JP2021163735A - Method for producing conductive member - Google Patents

Abstract

To provide a method for producing a conductive member having a conductive fine line having excellent conductivity.SOLUTION: A method for producing a conductive member has step 1 of forming, on a base material, a silver-containing layer in a fine line shape including metal silver and a polymer compound, including cavities inside, and having a line width of 2.0 μm or less, and step 2 of plating the silver-containing layer with a plating agent including a compound I represented by general formula (I) and metal ions, to form a conductive fine line.SELECTED DRAWING: None

Description

The present invention relates to a method for manufacturing a conductive member.

Conductive members having conductive thin wires (wires in the form of thin wires showing conductivity) are widely used in various applications such as touch panels, solar cells, and EL (Electroluminescence) elements. In particular, in recent years, the mounting rate of touch panels on mobile phones and mobile game devices has been increasing, and the demand for conductive members for capacitive touch panels capable of detecting multiple points is rapidly expanding.
As a method for manufacturing a conductive member, in Patent Document 1, a method of sequentially performing an exposure treatment, a development treatment, and the like on a photosensitive layer containing silver halide to form a conductive thin wire containing metallic silver. It is disclosed.

JP-A-2007-129205

On the other hand, in recent years, there has been a demand for further thinning of conductive thin wires.
The present inventor tried to form a conductive thin wire having a width further reduced (for example, a width of 2.0 μm or less) according to the method disclosed in Patent Document 1, and the conductivity of the obtained conductive thin wire was obtained. Was found to be inadequate.

In view of the above circumstances, it is an object of the present invention to provide a method for manufacturing a conductive member having a thin conductive wire having excellent conductivity.

As a result of diligent studies on the above problems, the present inventors have found that the above problems can be solved by the following configurations.

[1]
For step 1 of forming a fine linear silver-containing layer containing metallic silver and a polymer compound on a base material, having voids inside, and having a line width of 2.0 μm or less, and the silver-containing layer. A method for manufacturing a conductive member, which comprises a step 2 of forming a conductive thin wire by performing a plating treatment using a plating treatment agent containing a compound I represented by the general formula (I) described later and a metal ion. ..
[2]
The method for producing a conductive member according to [1], wherein the plating treatment agent is a plating solution containing compound I, the metal ions, and water.
[3]
The method for producing a conductive member according to [2], wherein the content of compound I in the plating solution is 0.01 to 0.2 mol / L with respect to the plating solution.
[4]
The method for producing a conductive member according to [1], wherein the plating treatment agent is a plating set comprising the metal ion-containing liquid containing metal ions and water and a reducing liquid containing compound I and water.
[5]
The method for producing a conductive member according to [4], wherein the content of compound I in the reducing solution is 0.01 to 0.2 mol / L with respect to the reducing solution.
[6]
The method for producing a conductive member according to any one of [1] to [5], wherein the compound I is the compound II represented by the general formula (II) described later.
[7]
The method for producing a conductive member according to any one of [1] to [6], wherein the metal ion is a silver ion.
[8]
When the inscribed circle of the region is drawn from the center point of the region where the metallic silver exists in the silver-containing layer in the cross section of the silver-containing layer along the direction orthogonal to the direction in which the silver-containing layer extends. [1] to [7], wherein the ratio of the region occupied by the metallic silver included in the inscribed circle to the total area of the inscribed circle is 30 to 60% in terms of area ratio. A method for manufacturing a conductive member.
[9]
When the inscribed circle of the region is drawn from the center point of the region where the metallic silver exists in the silver-containing layer in the cross section of the silver-containing layer along the direction orthogonal to the direction in which the silver-containing layer extends. The conductivity according to any one of [1] to [8], wherein the ratio of the region occupied by the voids included in the inscribed circle to the total area of the inscribed circle is 10 to 30% in terms of area ratio. Method of manufacturing sex members.
[10]
The method for producing a conductive member according to any one of [1] to [9], wherein the base material is a flexible base material.
[11]
In step 1, a fine linear silver-containing layer and a second fine linear silver-containing layer having a line width of more than 2.0 μm connected to the fine linear silver-containing layer are simultaneously formed, and in step 2, a wire is formed. The thin linear silver-containing layer having a width of 2.0 μm or less and the second fine linear silver-containing layer having a line width of more than 2.0 μm are plated [1] to [10]. The method for manufacturing a conductive member according to any one of.

According to the present invention, it is possible to provide a method for manufacturing a conductive member having a thin conductive wire having excellent conductivity.

It is a top view which shows an example of the mesh pattern formed by the fine line-shaped silver-containing layer. It is a top view which shows one Embodiment of a conductive member. It is a top view which shows the 1st detection electrode and the take-out wiring part arranged on the surface of the conductive member of FIG. It is a top view which shows the 2nd detection electrode and the take-out wiring part arranged on the back surface of the conductive member of FIG.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
Further, in the present specification, "g" and "mg" represent "mass g" and "mass mg", respectively.
Further, in the present specification, "polymer" or "polymer compound" means a compound having a weight average molecular weight of 2000 or more. Here, the weight average molecular weight is defined as a polystyrene-equivalent value measured by GPC (Gel Permeation Chromatography).

[Manufacturing method of conductive member]
The method for manufacturing a conductive member of the present invention (hereinafter, also referred to as “the present manufacturing method”) includes the following steps 1 and 2.
Step 1: A step of forming a fine linear silver-containing layer containing metallic silver and a polymer compound on a base material, having voids inside, and having a line width of 2.0 μm or less.
Step 2: The silver-containing layer formed in Step 1 is plated with a plating agent containing a compound represented by the general formula (I) described later and a metal ion to form conductive fine wires. Process to do.

The features compared with the prior art of the present invention are that when a thin conductive thin wire is obtained, a silver-containing layer having voids inside is plated, and in the plating treatment. The point is that a specific reducing agent (a compound represented by the general formula (I) described later) is used.
In the conventional method of manufacturing a conductive member using silver halide, as the thinning of the conductive thin wire progresses, the amount of metal in the obtained conductive thin wire becomes low, and sufficient conductivity may not be ensured. be. On the other hand, as a result of diligent studies, the present inventors formed a silver-containing layer having voids inside, and then carried out a plating treatment using a plating treatment agent containing a specific reducing agent and a metal ion. It was found that by filling the voids with metal (plated metal), the amount of metal in the finally obtained conductive thin wire increases, and even if the wire is thinned, a conductive thin wire showing excellent conductivity can be formed. ..

Hereinafter, the procedure of each step will be described in detail.

[Step 1]
Step 1 is a step of forming a fine linear silver-containing layer on the support. The fine linear silver-containing layer formed by this step (hereinafter, also referred to as “fine linear silver-containing layer”) contains metallic silver and a polymer compound, and has voids inside. The line width of the fine linear silver-containing layer is 2.0 μm or less.

<Base material>
The type of the base material used in the step 1 is not particularly limited, and examples thereof include a plastic substrate, a glass substrate, and a metal substrate, and a plastic substrate is preferable.
Further, as the base material, a flexible base material is preferable in that the obtained conductive member is excellent in bendability. Examples of the flexible base material include the above-mentioned plastic substrate.
The thickness of the base material is not particularly limited, and is often 25 to 500 μm. When the surface of the base material is used as the touch surface when the conductive member is applied to the touch panel, the thickness of the base material may exceed 500 μm.

Materials constituting the base material include polyethylene terephthalate (PET) (258 ° C.), polycycloolefin (134 ° C.), polycarbonate (250 ° C.), acrylic film (128 ° C.), polyethylene naphthalate (269 ° C.), polyethylene ( 135 ° C.), polypropylene (163 ° C.), polystyrene (230 ° C.), polyvinyl chloride (180 ° C.), polyvinylidene chloride (212 ° C.), and triacetyl cellulose (290 ° C.) at a melting point of about 290 ° C. or lower. Certain resins are preferred, and PET, polycycloolefin, and polycarbonate are more preferred.
The total light transmittance of the base material is preferably 85 to 100%.

An undercoat layer may be arranged on the surface of the base material.
The undercoat layer preferably contains a polymer compound described later. When this undercoat layer is used, the adhesion of the conductive thin wire described later to the base material is further improved.
The method for forming the undercoat layer is not particularly limited, and examples thereof include a method in which a composition for forming an undercoat layer containing a polymer compound is applied onto a substrate and heat treatment is performed as necessary. The undercoat layer forming composition may contain a solvent, if necessary. The type of the solvent is not particularly limited, and examples thereof include the solvent used in the composition for forming a photosensitive layer described later. Further, as the composition for forming the undercoat layer containing the polymer compound, a latex containing particles of the polymer compound may be used.
The thickness of the undercoat layer is not particularly limited, and 0.02 to 0.3 μm is preferable, and 0.03 to 0.2 μm is more preferable, in that the adhesiveness of the conductive thin wire to the substrate is more excellent.

<Fine linear silver-containing layer>
A fine linear silver-containing layer is formed on the support.
The line width of the fine linear silver-containing layer is 2.0 μm or less. Among them, 1.7 μm or less is preferable, and 1.5 μm or less is more preferable, from the viewpoint that the conductive thin wire produced by this production method is hard to be visually recognized. The lower limit is not particularly limited, but 0.5 μm or more is preferable, and 1.0 μm or more is more preferable, from the viewpoint of more excellent conductivity of the conductive thin wire.
The line width of the fine linear silver-containing layer means the total length of the silver-containing layer in the direction orthogonal to the direction in which the fine linear silver-containing layer extends in the direction along the surface of the base material. do.

The thickness of the fine linear silver-containing layer is not particularly limited, but is preferably 0.5 to 2.0 μm, more preferably 0.5 to 1.5 μm. The thickness of the silver-containing layer is defined in the cross section of the silver-containing layer along the direction orthogonal to the extending direction of the fine linear silver-containing layer (hereinafter, also referred to as "vertical cross section of the silver-containing layer"). It means the distance between the two most distant metallic silvers along the thickness direction. The thickness of the silver-containing layer can be measured according to a method for measuring the area occupied by metallic silver contained in the inscribed circle of the region A where metallic silver exists in the vertical cross section of the containing layer (described later).
The line width and thickness of the fine linear silver-containing layer are values obtained by arithmetically averaging the values measured at any 10 locations of one extending silver-containing layer, respectively.

The fine line-shaped silver-containing layer may form a predetermined pattern, for example, the pattern is not particularly limited, and triangles such as regular triangles, isosceles triangles, and right triangles, and quadrangles (for example, squares, etc.) Rectangle, rhombus, parallel quadrangle, trapezoid, etc.), (regular) hexagon, (regular) octagon, etc. (regular) n-sided, circle, ellipse, star, and geometric figures combining these It is preferable to have a mesh shape (mesh pattern), and it is more preferable to have a mesh shape (mesh pattern).

FIG. 1 shows an example of a mesh pattern formed by a silver-containing layer. The mesh pattern 10 shown in FIG. 1 has a plurality of intersecting silver-containing layers 12 and a plurality of openings 14 formed by the plurality of silver-containing layers 12.
The length L of one side of the opening 14 is not particularly limited, but is preferably 1500 μm or less, more preferably 1300 μm or less, and further preferably 1000 μm or less. The lower limit of L is not particularly limited, and is preferably 5 μm or more, more preferably 30 μm or more, and further preferably 80 μm or more. When the length of one side of the opening 14 is within the above range, the transparency can be kept good, and when the opening 14 is attached to the front surface of the display device as a conductive member, the display can be visually recognized without discomfort. Can be done.
The width of the fine line-shaped silver-containing layer 12 forming the mesh pattern 10 is not particularly limited, but is preferably 0.5 μm or more and less than 2.0 μm from the viewpoint of visible light transmittance.

In FIG. 1, the opening 14 has a diamond shape. However, the mesh pattern formed by the silver-containing layer may have a shape other than a rhombus. For example, the mesh pattern may be a polygon (eg, a triangle, a quadrangle, a hexagon, and a random polygon). Further, the shape of one side may be a curved shape or an arc shape in addition to a straight line shape. In the case of arcuate shape, for example, the two opposing sides may have an arcuate shape that is convex outward, and the other two opposite sides may have an arcuate shape that is convex inward. Further, the shape of each side may be a wavy line shape in which an arc convex outward and an arc convex inward are continuous. Of course, the shape of each side may be a sine curve.

From the viewpoint of visible light transmittance, the aperture ratio of the mesh pattern formed from the fine linear silver-containing layer is preferably 85% or more, more preferably 90% or more, further preferably 95% or more, and particularly 99% or more. preferable. The upper limit is not particularly limited, but may be less than 100%. The aperture ratio corresponds to the area ratio of the ratio of the region on the support excluding the region having the fine linear silver-containing layer to the whole.

(Metallic silver)
The metallic silver contained in the fine linear silver-containing layer is usually in the form of solid particles. The average particle size of metallic silver is preferably 10 to 1000 nm, more preferably 10 to 200 nm, and even more preferably 50 to 150 nm, which is equivalent to a sphere.
The spherical equivalent diameter is the diameter of spherical particles having the same volume. The "sphere-equivalent diameter" used as the average particle diameter of the object containing metallic silver is an average value, which is obtained by measuring the sphere-equivalent diameter of 100 objects and arithmetically averaging them. ..

The shape of the metallic silver particles is not particularly limited, and for example, spherical, cubic, flat plate (hexagonal flat plate, triangular flat plate, quadrangular flat plate, etc.), octahedron, tetradecahedron, etc. The shape can be mentioned.
The content of metallic silver in the fine linear silver-containing layer is not particularly limited, and 3.0 to 20.0 g / m ² is preferable, and 5.0 to 15.0 g is preferable in that the conductivity of the conductive member is more excellent. / M ² is more preferable.

The silver-containing layer has a more excellent conductivity of the conductive member, and is within the region A from the central point of the region where metallic silver exists (hereinafter, also referred to as “region A”) in the vertical cross section of the silver-containing layer. When drawing a tangent circle, the ratio of the area occupied by the metallic silver contained in the inscribed circle to the total area of the inscribed circle is preferably 15% or more, preferably 25% or more in terms of area ratio. More preferably, it is more preferably 30% or more.
Further, the region occupied by the voids inside the silver-containing layer becomes large, and the metal silver particles are joined to each other by filling the voids in the plating treatment, and as a result, the conductivity of the conductive member is further improved. The ratio of the area occupied by the metallic silver contained in the inscribed circle of the region A to the total area of the inscribed circle in the vertical cross section of the containing layer is preferably 80% or less, and is preferably 60% or less in terms of area ratio. Is more preferable, and 55% or less is further preferable.
In the present specification, the "thickness direction" of the silver-containing layer is the normal direction with respect to the substrate surface in the vertical cross section of the silver-containing layer, and the "width direction" of the silver-containing layer is the thickness direction. It means the direction perpendicular to each other. Further, the "center point" of the region A in the vertical cross section of the silver-containing layer is a straight line that passes through an intermediate position in the thickness direction of the region A and is parallel to the width direction as a first straight line and the width of the region A. It means the intersection of the first straight line and the second straight line when the straight line passing through the intermediate position in the direction and parallel to the thickness direction is set as the second straight line.
A more specific method for measuring the ratio of the area occupied by the metallic silver contained in the inscribed circle in the vertical cross section of the silver-containing layer to the total area of the inscribed circle will be described later.

(Polymer compound)
The polymer compound contained in the fine line-shaped silver-containing layer is not particularly limited, but is different from gelatin in that a silver-containing layer having higher strength and conductive fine lines can be formed by steps A to D described later (hereinafter referred to as gelatin). , Also referred to as “specific polymer”).
The type of the specific polymer is not particularly limited as long as it is different from gelatin, and a polymer that decomposes gelatin described later and is not decomposed by a proteolytic enzyme or an oxidizing agent is preferable.
Examples of the specific polymer include hydrophobic polymers (water-insoluble polymers), and examples thereof include (meth) acrylic resins, styrene resins, vinyl resins, polyolefin resins, polyester resins, and polyurethane resins. Consists of at least one resin selected from the group consisting of polyamide-based resins, polycarbonate-based resins, polydiene-based resins, epoxy-based resins, silicone-based resins, cellulose-based polymers, and chitosan-based polymers, or these resins. Examples thereof include a copolymer composed of a monomer.
Further, the specific polymer preferably has a reactive group that reacts with a cross-linking agent described later.
The specific polymer is preferably in the form of particles. That is, the photosensitive layer preferably contains particles of a specific polymer.
Among them, as the specific polymer, a polymer (copolymer) represented by the general formula (1) described later is preferable.

The content of the polymer compound in the fine linear silver-containing layer is not particularly limited, and 0.04 to 2.0 g / m ² is preferable, and 0.08 to 0. more preferably ^{40g / m 2, 0.10~0.40g / m} 2 is more preferable.
Further, the ratio of the area occupied by the polymer compound contained in the inscribed circle of the region A in the vertical cross section of the silver-containing layer to the total area of the inscribed circle of the region is the area ratio in that the conductivity of the conductive member is more excellent. It is preferably 30 to 80%, more preferably 40 to 60%.
A method for measuring the ratio of the region occupied by the polymer compound to the area of the inscribed circle in the region where metallic silver exists in the vertical cross section of the silver-containing layer will be described later.

(Void)
There are voids inside the fine linear silver-containing layer. Here, the void means a region in which the material (metal silver, polymer compound, other additives, etc.) constituting the silver-containing layer does not exist inside the fine linear silver-containing layer. The voids inside the silver-containing layer may be filled with a gas (mainly air), a liquid, or both of them.
Further, in the plating process, the metal silver particles are joined to each other by filling the voids with the plated metal, and as a result, the conductivity of the conductive member is further improved. The ratio of the area occupied by the voids contained in the inscribed circle to the total area of the inscribed circle is preferably 5% or more, more preferably 10% or more, and more preferably 15% or more in terms of area ratio. Is more preferable.
The upper limit is not particularly limited, but the area occupied by metallic silver becomes large and the conductivity of the conductive member is further improved. Therefore, the above ratio is preferably 40% or less, and is preferably 30% or less in terms of area ratio. More preferably, it is more preferably 25% or less.

In the vertical cross section of the silver-containing layer, the ratio of each inscribed circle of the region occupied by the metallic silver, the polymer compound and the voids contained in the inscribed circle of the region A where the metallic silver exists is a scanning electron microscope. It can be measured using (SEM: Scanning Electron Microscope).
More specifically, a microtome is used to cut the silver-containing layer along a direction orthogonal to the direction in which the fine linear silver-containing layer extends. Next, in order to impart conductivity to the surface of metallic silver, carbon vapor deposition was performed on the vertical cross section of the exposed silver-containing layer, and then a scanning electron microscope (S-5200 type SEM manufactured by Hitachi High Technologies America) was used. Observe the vertical cross section of the silver-containing layer. The SEM observation conditions are the reflected electron mode and the acceleration voltage is 5 kV.
The observed image thus obtained is analyzed using image processing software (Image J) to create a binarized cross-sectional image with the brightness as a threshold value. In the observation image of the vertical cross section of the silver-containing layer obtained by SEM, the brightness increases in the order of voids, polymer compound, and metallic silver. Therefore, by adjusting the brightness that is the threshold in the above analysis, metallic silver A cross-sectional image A divided into a region occupied by silver and a region occupied by other than metallic silver, and a cross-sectional image B divided into a region occupied by voids and a region occupied by other than voids are obtained.
In the cross-sectional image A obtained above, the region A in which the metallic silver exists is defined so as to include the entire region occupied by the metallic silver. Next, the midpoint between the two metal silvers most distant along the thickness direction is defined as the intermediate position in the thickness direction of the region A, and the midpoint between the two metal silvers most distant along the width direction is defined. Is defined as an intermediate position in the width direction of the region A. Then, the first straight line that passes through the intermediate position in the thickness direction of the region A and is parallel to the width direction and the second straight line that passes through the intermediate position in the width direction of the region A and is parallel to the thickness direction. The intersection is defined as the center point of the area A, and an inscribed circle of the area A centered on this center point is drawn. From the inscribed circle of the drawn area A, the area ratio of the ratio of the total area of the area occupied by the metallic silver included in the inscribed circle to the total area of the inscribed circle is measured.

Next, in the cross-sectional image B obtained above, the same circle as the inscribed circle of the region A in the cross-sectional image A is drawn. From the drawn inscribed circle, the area ratio of the ratio of the total area of the area occupied by the voids included in the inscribed circle to the total area of the inscribed circle is measured.
The polymer compound contained in the inscribed circle of region A based on the measurement result of the ratio of the region occupied by metallic silver and the region occupied by the voids to the total area of the inscribed circle obtained above. Measure the ratio of the total area of the area occupied by the inscribed circle to the total area.

The proportions of the regions occupied by the metallic silver, the polymer compound, and the voids are obtained from the respective observation images by observing the vertical cross section at any 10 locations of one extending silver-containing layer. It is obtained by arithmetically averaging the values to be obtained. That is, all of the above ratios correspond to average values.

The method for forming the fine linear silver-containing layer on the support is not particularly limited, and a known method is adopted. For example, a method of performing exposure and development using silver halide, a silver-containing layer is formed on the entire surface of a support, and then a part of the silver-containing layer is removed using a resist pattern to form a fine linear silver-containing layer. And a method of forming a fine linear silver-containing layer by ejecting a composition containing metallic silver and a resin onto a substrate by a known printing method such as inkjet.
Among them, a method of exposure and development using silver halide is preferable because the conductive thin wire is more excellent in conductivity.
Hereinafter, this method will be described in detail.

The method of exposing and developing with silver halide preferably has the following steps.
Step A: Forming a silver halide-containing photosensitive layer containing silver halide, gelatin, and a polymer different from gelatin on the support Step B: After exposing the silver halide-containing photosensitive layer, developing Process step C to form a fine linear silver-containing layer containing metallic silver, gelatin, and a polymer different from gelatin by treatment: Step step D to heat-treat the silver-containing layer obtained in step B. : Step of removing gelatin in the silver-containing layer obtained in step C The procedure of each step will be described in detail below.

<Step A>
Step A is a step of forming a silver halide-containing photosensitive layer (hereinafter, also referred to as “photosensitive layer”) containing silver halide, gelatin, and a specific polymer different from gelatin on the base material. .. By this step, a base material with a photosensitive layer to be subjected to the exposure treatment described later is produced.
First, the materials and members used in step A will be described in detail, and then the procedure of step A will be described in detail.

(Silver halide)
The halogen atom contained in silver halide may be any of chlorine atom, bromine atom, iodine atom and fluorine atom, and these may be combined. 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. In addition, silver salt bromide, silver iodide bromide, or silver iodide bromide is also preferably used.
Here, for example, "silver halide mainly composed of silver chloride" refers to silver halide in which the molar proportion of chloride ions in the total halide ions in the silver halide composition is 50% or more. The silver halide mainly composed of silver chloride may contain bromide ion and / or iodide ion in addition to chloride ion.

The silver halide is usually in the form of solid particles, and the average particle size of silver halide is preferably 10 to 1000 nm, more preferably 10 to 200 nm, and even more preferably 50 to 150 nm in terms of sphere-equivalent diameter.
The shape of the silver halide particles is not particularly limited, and for example, spherical, cubic, flat plate (hexagonal flat plate, triangular flat plate, quadrangular flat plate, etc.), octahedron, tetradecahedron, etc. The shape of is mentioned.

(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 enzymatic decomposition product of gelatin, and gelatin modified with an amino group and / or a carboxyl group (phthalated gelatin and acetylated gelatin) may be used.

(Specific polymer)
The photosensitive layer contains a polymer (specific polymer) different from gelatin. By including this specific polymer in the photosensitive layer, the strength of the silver-containing layer and the conductive fine wire formed from the photosensitive layer is more excellent.
Features such as the type, specific example, and shape of the specific polymer are as described above as the specific polymer contained in the fine linear silver-containing layer.

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 the general formula (1), A, B, C, and D each represent a repeating unit represented by the following general formulas (A) to (D).

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, preferably 0 or 1, more preferably 0.
R ² represents a methyl group or an ethyl group, and a methyl group is preferable.
R ³ represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable. L represents a divalent linking group, and a group represented by the following general formula (2) is preferable.
General formula (2):-(CO-X ¹ ) r-X ^2-
In the 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 may have a substituent (for example, a halogen atom, a nitro group, and a hydroxyl group), respectively. R ³⁰ includes 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 an acyl group). Benzoyl group) is preferred. As X ¹ , oxygen atom or NH- is preferable.
X ² represents an alkylene group, an arylene group, an alkylene arylene group, an arylene alkylene group, or an alkylene arylene alkylene group, and these groups include -O-, -S-, -CO-, -COO-, and -NH. _{-, - SO 2 -, -} N (R 31) -, _{^{or, -N (R 31) SO 2}} - and the like may be inserted in the middle. R ³¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of X ² include 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 preferable.
r represents 0 or 1.
q represents 0 or 1, preferably 0.

R ⁴ represents an alkyl group, an alkenyl group, or an alkynyl group, and an alkyl group having 5 to 50 carbon atoms is preferable, an alkyl group having 5 to 30 carbon atoms is more preferable, and an alkyl group having 5 to 20 carbon atoms is further preferable. preferable.
R ⁵ is a hydrogen atom, a methyl group, an ethyl group, a halogen atom, or represents -CH ₂ COOR ^6, a hydrogen atom, a methyl group, a halogen atom, or a -CH ₂ COOR ⁶ is preferably a hydrogen atom, a methyl group , Or -CH ₂ COOR ⁶ is more preferable, and a hydrogen atom is further preferable.
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 R 6} preferably has 1 to 70 carbon atoms, more preferably 1 to 60 carbon atoms.

In the general formula (1), x, y, z, and w represent the molar ratio of each repeating unit.
x is 3 to 60 mol%, preferably 3 to 50 mol%, 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), x is preferably 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%.

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

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

The polymer represented by the general formula (1) may contain a repeating unit other than the repeating units represented by the general formulas (A) to (D).
Examples of the monomer for forming other repeating units include acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, crotonic acid esters, itaconic acid diesters, maleic acid diesters, and fumaric acid diesters. Classes, 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 acid esters or methacrylic acid esters are preferable, and hydroxyalkyl methacrylate or hydroxyalkyl acrylate is more preferable.
The polymer represented by the general formula (1) preferably contains a repeating unit represented by the general formula (E).

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, more preferably an alkylene group having 2 to 4 carbon atoms.

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

In the above formula, a1, b1, c1, d1 and e1 represent the molar ratio of each repeating unit, a1 is 3 to 60 (mol%), b1 is 30 to 95 (mol%), and c1 is 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, the preferred range of b1 is the same as the preferred range of y, the preferred range of c1 is the same as the preferred range of z, and the preferred range of d1 is. It is the same as the preferable range of w above.
e1 is 1 to 10 mol%, preferably 2 to 9 mol%, more preferably 2 to 8 mol%.

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

The photosensitive layer may contain a material other than the above-mentioned materials, if necessary.
Examples of other materials include metal compounds belonging to Groups 8 and 9 such as rhodium compounds and iridium compounds used for stabilizing and increasing sensitivity of silver halide. Examples of other materials include antistatic agents, nucleating accelerators, spectrosensitizing dyes, surfactants, antifogging agents, and hard materials as described in paragraphs 0220 to 0241 of JP2009-004348A. Membrane agents, antistatic agents, redox compounds, monomethine compounds, and dihydroxybenzenes are also included. Further, the photosensitive layer may contain a physically developing nucleus.

Further, the photosensitive layer may contain a cross-linking agent used for cross-linking the specific polymers. By containing the cross-linking agent, cross-linking between the specific polymers proceeds, and even when gelatin is decomposed and removed, the connection between the metallic silver in the conductive thin wire is maintained.

(Procedure of step A)
The method for forming the photosensitive layer containing the above components in the step A is not particularly limited, but from the viewpoint of productivity, a composition for forming a photosensitive layer containing silver halide, gelatin and a specific polymer is placed on the substrate. A method of contacting them to form a photosensitive layer on the substrate is preferable.
Hereinafter, the form of the composition for forming a photosensitive layer used in this method will be described in detail, and then the procedure of the process will be described in detail.

(Material contained in the composition for forming a photosensitive layer)
The composition for forming a photosensitive layer contains the above-mentioned silver halide, gelatin, and a specific polymer. If necessary, the specific polymer may be contained in the composition for forming a photosensitive layer in the form of particles.
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.

The method of contacting the photosensitive layer forming composition with the base material is not particularly limited, and for example, a method of applying the photosensitive layer forming composition on the base material and a method of applying the photosensitive layer forming composition onto the base material, and in the photosensitive layer forming composition. Examples thereof include a method of immersing the base material.
After the above treatment, a drying treatment may be carried out if necessary.

(Silver halide-containing photosensitive layer)
The photosensitive layer formed by the above procedure contains silver halide, gelatin, and a specific polymer.
The content of silver halide in the photosensitive layer is not particularly limited, and is preferably ^{3.0 to 20.0 g / m 2 in terms of silver, preferably 5.0 to 15 in terms of more excellent conductivity of the conductive member.} .0 g / m ² is more preferable.
The silver conversion means that all the silver halide is reduced and converted into the mass of silver produced.
The content of the specific polymer in the photosensitive layer is not particularly limited, and 0.04 to 2.0 g / m ² is preferable, and 0.08 to 0.40 g / m 2 is preferable in that the conductivity of the conductive member is more excellent. m ² is more preferable, and 0.10 to 0.40 g / m ² is even more preferable.

<Process B>
Step B is a step of exposing the photosensitive layer and then developing it to form a fine linear silver-containing layer containing metallic silver, gelatin and a polymer and having a line width of 2.0 μm or less.

By applying the exposure treatment to the photosensitive layer, a latent image is formed in the exposed region.
The exposure may be carried out in a pattern. For example, in order to obtain a mesh pattern composed of conductive thin lines, which will be described later, an exposure method and a laser beam are scanned through a mask having a mesh-like aperture pattern. Then, a method of exposing in a mesh shape can be mentioned.
The type of light used for exposure is not particularly limited as long as it can form a latent image on silver halide, and examples thereof include visible light, ultraviolet rays, and X-rays.

By developing the exposed photosensitive layer, metallic silver is deposited in the exposed region (the region where the latent image is formed).
The method of development processing is not particularly limited, and examples thereof include known methods used for silver halide photographic films, photographic papers, printing plate making films, and emulsion masks for photomasks.
In the developing process, a developing solution is usually used. The type of 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.

This step may further include a fixing process performed for the purpose of removing and stabilizing the unexposed portion of silver halide.
The fixing process is carried out at the same time as the development and / or after the development. The method of fixing treatment is not particularly limited, and examples thereof include methods used for silver halide photographic films, photographic papers, printing plate making films, and emulsion masks for photomasks.
In the fixing process, a fixing solution is usually used. The type of fixer is not particularly limited, and examples thereof include the fixer described in "Chemistry of Photographs" (written by Sasai, Photograph Industry Publishing Co., Ltd.) p321.

By carrying out the above treatment, a fine linear silver-containing layer containing metallic silver, gelatin and a specific polymer and having a line width of 2.0 μm or less is formed.
Examples of the method of adjusting the line width of the silver-containing layer include a method of adjusting the opening width of the mask used at the time of exposure. For example, the exposure area can be adjusted by setting the opening width of the mask to 2.0 μm or less.
Further, when a mask is used at the time of exposure, the width of the formed silver-containing layer can be adjusted by adjusting the exposure amount. For example, when the opening width of the mask is narrower than the target width of the 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.
Further, when laser light is used, the exposure region can be adjusted by adjusting the focusing range and / or scanning range of the laser light.

Further, in the method for producing a conductive member, it is sufficient that a silver-containing layer having a width of 2.0 μm or less is formed in at least a part of the region on the base material, and the silver-containing layer is contained in the other region on the base material. A layer containing metallic silver other than the layer (for example, a layer containing metallic silver having a width of more than 2.0 μm) may be formed.

<Process C>
Step C is a step of heat-treating 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.

The method of heat treatment is not particularly limited, and examples thereof 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). The method of contacting with is preferable.

The superheated steam may be superheated steam or a mixture of superheated steam and another gas.
The contact time between the superheated steam and the silver-containing layer is not particularly limited, and is preferably 10 to 70 seconds.
The supply amount of superheated steam is preferably 500 to 600 g / m ³ , and the temperature of superheated steam is preferably 100 to 160 ° C. (preferably 100 to 120 ° C.) at 1 atm.

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

<Process D>
Step D is a step of removing gelatin in the silver-containing layer obtained in Step C. By carrying out this step, gelatin is removed from the silver-containing layer, and voids are formed inside the silver-containing layer.

The method for removing gelatin is not particularly limited, and for example, a method using a proteolytic enzyme (hereinafter, also referred to as “method 1”) and a method for decomposing and removing gelatin using an oxidizing agent (hereinafter, “method 2”). It is also called.).

Examples of the proteolytic enzyme used in Method 1 include enzymes known as plant or animal enzymes capable of hydrolyzing proteins such as gelatin.
Examples of the proteolytic enzyme include pepsin, rennin, trypsin, chymotrypsin, catepsin, papain, ficin, trombine, renin, collagenase, bromelain, and bacterial protease, and trypsin, papain, ficin, or bacterial protease is preferable. ..
The procedure in Method 1 may be a method in which the silver-containing layer and the above-mentioned proteolytic enzyme are brought into contact with each other. For example, a treatment solution containing the silver-containing layer and the proteolytic enzyme (hereinafter, also referred to as “enzyme solution”). There is a method of contacting the proteins. 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 on the silver-containing layer.
The content of the proteolytic enzyme in the enzyme solution is not particularly limited, and is preferably 0.05 to 20% by mass, preferably 0.5 to 20% by mass, based on the total amount of the enzyme solution, in that the degree of decomposition and removal of gelatin can be easily controlled. 10% by mass is more preferable.
The enzyme solution usually contains water in addition to the above-mentioned proteolytic enzyme.
If necessary, the enzyme solution may contain other additives (for example, pH buffer, antibacterial compound, wetting agent, and retaining agent).
The pH of the enzyme solution is selected so as to maximize the action of the enzyme, but is generally preferably 5 to 9.
The temperature of the enzyme solution is preferably a temperature at which the action of the enzyme is enhanced, specifically 25 to 45 ° C.

If necessary, a washing treatment may be carried out in which the obtained silver-containing layer is washed with warm water after the treatment with the enzyme solution.
The cleaning method is not particularly limited, and a method of bringing the silver-containing layer into contact with hot water is preferable, and examples thereof include a method of immersing the silver-containing layer in warm water and a method of applying hot water on the silver-containing layer.
The temperature of the hot water is appropriately selected depending on the type of proteolytic enzyme used, and is preferably 20 to 80 ° C, more preferably 40 to 60 ° C from the viewpoint of productivity.
The contact time (washing time) between the hot water and the silver-containing layer is not particularly limited, and is preferably 1 to 600 seconds, more preferably 30 to 360 seconds from the viewpoint of productivity.

The oxidizing agent used in Method 2 may be any oxidizing agent capable of decomposing gelatin, and an oxidizing agent having a standard electrode potential of + 1.5 V or more is preferable. Here, the standard electrode potential is intended to be the standard electrode potential (25 ° C., E0) with respect to the standard hydrogen electrode in the aqueous solution of the oxidizing agent.
Examples of the oxidizing agent include persulfate, percarbonic acid, perphosphoric acid, subperchloric acid, peracetic acid, metachloroperbenzoic acid, hydrogen peroxide solution, perchloric acid, perioic acid, potassium permanganate, and excess. Examples thereof include ammonium sulfate, ozone, hypochloric acid or a salt thereof, and from the viewpoint of productivity and economy, hydrogen peroxide solution (standard electrode potential: 1.76 V), hypochloric acid or a salt thereof is preferable. Sodium hypochlorate is more preferred.

The procedure in Method 2 may be a method in which the silver-containing layer and the above-mentioned oxidizing agent are brought into contact with each other. For example, a treatment liquid containing the silver-containing layer and the oxidizing agent (hereinafter, also referred to as “oxidizing agent liquid”) is used. There is a method of contacting. 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 on the silver-containing layer.
The type of solvent contained in the oxidizing agent liquid is not particularly limited, and examples thereof include water and organic solvents.

[Step 2]
The step 2 is a step of forming a conductive fine wire by subjecting the fine linear silver-containing layer obtained in the step 1 to a plating treatment using a specific plating treatment agent. By carrying out this step, plating is deposited on and inside the fine linear silver-containing layer. In particular, since voids are present in the silver-containing layer obtained in step 1, by carrying out this step, conductive thin wires filled with metal (plated metal) are formed in the internal voids.

<Plating agent>
For the plating treatment in this step, a plating treatment agent containing compound I and metal ions, which will be described later, is used.
In the plating treatment of this step, a plating solution containing compound I and metal ions may be used as the plating treatment agent, and a metal ion-containing solution containing metal ions and not containing a reducing agent and a reducing solution containing compound I A plating set consisting of the above may be used.
In addition, when only "plating liquid" is described in this specification, "plating liquid containing at least compound I and a metal ion" is intended.
Hereinafter, each component contained in the plating treatment agent will be described.

式中、Ｒは、ハロゲン原子、メチル基、ヒドロキシ基、アミノ基、スルホ基又はＮ−メチルアミノ基を表す。ｎは、１〜５の整数を表す。ｎが２以上を表すとき、Ｒは同一であっても、異なっていてもよい。
化合物Ｉは、還元剤として機能し、めっき液又は還元液に含まれる。 (Compound I)
The plating treatment agent contains compound I represented by the following general formula (I).

In the formula, R represents a halogen atom, a methyl group, a hydroxy group, an amino group, a sulfo group or an N-methylamino group. n represents an integer of 1 to 5. When n represents 2 or more, R may be the same or different.
Compound I functions as a reducing agent and is contained in the plating solution or the reducing solution.

Since compound I has a high reducing power, it functions as a good reducing agent for metal ions contained in the plating treatment agent even in the absence of a catalyst. In addition, compound I has a high affinity for silver and is easily adsorbed on metallic silver contained in the silver-containing layer. Therefore, by using the compound I as a reducing agent for the plating treatment on the silver-containing layer having voids inside, the compound I is adsorbed on the exposed portion of the metallic silver in the voids, and the metal is preferentially adsorbed in this portion. The present inventors speculate that an ion reduction reaction occurs, and as a result, the amount of metal in the conductive thin wire increases while maintaining the line width, so that a conductive thin wire with improved conductivity can be formed. There is.

In the general formula (I), R represents a halogen atom, a methyl group, a hydroxy group, an amino group, a sulfo group or an N-methylamino group. As R, a methyl group, a hydroxy group or an N-methylamino group is preferable. Further, in compound I, it is preferable that at least one R is a hydroxy group or an N-methylamino group.
The substitution position of R is not particularly limited, but the meta position or the para position is preferable with respect to the hydroxy group described in the general formula (I).
Further, in the general formula (I), n represents an integer of 1 to 5. n is preferably an integer of 1 to 3, more preferably 1 or 2.
In addition, compound I may form a salt with a counterion. The counterion forming a salt with compound I is not particularly limited, and examples thereof include a metal ion and an inorganic acid described later. Examples of the inorganic acid include nitric acid, hydrofluoric acid, perchloric acid and sulfuric acid. Further, when compound I forms a salt with a counterion, compound I may be ionized in a plating solution or a reducing solution.

式中、Ｒ_１は、ヒドロキシ基又はＮ−メチルアミノ基を表す。
Ｒ_２は、水素原子、メチル基又はヒドロキシ基を表す。Ｒ_２としては、水素原子又はメチル基が好ましい。 As the compound I, the compound II represented by the following general formula (II) is preferable.

In the formula, R ₁ represents a hydroxy group or an N-methylamino group.
R ₂ represents a hydrogen atom, a methyl group or a hydroxy group. The R _2, a hydrogen atom or a methyl group is preferable.

Examples of Compound I include hydroquinone, methylhydroquinone, N-methylaminophenol, pyrogallol, 1,2,4-trihydroxybenzene, hydroquinone sulfonic acid, and salts thereof.
Among them, hydroquinone, methylhydroquinone, or N-methylaminophenol is preferable, and methylhydroquinone is more preferable, because the conductive thin wire is more excellent in conductivity.

As the compound I, only one kind may be used, or two or more kinds may be used in combination.
The content of compound I in the plating agent is not particularly limited, but when the plating agent is a one-component plating solution, the content of compound I in the plating solution is 0.01 to 0.01 to the plating solution. It is preferably 0.2 mol / L, and more preferably 0.1 to 0.2 mol / L with respect to the plating solution in that the conductivity of the conductive thin wire is more excellent.
When the plating treatment agent is a plating set, the content of compound I in the reducing solution is 0.01 to 0.2 mol / L with respect to the total amount of the reducing solution and the metal ion-containing solution. Is preferable, and the amount of 0.1 to 0.2 mol / L is more preferable in that the conductivity of the conductive thin wire is more excellent. For example, when the metal ion-containing liquid and the reducing liquid are used in the same amount as the plating treatment agent in this step, the content of the compound I in the reducing liquid is 0.02 to 0.4 mol / L with respect to the reducing liquid. Is preferable, and 0.2 to 0.4 mol / L is more preferable.

(Metal ions)
The plating agent contains metal ions.
When the plating agent is a one-component plating solution, the metal ions are contained in the plating solution, and when the plating agent is a plating set, the metal ions are contained in the metal ion-containing solution.
The type of metal ion contained in the plating treatment agent can be appropriately selected depending on the type of metal precipitated in this step, and examples thereof include silver ion, copper ion, nickel ion, and cobalt ion.
Among them, silver ions or copper ions are preferable, and silver ions are more preferable, in that the conductivity of the conductive thin wires is more excellent and the visibility of the mesh pattern formed by the conductive thin wires is more excellent.

Only one type of metal ion may be used, or two or more types may be used in combination.
The content of the metal ion is not particularly limited, but when the plating agent is a one-component plating solution, it is preferably 0.01 to 5.0 mol / L with respect to the plating solution, and is 0.1 to 0.1. More preferably, it is 3.0 mol / L.
When the plating treatment agent is a plating set, the content of the compound I in the reducing liquid is 0.01 to 5.0 mol / L with respect to the total amount of the reducing liquid and the metal ion-containing liquid. Preferably, the amount is 0.1 to 3.0 mol / L, more preferably. For example, when the metal ion-containing liquid and the reducing liquid are used in the same amount as the plating treatment agent in this step, the content of the compound I in the reducing liquid is 0.02 to 10.0 mol / L with respect to the reducing liquid. Is preferable, and 0.2 to 6.0 mol / L is more preferable.

A metal salt may be used as the metal ion.
The type of metal salt is not particularly limited, and a water-soluble metal salt is preferable. The water-soluble metal salt means a metal salt that is dissolved in water in an amount of 0.1% by mass or more.
Examples of the metal salt include inorganic salts and organic salts, and inorganic salts are preferable. Examples of the inorganic salt include a salt composed of a metal ion and an acid selected from the group consisting of nitric acid, hydrofluoric acid, perchloric acid and sulfuric acid.

(water)
The plating solution, reducing solution and metal ion-containing solution preferably contain water as a solvent.
The content of water is not particularly limited, but in any of the plating solution, the reducing solution and the metal ion-containing solution, 60 to 95% by mass is preferable, and 80 to 90% by mass is preferable with respect to the total mass of each solution. More preferred.

(Other ingredients)
The plating treatment agent may contain components other than the above-mentioned compound I, metal ions and water.
The plating treatment agent may contain a complexing agent. Examples of the complexing agent include sulfites, thiosulfates, and organic compounds having an imide group or an amide group. More specific complexing agents include sodium sulfite, potassium sulfite, ammonium sulfite, sodium thiosulfate, potassium thiosulfite, ammonium thiosulfate, hydantin compounds, and imide compounds.
Only one kind of complexing agent may be used, or two or more kinds may be used in combination.
The content of the complexing agent in the plating treatment agent is not particularly limited, but is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, based on the total mass of each liquid of the plating treatment agent.

The plating solution and the reducing solution may contain a reducing agent other than compound I. Reducing agents other than Compound I include ascorbic acid compounds such as ascorbic acid and isoascorbic acid or salts thereof, hydrazines, hydrazine monohydrates, hydrazines such as hydrazine sulfate and hydrazine chloride or salts thereof, and pyrogallol monomethyl ether. , Pyrogalol-4-carboxylic acid, Pyrrobacterrol-4,6-dicarboxylic acid and derivatives of pyrogallol such as gallic acid.
As the reducing agent other than compound I, only one kind may be used, or two or more kinds may be used in combination.
When the plating solution or reducing solution contains a reducing agent other than compound I, the content of the reducing agent is not particularly limited, but the total content of compound I and the reducing agent other than compound I is the above-mentioned plating solution or reducing solution. It is preferably contained in the range of the preferable content of the compound I in the compound I.

The plating treatment agent may contain other additives (for example, pH adjuster, potassium iodide) in addition to the above. By adding potassium iodide to the plating treatment agent, it contributes to the improvement of the plating rate.

The pH of each liquid used as the plating treatment agent is not particularly limited, but the pH of the plating liquid and the metal ion-containing liquid is preferably 8.0 to 13.0, more preferably 9.0 to 11.0. The pH of the reducing solution is preferably 8.0 to 13.0, more preferably 9.0 to 11.0.
The pH is a value measured at 25 ° C.

The plating agent used for the plating treatment in this step is plating composed of a plating solution containing compound I, metal ions and water, or a metal ion-containing solution containing metal ions and water and a reducing solution containing compound I and water. A set is preferred.

<Plating process>
The plating treatment in step 2 is not particularly limited as long as it is a method of bringing the plating treatment agent into contact with the silver-containing layer. Examples thereof include a method of spraying or applying each liquid of the plating treatment agent to the surface of the formed base material.

When a plating set is used as the plating treatment agent, the metal ion-containing liquid and the reducing liquid are sequentially or simultaneously applied to the silver-containing layer, and the metal ion-containing liquid and the reducing liquid are brought into contact with the silver-containing layer to contain silver. Plating may be deposited on and inside the layer.

The temperature of the plating agent in the plating treatment is not particularly limited, and is preferably 0 to 90 ° C, more preferably 10 ° C to 60 ° C.
The contact time between the silver-containing layer and the plating agent in the plating treatment is not particularly limited, and is preferably 10 seconds to 30 minutes from the viewpoint of productivity.

When each liquid of the plating treatment agent is applied and brought into contact with the silver-containing layer, the application method is not particularly limited, and a known device such as a spinner or a coater may be used. When each liquid of the plating treatment agent is sprayed and brought into contact with the silver-containing layer, the spraying method is not particularly limited, and a known spraying device may be used.
When each liquid of the plating treatment agent is sprayed or applied to the surface of the base material on which the silver-containing layer is formed, the spraying amount or coating amount of each liquid is not particularly limited, but the spraying amount or coating amount of each liquid is silver. It is preferable to adjust the content to 0.001 to 0.1 mL / cm ^{2 with respect to the containing layer.}

As the plating treatment, a method of immersing the silver-containing layer in each liquid of the plating treatment agent is preferable because the conductive thin wire is excellent in conductivity and the number of steps is small to improve the productivity.
Further, in terms of reducing the contact of the plating treatment agent with the portion other than the surface of the base material on which the silver-containing layer is formed, each liquid of the plating treatment agent is sprayed or sprayed on the surface of the base material on which the silver-containing layer is formed. The method of coating is preferable.
When a plating solution containing compound I and metal ions is used as the plating treatment agent, a method of immersing the silver-containing layer in the plating solution is preferable, and the plating treatment agent contains the metal ion-containing liquid containing metal ions and compound I. When a plating set composed of a reducing liquid is used, a method of spraying or coating each of the metal ion-containing liquid and the reducing liquid on the surface of the base material on which the silver-containing layer is formed is preferable.

[Step 3]
The present manufacturing method may further include a step 3 in which the conductive thin wire obtained in the step 2 is subjected to a smoothing treatment after the step 2.
By carrying out this step, a conductive thin wire having more excellent conductivity can be obtained.

The method of smoothing treatment is not particularly limited, and for example, a calendar treatment step in which a substrate having conductive thin wires is passed between at least a pair of rolls under pressure is preferable. Hereinafter, the smoothing process using the calendar roll will be referred to as a calendar process.
Examples of the roll used for the calendering process include a plastic roll and a metal roll, and the plastic roll is preferable from the viewpoint of preventing wrinkles.
The pressure between the rolls is not particularly limited, and is preferably 2 MPa or more, more preferably 4 MPa or more, and preferably 120 MPa or less. The pressure between the rolls can be measured using a prescale (for high pressure) manufactured by FUJIFILM Corporation.
The temperature of the smoothing treatment is not particularly limited, and is preferably 10 to 100 ° C, more preferably 10 to 50 ° C.

[Step 4]
The present manufacturing method may further include a step 4 in which the conductive thin wire obtained in the step 3 is heat-treated after the step 3. By carrying out this step, a conductive thin wire having more excellent conductivity can be obtained.
The method of heat-treating the conductive thin wire is not particularly limited, and the method described in step C can be mentioned.

[Step 5]
The present production method may include a step 5 of forming a silver-free layer containing a polymer compound and not containing metallic silver between the base material and the conductive thin wire. The silver-free layer formed between the base material and the conductive thin wire by this step serves as a so-called antihalation layer and contributes to the improvement of the adhesion between the conductive thin wire and the base material.
The content of the polymer compound in the silver-free layer is not particularly limited, and ^{is often 0.03 g / m 2 or more, and 1.0 g / m 2} or more is more excellent in the adhesion of the conductive thin wire. preferable. The upper limit is not particularly limited, but it is often ^{1.63 g / m 2 or less.}
The thickness of the silver-free layer is not particularly limited, and is often 0.05 μm or more, and is preferably more than 1.0 μm, more preferably 1.5 μm or more, in that the adhesiveness of the conductive thin wire is more excellent. The upper limit is not particularly limited, but it is often 3.0 μm or less.

As a specific method of the step 5 for forming the silver-free layer, for example, in the case of forming the fine linear silver-containing layer by the method having steps A to D as the step 1, the base material is formed before the step A. A step E of forming a silver halide-free layer containing gelatin and a specific polymer and not containing silver halide can be mentioned. Step E is carried out before step A to form a silver halide-free layer between the base material and the silver halide-containing photosensitive layer, and then gelatin in the silver halide-free layer is formed by the above step D. By removing the above, a silver-free layer is formed.
Examples of the step E include a method in which a layer-forming composition containing gelatin and a specific polymer is applied onto a substrate and heat-treated as necessary.
The ratio of the mass of the specific polymer to the mass of the gelatin in the silver halide-free layer (mass of the specific polymer / mass of gelatin) is not particularly limited, and is preferably 0.1 to 5.0. 0 to 3.0 is more preferable.
The content of the specific polymer in the silver halide-free layer is not particularly limited, and ^{is often 0.03 g / m 2 or more, and 1.0 g / m 2} in that the adhesiveness of the conductive thin wire is more excellent. The above is preferable. The upper limit is not particularly limited, but it is often ^{1.63 g / m 2 or less.}
The layer-forming composition may contain a solvent, if necessary. Examples of the type of solvent include the solvent used in the above-mentioned composition for forming a photosensitive layer.

[Step 6]
The present production method may include a step 6 of forming a protective layer containing a polymer compound on a conductive thin wire. By providing the protective layer in this step, it is possible to prevent scratches on the conductive thin wires and improve the mechanical properties of the conductive member.
The content of the polymer compound in the protective layer is not particularly limited but is preferably 0 g / m ² Ultra 0.3 g / m ² or less, 0.005~0.1g / m ² is more preferable.
The thickness of the protective layer is not particularly limited, and is preferably 0.03 to 0.3 μm, more preferably 0.075 to 0.20 μm.

As a specific method of step 6 for forming the protective layer, for example, in the case of forming a fine linear silver-containing layer by a method having steps A to D as step 1, after step A and before step B, for example. A step F of forming a protective layer precursor layer containing gelatin and a specific polymer on the silver halide-containing photosensitive layer can be mentioned. A protective layer is formed by performing step F after step A and before step B to form a protective layer precursor layer, and then removing gelatin in the protective layer precursor layer by the above step D. NS.
Examples of the step F include a method in which a composition for forming a protective layer containing gelatin and a specific polymer is applied onto a silver halide-containing photosensitive layer, and heat treatment is performed as necessary.
The ratio of the mass of the specific polymer to the mass of the gelatin in the protective layer precursor layer (mass of the specific polymer / mass of gelatin) is not particularly limited, and is preferably more than 0 and 2.0 or less, and more than 0 and 1. It is more preferably 0 or less.
The content of the specific polymer of the protective layer precursor layer is not particularly limited but is preferably 0 g / m ² Ultra 0.3 g / m ² or less, 0.005~0.1g / m ² is more preferable.
The composition for forming the protective layer precursor layer may contain a solvent, if necessary. Examples of the type of solvent include the solvent used in the above-mentioned composition for forming a photosensitive layer.
The above-mentioned steps E, A and F may be simultaneously carried out by simultaneous layer coating.

In this production method, after step 1 and before step 2, the catalyst is adsorbed on the surface of the polymer compound contained in the fine linear silver-containing layer obtained in step 1, and is placed on the catalyst in the subsequent step 2. The activation treatment for precipitating the plating metal may be performed. Examples of the activation treatment include known methods using a palladium catalyst (catalyst-accelerator method, sensitize-activator method, etc.), a silver catalyst and / or a copper catalyst.
In this manufacturing method, the line width of the conductive thin wire can be narrowed as compared with the case where the above activation treatment is performed, and the visibility of the mesh pattern formed by the conductive thin wire is further improved. Therefore, it is preferable not to perform the activation treatment.

[Conductive member]
The structure of the conductive member obtained by this manufacturing method will be described below.
The conductive member includes at least a base material and a conductive thin wire arranged on the base material. The number of conductive thin wires arranged on the base material is not particularly limited.

The conductive thin wire contains a polymer compound and a metal.
The polymer compound contained in the conductive thin wire may be the same as the polymer compound contained in the above-mentioned fine wire-shaped silver-containing layer, including its preferred embodiment.
The metal contained in the conductive thin wire is a portion that guarantees the conductive characteristics of the conductive thin wire, and includes at least silver (metal silver) contained in the fine wire-shaped silver-containing layer. The metal is selected from the group consisting of silver alone or silver and copper (metal copper), gold (metal gold), nickel (metal nickel) and palladium (metal palladium) because of its superior conductivity. A mixture with one or more metals is preferable, silver alone or a mixture of silver and copper is more preferable, and silver alone is further preferable.
The conductive thin wire often has a structure in which a plurality of fine wire-shaped metals are dispersed in a polymer compound. Further, at least a part of the plurality of metals contained in the conductive thin wire may be joined by a metal derived from a metal ion used in the plating treatment of the above step 2.

The line width of the conductive thin wire produced by this production method is preferably 2.0 μm or less, more preferably 1.7 μm or less, still more preferably 1.5 μm or less, from the viewpoint of being difficult to see. The lower limit is not particularly limited, but 0.5 μm or more is preferable, and 1.0 μm or more is more preferable, from the viewpoint of more excellent conductivity of the conductive thin wire.
The thickness of the conductive thin wire is not particularly limited, but is preferably 0.5 to 2.5 μm, more preferably 1.0 to 2.0 μm.
The meanings of "line width" and "thickness" of the conductive thin wire are the same as the meanings of "line width" and "thickness" of the fine wire-shaped silver-containing layer described above.

The line resistance value of the conductive thin 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 further preferably less than 80 Ω / mm.
The linear resistance value is the resistance value measured by the 4-probe 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 from the mesh pattern, four (A, B, C, D) microprobes (Microsupport Co., Ltd.) A tungsten probe (diameter 0.5 μm) manufactured by Tungsten is brought into contact with the separated conductive thin wire, and a constant current I is applied to the outermost probes A and D. The constant current I is applied using a source meter (a source meter 2400 type general-purpose source meter manufactured by KEITHLEY), and the voltage V between the internal probes B and C is set to 5 mV. Next, the resistance value R = V / I is measured, and the obtained resistance value R is divided by the distance between B and C to obtain the linear resistance value.

The conductive thin wire may form a predetermined pattern, for example, the pattern is not particularly limited, and a triangle such as an equilateral triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid, etc. It is preferable that the geometrical figure is a combination of (regular) n-sided triangles such as a quadrangle, a (regular) hexagon, and a (regular) octagon, a circle, an ellipse, and a star, and is a mesh as shown in FIG. More preferably, it has a shape (mesh pattern).
When the conductive thin wire forms a mesh pattern, the length of one side of the opening, the shape of the opening, and the aperture ratio include the preferred aspects thereof, and the mesh pattern formed by the fine line-shaped silver-containing layer described above. May be the same as.

Further, the conductive member has at least one selected from the group consisting of a silver-free layer arranged between the base material and the conductive thin wire and a protective layer formed on the conductive thin wire. You may be.
Both the silver-free layer and the protective layer that the conductive member may have are as described above.

<Use>
The conductive member obtained as described above can be applied to various uses, such as a touch panel (or touch panel sensor), a semiconductor chip, various electric wiring boards, FPC (Flexible Printed Circuits), COF (Chip on Film), and the like. It can be applied to various applications such as TAB (Tape Automated Bonding), antennas, multilayer wiring boards, and motherboards. Among them, the conductive member is preferably used for a touch panel (capacitive touch panel).
When the conductive member is used for the touch panel, the above-mentioned conductive thin wire can effectively function as a detection electrode.
The conductive member may have a conductive portion having a width of more than 2.0 μm in the region where the metal exists, in addition to the conductive thin wire having the above-mentioned predetermined characteristics. This conductive portion may be connected to the above-mentioned conductive thin wire to be conductive.

A mode in which the conductive member is used as the touch panel sensor will be described with reference to FIG. The configuration of the conductive member is not limited to the mode shown in FIG. 2 as long as it functions as a touch sensor.
The conductive member 16 is electrically connected to at least one surface of the transparent flexible base material 25 to a detection unit 20 formed of a conductive layer and extending in one direction, and to each end of the detection unit 20. It has a take-out wiring portion 22 including a take-out wire 23. The take-out wiring portion 22 is provided on a peripheral edge portion 21 that surrounds the detection portion 20 in a continuous band shape.
The external connection terminal 26 of the take-out wiring portion 22 is arranged on the conductive member 16. A flexible wiring member such as a flexible circuit board 19 is electrically connected to the external connection terminal 26.
The conductive member 16 is provided with a detection unit 20 and a take-out wiring unit 22 on the front surface 25a and the back surface 25b of the flexible base material 25, respectively.

As shown in FIG. 2, the detection unit 20 has, for example, a plurality of first detection electrodes 30 and a plurality of second detection electrodes 32. The plurality of first detection electrodes 30 are band-shaped electrodes extending in the X direction in parallel with each other, and may be electrically insulated from each other in the Y direction with an interval 31 in the Y direction orthogonal to the X direction. It is provided on the surface 25a of the flexible base material 25. The plurality of second detection electrodes 32 are strip-shaped electrodes extending in the Y direction in parallel with each other, and are spaced apart from each other in the X direction by 31 and are electrically insulated from each other in the X direction. It is provided on the back surface 25b (see FIG. 2) of the above. The plurality of first detection electrodes 30 and the plurality of second detection electrodes 32 are provided orthogonally to each other, but are electrically insulated from each other by the flexible base material 25.
The interval 31 between the first detection electrode 30 and the second detection electrode 32 is a region that is separated from the first detection electrode 30 or the second detection electrode 32 and is not electrically connected. Therefore, as described above, the plurality of first detection electrodes 30 are electrically insulated from each other in the Y direction, and the plurality of second detection electrodes 32 are electrically insulated from each other in the X direction. be. A dummy electrode electrically insulated from the detection electrode may be installed at a distance 31 between the detection electrodes. The dummy electrode is an electrode that is electrically insulated from the detection electrode, and may be installed adjacent to the detection electrode. The shape of the dummy electrode is not particularly limited, but it is preferable that the dummy electrode has the same electrode form as the detection electrode. Further, there may be a broken portion in the dummy electrode.

As shown in FIG. 2, the detection unit 20 is provided with eight first detection electrodes 30 and nine second detection electrodes 32, but the number is not particularly limited and may be a plurality.
The first detection electrode 30 and the second detection electrode 32 are composed of the above-described conductive thin wire 33 of the present invention. As shown in FIG. 2, the conductive thin wires 33 are arranged in a mesh shape.
More specifically, FIG. 3 shows a plan view of the front surface 25a side on which the first detection electrode 30 is arranged, and FIG. 4 shows a plan view of the back surface 25b side on which the second detection electrode 32 is arranged. show. As shown in FIGS. 3 and 4, the first detection electrode 30 and the second detection electrode 32 are each composed of conductive thin wires 33 arranged in a mesh shape. As shown in FIG. 2, a mesh pattern composed of a finer grid is formed by overlapping the mesh patterns of the first detection electrode 30 and the second detection electrode 32.

The take-out wiring unit 22 is a member that plays a role of applying a voltage to the first detection electrode 30 and the second detection electrode 32. One end of the take-out wiring portion 22 is electrically connected to the end of the first detection electrode 30 or the second detection electrode 32. An external connection terminal 26 is provided at the terminal portion at the other end.
The take-out wiring unit 22 is composed of a plurality of take-out wires 23. One end of each of the take-out wires 23 is electrically connected to the end of the first detection electrode 30 or the end of the second detection electrode 32 described above. The other ends of the plurality of take-out wires 23 are collectively electrically connected to one external connection terminal 26. The other end of the plurality of take-out wires 23 is the end portion of the take-out wiring portion 22. The number of take-out wires 23 of the take-out wiring unit 22 is the same as the number of detection electrodes electrically connected.
As shown in FIG. 2, the take-out wiring unit 23 may be put together in one place, or may be taken out from a plurality of places.

The take-out wiring portion may be connected to both ends of the detection electrode, or may be connected to only one end of the detection electrode. In FIG. 2, the take-out wiring portion 22 is electrically connected to the first detection electrode 30 at the end in the X direction, and the take-out wiring portion 22 is electrically connected to the second detection electrode 32 at one end in the Y direction. It is connected, and the take-out wiring portion 22 is routed from three directions with respect to the first detection electrode 30 and the second detection electrode 32.
It is preferable that the detection unit 20 and the take-out wiring unit 22 have an integral configuration.

The line width of the take-out line 23 is preferably 500 μm or less, more preferably 50 μm or less, further preferably 30 μm or less, and particularly preferably 15 μm or less.
The distance between adjacent take-out lines 23 is preferably 500 μm or less, more preferably 50 μm or less, further preferably 30 μm or less, and particularly preferably 15 μm or less.
Further, a part or all of the take-out wiring portion 22 may be formed of a thin metal wire. In particular, the connection portion between the take-out wiring portion and the detection electrode is preferably formed of a thin metal wire having a line width of 10 μm or less, more preferably formed of a thin metal wire having a line width of 5 μm or less, and formed of a thin metal wire having a line width of 2 μm or less. It is more preferable to do so. The take-out wiring portion 22 may be formed by one thin metal wire or may be formed by a plurality of thin metal wires. Further, when formed by a plurality of thin metal wires, further thin metal wires connecting the plurality of thin metal wires may be added at regular intervals. By making the connection portion between the take-out wiring portion and the detection electrode a thin metal wire, the reason is not clear, but the visibility is improved. The thin metal wire constituting the take-out wiring portion may be formed together with the above-mentioned conductive thin wire at the time of the plating treatment in the above-mentioned step 2. For example, a second fine linear silver-containing layer containing metallic silver and a polymer compound on a base material, having voids inside, and having a line width of more than 2.0 μm is arranged, and the plating treatment in step 2 is performed. The above-mentioned thin metal wire may be formed by applying the above.

The external connection terminal 26 is, for example, a terminal to which a wiring member such as a flexible circuit board 19 is electrically connected. Therefore, the overall width of the external connection terminal 26 is wider than the width of the peripheral wiring, for example, about 100 to 200 μm.
Similar to the take-out wiring portion 22, the external connection terminal 26 may be partially or wholly formed of a thin metal wire. The first detection electrode 30 and the second detection electrode 32 are electrically connected to the outside by the external connection terminal 26 via a wiring member such as a flexible circuit board 19. The thin metal wire constituting the external connection terminal may be formed together with the above-mentioned conductive thin wire at the time of the plating treatment in the above-mentioned step 2.

The method of forming the take-out wiring portion 22 is not particularly limited, and the take-out wiring portion 22 may be formed at the same time as the first detection electrode 30 and the second detection electrode 32. Specifically, in step 1 described above, a fine linear silver-containing layer and a second fine linear silver-containing layer connected to the fine linear silver-containing layer and having a line width of more than 2.0 μm are simultaneously formed. Then, in step 2, the above plating treatment is applied to the fine linear silver-containing layer having a line width of 2.0 μm or less and the second fine linear silver-containing layer having a line width of more than 2.0 μm. As a result, the first detection electrode 30 and the second detection electrode 32 are formed from the fine linear silver-containing layer having a line width of 2.0 μm or less, and the second fine linear silver-containing layer having a line width of more than 2.0 μm is formed. The take-out wiring portion 22 may be formed from the layer.

Hereinafter, the present invention will be described in more detail with reference to examples of the present invention. The materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limited by the specific examples shown below.

<Example 1>
(Preparation of silver halide emulsion)
To the following liquid 1 kept at 38 ° C. and pH 4.5, an amount corresponding to 90% of each of the following liquids 2 and 3 was added simultaneously for 20 minutes while stirring the 1 liquid, and 0.16 μm nuclei particles were added. Was formed. Subsequently, the following 4 and 5 solutions were added to the obtained solution for 8 minutes, and the remaining 10% of the following 2 and 3 solutions were added over 2 minutes to grow the nuclear particles to 0.21 μm. I let you. Further, 0.15 g of potassium iodide was added to the obtained solution, and the mixture was aged for 5 minutes to complete particle formation.

Liquid 1:
750 ml of water
Gelatin 8.6g
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20 mg
Sodium benzenethiosulfonate 10 mg
Citric acid 0.7g
Liquid 2:
300 ml of water
Silver nitrate 150g
Liquid 3:
300 ml of water
Sodium chloride 38g
Potassium bromide 32g
Potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution) 5 ml
Ammonium hexachlororodium acid (0.001% NaCl 20% aqueous solution) 7 ml
Liquid 4:
100 ml of water
Silver nitrate 50g
Liquid 5:
100 ml of water
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5 mg

Then, it was washed with water by the floculation method according to a conventional method. Specifically, the temperature of the solution obtained above was lowered to 35 ° C., and the pH was lowered using sulfuric acid until the silver halide settled (pH was in the range of 3.6 ± 0.2). Next, about 3 liters of the supernatant was removed from the obtained solution (first washing with water). 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 the silver halide settled. Again, 3 liters of the supernatant was removed from the obtained solution (second wash). The same operation as the second water washing was repeated once more (third water washing), and the water washing and desalting steps were completed. After washing with water and desalting, the emulsion was adjusted to pH 6.4 and pAg 7.5, and gelatin 2.5 g, sodium benzenethiosulfonate 10 mg, sodium benzenethiosulfinate 3 mg, sodium thiosulfate 15 mg and gold chloride acid 10 mg were added. Chemical sensitization was performed at 55 ° C. to obtain optimum sensitivity. Then, 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 contains 0.08 mol% of silver iodide, and the ratio of silver bromide is 70 mol% of silver chloride and 30 mol% of silver bromide, and the average particle size (sphere equivalent diameter). It was a silver chloride cubic particle emulsion having a variation coefficient of 9% at 200 nm.

(Preparation of composition for forming a photosensitive layer)
1,3,3a above emulsion, 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 hardener were added to the composition. Got The pH of the composition was then adjusted to 5.6 with citric acid.
A dispersant comprising the polymer represented by the following (P-1) (hereinafter, also referred to as “polymer 1”) and dialkylphenyl PEO (PEO is an abbreviation for polyethylene oxide) sulfate ester in the above composition. Polymer latex containing water and water (the ratio of the mass of the dispersant to the mass of the polymer 1 (mass of the dispersant / mass of the polymer 1, the unit is g / g) is 0.02, and contains solid content. The ratio of the mass of the polymer 1 to the total mass of the gelatin in the composition (mass of the polymer 1 / mass of the gelatin, unit g / g) is 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, the unit is g / g) is 0. It was 11. Further, the numerical values (“8.6”, “58.9”, “2”, “25.4” and “5.1”) in the formula of the polymer 1 represent the molar ratio of each repeating unit.
Further, EPOXY RESIN DY 022 (trade name: manufactured by Nagase ChemteX Corporation) was added as a cross-linking agent to the obtained polymer latex-containing composition. The amount of the cross-linking agent added was adjusted so that the amount of the cross-linking agent in the silver halide-containing photosensitive layer described later was 0.09 g / m ^2.
The composition for forming a photosensitive layer was prepared as described above.
The polymer 1 was synthesized with reference to Japanese Patent No. 3305459 and Japanese Patent No. 3754745.

(Formation of undercoat layer)
The polymer latex was applied to a substrate made of a polyethylene terephthalate film having a thickness of 40 μm (a long roll-shaped film manufactured by FUJIFILM Corporation) to provide an undercoat layer having a thickness of 0.05 μm. This process was performed roll-to-roll, and each of the following processes (steps) was also performed roll-to-roll in the same manner. The roll width at this time was 1 m, and the length was 1000 m.

(Step E-1, Step A-1, Step F-1)
Next, on the undercoat layer, a silver halide-free layer forming composition in which the polymer latex and gelatin are mixed, a protective layer forming in which the photosensitive layer forming composition, and the polymer latex and gelatin are mixed is formed. The composition for use was simultaneously applied in multiple layers to form a silver halide-free layer, a silver halide-containing photosensitive layer, and a protective layer on the undercoat layer.
The thickness of the silver halide-free layer is 2.0 μm, and the mixed mass ratio of polymer 1 and gelatin (polymer 1 / gelatin) in the silver halide-free layer is 2/1, which is high. The content of the molecule 1 was 1.3 g / m ² .
The thickness of the silver halide-containing photosensitive layer is 2.5 μm, and the mixed mass ratio of polymer 1 and gelatin (polymer 1 / gelatin) in the silver halide-containing photosensitive layer is 0.25 / 1. The content of the polymer 1 was 0.19 g / m ² .
The thickness of the protective layer is 0.15 μm, the mixed mass ratio of polymer 1 and gelatin (polymer 1 / gelatin) in the protective layer is 0.1 / 1, and the content of polymer 1 is It was 0.015 g / m ^2.

(Step B-1)
The photosensitive layer prepared above was exposed to light through a square grid-shaped photomask using parallel light using a high-pressure mercury lamp as a light source. A pattern-forming mask is used as a photomask, and the silver-containing layer forming the unit square grid is exposed so that the line width is 1.3 μm and the length L of one side of the unit square grid (opening) is 600 μm. I set the conditions.

After the exposure, the obtained sample A is developed with a developing solution described later, further developed with a fixing solution (trade name: N3X-R for CN16X: manufactured by FUJIFILM Corporation), and then developed at 25 ° C. Was rinsed with pure water and then dried to obtain Sample A having a silver-containing layer containing metallic silver, which was formed in the mesh pattern shown in FIG. In sample A, a conductive mesh pattern region having a size of 21.0 cm × 29.7 cm was formed.

(Composition of developer)
The following compounds are contained in 1 liter (L) of the developing solution.
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 metabisulfate 0.187 mol / L

The sample A obtained above was immersed in warm water at 50 ° C. for 180 seconds. After that, the water was drained with an air shower and allowed to air dry.

(Step C-1)
The sample A obtained in step B-1 was carried into a superheated steam treatment tank at 110 ° C. and allowed to stand for 30 seconds to perform superheated steam treatment. The steam flow rate at this time was 100 kg / h.

(Step D-1)
Sample A obtained in step C-1 is placed in an aqueous solution of a proteolytic enzyme (Bioprese AL-15FG manufactured by Nagase ChemteX Corporation) (proteolytic enzyme concentration: 0.5% by mass, liquid temperature: 40 ° C.) for 120 seconds. Soaked. Sample A was taken out from the aqueous solution, and sample A was immersed in warm water (liquid temperature: 50 ° C.) for 120 seconds and then washed to obtain sample A.

The sample A obtained in step D-1 is a laminate in which a base material, an undercoat layer, a silver-free layer, a silver-containing layer, and a protective layer are laminated in this order, and the line width of the silver-containing layer is 1. It was 3 μm. Further, the sample A had a mesh pattern composed of a silver-containing layer and an opening.
A microscope VHX-5000 manufactured by KEYENCE Corporation was used to measure the line width of the silver-containing layer and the line width and thickness of the conductive thin wire described later.

The ratio of the region occupied by the metallic silver, the polymer compound (polymer 1) and the voids in the vertical cross section of the fine linear silver-containing layer of the sample A was measured by the following method.
Sample A obtained in step D-1 was cut using a microtome along a direction orthogonal to the direction in which the fine line-shaped silver-containing layer extends to expose the vertical cross section of the silver-containing layer. After carbon deposition was performed on the vertical cross section of the exposed silver-containing layer, the vertical cross section was observed with a scanning electron microscope (S-5200 type SEM manufactured by Hitachi High-Technologies Corporation). The observation conditions at this time were the backscattered electron mode and the acceleration voltage: 5 kV.
By analyzing the obtained observation image using image processing software (Image J) with the brightness set to 150 and 75 as the threshold value, the region occupied by metallic silver and the region occupied by other than metallic silver are binary values. A binarized cross-sectional image A and a binarized cross-sectional image B of a region occupied by a void and a region occupied by a region other than the void were created.
In the obtained cross-sectional image A, the inscribed circle of the region A where the metallic silver exists is drawn by the above method, and the inscribed circle of the total area of the region occupied by the metallic silver included in the inscribed circle of the drawn region A. The area ratio of the ratio to the total area of was calculated. Next, in the obtained cross-sectional image B, the same circle as the inscribed circle of the area A in the cross-sectional image A is drawn, and the total area of the inscribed circle is the total area of the area occupied by the voids included in the drawn inscribed circle. The area ratio of the ratio to the area was calculated. Based on the calculated total area of the area occupied by the metallic silver and the voids and the total area of the inscribed circle, the total area of the inscribed circle of the total area of the area occupied by the polymer 1 included in the inscribed circle of the area A. The ratio to was calculated.
As a result, in the vertical cross section of the silver-containing layer, the ratio of each inscribed circle of the region occupied by the metallic silver, the polymer compound, and the void contained in the inscribed circle of the region A where the metallic silver exists is the area. The ratios were 40%, 42% and 18%, respectively.

(Step 2-1)
The sample A obtained in step D-1 was immersed in a plating solution A (30 ° C.) having the composition shown below for 5 minutes. Sample A was taken out from the plating solution A, and sample A was immersed in warm water (liquid temperature: 50 ° C.) for 120 seconds for washing.

The composition of the plating solution A (total volume 1200 ml) was as follows. The pH of the plating solution A was 9.5, and the pH was adjusted by adding a predetermined amount of potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The content of methyl hydroquinone in the plating solution A was 0.1 mol / L with respect to the plating solution A.
The following components used in the plating solution A were all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

(Composition of plating solution A)
・ AgNO ₃ 8.8g
・ Sodium sulfite 72g
・ Sodium thiosulfate pentahydrate 66g
・ Potassium iodide 0.004g
・ Citric acid 12g
・ Methyl hydroquinone 14.9g
・ Potassium carbonate Prescribed amount ・ Water balance

(Step 3-1)
The sample A obtained in step 2-1 was calendar-processed at a pressure of 30 kN using a calendar device using a combination of a metal roll and a resin roll. Calendar processing was performed at room temperature.

(Step 4-1)
The sample A obtained in step 3-1 was carried into a superheated steam treatment tank at 110 ° C., allowed to stand for 30 seconds, and subjected to superheated steam treatment to obtain a conductive member. The steam flow rate at this time was 100 kg / h.
The conductive member obtained in Example 1 was formed of conductive thin wires and had a mesh pattern having the shape shown in FIG. The line width of the conductive thin wire was 1.3 μm, and the thickness of the conductive thin wire was 1.3 μm.

<Examples 2 to 11 and Comparative Examples 1 to 4>
As shown in Table 1 to be described later, the conductive members of Examples 2 to 11 and Comparative Examples 1 to 4, respectively, were produced according to the same procedure as in Example 1 except that the manufacturing conditions of the conductive members were changed. ..
The conductive members produced in each of the examples and the comparative examples were each formed of conductive thin wires and had a mesh pattern having the shape shown in FIG. Further, Table 1 described later shows the line width and thickness of the conductive thin wires of each Example and each Comparative Example.

(Examples 2 to 7)
In Examples 2 to 7, conductive thin wires were produced according to the method described in Example 1 except that the following plating solutions B to G were used instead of the plating solutions A.
The plating solutions B, C and E were prepared in the same manner as the plating solution A except that N-methylaminophenol, hydroquinone and pyrogallol were used instead of methylhydroquinone. At this time, the contents of N-methylaminophenol, hydroquinone, and pyrogallol were adjusted so that the molar concentration of compound I in each plating solution was the same as that of plating solution A.
The composition of the plating solution D was the same as that of the plating solution A, except that 8.3 g of copper sulfate was used instead of _{silver nitrate (AgNO 3).}
The plating solutions F and G were prepared by the same method as the plating solution A, except that the amount of methyl hydroquinone used in each plating solution was changed so as to have the molar concentration shown in Table 1.

(Example 8)
In Example 8, in the method for preparing the composition for forming a photosensitive layer, the contents of the polymer latex and gelatin were adjusted, and the ratio of the mass of the polymer 1 to the total mass of the gelatin (mass of the polymer 1). / Mass of gelatin, unit g / g) is 0.25, and the ratio of the total 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 0.22, a fine linear silver-containing layer was prepared according to the method described in Example 1, except that the composition for forming a photosensitive layer was prepared. The line width of the fine linear silver-containing layer produced in Example 8 was 1.4 μm. Further, in the vertical cross section of the fine linear silver-containing layer produced in Example 8, the inscribed circle of the region occupied by each of the metallic silver, the polymer compound, and the void contained in the inscribed circle of the region A in which the metallic silver exists. The ratio of the circle to the total area was 20%, 60% and 20%, respectively, in terms of area ratio.
The obtained fine wire-shaped silver-containing layer was plated in the same manner as in Example 1 to prepare a conductive thin wire.

(Example 9)
In Example 9, a fine line-shaped silver-containing layer was prepared according to the method described in Example 1, except that a glass plate having a thickness of 1 mm was used instead of the polyethylene terephthalate film having a thickness of 40 μm as the base material. The obtained fine wire-shaped silver-containing layer was plated to prepare a conductive thin wire.
The line width of the fine linear silver-containing layer produced in Example 9 was 1.3 μm. Further, in the vertical cross section of the fine linear silver-containing layer produced in Example 9, the inscribed circle of the region occupied by each of the metallic silver, the polymer compound, and the void contained in the inscribed circle of the region A in which the metallic silver exists. The ratio of the circle to the total area was 40%, 42% and 18%, respectively, in terms of area ratio.

(Example 10)
In Example 10, in the method for preparing the composition for forming a photosensitive layer, the contents of the polymer latex and gelatin were adjusted, and the ratio of the mass of the polymer 1 to the total mass of gelatin (mass of the polymer 1). / Gelatin mass, unit g / g) is 0.25, and the ratio of the total mass of gelatin to the mass of silver halide-derived silver (gelatin mass / mass of silver halide-derived silver, unit g / g) ) Was 0.05, a fine linear silver-containing layer was prepared according to the method described in Example 1 except that a composition for forming a photosensitive layer was prepared, and the obtained fine linear silver-containing layer was formed. On the other hand, a plating treatment was performed to prepare a conductive thin wire.
The line width of the fine linear silver-containing layer produced in Example 10 was 1.4 μm. Further, in the vertical cross section of the fine linear silver-containing layer produced in Example 8, the inscribed circle of the region occupied by each of the metallic silver, the polymer compound, and the void contained in the inscribed circle of the region A in which the metallic silver exists. The ratio of the circle to the total area was 70%, 20% and 10%, respectively, in terms of area ratio.

(Example 11 (step 2-2))
In Example 11, as the plating treatment for the sample A obtained in step D-1, the following step 2-2 was carried out in place of the step 2-1 carried out in Example 1.
In step 2-2, a plating set H composed of a reducing liquid h1 and a metal ion-containing liquid h2 was used as the plating treatment agent. Specifically, a reducing liquid h1 and a metal having the composition shown below are used on the surface of the sample A obtained in step D-1 on the silver-containing layer side using a spray device (0.1 ml / sec). The ion-containing liquid h2 was sequentially sprayed for 20 seconds each. Then, the sample A was allowed to stand for 1 minute, and then immersed in warm water (liquid temperature: 50 ° C.) for 120 seconds for washing.
The compositions of the reducing liquid h1 (total volume 500 ml) and the metal ion-containing liquid h2 (total volume 500 ml) were as follows. The pH of the reducing liquid h1 and the metal ion-containing liquid h2 was 9.5, and the pH was adjusted by adding a predetermined amount of potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The content of methyl hydroquinone in the reducing liquid h1 was 0.2 mol / L with respect to the reducing liquid h1.

(Reducing liquid h1)
・ Sodium sulfite 36g
・ Citric acid 12g
・ Methyl hydroquinone 12.4g
・ Potassium carbonate Prescribed amount ・ Water balance

(Metal ion-containing liquid h2)
・ AgNO ₃ 8.8g
・ Sodium sulfite 36g
・ Sodium thiosulfate pentahydrate 66g
・ Potassium iodide 0.004g
・ Water residue

Steps 3-1 and 4-1 described in Example 1 were carried out on the sample A obtained in step 2-1 to produce a conductive thin wire.
No change in line width was observed before and after the plating treatment in step 2-2. The thickness of the conductive thin wire was 1.3 μm.

<Example 12>
(Formation of undercoat layer)
The polymer latex was applied to both sides of a base material made of a polyethylene terephthalate film having a thickness of 40 μm (a long roll-shaped film manufactured by Fujifilm Corporation) to provide an undercoat layer having a thickness of 0.05 μm. This treatment was performed roll-to-roll on each side, and each of the following treatments (processes) was also performed roll-to-roll in the same manner. The roll width at this time was 1 m, and the length was 1000 m.

(Step E-1, Step A-1, Step F-1)
Next, on the undercoat layer arranged on one surface of the base material, the silver halide-free layer forming composition in which the polymer latex and gelatin are mixed, the photosensitive layer forming composition, and the photosensitive layer forming composition. A composition for forming a protective layer in which polymer latex and gelatin were mixed was simultaneously applied in multiple layers to form a silver halide-free layer, a silver halide-containing photosensitive layer, and a protective layer on the undercoat layer. Then, a silver halide-free layer, a silver halide-containing photosensitive layer, and a protective layer were similarly formed on the opposite surface.
The thickness of the silver halide-free layer is 2.0 μm, and the mixed mass ratio of polymer 1 and gelatin (polymer 1 / gelatin) in the silver halide-free layer is 2/1, which is high. The content of the molecule 1 was 1.3 g / m ² .
The thickness of the silver halide-containing photosensitive layer is 2.5 μm, and the mixed mass ratio of polymer 1 and gelatin (polymer 1 / gelatin) in the silver halide-containing photosensitive layer is 0.25 / 1. The content of the polymer 1 was 0.19 g / m ² .
The thickness of the protective layer is 0.15 μm, the mixed mass ratio of polymer 1 and gelatin (polymer 1 / gelatin) in the protective layer is 0.1 / 1, and the content of polymer 1 is It was 0.015 g / m ^2.

(Step B-1)
A high-pressure mercury lamp is placed on a silver halide-containing photosensitive layer prepared on one surface of a polyethylene terephthalate (PET) film via a photomask in which a first detection electrode and its extraction wiring portion are arranged as shown in FIG. A photomask in which a second detection electrode and its take-out wiring portion are arranged on a silver halide-containing photosensitive layer prepared on the other surface by exposure using parallel light as a light source as shown in FIG. 4 is used. Exposure was performed using parallel light using a high-pressure mercury lamp as a light source.
On each surface of the polyethylene terephthalate film, the extending direction of the mesh-shaped first detection electrode and the extending direction of the mesh-shaped second detection electrode are formed so as to be orthogonal to each other as shown in FIG. The take-out wire of the take-out wiring portion connected to the detection electrode is formed so as to be arranged in the peripheral region.
The mesh of the first detection electrode and the second detection electrode is composed of a square lattice, the line width of the silver-containing layer forming the unit square lattice is 1.7 μm, and the length L of one side of the unit square lattice (opening) is The exposure conditions were set so as to be 600 μm. The square lattices of the first detection electrode and the second detection electrode are arranged at an angle of 45 degrees with respect to the extending direction of the first detection electrode, and the first detection electrode and the second detection electrode are silver-containing layers forming the square lattice. Are arranged so as to be offset from each other by 300 μm and the intersection of the square lattices of the first detection electrode is located at the center of the square lattice of the second detection electrode. Further, as shown in FIG. 2, since nine take-out wires are taken out from the second detection electrode and the first detection electrode is taken out from two places at both ends, there are 16 take-out lines of 8 × 2.
The finally obtained first detection electrode has a configuration in which eight detection electrodes having a width of 2 mm are arranged, and dummy electrodes having a width of 2 mm are arranged between the detection electrodes, and the detection electrodes and the dummy electrodes are arranged alternately. .. The dummy electrode has a mesh shape having the same shape as the first detection electrode, and has one place at a random point on the side (600 μm) of the square lattice constituting the mesh, and a place where the silver wire having a width of 10 μm is interrupted. The distance between the detection electrode and the dummy electrode is 10 μm at the shortest, and is electrically insulated.
The second detection electrode has a configuration in which nine electrode portions having a width of 3 mm are arranged, and dummy electrodes having a width of 1 mm are arranged between the detection electrodes, and the detection electrodes and the dummy electrodes are arranged alternately. The distance between the detection electrode and the dummy electrode is 10 μm at the shortest, and is electrically insulated.
The line width of the silver-containing layer serving as the take-out line was 20 μm, and the distance between the take-out lines was 20 μm. Further, the external connection terminal to which each take-out wire is connected is formed of a rectangular silver-containing layer having a width of 150 μm and a length of 1.5 mm.

After the exposure, the obtained sample B is developed with the above-mentioned developer, further developed with a fixer (trade name: CN16X N3X-R: manufactured by FUJIFILM Corporation), and then developed at 25 ° C. A sensor as shown in FIG. 2, which has a mesh-patterned detection electrode and a dummy electrode shown in FIG. 1 and a take-out wiring portion connected to each detection electrode in the detection unit after rinsing with pure water and then drying. Sample B having a silver-containing layer containing metallic silver formed in a pattern was obtained.

The sample B obtained above was immersed in warm water at 50 ° C. for 180 seconds. After that, the water was drained with an air shower and allowed to air dry.

(Step C-1)
The sample B obtained in step B-1 was carried into a superheated steam treatment tank at 110 ° C. and allowed to stand for 30 seconds to perform superheated steam treatment. The steam flow rate at this time was 100 kg / h.

(Step D-1)
Sample B obtained in step C-1 is placed in an aqueous solution of a proteolytic enzyme (Bioprese AL-15FG manufactured by Nagase ChemteX Corporation) (proteolytic enzyme concentration: 0.5% by mass, liquid temperature: 40 ° C.) for 120 seconds. Soaked. Sample B was taken out from the aqueous solution, and sample B was immersed in warm water (liquid temperature: 50 ° C.) for 120 seconds and then washed to obtain sample B.

The sample B obtained in step D-1 is a laminate in which a base material, an undercoat layer, a silver-free layer, a silver-containing layer, and a protective layer are laminated in this order on both sides, and silver constituting a detection electrode. The line width of the containing layer was 1.7 μm.

(Step 2-1)
The sample B obtained in step D-1 was immersed in the above-mentioned plating solution A (30 ° C.) for 5 minutes. Sample B was taken out from the plating solution A, and sample B was immersed in warm water (liquid temperature: 50 ° C.) for 120 seconds for washing.

(Step 3-1)
The sample B obtained in step 2-1 was calendar-processed at a pressure of 30 kN using a calendar device using a combination of a metal roll and a resin roll. Calendar processing was performed at room temperature.

(Step 4-1)
The sample B obtained in step 3-1 was carried into a superheated steam treatment tank at 110 ° C., allowed to stand for 30 seconds, and subjected to superheated steam treatment to obtain a conductive member. The steam flow rate at this time was 100 kg / h.
In the conductive member obtained in Example 12, the detection electrode was formed of a conductive thin wire and had a mesh pattern having the shape shown in FIG. The line width of the conductive thin wire constituting the detection electrode was 1.75 μm, and the thickness of the conductive thin wire was 1.3 μm.
In the conductive member obtained in Example 12, a take-out wiring portion was formed together with the detection electrode.

<Example 13>
A conductive member was produced according to the method described in Example 12, except that the photomask for exposure was changed.
The changes in the exposure photomask were as follows.
The take-out wiring part has a form in which two conductive thin wires having a line width of 1.7 μm are installed at an interval of 16.6 μm, and two silver wires having a line width of 1.7 μm are connected at an interval of 250 μm. (Hereinafter referred to as the ladder pattern). Further, the external connection terminal is set to be a rectangular mesh having a unit square lattice (opening) having a side length L of 50 μm, an outer shape of 150 μm, and a length of 1.5 mm (hereinafter, It is called a mesh-shaped external connection terminal).

<Example 14>
A conductive member was produced according to the method described in Example 12, except that the photomask for exposure was changed.
The changes in the exposure photomask were as follows.
As for the take-out wiring part, the take-out wiring from the connection part with the detection electrode to the position of 70 mm has the same ladder pattern as in Example 13, and the take-out wiring from the position of 70 mm to the external connection terminal has the same take-out wiring as in Example 12. Further, as the external connection terminal, when the length of the take-out wiring portion is 70 mm or less, the mesh-like external connection terminal similar to that of the thirteenth embodiment is adopted, and otherwise the external connection terminal is the same as that of the twelfth embodiment.

(Comparative Example 1)
In Comparative Example 1, a conductive thin wire was produced according to the method described in Example 1 except that the following plating solution X was used instead of the plating solution A.
For the plating solution X, formalin was used instead of methylhydroquinone, and the amount of formalin was adjusted so that the molar concentration of formalin in the plating solution X was the same as the molar concentration of methylhydroquinone in the plating solution A. Was prepared in the same manner as the plating solution A.

(Comparative Example 2 (Step 2-3))
In Comparative Example 2, the following steps 2-3 were carried out on the sample A obtained in step D-1 instead of step 2-1.
In step 2-3, before carrying out step 2-1 the sample A obtained in step D-1 is subjected to a palladium (Pd) catalyst-containing liquid having a liquid temperature of 30 ° C. (“OIC Axela”, In The Back Pharmaceutical Industry Co., Ltd.). It was immersed in (manufactured by Co., Ltd.) for 3 minutes, and a pretreatment was carried out in which Pd was adsorbed on the exposed polymer 1 on the surface of sample A. After performing this pretreatment, it was rinsed with running water for 1 minute, and then the plating treatment was carried out according to the method described in step 2-1 above.
The steps 3-1 and 4-1 described in Example 1 were performed on the sample A obtained in the above steps 2-3 to prepare the conductive member of Comparative Example 2.

(Comparative Example 3)
In Comparative Example 3, the conductive member of Comparative Example 3 was obtained by performing only Step 3-1 and Step 4-1 without performing Step 2-1 on the sample A obtained in Step D-1. Was produced.

(Comparative Example 4)
In Comparative Example 4, in step B-1, the exposure amount of the parallel light applied to the photosensitive layer was adjusted to prepare sample A having a mesh pattern consisting of a silver-containing layer having a line width of 2.7 μm and an opening. bottom. The obtained sample A was formed by the method described in steps 2-1, 3-1 and 4-1 of Example 1 and formed of conductive thin wires having a line width of 3.0 μm, and is shown in FIG. A conductive member having a mesh pattern having the shape shown was obtained.

<Evaluation>
(Conductivity)
The linear resistance value of the conductive mesh pattern region of the obtained conductive member was measured. The linear resistance value is the resistance value measured by the 4-probe 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 from the mesh pattern, four (A, B, C, D) microprobes (Microsupport Co., Ltd.) A tungsten probe (diameter 0.5 μm) manufactured by Tungsten was brought into contact with the separated conductive thin wire, and a constant current I was applied to the outermost probes A and D. The constant current I was applied using a source meter (a source meter manufactured by KEITHLEY, a 2400 type general-purpose source meter), and the voltage V between the internal probes B and C at intervals of 250 μm was set to 5 mV. Next, the resistance value R = V / I was measured, and the obtained resistance value R was divided by the distance between B and C to obtain the linear resistance value. From the average value of the line resistance values measured at any 10 points, the conductivity of the conductive members of each Example and Comparative Example was evaluated according to the following criteria.
As the conductive member, the evaluation result by the above method is preferably 3 or more, more preferably 4 or more, and further preferably 5 or more.

(Conductivity evaluation criteria)
5: The line resistance value is less than 40 Ω / mm.
4: The line resistance value is 40 Ω / mm or more and less than 50 Ω / mm.
3: The line resistance value is 50 Ω / mm or more and less than 60 Ω / mm.
2: The line resistance value is 60 Ω / mm or more and less than 80 Ω / mm.
1: The line resistance value is 80Ω / mm or more.

(Visibility)
The obtained conductive members were laminated in the order of glass / conductive member / polarizing plate / polarizing plate / black PET (manufactured by Panac Co., Ltd., industrial black PET (GPH100E82A04)) to obtain a laminated body. In the conductive member, the conductive member was arranged so that the conductive mesh pattern was located on the glass side and the base material was located on the polarizing plate side. Further, the two polarizing plates were laminated so that the planes of polarization were orthogonal to each other.
Next, 10 observers visually observed the obtained laminate with 500 lux ambient light from the front surface on the glass surface side and an angle of 30 to 60 °, and according to the following criteria. evaluated. The results are summarized in Table 1. When the mesh pattern is difficult to see, the optical characteristics are excellent, and moire generated when the conductive member is laminated on the display is reduced.

(Visibility evaluation criteria)
When observing the conductive member from a position 5:15 cm away, no observer visually recognized the mesh pattern.
When observing the conductive member from a position 4:30 cm away, there were 0 or 1 observers who visually recognized the mesh pattern.
When observing the conductive member from a position 3:30 cm away, there were 2 to 4 observers who visually recognized the mesh pattern.
When observing the conductive member from a position 2:30 cm away, there were five or more observers who visually recognized the mesh pattern.
When observing the conductive member from a position 1:50 cm away, there were five or more observers who visually recognized the mesh pattern.

The "base material" column in Table 1 represents the material constituting the base material.
In the "Composition ratio (cross section)" column of the "Silver-containing layer" in Table 1, the inscribed circle of the region occupied by the metallic silver, the polymer compound, and the voids contained in the inscribed circle of the region A in which the metallic silver exists. Represents the area ratio (%) to the total area of the circle.
The “line width [μm]” column of the “silver-containing layer” in Table 1 represents the line width of the silver-containing layer obtained after the exposure development treatment such as step D-1.
The "type" column of "plating agent" in Table 1 indicates the type of plating agent used in the plating process.
The "metal" column in Table 1 represents the type of metal ion contained in each plating agent. That is, when the "metal" column is "Ag", it means that the plating agent contains silver ions and silver is precipitated by the plating process, and when the "metal" column is "Cu", the plating agent is It contains copper ions and indicates that copper was precipitated by the plating treatment.
The "type" column of "reducing agent" in Table 1 represents the type of reducing agent contained in the plating treatment agent used in step 2-1 and the "concentration [mol / L]" column of "reducing agent" is. , Indicates the concentration of the reducing agent with respect to the plating solution or the reducing solution.
The "line width [μm]" column and the "thickness [μm]" column of the "conductive thin wire" in Table 1 represent the line width and thickness of the obtained conductive thin wire, respectively.

As shown in Table 1, it was confirmed that according to the production method of the present invention, a conductive member having a desired effect can be obtained.

Further, when the compound I was hydroquinone, methylhydroquinone, or N-methylaminophenol, it was confirmed that the conductivity of the conductive thin wire was more excellent (comparison between Examples 1 to 3 and Example 5), and the compound. When I was methylhydroquinone, it was confirmed that the conductivity of the conductive thin wire was further excellent (comparison between Example 1 and Examples 2 and 3).

It was confirmed that when the plating agent contains silver ions, the conductivity of the conductive thin wires is more excellent, and the visibility of the mesh pattern formed by the conductive thin wires is more excellent (Examples 1 and Example). Comparison with 4).

When the content of compound I in the plating solution was 0.01 mol / L or more with respect to the plating solution, it was confirmed that the conductivity of the conductive thin wire was more excellent (Examples 1 and 6). comparison).
Further, it was confirmed that when the content of the compound I in the plating solution is 0.2 mol / L or less with respect to the plating solution, the visibility of the mesh pattern formed by the conductive thin wires is more excellent (). Comparison between Example 1 and Example 7).

Conductivity when the ratio of the area occupied by the metallic silver in the inscribed circle of the region A where the metallic silver exists in the vertical cross section of the silver-containing layer to the total area of the inscribed circle is 30 to 60% in terms of area ratio. It was confirmed that the thin wire had better conductivity (comparison between Example 1 and Examples 8 and 10).

When the plating treatment in step 2 was a method of immersing the silver-containing layer in the plating solution, it was confirmed that the conductivity of the conductive thin wire was more excellent (comparison between Example 1 and Example 11).

10 Mesh pattern 12 Silver-containing layer 14 Opening 16 Conductive member 19 Flexible circuit board 20 Detection part 21 Peripheral part 22 Extraction wiring part 23 Extraction line 25 Flexible base material 26 External connection terminal 30 First detection electrode 31 Spacing 32nd 2 Detection electrode 33 Conductive thin wire

Claims (11)

Step 1 of forming a fine linear silver-containing layer containing metallic silver and a polymer compound on a base material, having voids inside, and having a line width of 2.0 μm or less.
The silver-containing layer is subjected to a plating treatment using a plating treatment agent containing a compound I represented by the following general formula (I) and a metal ion to form a conductive fine wire. A method for manufacturing a sex member.

In the formula, R represents a halogen atom, a methyl group, a hydroxy group, an amino group, a sulfo group or an N-methylamino group. n represents an integer of 1 to 5. When n represents 2 or more, R may be the same or different. The method for producing a conductive member according to claim 1, wherein the plating agent is a plating solution containing the compound I, the metal ions, and water. The method for producing a conductive member according to claim 2, wherein the content of the compound I in the plating solution is 0.01 to 0.2 mol / L with respect to the plating solution. The method for producing a conductive member according to claim 1, wherein the plating treatment agent is a plating set comprising the metal ion-containing liquid containing the metal ions and water and the reducing liquid containing the compound I and water. The conductivity according to claim 4, wherein the content of the compound I in the reducing solution is 0.01 to 0.2 mol / L with respect to the total amount of the reducing solution and the metal ion-containing solution. Method of manufacturing sex members. The method for producing a conductive member according to any one of claims 1 to 5, wherein the compound I is a compound II represented by the following general formula (II).

In the formula, R ₁ represents a hydroxy group or an N-methylamino group. R ₂ represents a hydrogen atom, a methyl group or a hydroxy group. The method for producing a conductive member according to any one of claims 1 to 6, wherein the metal ion is a silver ion. When the inscribed circle of the region is drawn from the center point of the region where the metallic silver exists in the silver-containing layer in the cross section of the silver-containing layer along the direction orthogonal to the extending direction of the silver-containing layer. The method according to any one of claims 1 to 7, wherein the ratio of the region occupied by the metallic silver contained in the inscribed circle to the total area of the inscribed circle is 30 to 60% in terms of area ratio. A method for manufacturing a conductive member. When the inscribed circle of the region is drawn from the center point of the region where the metallic silver exists in the silver-containing layer in the cross section of the silver-containing layer along the direction orthogonal to the extending direction of the silver-containing layer. The conductivity according to any one of claims 1 to 8, wherein the ratio of the region occupied by the void included in the inscribed circle to the total area of the inscribed circle is 10 to 30% in terms of area ratio. Method of manufacturing sex members. The method for producing a conductive member according to any one of claims 1 to 9, wherein the base material is a flexible base material. In the step 1, the fine linear silver-containing layer and the second fine linear silver-containing layer connected to the fine linear silver-containing layer and having a line width of more than 2.0 μm are simultaneously formed.
In the step 2, the plating treatment is applied to the fine linear silver-containing layer having a line width of 2.0 μm or less and the second fine linear silver-containing layer having a line width of more than 2.0 μm. The method for manufacturing a conductive member according to any one of claims 1 to 10.

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