JP2016192200A - Manufacturing method of conductive sheet, and touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a conductive sheet including conductive thin wires that are hardly visually recognized even after take-up work is performed, and a touch panel including the conductive sheet.SOLUTION: A manufacturing method of a conductive sheet includes: a silver halide-containing photosensitive layer forming step A (S102) of forming a silver halide-containing photosensitive layer by bringing silver halide, gelatin, and a composition for forming a silver halide-containing photosensitive layer, the composition including a polymer different from gelatin, into contact with both faces of a long support; an exposure step B (S104) of exposing the silver halide-containing photosensitive layer; a developing step C (S106) of performing developing processing to form conductive thin wires containing metal silver in order to obtain a support with conductive thin wires; and a gelatin removing step D (S110) of removing gelatin in the support with conductive thin wires while conveying the support with conductive thin wires to obtain a conductive sheet, and taking up the conductive sheet in a roll state. In the gelatin removing step D, the take-up surface pressure during take-up of the conductive sheet is 0.3 MPa or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for manufacturing a conductive sheet and a touch panel.

A conductive sheet having conductive thin wires formed on a support is composed of electrodes for various electronic devices such as solar cells, inorganic EL (electroluminescence) elements, organic EL elements, electromagnetic wave shields for various display devices, touch panels, and transparent sheet heat generation. Widely used on the body. In particular, in recent years, the rate of mounting touch panels on mobile phones, portable game devices, and the like has increased, and the demand for conductive sheets used as touch panel sensors is rapidly expanding.
As such a conductive sheet, for example, Patent Document 1 discloses a conductive sheet having a conductive thin wire containing silver and formed using a silver halide-containing photosensitive layer. In Patent Document 1, when a conductive sheet is obtained, a step of decomposing and removing gelatin using a proteolytic enzyme that decomposes gelatin is performed.

JP 2014-209332 A

On the other hand, in view of industrial productivity, it is preferable that the conductive sheet can be manufactured by so-called roll-to-roll.
The present inventors performed the operation of winding a conductive sheet, which has been treated with a proteolytic enzyme, described in Patent Document 1 into a roll shape, and after winding the conductive sheet into a roll shape, As a result of unwinding the conductive sheet wound up and evaluating its characteristics, it was found that the conductive thin wire may be easily visible as compared to before performing the winding process. In particular, when a mesh pattern made of conductive thin wires is produced in order to apply the conductive thin wires to the detection electrodes (sensor electrodes) of the touch panel, the above-described winding operation increases the reflectance of extraneous light peculiar to metals. The mesh pattern increased and it became easier to see.

In view of the above circumstances, an object of the present invention is to provide a method for manufacturing a conductive sheet in which a conductive thin wire is difficult to visually recognize even after a winding operation is performed.
Moreover, this invention makes it a subject to also provide the touchscreen containing the electrically conductive sheet obtained from the said manufacturing method.

As a result of intensive studies on the above problems, the present inventors have found that a desired effect can be obtained by controlling the winding surface pressure during winding of the conductive sheet.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) A silver halide, gelatin, and a polymer different from gelatin are included on both sides of a long support, and the mass ratio R1 of the mass Y1 of the polymer to the mass X1 of gelatin is 0.1 or more. Contacting a certain silver halide-containing photosensitive layer forming composition to form a silver halide-containing photosensitive layer; and
Step B for exposing the silver halide-containing photosensitive layer;
Step C of developing the photosensitive layer containing silver halide after exposure to form a conductive thin wire containing metallic silver to obtain a support with a conductive thin wire;
A process D for removing the gelatin in the support with conductive fine wires while obtaining the conductive fine wire while transporting the support with conductive fine wires, and winding the conductive sheet into a roll;
The process for producing a conductive sheet, wherein in step D, the winding surface pressure during winding of the conductive sheet is 0.3 MPa or less. In addition, mass ratio R1 represents mass Y1 / mass X1.
(2) The method for producing a conductive sheet according to (1), wherein the winding surface pressure in step D is less than 0.2 MPa.
(3) Step D is a step of winding the conductive sheet into a roll around a core with a coating layer,
The production of the conductive sheet according to (1) or (2), wherein the core with a coating layer has a core and a coating layer having a 25% compressive stress of 275 KPa or less disposed on the outer peripheral surface of the core. Method.
(4) The process E which heat-processes a support body with an electroconductive fine wire, and winds a support body with an electroconductive thin wire in roll shape, conveying a support body with an electroconductive thin wire between the process C and the process D. Further comprising
In the process D, the method for producing a conductive sheet according to any one of (1) to (3), wherein a winding surface pressure at the time of winding the support with conductive thin wires is 0.3 MPa or less.
(5) The manufacturing method of the electrically conductive sheet as described in (4) whose winding surface pressure in the process E is 0.2 Mpa or less.
(6) Step E is a step of winding the support with a conductive fine wire in a roll shape around a core with a coating layer,
The production of the conductive sheet according to (4) or (5), wherein the core with a coating layer has a core and a coating layer having a 25% compressive stress of 275 KPa or less disposed on the outer peripheral surface of the core. Method.
(7) After Step D, Step F is used to unwind and convey the conductive sheet from a conductive sheet roll formed by winding the conductive sheet into a roll, heat-treat the conductive sheet, and wind the conductive sheet into a roll. In addition,
In the process F, the manufacturing method of the conductive sheet in any one of (1)-(6) whose winding surface pressure at the time of winding of a conductive sheet is 0.3 Mpa or less.
(8) The method for producing a conductive sheet according to (7), wherein the winding surface pressure in step F is 0.2 MPa or less.
(9) Step F is a step of winding the conductive sheet into a roll around a core with a coating layer,
The production of the conductive sheet according to (7) or (8), wherein the core with a coating layer has a core and a coating layer having a 25% compressive stress of 275 KPa or less disposed on the outer peripheral surface of the core. Method.
(10) After step D, the conductive sheet is unwound and conveyed from a conductive sheet roll formed by winding the conductive sheet into a roll, and subjected to a crosslinking treatment to crosslink the polymer contained in the conductive sheet. A process G that is wound into a shape;
The process for producing a conductive sheet according to any one of (1) to (9), wherein in step F, the winding surface pressure during winding of the conductive sheet is 0.3 MPa or less.
(11) The method for producing a conductive sheet according to (10), wherein the winding surface pressure in step G is 0.2 MPa or less.
(12) Step G is a step of winding the conductive sheet into a roll around a core with a coating layer,
Production of conductive sheet according to (10) or (11), wherein the core with a coating layer has a core and a coating layer having a 25% compressive stress of 275 KPa or less disposed on the outer peripheral surface of the core. Method.
(13) The process for producing a conductive sheet according to any one of (1) to (12), wherein in step D, the conductive thin wire is subjected to a smoothing treatment before being wound into a roll.
(14) A touch panel including a conductive sheet manufactured by the method for manufacturing a conductive sheet according to any one of (1) to (13).

According to the present invention, it is possible to provide a method for manufacturing a conductive sheet in which the conductive thin wire is difficult to visually recognize even after the winding operation is performed.
Moreover, according to this invention, the touch panel containing the electrically conductive sheet obtained from the said manufacturing method can also be provided.

It is a flowchart which shows the manufacturing process of the suitable aspect of the manufacturing method of the electrically conductive sheet of this invention. It is a schematic diagram showing a flow of a preferred embodiment of step A. It is a schematic diagram which shows the flow of the suitable aspect of the process B. 2 is a schematic diagram showing a flow of a preferred embodiment of step D. FIG. It is a schematic diagram showing a flow of a preferred embodiment of step C. 2 is a schematic diagram showing a flow of a preferred embodiment of step F. FIG. 2 is a schematic diagram showing a flow of a preferred embodiment of process G. FIG. It is a top view which shows one embodiment of the mesh pattern formed with an electroconductive thin wire. It is the schematic explaining the aspect of the calendar process implemented in the Example.

Below, the suitable aspect of the manufacturing method of the electroconductive sheet of this invention is demonstrated.
First, as a feature of the present invention, when gelatin is removed from a support with a conductive fine wire, when the obtained conductive sheet is wound, the surface pressure during winding is not more than a predetermined value (0.3 MPa or less). ) Is adjusted.
As described above, the present inventors wound up the conductive sheet in a roll shape, and then unwound the conductive sheet wound up in a roll shape and evaluated its characteristics. In comparison, it was found that the conductive thin wires are easily visible. When the above-mentioned cause was examined, when winding a conductive sheet in which conductive thin wires are arranged on both sides in a roll shape, the conductive thin wires arranged on one surface in the roll state and on the other surface The surface of the conductive thin wire comes into contact with the winding when it is wound, and the surfaces of both surfaces are pressed by the winding surface pressure to flatten the surface of the conductive thin wire. The thin line was easy to see. In particular, after the gelatin is removed from the conductive thin wire, the mechanical strength of the conductive thin wire itself is lowered, so that the above problem is likely to occur remarkably.
In the present invention, when the conductive sheet is wound into a roll based on the above cause, the conductive thin wires are brought into contact with each other in the roll of the conductive sheet by adjusting the winding surface pressure to be a predetermined value or less. However, both surfaces are prevented from being flattened.

FIG. 1 is a flowchart showing manufacturing steps in the first embodiment of the method for manufacturing a conductive sheet of the present invention.
As shown in FIG. 1, the method for producing a conductive sheet includes a step A (silver halide-containing photosensitive layer forming step A) (S102) for forming a predetermined silver halide-containing photosensitive layer on a support. Step B (exposure step B) (S104) for exposing the silver-containing photosensitive layer, Step C (development step C) (S106) for exposing the silver halide-containing photosensitive layer, Step E (first heating) Step E) (S108), gelatin removal step D (gelatin removal step D) (S110), heat treatment step F (second heating step F) (S112), and polymer crosslinking treatment The process G to perform (crosslinking process G) (S114) is provided.
In addition, in the said 1st embodiment, although the 1st heating process E, the 2nd heating process F, and the bridge | crosslinking process G are included, these are arbitrary processes and do not need to implement. That is, the method for producing a conductive sheet of the present invention only needs to include a silver halide-containing photosensitive layer forming step A, an exposure step B, a developing step C, and a gelatin removing step D.
Further, in the subsequent stage, a mode in which processing is performed in a roll-to-roll mode (RtoR mode) in each of the processes A, B, C, and D is described. You may implement from A to the process D by RtoR system with one conveyance line. Moreover, you may implement combining each process, for example, the process A-the process C may be implemented by the RtoR system by one conveyance line, and the process D may be implemented by the RtoR system by another conveyance line. Good. Furthermore, the process A may be performed by the RtoR method, and the process B to the process D may be performed by the RtoR method with one transport line.
Below, the material used in each process and its procedure are explained in full detail.

<Step A (silver halide-containing photosensitive layer forming step A)>
Step A is a silver halide-containing photosensitive layer (hereinafter referred to simply as “polymer”) containing silver halide, gelatin and a polymer different from gelatin on both sides of a long support. In this process, a silver halide-containing photosensitive layer is formed by applying a forming composition. The mass ratio R1 of the polymer mass Y1 to the gelatin mass X1 is 0.1 or more. By carrying out this step, a silver halide (for example, silver bromide grain, silver chlorobromide grain or silver iodobromide grain), gelatin and gelatin are different polymers on both sides of the long support. A photosensitive layer containing is formed.
First, the materials and members used in this step A will be described in detail, and then the procedure of step A will be described in detail.

(Support)
The type of support is not particularly limited as long as it can support conductive thin wires described later and is long, and is preferably a transparent support, and particularly preferably a plastic film.
The long support is a support extending in the longitudinal direction. Specifically, the support having a length in the longitudinal direction of 10 m or more is intended, and 500 m or more is preferable from the viewpoint of productivity. The length in the longitudinal direction is not particularly limited, and is often 5000 m or less.
The width of the support is not particularly limited, but is often 150 to 1000 mm, and preferably 300 to 500 mm.
Although the thickness in particular of a support body is not restrict | limited, Usually, it can arbitrarily select in 25-500 micrometers from the point of application to uses, such as a touch panel and an electromagnetic wave shield. In addition, in addition to the function of the support of the transparent conductive film, it can be designed with a thickness exceeding 500 μm when it also functions as a touch surface.

  Specific examples of the material constituting the support include polyethylene terephthalate (PET) (258 ° C.), polycycloolefin (134 ° C.), polycarbonate (250 ° C.), acrylic film (128 ° C.), polyethylene naphthalate (PEN) ( 269 ° C), polyethylene (PE) (135 ° C), polypropylene (PP) (163 ° C), polystyrene (230 ° C), polyvinyl chloride (180 ° C), polyvinylidene chloride (212 ° C) and triacetylcellulose (TAC) A plastic film having a melting point of about 290 ° C. or less such as (290 ° C.) is preferable, and PET, polycycloolefin, and polycarbonate are particularly preferable. Figures in parentheses are melting points. The total light transmittance of the support is preferably 85% to 100%.

One preferred embodiment of the support includes a treated support that has been subjected to at least one surface treatment selected from the group consisting of atmospheric pressure plasma treatment, corona discharge treatment, and ultraviolet irradiation treatment. By performing the above treatment, a hydrophilic group such as an OH group is introduced on the treated support surface, and the adhesion of the conductive thin wire described later is further improved.
Among the above treatments, atmospheric pressure plasma treatment is preferable in that the adhesion of the conductive fine wire is further improved.

As another preferred embodiment of the support, it is preferable to have an undercoat layer containing a polymer different from gelatin described later on the surface thereof. By forming the photosensitive layer on the undercoat layer, the adhesion of the conductive thin wire described later 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 is applied on a support and subjected to heat treatment as necessary. The undercoat layer forming composition may contain a solvent, if necessary. The kind in particular of solvent is not restrict | limited, The solvent used by the composition for silver halide containing photosensitive layer formation mentioned later is illustrated. Further, latex containing polymer fine particles may be used as the composition for forming an undercoat layer containing polymer.
The thickness of the undercoat layer is not particularly limited, but is preferably 0.02 to 0.3 μm, more preferably 0.03 to 0.2 μm, from the viewpoint that the adhesiveness of the conductive fine wire is more excellent.

(Silver halide)
The halogen element contained in the silver halide may be any of chlorine, bromine, iodine and fluorine, or a combination thereof. For example, silver halide mainly composed of silver chloride, silver bromide and silver iodide is preferably used, and silver halide mainly composed of silver bromide and silver chloride is preferably used. Silver chlorobromide, silver iodochlorobromide and silver iodobromide are also preferably used. More preferred are silver chlorobromide, silver bromide, silver iodochlorobromide and silver iodobromide, and most preferred are silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride. Used.
Here, “silver halide mainly composed of silver bromide” refers to silver halide in which the molar fraction of bromide ions in the silver halide composition is 50% or more. The silver halide grains mainly composed of silver bromide may contain iodide ions and chloride ions in addition to bromide ions.

Silver halide is in the form of solid grains, and from the viewpoint of the patternability of the conductive fine wires formed after exposure and development processing, the average grain size of silver halide is 0.1 to 1000 nm (1 μm) in terms of sphere equivalent diameter. It is preferable that it is 0.1-100 nm, It is more preferable that it is 1-50 nm.
The sphere equivalent diameter of silver halide grains is the diameter of spherical grains having the same volume.

The shape of the silver halide grains is not particularly limited. For example, various shapes such as a spherical shape, a cubic shape, a flat plate shape (hexagonal flat plate shape, triangular flat plate shape, tetragonal flat plate shape, etc.), octahedral shape, and tetradecahedral shape are available. Can be mentioned.
Further, regarding the use of metal compounds belonging to Groups 8 and 9, such as rhodium compounds and iridium compounds, and palladium compounds, which are used for stabilizing and enhancing the sensitivity of silver halide, paragraphs 0039 to JP-A-2009-188360. Reference can be made to the description in paragraph 0042. Furthermore, regarding chemical sensitization, reference can be made to the technical description in paragraph 0043 of JP-A-2009-188360.

(gelatin)
The type of gelatin is not particularly limited. For example, in addition to lime-processed gelatin, acid-processed gelatin may be used. Gelatin hydrolyzate, gelatin enzyme-decomposed product, gelatin modified with amino groups and carboxyl groups (phthalated) Gelatin or acetylated gelatin) can also be used.

(High molecular)
The type of polymer used is not particularly limited as long as it is different from gelatin, but a polymer that is not decomposed by an oxidizing agent that decomposes gelatin described later is preferable. Examples of the polymer include hydrophobic polymers (hydrophobic resins), and more specifically, acrylic resins, styrene resins, vinyl resins, polyolefin resins, polyester resins, polyurethane resins. , Polyamide-based resin, polycarbonate-based resin, polydiene-based resin, epoxy-based resin, silicone-based resin, cellulose-based polymer, and chitosan-based polymer, or at least one of these resins And a copolymer made of the monomer to be used.
The polymer preferably contains a reactive group that reacts with a cross-linking agent described later.
Furthermore, another preferred embodiment of the polymer includes a polymer (copolymer) represented by the following general formula (1) from the viewpoint that water can be further prevented from entering.
General formula (1):-(A) x- (B) y- (C) z- (D) w-
In general formula (1), A, B, C, and D each represent the following repeating unit.

R ¹ represents a methyl group or a halogen atom, preferably a methyl group, a chlorine atom, or a bromine atom. p represents an integer of 0 to 2, 0 or 1 is preferable, and 0 is more preferable.

R ² represents a methyl group or an ethyl group, preferably a methyl group.
R ³ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. L represents a divalent linking group, preferably a group represented by the following general formula (2).
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 each may have a substituent (for example, a halogen atom, a nitro group, a hydroxyl group, etc.). R ³⁰ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, n-butyl group, n-octyl group, etc.), acyl group (for example, acetyl group, benzoyl group, etc.) It is. Particularly preferred as X ¹ is an oxygen atom or —NH—.
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—, —OCO—, —CO—, —COO—. , —NH—, —SO ₂ —, —N (R ³¹ ) —, —N (R ³¹ ) SO ₂ — and the like may be inserted in the middle. Here, R ³¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, and an isopropyl group. Preferred examples of X ² include dimethylene group, trimethylene group, tetramethylene group, o-phenylene group, m-phenylene group, p-phenylene group, —CH ₂ CH ₂ OCOCH ₂ CH ₂ —, —CH ₂ CH ₂ OCO. (C ₆ H ₄₎ - and the like.
r represents 0 or 1;
q represents 0 or 1, and 0 is preferable.

R ⁴ represents an alkyl group having 5 to 80 carbon atoms, an alkenyl group, or an alkynyl group, preferably an alkyl group having 5 to 50 carbon atoms, more preferably an alkyl group having 5 to 30 carbon atoms, Preferably it is a C5-C20 alkyl group.
R ⁵ is a hydrogen atom, a methyl group, an ethyl group, a halogen atom, or a -CH ₂ COOR ^6, a hydrogen atom, a methyl group, a halogen atom, -CH ₂ COOR ⁶ are preferred, hydrogen atom, a methyl group, -CH ₂ COOR ⁶ is more preferred, and a hydrogen atom is still more preferred.
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 general formula (1), x, y, z, and w represent the molar ratio of each repeating unit.
As x, it is 3-60 mol%, Preferably it is 3-50 mol%, More preferably, it is 3-40 mol%.
y is 30 to 96 mol%, preferably 35 to 95 mol%, more preferably 40 to 90 mol%.
Moreover, as z, it is 0.5-25 mol%, Preferably it is 0.5-20 mol%, More preferably, it is 1-20 mol%.
As w, it is 0.5-40 mol%, Preferably it is 0.5-30 mol%.
In the general formula (1), it is particularly preferable that x is 3 to 40 mol%, y is 40 to 90 mol%, z is 0.5 to 20 mol%, and w is 0.5 to 10 mol%.

  The polymer represented by the general formula (1) is preferably a polymer represented by the following general formula (2).

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

The polymer represented by the general formula (1) may include other repeating units other than the general formulas (A), (B), (C) and (D). Examples of monomers 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. , Acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocycles, glycidyl esters, unsaturated nitriles, and the like. These monomers are also described in [0010] to [0022] of Japanese Patent No. 3754745.
From the viewpoint of hydrophobicity, acrylic acid esters and methacrylic acid esters are preferable, and hydroxyalkyl methacrylates such as hydroxyethyl methacrylate or hydroxyalkyl acrylates are more preferable. The polymer represented by the general formula (1) preferably contains a repeating unit represented by the following general formula (E) in addition to the above general formulas (A), (B), (C) and (D).

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), a 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 The same as the preferable range of w.
e1 is 1 to 10 mol%, preferably 2 to 9 mol%, more preferably 2 to 8 mol%.

  1000-1 million are preferable, as for the weight average molecular weight of the polymer represented by General formula (1), 2000-750,000 are more preferable, and 3000-500,000 are more preferable.

  The polymer represented by the general formula (1) can be synthesized with reference to, for example, Japanese Patent No. 3305459 and Japanese Patent No. 3754745.

(Other)
The silver halide-containing photosensitive layer forming composition may contain other materials than the above-described materials as necessary. Examples thereof include metal compounds belonging to Groups 8 and 9, such as rhodium compounds and iridium compounds used for stabilizing silver halide and increasing sensitivity. Alternatively, as described in paragraphs [0220] to [0241] of JP2009-004348A, an antistatic agent, a nucleation accelerator, a spectral sensitizing dye, a surfactant, an antifoggant, and a hardener. , Black spot prevention agents, redox compounds, monomethine compounds, dihydroxybenzenes and the like. Furthermore, physical development nuclei may be included.

  Especially, it is preferable that the crosslinking agent used in order to bridge | crosslink the said polymers is contained in the composition for silver halide containing photosensitive layer forming. By including the cross-linking agent, cross-linking between the polymers proceeds, and even when gelatin is decomposed and removed in Step C, which will be described later, the connection between the metallic silver in the conductive fine wires is maintained, and as a result An excellent conductive fine wire is obtained due to the characteristics.

The silver halide-containing composition for forming a photosensitive layer contains a solvent, if necessary.
Examples of the solvent used include water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, sulfoxides such as dimethyl sulfoxide, esters such as ethyl acetate, ethers, and the like. Etc.), ionic liquids, or mixed solvents thereof.
The content of the solvent used is not particularly limited, but is preferably in the range of 30 to 90% by mass and more preferably in the range of 50 to 80% by mass with respect to the total mass of the composition.

  In the composition for forming a photosensitive layer containing silver halide, the mass ratio R1 (Y1 / X1) of the mass X1 of gelatin and the mass Y1 of the polymer is 0.1 or more. Especially, 0.2 or more are preferable and 0.5 or more are more preferable at the point which ion migration suppression ability is more excellent. The upper limit is not particularly limited, but is usually 2.0 or less in many cases.

(Procedure of step A)
In Step A, the method for bringing the silver halide-containing photosensitive layer-forming composition containing the above components into contact with both surfaces of the support is not particularly limited, and a known method can be adopted. For example, the method of apply | coating the composition for silver halide containing photosensitive layer formation on a support body, the method of immersing a support body in the composition for silver halide content photosensitive layer formation, etc. are mentioned.
In addition, after the said process, you may implement a drying process as needed.

The content of the silver halide in the formed silver halide-containing photosensitive layer is not particularly limited, but is 3.0 to 20.0 g / m ^{2 in} terms of silver in that the conductive properties of the conductive fine wire are more excellent. Preferably, 5.0 to 15.0 g / m ² is more preferable.
Further, the content of the polymer in the silver halide-containing photosensitive layer is not particularly limited, but is preferably 0.04 to 2.0 g / m ^{2 in} terms of more excellent adhesion of the conductive fine wire, 0.8 -0.4 g / m < ² > is more preferable, and 0.1-0.4 g / m < ² > is further more preferable.

In addition, before the said process A, you may further have the process of forming the silver halide non-containing layer containing gelatin and the polymer different from gelatin on a support body. In addition, regarding the procedure of this process, the procedure of Paragraphs 0068-0070 of Unexamined-Japanese-Patent No. 2014-112512 can be referred.
Further, after the step A and before the step B described later, a step of forming a protective layer containing gelatin and a polymer different from gelatin on the silver halide-containing photosensitive layer may be further included. . In addition, regarding the procedure of this process, the procedure of Paragraphs 0071-0072 of Unexamined-Japanese-Patent No. 2014-112512 can be referred.

(Preferred embodiment of step A)
In the process A, it is preferable to implement by what is called a roll-to-roll system from the point of productivity. That is, the process A includes the above components on both sides of the support while unwinding (sending out) the support from the support roll formed by winding the long support in a roll shape and transporting it in the longitudinal direction. A silver halide-containing photosensitive layer is formed by contacting a composition for forming a silver halide-containing photosensitive layer, and then a support having a silver halide-containing photosensitive layer (hereinafter also referred to as a support with a photosensitive layer). ) Is preferably wound into a roll.
FIG. 2 is a schematic diagram showing the flow of a preferred embodiment of step A. As shown in FIG. 2, first, a support roll 10 formed by winding a long support in a roll shape is mounted on the feed roller 12A, and the long support S1 is unwound from the support roll 10. The long support S1 is continuously conveyed in the longitudinal direction (the direction of the arrow in FIG. 2). The long support S1 is conveyed to the coating device 14, and the silver halide-containing photosensitive layer forming composition is continuously applied to both sides of the long support S1, and the silver halide-containing photosensitive material is applied. A conductive layer is formed. Thereafter, the support having the silver halide-containing photosensitive layer that has passed through the coating device 14 is again wound into a roll by the winding roller 16A. In FIG. 2, a winding core (winding core portion) (not shown) is mounted on the winding roller 16A, and a support having a silver halide-containing photosensitive layer is wound around the winding core (winding core portion). . As the core, a core with a coating layer, which will be described in detail later, may be used.
The feed roller 12A and the take-up roller 16A are rotated counterclockwise in the drawing by a drive source (for example, a motor) (not shown).
The coating device 14 is not particularly limited as long as it is a device that can apply the above-described silver halide-containing photosensitive layer forming composition to a support. For example, a bar coating device, a roll coating device, a gravure coating, and the like. Examples thereof include devices.
If necessary, a drying device for performing a drying treatment on a support having a silver halide-containing photosensitive layer is installed on the downstream side in the transport direction of the coating device 14, and a composition for forming a silver halide-containing photosensitive layer is provided. After applying to the support, a drying treatment may be performed.

<Process B (Exposure Process B)>
Step B is a step of exposing the silver halide-containing photosensitive layer. By carrying out this step, the silver halide forms a latent image in the exposed portion. In addition, you may implement exposure in a pattern form, for example, in order to obtain the mesh pattern which consists of a conductive fine wire mentioned later, the exposure method is mentioned through the mask which has a mesh-shaped opening pattern.
Below, the exposure process implemented at this process is explained in full detail.

(Exposure processing)
The exposure process is a process for exposing the photosensitive layer. By subjecting the photosensitive layer to pattern exposure, the silver halide in the photosensitive layer in the exposed region forms a latent image. In the region where the latent image is formed, a conductive portion is formed by development processing described later.
The light source used in the exposure is not particularly limited, and examples thereof include light such as visible light and ultraviolet light, and radiation such as X-rays.
The method for performing pattern exposure is not particularly limited. For example, surface exposure using a photomask may be performed, or scanning exposure using a laser beam may be performed. The shape of the pattern is not particularly limited, and is appropriately adjusted according to the pattern of the conductive fine wire to be formed.

(Preferred embodiment of step B)
In the process B, it is preferable to implement by what is called a roll-to-roll system from the point of productivity. That is, in the step B, the support with the photosensitive layer is unwound (sent out) from the support roll with the photosensitive layer formed by winding the support with the photosensitive layer into a roll, and supported in the longitudinal direction. After exposing the silver halide-containing photosensitive layers disposed on both sides of the body, a support having an exposed silver halide-containing photosensitive layer (hereinafter also referred to as an exposure-treated support) in a roll shape A winding step is preferred.
Hereinafter, FIG. 3 is a schematic diagram showing a flow of a preferred embodiment of step B. As shown in FIG. 3, first, a support roll 18 with a photosensitive layer obtained by winding a support roll with a photosensitive layer into a roll shape is mounted on the feed roller 12B, and the photosensitive roll is supported from the support roll 18 with the photosensitive layer. The support S2 with a layer is unwound, and the support S2 with a photosensitive layer is continuously conveyed in the longitudinal direction (the direction of the arrow in FIG. 3). The support S2 with the photosensitive layer is conveyed to the exposure device 20, and the exposure process is continuously performed on the photosensitive layer in the support S2 with the photosensitive layer. Thereafter, the exposure-treated support that has passed through the exposure apparatus 20 is wound up in a roll shape by the take-up roller 16B. In FIG. 3, a winding core (winding core portion) (not shown) is attached to the winding roller 16 </ b> B, and an exposed support is wound around the winding core (winding core portion).

The feed roller 12B and the take-up roller 16B are rotated counterclockwise in the drawing by a driving source (for example, a motor) (not shown).
Moreover, the exposure apparatus 20 is an apparatus which exposes the photosensitive layer mentioned above, and a well-known exposure apparatus is used.

The winding surface pressure when the exposed support is wound into a roll is not particularly limited, but the conductive thin wire is more difficult to visually recognize (hereinafter also referred to simply as “the point where the effect of the present invention is more excellent”). Is preferably 0.3 MPa or less, more preferably 0.25 MPa or less, further preferably 0.2 MPa or less, particularly preferably 0.15 MPa or less, and most preferably 1.0 MPa or less. Although a minimum in particular is not restrict | limited, 0.01 Mpa or more is preferable and 0.03 Mpa or more is more preferable at the point which a winding gap | deviation does not produce easily.
In addition, a winding surface pressure is a long board | substrate (In the process B, the support body by which exposure processing was carried out. In the process E mentioned later, a support body with an electroconductive thin wire. In the process D mentioned later, a conductive sheet. The process mentioned later. In F, when a conductive sheet is wound up in a roll shape, the contact pressure applied to the substrate disposed in an overlapping manner is intended. That is, it corresponds to the pressing force applied in the direction of pressing (compressing) the surfaces of the substrates gathered in a roll shape by the force (tension) for winding and squeezing the long substrate. In other words, it corresponds to the compressive stress in the roll radial direction. In the above case, when the exposed support is rolled up, it corresponds to the surface pressure (roll radial direction compressive stress) applied to the exposed support that is arranged to overlap.
For the measurement of the winding surface pressure as described above, a prescale (for ultra-low pressure (LLLW) or ultra-low pressure (LLW)) manufactured by FUJIFILM Corporation, which is a pressure measurement film (pressure sensor), is used. Specifically, the pressure measuring film (pressure sensor) (prescale manufactured by Fuji Film Co., Ltd.) is wound over the entire width direction of the core (core part), and then measured on the core (core part). The end surface in the length direction of the subject exposed support is fixed, and the exposed support (width: 500 mm) is wound over a winding length of 10 m or more (for example, 200 m) to obtain a roll sample. Is made. Immediately after making the roll sample, unwind the roll, visually observe the color of the prescale that has developed on the core (core portion), check the degree of coloring, and take-up surface pressure applied to the prescale ( (Roll diameter direction compressive stress) is converted. In addition, when the winding surface pressure is 0.5 MPa or more, a prescale (for ultra-low pressure (LLW)) is used.
In addition, also when using the core with a coating layer explained in full detail behind as a said core, a winding surface pressure can be measured by the same procedure.

  The method for controlling the winding surface pressure is not particularly limited, and examples thereof include a method for controlling the rotation direction and the rotation speed of the feeding roller and the winding roller. For example, there is a method of applying a back tension to the support body by urging the feed roller in a direction opposite to the direction of feeding the support body, adjusting the tension related to the support body, and adjusting the winding surface pressure.

In the step B, as described above, the exposure-treated support is usually wound around the core and wound. The winding core is usually cylindrical.
The material of the core is not particularly limited, and examples thereof include paper or plastic. The type of plastic is not particularly limited. For example, polyolefin resins such as polyethylene and polypropylene, vinyl chloride resins, polystyrene resins, ABS (acrylonitrile / butadiene / styrene copolymer) resins, polyamide resins, polyester resins, fibers Examples include reinforced plastic.

  In step B, when winding the exposed support, a core with a coating layer (core core with a coating layer) may be used. The core with a coating layer has a core and a coating layer disposed on the outer circumferential surface of the core so as to cover the outer circumferential surface, and the coating layer has an elasticity whose 25% compressive stress is a predetermined value or less. Is a layer. By disposing such a coating layer on the winding core, it is possible to relieve the stress received by the exposed support during winding. Normally, when the exposure-treated support is wound using a winding core, a step is likely to occur between the winding start end of the exposure-treated support and the portion that is wound thereon. When the core with a covering layer is used, the step is easily eliminated, and as a result, it is possible to make the conductive thin wire more difficult to visually recognize in the initial portion of the conductive sheet that is finally obtained.

  The coating layer preferably has a compressive stress at 25% strain (hereinafter referred to as “25% compressive stress”) of 275 kPa or less as measured according to JIS K6767: 1999, in that the effect of the present invention is more excellent. . If it is in the said range, even if a tension | tensile_strength will be applied at the time of winding up an electrically conductive sheet etc., a coating layer will fully be distorted and buffer property will be acquired and the effect of this invention will be more excellent. The lower limit of the 25% compressive stress is not particularly limited, and is preferably 30 kPa or more from the viewpoint that uniform and stable winding can be performed.

The material of the coating layer is not particularly limited, and examples thereof include a synthetic rubber sheet or a resin foam sheet.
The type of the synthetic rubber sheet is not particularly limited, and examples thereof include styrene butadiene rubber, acrylonitrile butadiene rubber (NBR), chloroprene rubber, butyl rubber, ethylene propylene rubber, silicone rubber, fluorine rubber, and urethane rubber.
The type of the resin foam sheet is not particularly limited. For example, polyethylene foam, polystyrene foam, polyethylene foam, polypropylene foam, polyvinyl chloride foam, viscose sponge, rubber foam, EVA foam, ABS foam, nylon foam, acrylic resin foam, Examples include polyurethane foam, felt foam, urea resin foam, silicon resin foam, and epoxy resin foam.

  The method for forming the coating layer is not particularly limited, and examples thereof include a method in which a synthetic rubber sheet or a resin foam sheet is wound around the surface of a cylindrical core in a spiral shape and bonded and fixed.

<Process C (Development Process C)>
Step C is a step of developing the exposed silver halide-containing photosensitive layer obtained in Step B to form a conductive fine wire containing metallic silver to obtain a support with a conductive fine wire. By carrying out this step, conductive thin lines are formed in the exposed region (region where the latent image is formed). On the other hand, in the unexposed areas where the exposure has not been performed, the silver halide dissolves and flows out of the photosensitive layer during the development process, and a transparent film (non-conductive part) is obtained.
Below, the development process implemented at this process is explained in full detail.

(Development processing)
The development processing method is not particularly limited. For example, a normal development processing technique used for silver salt photographic film, photographic paper, printing plate making film, photomask emulsion mask, and the like can be used.
The type of developer used in the development process is not particularly limited. For example, PQ (phenidone hydroquinone) developer, MQ (Metol hydroquinone) developer, MAA (methol / ascorbic acid) developer may be used. it can.
The development process can include a fixing process performed for the purpose of removing and stabilizing the silver salt in the unexposed part. For the fixing process, a technique of a fixing process used for a silver salt photographic film, a photographic paper, a printing plate-making film, a photomask emulsion mask, or the like can be used.
The fixing temperature in the fixing step is preferably about 20 ° C. to about 50 ° C., and more preferably 25 to 45 ° C. The fixing time is preferably 5 seconds to 1 minute, and more preferably 7 seconds to 50 seconds.

  The photosensitive layer that has been subjected to development and fixing treatment is preferably subjected to water washing treatment or stabilization treatment.

(Preferred embodiment of step C)
In the process C, it is preferable to implement by what is called a roll-to-roll system from the point of productivity. In other words, in step C, the exposed support is unwound from an exposed support roll formed by winding the exposed support in a roll shape, and is transported in the longitudinal direction. The silver halide-containing photosensitive layer disposed on the substrate is developed to form a conductive thin wire containing metallic silver, and then again a support having conductive thin wires (hereinafter also referred to as a support with conductive thin wires). ) Is preferably wound into a roll.
FIG. 4 is a schematic diagram showing the flow of a preferred embodiment of step B. As shown in FIG. 4, first, an exposure-treated support roll 22 formed by winding an exposure-treated support in a roll shape is attached to the feed roller 12C, and the exposure-treated support body is then removed from the exposure-treated support roll 22. S3 is unwound and the exposed support S3 is continuously conveyed in the longitudinal direction (the direction of the arrow in FIG. 4). The exposed support S3 is conveyed to the developing device 24, and the exposure process is continuously performed on the photosensitive layer in the exposed support S3. Thereafter, the support having conductive thin wires that have passed through the developing device 24 is wound up in a roll shape by the winding roller 16C. In FIG. 4, a winding core (winding core portion) (not shown) is mounted on the winding roller 16C, and a support with conductive thin wires is wound around the winding core (winding core portion).
As shown in FIG. 4, a support 104 with conductive thin wires is obtained in which conductive thin wires 102 having a predetermined pattern are arranged on both surfaces of the support 100 that has passed through the developing device 24.
As the winding core (winding core portion), the above-described winding core with a coating layer may be used, and the coating layer can be made more difficult to visually recognize the conductive fine wire at the initial part of the winding of the conductive sheet. It is preferable to use an attached core.

The feed roller 12C and the take-up roller 16C are rotated counterclockwise in the drawing by a driving source (for example, a motor) (not shown).
The developing device 24 is a device that performs development processing, and a known developing device is used.
If necessary, a drying device for drying the support with conductive fine wires may be installed on the downstream side in the transport direction of the developing device 24, and the support with conductive fine wires may be dried after the development processing. .

The winding surface pressure at the time of winding the support with conductive fine wires in a roll shape is not particularly limited, but is preferably 0.3 MPa or less, more preferably 0.25 MPa or less, in terms of more excellent effects of the present invention. 0.2 MPa or less is more preferable, 0.15 MPa or less is particularly preferable, and 1.0 MPa or less is most preferable. Although a minimum in particular is not restrict | limited, 0.01 Mpa or more is preferable and 0.03 Mpa or more is more preferable at the point which a winding gap | deviation does not produce easily.
The definition, measurement method, and control method of the winding surface pressure are as described above (preferred embodiment of step B), and a support substrate with conductive thin wires is used as a measurement target.

<Process E (first heating process E)>
Step E is a step of performing heat treatment on the support with conductive thin wires obtained in Step C. By carrying out this step, polymers different from gelatin in the conductive fine wires are fused together to form a stronger layer. More specifically, polymer particles different from gelatin are fused together to form a uniform film. When such a uniform film is formed, the film strength can be maintained even after the gelatin is removed, and an increase in haze value can be prevented.
As described above, this step is an arbitrary step.

  As the conditions for the heat treatment, optimum conditions are appropriately selected according to the type of polymer different from the gelatin to be used, but a heating condition higher than the glass transition point of the polymer different from gelatin is preferable.

As one of the heat treatment methods, there is a treatment (hereinafter, also referred to as “superheated steam treatment”) in which a support with conductive thin wires is brought into contact with superheated steam. The superheated steam may be superheated steam, or may be a mixture of superheated steam with another gas.
It is preferable that the superheated steam is brought into contact with the conductive thin wire within a supply time of 10 seconds to 70 seconds. When the supply time is 10 seconds or more, the effect of improving the conductivity is great. In addition, since the improvement in conductivity becomes saturated from around 70 seconds, setting a time longer than 70 seconds is not preferable from the viewpoint of economy.
Also, superheated steam may be the amount of feed is contacted in the electroconductive thin line in the range of ^{500g / m 3 ~600g / m 3} , the temperature of the superheated steam is 100 to 160 ° C. at one atmosphere (preferably 100 to 120 ° C) is preferably controlled.

  As another method of heat treatment, it is 100 to 200 ° C. (preferably 100 to 150 ° C., more preferably 110 to 130 ° C.) for 1 to 240 minutes (preferably 60 to 150 minutes, more preferably 90 to 120 minutes). The method of performing heat processing is mentioned.

(Preferred embodiment of step E)
In the process E, it is preferable to implement by what is called a roll-to-roll system from the point of productivity. That is, in the process E, the conductive thin wire support is unwound from a support roll with conductive thin wire formed by winding the support with conductive thin wire in a roll shape, and the conductive wire is conveyed in the longitudinal direction. It is preferable that it is a process which heat-processes to a support body with a conductive fine wire, and winds up a support body with a conductive thin wire in roll shape after that.
Hereinafter, FIG. 5 is a schematic diagram showing a flow of a preferred embodiment of step E. As shown in FIG. 5, first, a support roll 26 with a conductive thin wire formed by winding a support with a conductive fine wire in a roll shape is attached to the feed roller 12D, and the conductive roll 26 is electrically conductive from the support roll 26 with a conductive thin wire. The support S4 with fine wires is unwound, and the support S4 with conductive fine wires is continuously conveyed in the longitudinal direction (the direction of the arrow in FIG. 5). The support S4 with conductive fine wires is conveyed to the heating device 28, and the support S4 with conductive fine wires is continuously subjected to heat treatment. After that, the support with conductive thin wires that has passed through the heating device 28 is wound up again in a roll shape by the winding roller 16D. In FIG. 5, a winding core (winding core portion) (not shown) is attached to the winding roller 16 </ b> D, and a support with conductive thin wires is wound around the winding core (winding core portion).
As the winding core (winding core portion), the above-described winding core with a coating layer may be used, and the coating layer can be made more difficult to visually recognize the conductive fine wire at the initial part of the winding of the conductive sheet. It is preferable to use an attached core.
The feed roller 12D and the take-up roller 16D are rotated counterclockwise in the drawing by a drive source (for example, a motor) not shown.
The heating device 28 is a device that performs the above-described heating (for example, superheated steam treatment), and a known heating device is used.

The winding surface pressure when the support with conductive thin wire is again wound into a roll is not particularly limited, but is preferably 0.3 MPa or less, more preferably 0.25 MPa or less, in terms of more excellent effects of the present invention. 0.2 MPa or less is more preferable, 0.15 MPa or less is particularly preferable, and 1.0 MPa or less is most preferable. Although a minimum in particular is not restrict | limited, 0.01 Mpa or more is preferable and 0.03 Mpa or more is more preferable at the point which a winding gap | deviation does not produce easily.
The definition, measurement method, and control method of the winding surface pressure are as described in the above (preferred embodiment of step B), and the support with conductive thin wires subjected to the heat treatment is used as a measurement target. The

<Process D (gelatin removal process D)>
Step D is a step of removing the gelatin in the support with conductive fine wires to obtain a conductive sheet while winding the support with conductive fine wires, and winding the conductive sheet into a roll. By carrying out this step, gelatin is decomposed and removed from the support with conductive fine wires obtained in step E, and ion migration between the conductive fine wires is further suppressed.
Hereinafter, FIG. 6 is a schematic diagram showing a flow of a preferred embodiment of step D. As shown in FIG. 6, first, a support roll 30 with a conductive thin wire formed by winding a support with a conductive fine wire in a roll shape is attached to the feed roller 12E, and the conductive roll 30 is electrically conductive. The support S5 with fine wires is unwound, and the support S5 with conductive fine wires is continuously conveyed in the longitudinal direction (the direction of the arrow in FIG. 6). The support with conductive fine wires S5 is conveyed to the gelatin removing device 32, and the process of removing gelatin in the support with conductive fine wires is continuously performed. After that, the support with conductive thin wires (corresponding to a conductive sheet) that has been subjected to the process of removing gelatin that has passed through the gelatin removing device 32 is wound up in a roll shape by a winding roller 16E. In FIG. 6, a winding core (winding core portion) (not shown) is mounted on the winding roller 16E, and a conductive sheet is wound around the winding core (winding core portion).
As the winding core (winding core portion), the above-described winding core with a coating layer may be used, and the coating layer can be made more difficult to visually recognize the conductive fine wire at the initial part of the winding of the conductive sheet. It is preferable to use an attached core.
The feed roller 12E and the take-up roller 16E are rotated counterclockwise in the drawing by a drive source (for example, a motor) not shown.

The gelatin removing device 32 is a device that performs a process for removing gelatin from a support with conductive fine wires.
The method for removing gelatin is not particularly limited, and examples thereof include a method of decomposing and removing gelatin using a proteolytic enzyme (Method A) and a method of decomposing and removing gelatin using a predetermined oxidizing agent (Method B). It is done.

Examples of the proteolytic enzyme (hereinafter also referred to as an enzyme) used in Method A include the enzymes described in paragraph 0085 of JP-A No. 2014-209332.
In the case of carrying out method A, the gelatin removal apparatus is provided with a tank filled with the treatment liquid (enzyme liquid) containing the enzyme, and transported so as to immerse the support with conductive thin wires in this tank. preferable. In addition to this aspect, the gelatin removing apparatus may be an aspect in which the treatment liquid is applied to a support with conductive fine wires.
The enzyme content in the treatment liquid is not particularly specified, and the enzyme content is suitably about 0.05 to 20% by mass with respect to the total amount of the treatment liquid in terms of easy control of the degree of degradation and removal of gelatin. More preferably, it is 5-10 mass%.
The pH of the treatment liquid is selected by experiments so that the function of the enzyme can be obtained to the maximum. In general, it is preferably 5 to 7. Moreover, it is preferable that the temperature of a process liquid is also the temperature which the effect | action of an enzyme increases, specifically 25-45 degreeC.

Examples of the oxidizing agent used in Method B include the oxidizing agents described in paragraph 0065 of JP 2014-112512 A.
In the case of carrying out the method B, it is preferable that the gelatin removing apparatus is provided with a tank filled with the treatment liquid containing the oxidizing agent and transported so as to immerse the support with conductive fine wires in the tank.

The winding surface pressure when the conductive sheet is wound into a roll is 0.3 MPa or less, and is preferably less than 0.2 MPa, more preferably 0.15 MPa or less, and more preferably 1.0 MPa in that the effect of the present invention is more excellent. The following is more preferable. Although a minimum in particular is not restrict | limited, 0.01 Mpa or more is preferable and 0.03 Mpa or more is more preferable at the point which a winding gap | deviation does not produce easily.
The definition, measurement method, and control method of the winding surface pressure are as described in the above (preferred embodiment of step B), and the conductive sheet is used as a measurement target.

If necessary, a smoothing device for smoothing the conductive thin wires of the conductive sheet is installed on the downstream side of the gelatin removal device in the conveying direction so that the conductive sheet is smoothed (for example, a calendar). Treatment).
Examples of the smoothing method include the methods described in paragraphs 0077 to 0079 of JP2014-112512A.

<Process F (2nd heating process F)>
Step F is a step of performing heat treatment on the conductive sheet obtained in Step D. By carrying out this step, polymers different from gelatin in the conductive fine wires are fused together to form a stronger layer.
As described above, this step is an arbitrary step.

  Examples of the heat treatment method and conditions include the heat treatment methods and conditions described in the above-described step E (first heating step E).

(Preferred embodiment of step F)
In the process F, it is preferable to implement by what is called a roll-to-roll system from the point of productivity. That is, in the process F, the conductive sheet is unwound (sent out) from the conductive sheet roll formed by winding the conductive sheet into a roll shape and conveyed in the longitudinal direction, and then the conductive sheet is subjected to heat treatment. The step is preferably a step of winding the sheet again into a roll. When winding up, a winding core may be used. In addition, as a core (winding core part), you may use the core with a coating layer mentioned above, and the point which can make a conductive fine wire more difficult to visually recognize in the initial part of the winding start of a conductive sheet, It is preferable to use a core with a coating layer.
The suitable aspect of the said process F is the same as the suitable aspect of the process E mentioned above except the point which uses a conductive sheet instead of a support body with an electroconductive thin wire. In addition, the suitable conditions of the winding surface pressure in the process F are also the same as the process E.

<Process G (crosslinking process G)>
Process G unwinds (sends out) and transports the conductive sheet from a conductive sheet roll formed by winding the conductive sheet into a roll, and performs a crosslinking treatment to crosslink the polymer contained in the conductive sheet, and rolls the conductive sheet. It is the process of winding up into a shape.
In this embodiment, the process G is performed after the process F. However, when the process F is not performed, the process G may be performed after the process D.

Hereinafter, FIG. 7 is a schematic diagram showing a flow of a preferred embodiment of the process G. As shown in FIG. 7, first, a conductive sheet roll 34 formed by winding a conductive sheet into a roll shape is attached to the feed roller 12F, and the conductive sheet S6 is unwound from the conductive sheet roll 34, and the longitudinal direction (in FIG. The conductive sheet S6 is continuously conveyed in the direction of the arrow). The conductive sheet S6 is transported to the cross-linking processing device 36, and a cross-linking process for cross-linking the polymer contained in the conductive sheet S6 is continuously performed. Thereafter, the conductive sheet that has passed through the cross-linking device 36 is again wound into a roll by the winding roller 16F. In FIG. 7, a winding core (winding core portion) (not shown) is mounted on the winding roller 16F, and a conductive sheet is wound around the winding core (winding core portion).
As the winding core (winding core portion), the above-described winding core with a coating layer may be used, and the coating layer can be made more difficult to visually recognize the conductive fine wire at the initial part of the winding of the conductive sheet. It is preferable to use an attached core.
The feed roller 12F and the take-up roller 16F are rotated counterclockwise in the drawing by a drive source (for example, a motor) not shown.

The crosslinking treatment apparatus is an apparatus that performs a crosslinking treatment for crosslinking the polymer contained in the conductive sheet.
The method for crosslinking the polymer is not particularly limited, but a method using a crosslinking agent is preferred.
In the case of using a crosslinking agent, a mode in which a tank filled with a treatment liquid containing a crosslinking agent is provided in the crosslinking processing apparatus and the conductive sheet is conveyed so as to be immersed in this tank is preferably exemplified.
In addition, the kind in particular of crosslinking agent to be used is not restrict | limited, The optimal crosslinking agent is suitably selected according to the structure of the polymer used.
The contact time between the conductive sheet and the cross-linking agent is not particularly limited, and optimal conditions are appropriately selected depending on the type of the cross-linking agent used and the like, but usually 1 to 300 seconds is preferable.

The winding surface pressure when the conductive sheet is wound into a roll is not particularly limited, but is preferably 0.3 MPa or less, more preferably 0.25 MPa or less, and 0.2 MPa or less in that the effect of the present invention is more excellent. More preferred is 0.15 MPa or less, most preferred is 1.0 MPa or less. Although a minimum in particular is not restrict | limited, 0.01 Mpa or more is preferable and 0.03 Mpa or more is more preferable at the point which a winding gap | deviation does not produce easily.
The definition, measurement method, and control method of the winding surface pressure are as described in the above (preferred embodiment of step B), and the conductive sheet is used as a measurement target.

  In addition, as needed, the washing process apparatus which performs the washing process to a conductive sheet may be installed in the conveyance direction downstream side of a bridge | crosslinking processing apparatus, and a conductive sheet may be subjected to a washing process.

<Conductive sheet>
The conductive sheet obtained through the above steps has at least a support and conductive fine wires.
The line width of the conductive thin wire is not particularly limited, but is preferably 30 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, particularly preferably 9 μm or less, most preferably 7 μm or less, and preferably 0.5 μm or more. 0 μm or more is more preferable. If it is the said range, a low resistance electrode can be formed comparatively easily.
The thickness of the conductive thin wire is not particularly limited, but is preferably 0.001 μm to 0.2 mm, more preferably 30 μm or less, further preferably 20 μm or less, particularly preferably 0.01 to 9 μm, and most preferably 0.05 to 5 μm. . If it is the said range, it is a low resistance electrode and can form the electrode excellent in durability comparatively easily.

  The conductive thin line may form a predetermined pattern, for example, the pattern is not particularly limited, and is a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid, etc. Preferably, it is a geometric figure combining (positive) n-gons such as quadrangle, (positive) hexagon, (positive) octagon, circle, ellipse, star, etc., and is in the form of a mesh (mesh pattern) Is more preferable. As shown in FIG. 8, the mesh shape means a shape including a plurality of square-shaped openings (lattices) 106 formed by intersecting conductive thin wires 102.

The length Pa of one side of the opening 106 is not particularly limited, but is preferably 1500 μm or less, more preferably 1300 μm or less, further preferably 1000 μm or less, preferably 5 μm or more, more preferably 30 μm or more, and further preferably 80 μm or more. preferable. When the length of the side of the opening is in the above range, it is possible to keep the transparency even better, and when the conductive sheet is attached to the front surface of the display device, the display can be visually recognized without a sense of incongruity. it can.
From the viewpoint of visible light transmittance, the aperture ratio of the mesh pattern formed from the conductive thin wires is preferably 85% or more, more preferably 90% or more, and most preferably 95% or more. The aperture ratio corresponds to the ratio of the area of the conductive thin wire to the entire support.

Usually, the exposure is carried out in a pattern, and the unexposed portion forms a non-conductive portion. Silver halide and gelatin contained in the unexposed portion are removed by Step C and Step D. As a result, after Step D, a polymer is contained in the non-conductive portion. That is, the non-conductive portion contains a polymer as a main component.
The transmittance in the non-conductive portion is preferably 90% or more, more preferably 95% or more, as shown by the minimum transmittance in the wavelength range of 380 to 780 nm excluding the contribution of light absorption and reflection of the support. 97% or more is more preferable, 98% or more is particularly preferable, and 99% or more is most preferable.

The conductive sheet can be used for various applications. For example, it can be used as various electrodes (for example, electrodes for touch panels, electrodes for inorganic EL elements, electrodes for organic EL elements, or electrodes for solar cells), heat generating sheets, or printed wiring boards. Especially, it is preferable that a conductive sheet is used for a touch panel, and it is especially preferable to be used for a capacitive touch panel.
As another application, the conductive sheet can also be used as an electromagnetic wave shield that blocks electromagnetic waves such as radio waves or microwaves (extremely short waves) generated from personal computers or workstations, and prevents static electricity. In addition to the electromagnetic wave shield used for the personal computer body, it can also be used as an electromagnetic wave shield used in video imaging equipment, electronic medical equipment, and the like.
Furthermore, the conductive sheet can also be used as a transparent heating element.

As described above, the conductive fine wires in the conductive sheet may form a mesh pattern as shown in FIG.
Conventionally, when evaluating the visibility of such a mesh pattern, it has been necessary to rely on sensory evaluation by an observer, but in the present invention, it is obtained from image processing software ImageJ described in detail later. It has been found that the “easiness of visibility of the mesh pattern” can be quantified by using the Gray value, and that the mesh pattern is difficult to see (it is difficult to see) when the Gray value is in a predetermined range.
“ImageJ” is an open source public domain image processing software developed by the National Institutes of Health (NIH).

More specifically, a support, a first mesh pattern composed of conductive thin wires arranged on one surface of the support, and a second conductive wire arranged on the other surface of the support. In a conductive sheet having a mesh pattern, an image obtained by photographing the first mesh pattern from the first mesh pattern side of the conductive sheet is taken into the image processing software ImageJ, and the Gray value calculated by the image processing software ImageJ is set as the GrayA value and the conductive When an observation drawing of the second mesh pattern taken from the second mesh pattern side of the sheet is taken into the image processing software ImageJ and the Gray value calculated by the image processing software ImageJ is set as the GrayB value, the following formulas (1) to (1) The conductive sheet satisfying the relationship (4) is a conductive sheet in which the mesh pattern is difficult to see. It is below.
Formula (1) GrayA value <−55
Formula (2) GrayB value <−55
Expression (3) | Gray A value−Gray B value | <20
Expression (4) GrayB value <GrayA value

  The Gray value is a “brightness value” obtained by ImageJ, and the larger the value is, the more white it is, and the smaller the value, the more visually recognized it is.

As a preferable range of the formula (1), the range of the following formula (1-1) can be given in that the conductive thin wire is more difficult to see.
Formula (1-1) -80 <Gray A value <-60
As a preferable range of the formula (2), the range of the following formula (2-1) can be given in that the conductive thin wire is less visible.
Formula (2-1) −80 <Gray B value <−70
As a preferable range of the formula (3), the range of the following formula (3-1) can be given in that the conductive thin wire is less visible.
Formula (3-1) | Gray A Value−Gray B Value | <10

  If it is a conductive sheet satisfying the relations of the above formulas (1) to (4), it is difficult to see the conductive thin wires (or mesh patterns). Therefore, it is evaluated whether or not the above formulas (1) to (4) are satisfied with respect to the difficulty of only the conductive thin wires in the conductive sheet manufactured in large quantities. It is also difficult to adopt an evaluation method in which it is easy to see the conductive thin wires if they are not satisfied.

The method for calculating the Gray value will be described in detail in the “Example” section later. The mesh pattern is photographed by a predetermined apparatus, the obtained captured image is taken into the image processing software ImageJ, and a predetermined operation is performed. Thus, the Gray value can be calculated.
Note that a digital microscope (VHX-2000 (lens; VHZ-100R)) (lens magnification × 500 times, illumination luminance 70%) manufactured by KEYENCE is used as an apparatus for photographing a mesh pattern.
In addition, the Gray value in the above formulas (1) to (4) is an average value (average Gray value: average GrayA value, average GrayB value), and a value obtained by measuring three times for one image (Gray). Value).

  Hereinafter, the present invention will be described more specifically with reference to examples of the present invention. In addition, the material, usage-amount, ratio, processing content, processing procedure, etc. which are shown in the following Examples can be changed suitably unless it deviates from the meaning of this invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<Example 1>
(Preparation of silver halide emulsion)
To the following 1 liquid maintained at 38 ° C. and pH 4.5, an amount corresponding to 90% of each of the following 2 liquids and 3 liquids was simultaneously added over 20 minutes with stirring to form 0.12 μm core particles. Subsequently, the following 4 and 5 solutions were added over 8 minutes, and the remaining 10% of the following 2 and 3 solutions were added over 2 minutes to grow to 0.21 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete the grain formation.

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

  Then, it washed with water by the flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., and the pH was lowered using sulfuric acid until the silver halide precipitated (the pH was in the range of 3.6 ± 0.2). Next, about 3 liters of the supernatant was removed (first washing). Further, 3 liters of distilled water was added, and sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting step. The emulsion after washing with water and desalting was adjusted to pH 6.4 and pAg 7.5, and 2.5 g of gelatin, 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 15 mg of sodium thiosulfate and 10 mg of chloroauric acid were added. Chemical sensitization was performed to obtain an optimum sensitivity at 0 ° C., and 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 It was. The finally obtained emulsion contains 0.08 mol% of silver iodide, and the ratio of silver chlorobromide is 70 mol% of silver chloride and 30 mol% of silver bromide. It was a silver iodochlorobromide cubic grain emulsion having a coefficient of 9%.

(Preparation of silver halide-containing photosensitive layer forming composition)
1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / Mol Ag, 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 0.90 g / mol Ag, a trace amount of hardener was added, and the coating solution pH was adjusted to 5.6 using citric acid. Adjusted.
Polymer latex containing a dispersant represented by (P-1) below and a dialkylphenyl PEO sulfate ester (dispersant / polymer mass ratio is 2.0) with respect to gelatin contained in the coating solution. /100=0.02) and polymer / gelatin (mass ratio) = 0.5 / 1.

Furthermore, a vinyl sulfone-based crosslinking agent was added as a crosslinking agent. In addition, the addition amount of the crosslinking agent was adjusted so that the amount of the crosslinking agent in the silver halide-containing photosensitive layer described later was 0.03 g / m ² .
A silver halide-containing photosensitive layer forming composition was prepared as described above.
In addition, the polymer represented by (P-1) exemplified above was synthesized with reference to Japanese Patent No. 3305459 and Japanese Patent No. 3754745.

(Process for forming photosensitive layer containing silver halide)
A long polyethylene terephthalate (PET) film roll having a width of 500 mm, a length of 200 m, and a thickness of 38 μm is prepared, and as shown in FIG. The above polymer latex was applied to provide an undercoat layer having a thickness of 0.05 μm.
Next, on the undercoat layer, a silver halide-free layer forming composition in which the polymer latex and gelatin were mixed was applied on both sides to provide a 1.0 μm-thick silver halide-free layer. The mixing mass ratio of polymer and gelatin (polymer / gelatin) was 2/1, and the polymer content was 0.65 g / m ² .
Next, the silver halide-containing photosensitive layer forming composition was applied on the silver halide-free layer to provide a silver halide-containing photosensitive layer having a thickness of 2.5 μm. The mixing ratio of the polymer and gelatin in the silver halide-containing photosensitive layer (polymer / gelatin) is 0.5 / 1, the polymer content is 0.22 g / m ² , and the silver content is The amount was 6.0 g / m ² .
Next, a protective layer-forming composition in which the polymer latex and gelatin were mixed was applied onto the silver halide-containing photosensitive layer to provide a protective layer having a thickness of 0.15 μm. The mixing mass ratio of polymer to gelatin (polymer / gelatin) was 0.1 / 1, and the polymer content was 0.015 g / m ² .
Then, the PET film in which each layer was arrange | positioned was wound up in roll shape using the winding roller. When winding, a winding core C1 (outer diameter 6 inches, width 19.7 inches, made of FRP (Fiber Reinforced Plastics), no coating layer, 25% compression stress of the winding core itself is 118 MPa) It was mounted on a take-up roller and wound up.

(Exposure and development process)
Next, as shown in FIG. 3, the PET film wound in a roll shape is unwound and conveyed using a feed roller, and conductive thin wires (line width) / non-conductive are formed on both sides of the PET film being conveyed. Exposure of parallel light using a high-pressure mercury lamp as a light source through a grid-like photomask (width: 500 mm, length: 600 mm) where the conductive portion (corresponding to Pa in FIG. 8) gives a conductive pattern of 3.5 μm / 297 μm did. Thereafter, the PET film being transported that had been subjected to the exposure treatment was wound up into a roll shape using a winding roller. In addition, the surface pressure at the time of winding was 0.1 MPa. In winding, the winding core C1 was mounted on a winding roller and wound.
Next, as shown in FIG. 4, by using a feed roller, the PET film wound in a roll shape is unwound and conveyed, and both sides of the PET film being conveyed using an automatic developing machine, Development processing using the following developing solution, fixing processing using a fixing solution (trade name: N3X-R for CN16X: manufactured by Fuji Film), rinsing processing with pure water, and drying processing are performed in this order. Thus, a PET film having conductive fine wires / non-conductive portions having mesh pattern electrodes of 3.5 μm / 297 μm was manufactured. The obtained PET film was wound up into a roll using a winding roller. In addition, the surface pressure at the time of winding was 0.1 MPa. Moreover, the binder part containing the said polymer was between the electroconductive thin wires on the said support body. In winding, the winding core C1 was mounted on a winding roller and wound.
(Developer composition)
The following compounds are contained in 1 liter (L) of the developer.
Hydroquinone 0.037mol / L
N-methylaminophenol 0.016 mol / L
Sodium metaborate 0.140 mol / L
Sodium hydroxide 0.360 mol / L
Sodium bromide 0.031 mol / L
Potassium metabisulfite 0.187 mol / L

(First heat treatment (first heating step E))
Next, as shown in FIG. 5, the roll-shaped PET film obtained in the above (exposure / development process) is unwound and conveyed using a feed roller, and the PET film is superheated steam in a superheated steam device. The tank (temperature: 120 ° C.) was passed through for 20 seconds to perform heat treatment, and then the PET film was wound into a roll using a winding roller. The surface pressure at the time of winding was 0.3 MPa. In winding, the winding core C1 was mounted on a winding roller and wound.

(Gelatin removal treatment (gelatin removal step D))
Next, using the feed roller, the roll-like PET film obtained in the above (first heat treatment) was unwound and conveyed, and the PET film was filled with an aqueous protease solution (40 ° C.) described later. Immerse in an aqueous protease treatment bath so that the immersion time is 120 seconds, and then immerse the PET film in a hot water treatment bath filled with warm water (50 ° C.) so that the immersion time is 120 seconds. The PET film was subjected to a drying process, and further subjected to a calendering process described later, and then the PET film (corresponding to a conductive sheet) was wound into a roll using a winding roller. The surface pressure at the time of winding was 0.3 MPa. In winding, the winding core C1 was mounted on a winding roller and wound.
(Calendar processing)
As shown in FIG. 9, the calendar process used a mat member 42 having an uneven surface 42A and a pair of calendar rollers (first calendar roller 44A and second calendar roller 44B) arranged to face each other. Specifically, as shown in FIG. 9A, the PET film 40 (which has been subjected to the drying process) and the mat member 42 are laminated so that the unevenness of the mat member 42 contacts the PET film 40. As shown in FIG. 9B, the sheet was conveyed between the pair of calendar rollers. The first calender roller 44A was a metal roll, and the second calender roller 44B was a polyimide resin roll, and the surface pressure was 5 MPa.
The mesh pattern on the mat member side was defined as the first sensor electrode, and the mesh pattern on the resin roll side was defined as the second sensor electrode.
(Preparation of aqueous protease solution)
Triethanolamine and sulfuric acid were added to an aqueous solution of proteolytic enzyme (Biolase 30L, manufactured by Nagase ChemteX) (proteolytic enzyme concentration: 0.5% by mass) to adjust the pH to 8.5. An aqueous solution was prepared.

(Second heat treatment (second heating step F))
Next, as shown in FIG. 5, the roll-shaped PET film obtained in the above (gelatin removal treatment and calendar treatment) is unwound and conveyed using a feed roller, and the PET film is heated in a superheated steam device. Heat treatment was carried out by passing through a superheated steam bath (temperature: 120 ° C.) for 20 seconds, and then the PET film was wound into a roll using a winding roller. The surface pressure at the time of winding was 0.3 MPa. In winding, the winding core C1 was mounted on a winding roller and wound.

(Crosslinking treatment (crosslinking treatment step G))
Next, as shown in FIG. 7, the roll-shaped PET film obtained in the above (second heat treatment) is unwound and conveyed using a feed roller, and the PET film is carbodilite V-02-L2 ( (Product name: Nisshinbo Co., Ltd.) Immerse in a tank filled with 1% by mass aqueous solution so that the immersion time is 30 seconds, and then immerse the PET film in a washing tank filled with pure water (room temperature). After dipping for 60 seconds and then drying the PET film, the PET film was wound into a roll using a winding roller. The surface pressure at the time of winding was 0.3 MPa. In winding, the winding core C1 was mounted on a winding roller and wound.

<Examples 2-6, Comparative Examples 1-2>
As shown in Table 1, a conductive sheet was produced according to the same procedure as in Example 1 except that the surface pressure (winding surface pressure) at the time of winding in each step was changed.
Note that the winding surface pressure was changed by changing the winding tension. As described above, the method for measuring the winding surface pressure was a method using a prescale (for ultra-low pressure (LLLLW) or ultra-low pressure (LLW)) manufactured by FUJIFILM Corporation.

<Example 7>
When winding in each step, instead of the core C1, a core C2 with a coating layer (core: outer diameter 6 inches, width 19.7 inches, made of FRP, coating layer: polyethylene foam, 25% compression stress is 275 kPa) A conductive sheet was produced according to the same procedure as in Example 1 except that it was used.

<Examples 8 to 9>
At the time of winding in each step, instead of the core C1, a core C3 with a coating layer (core: outer diameter 6 inches, width 19.7 inches, made of FRP, coating layer: polyethylene foam, 25% compressive stress is 63 kPa) A conductive sheet was produced according to the same procedure as in Example 1 except that it was used.

<Various evaluations>

(Gray value evaluation)
A transparent optical adhesive film (manufactured by 3M, 8146-2) is bonded onto one surface (first sensor electrode side) of the conductive sheet, and further a white plate is formed on one surface of the bonded transparent optical adhesive film. Glass was pasted together. In addition, a transparent optical adhesive film is laminated on the other surface (second sensor electrode side) of the conductive film, and further 100 μm of PET (polyethylene terephthalate) is formed on one surface of the laminated transparent optical adhesive film. The film was bonded together and the evaluation sample by which the mesh pattern electrode which consists of a conductive thin wire with white board glass and PET film was pinched | interposed was produced.
Next, using a digital microscope (VHX-2000 (lens; VHZ-100R)) manufactured by KEYENCE, observed with reflected light of the evaluation sample as follows at a lens magnification of x500 and an illumination luminance of 70%. Shoot.
Place the evaluation sample on the table with the color plate glass up (viewing side), adjust the white balance, and then focus on the mesh part of the mesh pattern electrode (first sensor electrode) in the conductive sheet placed on the white plate glass side. And the amount of light was adjusted by the BGR display function so that the luminance of the portion without the mesh portion was 225 ± 5. The photographed image was saved in jpeg format. The standard image size [1600 × 1200] was selected. The image processing software ImageJ was activated and the captured images were captured as follows.
(1) Select “* straight *” from the toolbar.
(2) Place the cursor at the center of the mesh part and drag to draw a line corresponding to 20 μm on the mesh part.
(3) A value is read by Analyze-Measure Ctrl + M.
(4) Move the cursor to a location that is not an adjacent mesh portion, drag, draw a line corresponding to 20 μm to a portion that is not a mesh portion, and read in the same procedure as in (3).
(5) Right-click on the Results window and select “SelectALL” → “Copy” to import it into an Excel file, and the GrayA value was calculated as follows.
GrayA value = value at the mesh portion−value at a portion other than the mesh portion (6) For the above (1) to (5), an average value obtained three times per image was defined as the GrayA value.

Next, similarly, after placing the evaluation sample on the table with the first sensor electrode side up and adjusting the white balance, the mesh pattern electrode (second sensor electrode) in the conductive sheet placed on the PET film side The mesh portion was brought into focus, and the image taken by the BGR display was saved in jpeg format. The standard image size [1600 × 1200] was selected. The image processing software ImageJ was activated and the captured images were captured as follows.
(7) Select “* straight *” from the toolbar.
(8) Place the cursor at the center of the mesh part and drag to draw a line corresponding to 20 μm on the mesh part.
(9) A value is read with Analyze-Measure Ctrl + M.
(10) Move the cursor to a location that is not an adjacent mesh portion, drag, draw a line corresponding to 20 μm to a portion that is not a mesh portion, and read in the same procedure as in (9).
(11) Right-click the Results window and select “SelectALL” → “Copy” to import it into an Excel file, and the GrayB value was calculated as follows.
GrayB value = value in the mesh portion−value in a portion other than the mesh portion (12) For the above (7) to (11), an average value obtained three times per image was taken as the GrayB value.
In addition, the conductive sheet piece A produced by the below-mentioned (mesh appearance evaluation) was used for the conductive sheet used by the measurement of the said Gray value.

(Evaluation of mesh appearance)
The conductive sheet wound up in a roll shape was attached to a feed roller, the conductive sheet was sent out, and a piece of conductive sheet was cut out from two places in the long conductive sheet to obtain a sample. Specifically, the conductive sheet piece A cut out from a position 20 m from the core (about 41 circumferential length portion), and a position (one circumferential length portion) in contact with the winding core (or the core with the coating layer). Conductive sheet pieces B were obtained. An evaluation sample was prepared by the method described above (Evaluation of Gray value) using the cut conductive sheet piece. Place the prepared evaluation sample on the LCD (liquid crystal display) so that the white glass surface is on top, and change the direction of light exposure and pattern observation under fluorescent lamps and sunlight. The difficulty of pattern visibility was evaluated.
“A”: When it is difficult to visually recognize the mesh pattern and there is no problem in practical use. “B”: Under a strong light source (under sunlight), all or part of the mesh pattern may be noticeable depending on the angle. “C”: When the use range is limited “C”: Even under a weak light source (under fluorescent light), all or part of the mesh pattern may be conspicuous depending on the angle, and “D”: All Or if some mesh patterns are conspicuous and cause harm, they cannot be used.

(Winding misalignment)
For evaluation of the deviation at the time of winding, the deviation amount on the roll side surface was measured by using a mold taking gauge (Yamano Seisakusho).
“A”: When the amount of deviation is less than 2 mm “B”: When the amount of deviation is 2 mm or more and less than 5 mm “C”: When the amount of deviation is 5 mm or more

  In Table 1, “A value” is a GrayA value, and “B value” is a GrayB value.

As shown in Table 1 above, in the conductive sheet obtained from the production method of the present invention, it was difficult to visually recognize the conductive thin wire. In particular, as shown in Examples 4 to 6, when the winding surface pressure in Step C was less than 0.2 PMa, the effect was more excellent.
Moreover, in Examples 7-9 using the core with a coating layer which has a coating layer whose 25% compressive stress is 275 kPa or less, the mesh appearance is more suppressed in the conductive sheet cut out from the position in contact with the core. confirmed.
On the other hand, in Comparative Examples 1 and 2 having a large winding surface pressure, the desired effect was not obtained.

DESCRIPTION OF SYMBOLS 10 Support body roll 12A, 12B, 12C, 12D, 12E, 12F Feeding roller 14 Coating apparatus 16A, 16B, 16C, 16D, 16E, 16F Take-up roller 18 Support body roll with photosensitive layer 20 Exposure apparatus 22 Exposed support Body roll 24 Developing device 26, 30 Support roll with conductive thin wire 28 Heating device 32 Gelatin removal device 34 Conductive sheet roll 36 Cross-linking treatment device 40 PET film 42 Mat member 44A First calendar roll 44B Second calendar roll 100 Support 102 Conductive fine wire 104 Support with conductive fine wire 106 Opening

Claims (14)

On both sides of the elongated support, silver halide, gelatin and a polymer different from gelatin are contained, and the mass ratio R1 of the polymer mass Y1 to the gelatin mass X1 is 0.1 or more. Contacting a certain silver halide-containing photosensitive layer forming composition to form a silver halide-containing photosensitive layer; and
Exposing the silver halide-containing photosensitive layer B;
Developing the silver halide-containing photosensitive layer after the exposure to form a conductive fine wire containing metallic silver to obtain a support with a conductive fine wire; and
A step D of removing the gelatin in the support with conductive thin wires while obtaining the conductive thin wire support to obtain a conductive sheet, and winding the conductive sheet into a roll;
In the step D, a method for producing a conductive sheet, wherein a winding surface pressure during winding of the conductive sheet is 0.3 MPa or less. The mass ratio R1 represents mass Y1 / mass X1.   The method for producing a conductive sheet according to claim 1, wherein the winding surface pressure in the step D is less than 0.2 MPa. The step D is a step of winding the conductive sheet around a core with a coating layer in a roll shape,
The said core with a coating layer has a winding core, and the manufacturing of the electrically conductive sheet of Claim 1 or 2 with which the 25% compressive stress arrange | positioned on the outer peripheral surface of the said core is 275 KPa or less. Method. Between the said process C and the said process D, heat-treating to the said support body with an electroconductive fine wire, conveying the said support body with an electroconductive thin wire, and winding up the said support body with an electroconductive thin wire in roll shape And further comprising step E
The manufacturing method of the electrically conductive sheet of any one of Claims 1-3 whose winding surface pressure at the time of winding of the said support body with an electroconductive thin wire in the said process E is 0.3 Mpa or less.   The manufacturing method of the electrically conductive sheet of Claim 4 whose said winding surface pressure in the said process E is 0.2 Mpa or less. The step E is a step of winding the support with conductive thin wires around a core with a coating layer in a roll shape,
The conductive sheet according to claim 4 or 5, wherein the core with a covering layer has a core and a covering layer having a 25% compressive stress of 275 KPa or less disposed on an outer peripheral surface of the core. Method. After the step D, the step F of unwinding and transporting the conductive sheet from a conductive sheet roll formed by winding the conductive sheet into a roll, heat-treating the conductive sheet, and winding the conductive sheet into a roll Further comprising
The said manufacturing method of the conductive sheet of any one of Claims 1-6 whose winding surface pressure at the time of winding of the said conductive sheet is 0.3 Mpa or less in the said process F.   The method for producing a conductive sheet according to claim 7, wherein the winding surface pressure in the step F is 0.2 MPa or less. The step F is a step of winding the conductive sheet around a core with a coating layer in a roll shape,
The conductive sheet according to claim 7 or 8, wherein the core with a covering layer has a core and a covering layer having a 25% compressive stress of 275 KPa or less disposed on an outer peripheral surface of the core. Method. After the step D, the conductive sheet is unwound and conveyed from a conductive sheet roll formed by winding the conductive sheet into a roll, and subjected to a crosslinking treatment to crosslink the polymer contained in the conductive sheet. The process G is further wound into a roll,
The method for producing a conductive sheet according to any one of claims 1 to 9, wherein in the step G, a winding surface pressure at the time of winding the conductive sheet is 0.3 MPa or less.   The method for producing a conductive sheet according to claim 10, wherein the winding surface pressure in the step G is 0.2 MPa or less. The step G is a step of winding the conductive sheet around a core with a coating layer in a roll shape,
The said core with a coating layer has a winding core, and manufacture of the electrically conductive sheet of Claim 10 or 11 with which the coating layer which is 25% compressive stress arrange | positioned on the outer peripheral surface of the said core is 275 KPa or less. Method.   In the said process D, before winding up the said conductive sheet in roll shape, the manufacturing method of the conductive sheet of any one of Claims 1-12 which performs a smoothing process to the said conductive thin wire | line.   The touch panel containing the conductive sheet manufactured from the manufacturing method of the conductive sheet of any one of Claims 1-13.