gelatin in the peripheral wiring after Step 3. The "Peripheral Pattern" column in Table 2 represents the C / Ag ratio at the shield electrode.

[0196]

Table 2

[0197] As shown in Table 2, it was confirmed that a predetermined effect can be obtained even when the gelatin removal time and the contact time with Solution X are changed.

[0198] <Example 29> A conductive substrate was manufactured according to the same procedure as in Example 1, except that the photomask was changed so as to obtain the detection electrode (length 18 cm, width 2 mm, line width of conductive fine wire 1.8 μm, aperture ratio 99) and the peripheral wiring (width 20 μm, length 11 cm) shown in FIG. 12, and the temperature and immersion time of Solution X were changed.

[0199] <Example 30> A conductive substrate was manufactured according to the same procedure as in Example 29, except that the exposure amount of the peripheral wiring was adjusted to be 0.3 times the exposure amount of the detection electrode.

[0200] <Example 31> A conductive substrate was manufactured according to the same procedure as in Example 1, except that the photomask was changed so as to obtain the detection electrode (length 18 cm, width 2 mm, line width of conductive fine wire 1.8 μm, aperture ratio 99) and the peripheral wiring (first wiring part: width 10 μm, length 7 cm, second wiring part: width 20 μm, length 4 cm) shown in FIG. 13, and the temperature and immersion time of Solution X were changed.

[0201] <Example 32> A conductive substrate was manufactured according to the same procedure as in Example 31, except that the exposure amount of the peripheral wiring was adjusted to be 0.3 times the exposure amount of the detection electrode.

[0202] <Example 33> A conductive substrate was manufactured according to the same procedure as in Example 31, except that the width of the first wiring portion was changed to 5 mm.

[0203] <Example 34> A conductive substrate was manufactured according to the same procedure as in Example 33, except that the exposure amount of the peripheral wiring was adjusted to be 0.3 times the exposure amount of the detection electrode.

[0204] As shown in Table 3, it was confirmed that the predetermined effect can be obtained even when the pattern to which the peripheral wiring is connected is changed or the film thickness of the peripheral wiring is changed.

[0205]

Table 3

[0206] <Example 35> A conductive substrate was manufactured according to the same procedure as in Example 27, except that the photomask was changed so that the detection electrode (length 18 cm, width 2 mm, line width of the conductive fine wire 1.8 μm, aperture ratio 99) and the peripheral wiring (width 20 μm, length 11 cm) shown in FIG. 12 were obtained.

[0207] <Example 36> Regarding the photomask used in Example 35, a conductive substrate was manufactured according to the same procedure as in Example 35, except that a halftone mask having a semi-transmissive film applied only to the peripheral wiring portion was used so that the exposure amount of the peripheral wiring was 0.35 times the exposure amount of the detection electrode.

[0208] <Example 37> Regarding the photomask used in Example 35, a conductive substrate was manufactured according to the same procedure as in Example 35, except that a halftone mask having a semi-transmissive film applied only to the peripheral wiring portion was used so that the exposure amount of the peripheral wiring was 0.25 times the exposure amount of the detection electrode.

[0209] <Example 38> A conductive substrate was manufactured according to the same procedure as in Example 27, except that the photomask was changed so that the detection electrode (length 18 cm, width 2 mm, line width of conductive fine wire 1.8 μm, aperture ratio 99) and the peripheral wiring (first wiring part: width 10 μm, length 7 cm, second wiring part: width 20 μm, length 4 cm) shown in FIG. 13 were obtained.

[0210] <Example 39> A conductive substrate was manufactured according to the same procedure as in Example 35, except that for the photomask used in Example 38, a halftone mask with a semi-transmissive film applied only to the peripheral wiring part was used so that the exposure amount of the peripheral wiring with respect to the exposure amount of the detection electrode was 0.35 times.

[0211] <Example 40> A conductive substrate was manufactured according to the same procedure as in Example 35, except that for the photomask used in Example 38, a halftone mask with a semi-transmissive film applied only to the peripheral wiring part was used so that the exposure amount of the peripheral wiring with respect to the exposure amount of the detection electrode was 0.25 times.

[0212] <Example 41> A conductive substrate was manufactured according to the same procedure as in Example 38, except that the width of the first wiring part was changed to 5 mm.

[0213] <Example 42> A conductive substrate was manufactured according to the same procedure as in Example 39, except that the width of the first wiring part was changed to 5 mm.

[0214] <Example 43> A conductive substrate was manufactured according to the same procedure as in Example 40, except that the width of the first wiring part was changed to 5 mm.

[0215] As shown in Table 4, it was confirmed that the predetermined effects can be obtained even when the pattern to which the peripheral wiring is connected is changed or when the film thickness of the peripheral wiring is changed.

[0216]

Table 4

[0217] <Example 44> Using the same procedure as in Example 1, 100 sheets of Sample A were continuously produced. The same solutions were continuously used for the developer and fixing solution in Step B, the aqueous proteinase solution in Step D-1, the 1% by mass glutaric acid aqueous solution in Step 2-1, and the 1% by mass citric acid buffer solution in Step 3-1. For the other solutions, new solutions were used each time. The same evaluation as in Example 1 was performed on the 100th sample. <Example 45> It was produced according to the same procedure as in Example 44, except that the 1% by mass citric acid buffer solution in Step 3-1 was changed to a 0.15% by mass aqueous citric acid solution (pH: 2.7). <Example 46> It was produced according to the same procedure as in Example 44, except that the 1% by mass citric acid buffer solution in Step 3-1 was changed to pure water.

[0218] As shown in Table 5, in Example 44, a buffer solution was used in the plating stop solution, and even if the plating solution was mixed in, the increase in pH was suppressed, and the performance equivalent to that of the first sheet could be maintained even after continuous processing of 100 sheets. In Example 45, the pH of the buffer solution used in the plating stop solution was low, sulfur and the like were generated from sulfurous acid derived from the plating solution, and the conductivity decreased slightly. In Example 46, pure water was used in the plating stop solution, and as the plating solution was mixed in, the pH increased, making it difficult for the plating reaction to stop, the gray value increased, and the visibility became slightly worse.

[0219]

Table 5

Explanation of Symbols

[0220] 10 Conductive substrate 12 Substrate 12a, 14a Surfaces 12b Back surface 14, 14B Conductive fine wires 15 Metal 16 Polymer 18 Opening 20 Outer circumscribed quadrilateral 20a, 23a Side 20b, 20c Sides 21, 22 Contacts 22a Upper contact 23 Upper outer circumscribed quadrilateral 30, 30a Touch panel sensor 32 Detection unit 33 Peripheral wiring part 34A First detection electrode layer 34B Second detection electrode layer 35 First detection electrode 36a First dummy electrode 36b Second dummy electrode 37 Second detection electrode 38 First electrode terminal 39 Second electrode terminal 40a First peripheral wiring 40b Second peripheral wiring 41a First external connection terminal 41b Second external connection terminal 42 Flexible circuit board 43 Shield electrode 43a First wiring part 43b Second wiring part 43c Third wiring part 43d Fourth wiring part Ac Vertical cross-section DL Direction DW Direction E 1 Detection area E 2 Peripheral area R Observation area R L Contour line Rb Area Rm Contour line S Maximum inscribed circle T Height Wa Line width

Claims

1. A method for manufacturing a conductive substrate including a substrate and conductive fine lines disposed on the substrate, the method comprising: Step 1 of forming fine lines containing a metal on the substrate; Step 2 of bringing the fine lines into contact with a solution containing an organic acid; Step 3 of performing a plating process on the fine lines to form conductive fine lines, in this order; The method for manufacturing a conductive substrate further comprising Step 4 of performing a plating process on the fine lines between Step 1 and Step 2.

2. The method for manufacturing a conductive substrate according to Claim 1, wherein the pH value of the solution containing the organic acid is in the range of 1.5 to 6.0 at a temperature of 25°C.

3. The method for manufacturing a conductive substrate according to Claim 1 or 2, wherein the solution containing the organic acid contains a carboxylic acid.

4. The method for manufacturing a conductive substrate according to Claim 3, wherein the carboxylic acid is a dicarboxylic acid or higher.

5. The method for manufacturing a conductive substrate according to Claim 3 or 4, wherein the carboxylic acid is any one selected from the group consisting of glutaric acid and citric acid.

6. The method for manufacturing a conductive substrate according to any one of Claims 1 to 5, wherein the solution containing the organic acid further contains a quaternary ammonium salt.

7. The method for manufacturing a conductive substrate according to Claim 6, wherein the quaternary ammonium salt is selected from the group consisting of a compound represented by general formula (X), a compound represented by general formula (Y), and a compound represented by general formula (Z). 【Chemical 1】 In the general formula (X), R ａ１ and R ａ２ each independently represents an alkyl group having 4 or less carbon atoms which may have a substituent, and R ａ３ and R ａ４ each independently represents an alkyl group having 8 or more carbon atoms which may have a substituent. In the general formula (Y), R ｂ１ ~R ｂ３ each independently represents an alkyl group having 4 or less carbon atoms which may have a substituent, and R ｂ４ represents an alkyl group having 8 or more carbon atoms which may have a substituent. In the general formula (Z), R ｃ１ represents an alkyl group having 8 or more carbon atoms which may have a substituent.

8. The method for manufacturing a conductive substrate according to any one of Claims 1 to 7, wherein the solution containing the organic acid contains a dicarboxylic acid or higher and a compound selected from the group consisting of a compound represented by general formula (X), a compound represented by general formula (Y), and a compound represented by general formula (Z). [Chemical Formula 2] In the general formula (X), R ａ１ and R ａ２ each independently represents an alkyl group having 4 or fewer carbon atoms which may have a substituent, and R ａ３ and R ａ４ each independently represents an alkyl group having 8 or more carbon atoms which may have a substituent. In the general formula (Y), R ｂ１ ~R ｂ３ each independently represents an alkyl group having 4 or fewer carbon atoms which may have a substituent, and R ｂ４ represents an alkyl group having 8 or more carbon atoms which may have a substituent. In the general formula (Z), R ｃ１ represents an alkyl group having 8 or more carbon atoms which may have a substituent.

9. The method for manufacturing a conductive substrate according to any one of Claims 1 to 8, wherein in Step 2, the contact time between the fine lines and the solution containing the organic acid is 5 to 180 seconds.

10. Between Step 1 and Step 2, or between Step 2 and Step 3, The method for manufacturing a conductive substrate according to any one of Claims 1 to 9 further comprising Step 5 of bringing the fine lines into contact with a solution containing a quaternary ammonium salt.

11. The manufacturing method of the conductive substrate according to any one of claims 1 to 10, wherein the step 3 or the step 4 has a neutralization washing step of bringing the fine wire into contact with an acidic solution having a pH of 3 to 7 to stop the plating reaction by the plating treatment.

12. The manufacturing method of the conductive substrate according to claim 11, wherein the acidic solution has a buffering action.

13. The manufacturing method of the conductive substrate according to any one of claims 1 to 12, wherein the fine wire contains a polymer.

14. A conductive substrate including a substrate and a conductive fine wire disposed on the substrate and containing a metal, In a vertical cross-section of the conductive fine wire in a direction orthogonal to the direction in which the conductive fine wire extends, The ratio of the area showing the metal within the maximum inscribed circle of the observation region where the metal is observed is 81 to 99%, A conductive substrate, wherein the gray value obtained by imaging the conductive fine wire using reflected light is 150 or less in terms of the luminance value represented by 256 gradations.

15. In a circumscribed rectangle having four corners each with an angle of 90° and one side parallel to the surface of the substrate, which circumscribes the observation region where the metal is observed, among the contact points between the side perpendicular to the surface of the substrate of the circumscribed rectangle and the observation region, taking the upper contact point at the position farthest from the surface of the substrate as one corner, a rectangular region on the opposite side of the surface of the substrate from the upper contact point of the circumscribed rectangle is defined as the upper circumscribed rectangle. The upper circumscribed rectangle has four corners each with an angle of 90° and one side parallel to the surface of the substrate. In the upper circumscribed rectangle, when the length of the contour of the region where the metal exists is denoted as Lm, the total length of the four sides of the upper circumscribed rectangle is denoted as Ls, and the ratio represented by Lm / Ls is denoted as γ, 1.3 ≤ γ ≤ 2.

0. The conductive substrate according to claim 14.

16. The conductive substrate according to claim 14 or 15, wherein the line width of the conductive fine wire is 0.1 μm or more and less than 5.0 μm.

17. In a vertical cross-section of the conductive fine wire in a direction orthogonal to the direction in which the conductive fine wire extends, The ratio of the height of the conductive fine wire to the line width of the conductive fine wire is 0.6 or more and less than 1.

5. The conductive substrate according to any one of claims 14 to 16.

18. The conductive substrate according to any one of claims 14 to 17, wherein the substrate is composed of a flexible film.

19. The flexible film includes polyethylene terephthalate, cycloolefin polymer, cycloolefin copolymer, or polycarbonate, and the conductive substrate according to claim 18.

20. The metal included in the conductive fine wire includes silver, and the conductive substrate according to any one of claims 14 to 19.

21. The metal included in the conductive fine wire is silver, and the conductive substrate according to any one of claims 14 to 20.

22. The metal included in the conductive fine wire is in particulate form, and the conductive substrate according to any one of claims 14 to 21.

23. The conductive fine wire includes a polymer, and the conductive substrate according to any one of claims 14 to 22.

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