JP2008244067A - Photosensitive material for forming transparent conductive film, transparent conductive film and its forming method, electromagnetic wave shielding material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent conductive film having high conductivity and a high light transmission property while being reduced in interference unevenness and moire, its forming method, an electromagnetic wave shielding material employing the transparent conductive film and a photosensitive material for forming the transparent conductive film employed for forming the transparent conductive film and excellent in a coating property. <P>SOLUTION: An emulsion layer containing at least a silver halide and a binder is formed on a support and a metal silver unit is formed so as to have a shape of a mesh by development treatment after exposure, whereby the photosensitive material for forming the transparent conductive film which is the photosensitive material for forming the transparent conductive film capable of forming the transparent conductive film and whose emulsion layer contains a fluorine surfactant having a desaturation carbon bond can be obtained. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a transparent conductive film for forming a conductive material that can block electromagnetic waves generated from electronic devices such as mobile phones, microwave ovens, CRTs, and flat panel displays and that requires transparency. The present invention relates to a forming photosensitive material, a transparent conductive film, a method for producing the same, and an electromagnetic wave shielding material.

  In recent years, there has been an increasing need to reduce electromagnetic interference (EMI) due to increased use of electronic devices. It has been pointed out that EMI causes malfunctions and failures of electronic and electrical devices and also harms human bodies. For this reason, electronic devices are required to keep the intensity of electromagnetic wave emission within the standards or regulations.

  In particular, the plasma display panel (PDP) generates electromagnetic waves in principle because it is based on the principle that a rare gas is made into a plasma state to emit ultraviolet rays and phosphors emit light with this light. In addition, near infrared rays are also emitted at this time, which causes malfunction of an operating element such as a remote controller. The electromagnetic wave shielding ability can be simply expressed by a surface resistance value, and a light-transmitting electromagnetic wave shielding material for PDP is required to be 10Ω / □ or less, and in a consumer plasma television using PDP, 1Ω / □. There is a high need for the following, more desirably, extremely high conductivity of 0.1 Ω / □ or less is required.

  Among the above problems, in particular, in order to solve the electromagnetic wave prevention, a method for manufacturing an electromagnetic wave shielding material using a metal mesh having an opening, such as an etching mesh using an photolithography method or an electrodeposited mesh, has been proposed so far. (For example, refer to Patent Documents 1 and 2.) However, these have complicated manufacturing processes, and have been disadvantageous in that the intersections of the moire and the metal line portions are thickened.

  In order to solve the above problems, various materials and methods have been proposed that achieve both electromagnetic shielding properties and translucency using a conductive mesh having openings. Among them, a method of forming a translucent electromagnetic wave shield has been proposed that uses a silver salt photosensitive material to provide a thin line pattern of a conductive mesh in a large amount at a low cost (see, for example, Patent Documents 3 and 4).

In this method, a photosensitive silver material is exposed to a mesh to form a metallic silver portion through a development process and a fixing process, and then conductive metal particles are supported on the metallic silver section by physical development and / or plating treatment. Although it is a method of forming a mesh, there has been a problem of reduced light transmission and moire in the light transmitting portion after physical development and / or plating. In order to improve the light transmittance, it is necessary to add a treatment for removing the conductive metal particles in the light transmitting portion by an oxidation treatment, and the increase in manufacturing cost has been a problem. Furthermore, in order to eliminate moire, a technique for uniformly coating thin film of photosensitive material is required. However, the photosensitive material coating solution used for this purpose requires high conductivity, and the silver / binder ratio is 10 times that of photographic photosensitive material. As described above, thin film uniform coating was difficult.
JP 2003-46293 A JP-A-11-26980 JP 2004-221564 A International Publication No. 06/98333 Pamphlet

  SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide a transparent conductive film having high conductivity and light transmission, reduced interference unevenness and moire, a method for manufacturing the same, and the transparent conductive film It is an object to provide an electromagnetic wave shielding material using, and a photosensitive material for forming a transparent conductive film, which is used for producing the transparent conductive film.

  The above object of the present invention is achieved by the following configurations.

  1. Forming a transparent conductive film on the support having an emulsion layer containing at least silver halide and a binder, and after the exposure, developing treatment to form a metallic silver part in a mesh shape A photosensitive material for forming a transparent conductive film, wherein the emulsion layer contains a fluorine-containing surfactant having an unsaturated carbon bond.

  2. A transparent conductive film is formed by forming an emulsion layer containing at least silver halide and a binder on a support, developing a light-sensitive layer after exposure, and further performing a reinforcement treatment to form a metallic silver portion in a mesh shape. A photosensitive material for forming a transparent conductive film, wherein the emulsion layer contains a fluorine-containing surfactant having an unsaturated carbon bond.

3. 3. The photosensitive material for forming a transparent conductive film according to 1 or 2, wherein the silver halide coating silver amount is 1 g / m ² or less and the dry thickness of the emulsion layer is 0.5 μm or less.

  4). 1 to 3 above, wherein the thickness of the emulsion layer of the non-mesh part (light transmitting part) of the transparent conductive film obtained by forming the metallic silver part in the mesh form is 0.1 μm or less. The photosensitive material for transparent conductive film formation of any one of Claims 1.

  5. The support has an easy-adhesion layer on the emulsion layer side, the refractive index of the easy-adhesion layer is smaller than the refractive index of the support, and the difference in refractive index between the easy-adhesion layer and the support is 0. 5. The photosensitive material for forming a transparent conductive film according to any one of 1 to 4 above, wherein the photosensitive material is 1 or less.

  6). 6. A method for producing a transparent conductive film, comprising: exposing the photosensitive material for forming a transparent conductive film according to any one of 1 to 5 above, and performing a development process to form a metallic silver portion in a mesh shape.

  7. 6. The transparent conductive film according to any one of 1 to 5, wherein the photosensitive material for forming a transparent conductive film is exposed, developed, and further intensified to form a metallic silver portion in a mesh shape. Manufacturing method.

  8). A transparent conductive film obtained by the production method according to 6 or 7 above.

  9. 9. The electromagnetic wave shielding material using the transparent conductive film as described in 8 above.

  According to the present invention, a transparent conductive film having high conductivity and light transmissivity and having reduced interference unevenness and moire, a manufacturing method thereof, an electromagnetic wave shielding material using the transparent conductive film, and the transparent conductive film It is possible to provide a transparent conductive film-forming photosensitive material having good coatability used for production.

  As a result of intensive studies in view of the above problems, the present inventors have obtained an emulsion of a light-sensitive material used for obtaining a transparent conductive film having high conductivity and light transmission and reduced moire. By making the layer (which becomes a transparent conductive film after development) extremely thin, the light transmittance of the non-mesh part (light transmissive part) can be improved, and the moire can be reduced because the height of the mesh part is low. I understood. However, uniform coating of an ultra-thin emulsion layer (no coating unevenness / density unevenness) is difficult, and if uniform coating cannot be performed and the film thickness is uneven, the light reflected from the support surface and the emulsion layer surface are reflected. There is a problem that the light to be interfered causes interference unevenness. As a result of further investigations, the present inventors have found that when a fluorine-containing surfactant having a specific structure is used, a uniform coating film can be obtained even with an extremely thin thin film. It is. Such effects are manifested in that when the fluorine-containing surfactant having a specific structure according to the present invention is added to the coating liquid, the leveling effect of the coating film (coating liquid film) is large and a uniform coating film can be obtained. I believe.

  Hereinafter, the present invention will be described in detail.

<Fluorine-containing surfactant having an unsaturated carbon bond>
The photosensitive material for forming a transparent conductive film of the present invention (hereinafter also simply referred to as a photosensitive material) has an emulsion layer containing at least silver halide and a binder on a support, and the emulsion layer is not present in a hydrophobic portion. It contains a fluorine-containing surfactant having a saturated carbon bond. The hydrophilic portion may be an ionic group (for example, anion, cation, betaine) or a nonionic group, but among these, an anionic group is preferable in terms of affinity with the coating solution. By using a fluorine-containing surfactant having an unsaturated carbon bond, the surface tension of the emulsion layer coating solution can be set to the 20 mN / m range, and uniform coating can be realized with a thin film.

  Although the specific example of the fluorine-containing surfactant which has an unsaturated carbon bond used for this invention is shown, this invention is not limited to this.

  These compounds are commercially available from Neos.

  The content of the fluorine-containing surfactant contained in the emulsion layer according to the present invention is not particularly limited, but is preferably an amount that makes the surface tension of the emulsion layer coating solution 20 mN / m.

  Hereinafter, other configurations of the photosensitive material of the present invention will be described.

<Support>
In the photosensitive material of the present invention, a plastic film, a plastic plate, glass or the like can be used as a support. Examples of raw materials for plastic films and plastic plates include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), vinyl resins such as polyethylene (PE), polypropylene (PP), and polystyrene, and polycarbonate (PC). Triacetyl cellulose (TAC) or the like can be used.

  From the viewpoint of transparency, heat resistance, ease of handling, and price, the plastic film is preferably PET, PEN, or TAC.

  Since the electromagnetic wave shielding material for a display requires transparency, it is desirable that the support has high transparency. In this case, the total visible light transmittance of the plastic film or plastic plate is preferably 70 to 100%, more preferably 80 to 100%, and further preferably 90 to 100%. Moreover, in this invention, what colored the said plastic film and the plastic board to the extent which does not interfere with the objective of this invention can also be used as a color tone regulator.

<Emulsion layer>
In the light-sensitive material of the present invention, an emulsion layer containing silver halide is provided on a support as an optical sensor. The emulsion layer can contain a binder, a solvent and the like in addition to silver halide.

<Silver halide>
As the silver halide used in the present invention, techniques conventionally used in various silver halide photographic light-sensitive materials can be used as they are in the present invention.

  The halogen element contained in the silver halide grains may be any of chlorine, bromine and iodine, or a combination thereof. For example, silver halide mainly composed of AgCl, AgBr, and AgI is preferably used, and silver halide mainly composed of AgCl is preferably used.

  Here, “silver halide mainly composed of AgCl” refers to silver halide in which the molar fraction of chloride ions in the silver halide composition is 50% or more. The silver halide grains mainly composed of AgCl may contain iodide ions and bromide ions in addition to chloride ions.

  For silver halide grains, from the viewpoint of image quality of the patterned metallic silver layer formed after exposure and development, the average grain size is preferably 0.1 to 1000 nm (1 μm) in terms of sphere equivalent diameter. The thickness is more preferably 0.1 to 100 nm, and further preferably 1 to 50 nm. The sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and having a spherical shape.

  The shape of the silver halide grains is not particularly limited, and may be various shapes such as, for example, spherical shape, cubic shape, flat plate shape (hexagon flat plate shape, triangular flat plate shape, rectangular flat plate shape, etc.), octahedron shape, tetrahedron shape, etc. Can be.

The silver halide grains used in the present invention may further contain other elements. For example, in a silver halide grain photographic emulsion, it is also useful to dope metal ions used for obtaining a high gradation. In particular, transition metal ions such as rhodium ions and iridium ions are preferably used because a difference between an exposed portion and an unexposed portion tends to occur clearly when a metallic silver image is generated. Transition metal ions represented by rhodium ions and iridium ions can also be compounds having various ligands. Examples of such a ligand include cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions, and the like. Specific examples of the compound include K ₃ Rh ₂ Br ₉ and K ₂ IrCl ₆ .

In the present invention, the content of the rhodium compound and / or iridium compound contained in the silver halide is 10 ⁻¹⁰ to 10 ⁻² mol / mol Ag with respect to the number of moles of silver in the silver halide. Preferably, it is 10 ⁻⁹ to 10 ⁻³ mol / mol Ag.

  In the present invention, in order to further improve the sensitivity as an optical sensor, chemical sensitization performed with a silver halide grain photographic emulsion can be performed. As chemical sensitization, gold sensitization, noble metal sensitization such as palladium, chalcogen sensitization such as sulfur, selenium and tellurium, reduction sensitization, and the like can be used.

  Examples of the emulsion that can be used in the present invention include color negatives described in Examples of JP-A-11-305396, JP-A-2000-321698, JP-A-13-281815, and JP-A-2002-72429. Film emulsions, color reversal film emulsions described in JP-A No. 2002-214731, color photographic paper emulsions described in JP-A No. 2002-107865, and the like can be suitably used.

<binder>
In the silver salt-containing layer according to the present invention, the binder (resin) can be used for the purpose of uniformly dispersing the silver salt particles and assisting the adhesion between the silver salt-containing layer and the support. As the binder used in the present invention, gelatin is preferable. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and various modified gelatins such as phthalated gelatin and phenylcarbamoylated gelatin.

  Content of the binder contained in the silver salt content layer concerning this invention is not specifically limited, It can determine suitably in the range which can exhibit a dispersibility and adhesiveness. The content of the binder in the silver salt-containing layer is preferably 1/5 to 5 in terms of Ag / binder volume ratio, more preferably 1/3 to 3, and more preferably 1/2 to 2. Further preferred. If the silver salt-containing layer contains a binder of 1/4 or more by Ag / binder volume ratio, the metal particles can easily come into contact with each other in the physical development and / or plating process, and high conductivity can be obtained. Therefore, it is preferable. When the Ag / binder volume ratio exceeds 5, there are problems such as the occurrence of aggregation of silver halide grains, significant deterioration of coating properties, and the occurrence of cracks after drying due to insufficient binder.

  The binder may be crosslinked with a crosslinking agent when forming the silver salt-containing layer. As the crosslinking agent, known agents can be used. For example, vinyl sulfone type hardeners and chlorotriazine type hardeners described in JP-A-61-249045 and JP-A-61-245153 can be used. .

  In the present invention, the original plate for electromagnetic wave shielding material may contain a water-soluble compound such as dextrin in addition to the gelatin binder resin.

<solvent>
The solvent that can be used in the preparation of the emulsion layer coating solution and the like according to the present invention is not particularly limited, and examples thereof 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), ionic liquids, and mixed solvents thereof. Since photographic silver halide gelatin emulsions are used, water-based solvents are preferred.

In the present invention, as described above, by reducing the film thickness, the light transmittance of the non-mesh part (light transmission part) is improved and the height of the mesh part is low and moire is reduced. The coated silver amount is preferably 1 g / m ² or less, and the dry thickness of the emulsion layer is preferably 0.5 μm or less.

  For the same reason, the thickness of the emulsion layer of the non-mesh portion (light transmitting portion) of the transparent conductive film obtained by forming the metallic silver portion in a mesh shape is preferably 0.1 μm or less.

《Easily adhesive layer》
In the present invention, the support has an easy adhesion layer on the emulsion layer side, the refractive index of the easy adhesion layer is smaller than the refractive index of the support, and the difference in refractive index between the easy adhesion layer and the support. Is preferably within 0.1.

  This is because a polyester support having a high refractive index in the surface direction of around 1.66 (polyester is most preferable as the support) and an emulsion layer (transparent conductive material) in which the main binder is gelatin having a refractive index of about 1.52. By providing an easy adhesion layer having an intermediate refractive index between the polyester support and the easy adhesion layer adjacent to the polyester support, and the interface between the transparent conductive film and the easy adhesion layer. This is because the difference in refractive index is reduced to suppress interface reflection and to reduce interference light as a transparent conductive film.

  The easy-adhesion layer used in the present invention contains at least a resin (binder) for achieving adhesion and a material (refractive index adjusting agent) for obtaining a desired refractive index.

(resin)
As resin, the well-known material used as an easily bonding layer of a support body can be used, for example, acrylic resin, polyester-type resin, and urethane-type resin can be used.

  The acrylic resin can be obtained by acrylic monomers alone or by copolymerizing a plurality of types of acrylic monomers. Furthermore, it can also be produced using other monomers (comonomer).

  Examples of the acrylic monomer include acrylic acid; methacrylic acid; acrylic acid ester, such as alkyl acrylate (for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t- Butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, phenylethyl acrylate, etc.), hydroxy-containing alkyl acrylates (eg, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc.); Alkyl methacrylates (eg, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate) Salts, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenylethyl methacrylate, etc., hydroxy-containing alkyl methacrylate (for example, 2-hydroxyethyl) Methacrylates, 2-hydroxypropyl methacrylate, etc.); acrylamides; substituted acrylamides (eg, N-methylacrylamide, N-methylolacrylamide, N, N-dimethylolacrylamide, N-methoxymethylacrylamide, etc.); methacrylamide; substituted methacrylamide ( For example, N-methyl methacrylamide, N-methylol methacrylamide, , N-dimethylol methacrylamide, N-methoxymethyl methacrylamide, etc.); amino group substituted alkyl acrylate (eg, N, N-diethylaminoethyl acrylate); amino group substituted alkyl methacrylate (eg, N, N-diethylamino methacrylate); Epoxy group-containing acrylate (for example, glycidyl acrylate); Epoxy group-containing methacrylate (for example, glycidyl methacrylate); Acrylic acid salt (for example, sodium salt, potassium salt, ammonium salt); Methacrylic acid salt (for example, sodium salt, potassium salt) Salt, ammonium salt). The above-mentioned monomers can be used alone or in combination of two or more.

  Examples of comonomers include styrene and its derivatives; unsaturated dicarboxylic acids (eg, itaconic acid, maleic acid, fumaric acid); esters of unsaturated dicarboxylic acids (eg, methyl itaconate, dimethyl itaconate, methyl maleate, maleate) Dimethyl acid, methyl fumarate, dimethyl fumarate); unsaturated dicarboxylic acid salts (for example, sodium salts, potassium salts, ammonium salts); monomers containing sulfonic acid groups or salts thereof (for example, styrene sulfonic acid, vinyl sulfone) Acid and their salts (sodium salt, potassium salt, ammonium salt)); acid anhydrides such as maleic anhydride and itaconic anhydride; vinyl isocyanate; allyl isocyanate; vinyl methyl ether; vinyl ethyl ether; The above-mentioned monomers can be used alone or in combination of two or more.

  Examples of the polyester resin include an aqueous polyester obtained by a condensation polymerization reaction of a mixed dicarboxylic acid component and a glycol component.

  The dicarboxylic acid component is a dicarboxylic acid component having a sulfonic acid salt (dicarboxylic acid having a sulfonic acid salt and / or an ester-forming derivative thereof) in an amount of 5 to 5 with respect to all dicarboxylic acid components in the water-soluble polyester copolymer. It is a dicarboxylic acid component containing 15 mol%.

  As the dicarboxylic acid having a sulfonate and / or an ester-forming derivative thereof used in the present invention, those having an alkali metal sulfonate group are particularly preferable. For example, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, Alkali metal salts such as sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- [4-sulfophenoxy] isophthalic acid or ester-forming derivatives thereof are used. Isophthalic acid sodium salt or an ester-forming derivative thereof is particularly preferred. The dicarboxylic acid and / or ester-forming derivative thereof having these sulfonates is particularly preferably used in an amount of 6 to 10 mol% based on the total dicarboxylic acid component from the viewpoint of water solubility and water resistance.

  Other dicarboxylic acid components include aromatic dicarboxylic acid components (aromatic dicarboxylic acids and / or ester-forming derivatives thereof), alicyclic dicarboxylic acid components (alicyclic dicarboxylic acids and / or ester-forming derivatives thereof), Aliphatic dicarboxylic acid components (aliphatic dicarboxylic acid and / or ester-forming derivatives thereof) and the like.

  Examples of the aromatic dicarboxylic acid component mainly include a terephthalic acid component (terephthalic acid and / or an ester-forming derivative thereof), an isophthalic acid component (isophthalic acid and / or an ester-forming derivative thereof), and the like.

  Specific examples of the aromatic dicarboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and the like. Examples include ester-forming derivatives.

  Examples of the alicyclic dicarboxylic acid and / or ester-forming derivatives thereof include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 4 4,4'-bicyclohexyldicarboxylic acid or the like, or ester-forming derivatives thereof.

  In the present invention, a linear aliphatic dicarboxylic acid and / or an ester-forming derivative thereof may be used within a range of 15 mol% or less of the total dicarboxylic acid component. Examples of such dicarboxylic acid components include aliphatic dicarboxylic acids such as adipic acid, pimelic acid, speric acid, azelaic acid, and sebacic acid, and ester-forming derivatives thereof.

  In the present invention, ethylene glycol is preferably used in an amount of 50 mol% or more based on the total glycol component from the viewpoint of the mechanical properties of the polyester copolymer and the adhesiveness to the polyester film. As the glycol component used in the present invention, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyethylene glycol and the like may be used in combination in addition to ethylene glycol.

  As the polyurethane-based resin, the following commercially available aqueous polyurethane can be used.

  Examples of commercially available water-based polyurethanes include Takelac series W-7004, W-6010, W-605, W-512, W-511, W-405, Bayer's Impranil manufactured by Mitsui Chemicals Polyurethanes. DLH and Impranyl DLN, Daiichi Kogyo Seiyaku Co., Ltd. Superflex 100, Superflex 200, Superflex 300, Hydran HW-140, Hydran HW-111, Hydran HW-100, Hydran HW-101, Hydran HW-312, Hydran HW-311, Hydran HW-310, Hydran LW-513, Hydran HC-200, Hydran HC-400M, Bondick 1010C, Bondick 1050, Bondick 1070, Bondick 1310B, Bond Ikku 1310F, Bonn Dick 1310NS, Bonn Dick 1340, Bonn Dick 1510, Bonn Dick 1610NS, Bonn Dick 1630, Bonn Dick 1640, Bonn Dick 1670 (N), may be mentioned carbon Dick 1670-40 like. Among these commercially available water-based polyurethanes, particularly preferred products are W-7004, W-605, Impranyl DLH, Impranyl DLN, Superflex 100, Superflex 200, Hydran HW-312, Hydran HW-140, Hydran HW-310, And Hydran HW-311.

(Refractive index adjusting agent)
The refractive index adjusting agent used for the easy-adhesion layer is not particularly limited as long as the desired refractive index can be achieved, but the refractive index of the binder resin is generally around 1.5, which is relatively low. It is preferable that the agent has a relatively high refractive index such that the refractive index exceeds 1.7. Examples of such a high refractive index material include metal oxides such as tin oxide, cerium oxide, titanium oxide, yttrium oxide, lanthanum oxide, niobium oxide, and zirconium oxide. However, when the particle diameter of such a metal oxide exceeds 100 nm, the haze of the film increases. Therefore, the primary particle diameter is preferably 1 to 100 nm, and more preferably 1 to 50 nm. As the agent for achieving such a particle size, the above-mentioned metal oxide sol can be preferably used. Of these, tin oxide sol and cerium oxide sol are preferable.

  The metal oxide sol can be produced by a known method. For example, for the tin oxide sol, the method described in JP-B-35-6616 can be used.

  The metal oxide sol described above is commercially available from Taki Chemical Co., Ltd., and such materials can be used.

  The easy-adhesion layer according to the present invention can be formed by coating and drying on a plastic film using a generally well-known coating method.

  Examples of coating methods that can be used include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or US Pat. No. 2,681,294. Examples include the extrusion coating method using the described hopper. In addition, as required, U.S. Pat. Nos. 2,761,791, 3,508,947, 2,941,898, and 3,526,528, Harasaki A method of simultaneously applying two or more layers described in Yuji's “Coating Engineering”, page 253 (published by Asakura Shoten in 1973) can also be used. Drying conditions are generally 100 to 200 ° C. and about 10 seconds to 10 minutes.

  In applying the coating liquid for the easy adhesion layer onto the support, the support can be pretreated. Pretreatment includes chemical treatment, alkali treatment, mixed acid treatment, mechanical surface-roughening treatment, corona discharge treatment, ultraviolet treatment, high-frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, ozone treatment, and other surface activation treatments. Can be mentioned.

  When providing an easy-adhesion layer on the support, it can be provided before or after stretching during film formation of the support film, but it is not necessary to consider the stretchability of the easy-adhesion layer. is there.

  If necessary, a surfactant, a swelling agent, a matting agent, an antihalation dye, a pigment, an antifoggant, a preservative, and the like may be added to the coating solution.

  Moreover, you may provide a 2nd easily bonding layer on an easily bonding layer as needed. At this time, the refractive index of the second easy-adhesion layer is preferably the same as or smaller than the refractive index of the first easy-adhesion layer adjacent to the support, and is equal to or greater than the refractive index of the binder of the electromagnetic wave shielding layer. It is preferable. In particular, from the viewpoint of adhesiveness of the transparent conductive film and reduction of interference unevenness, the second easy-adhesion layer is preferably made of gelatin as a main binder.

<< Transparent conductive film and manufacturing method thereof >>
In the method for producing a transparent conductive film of the present invention, after exposing the photosensitive material for forming a transparent conductive film, development processing is performed to form a metallic silver part in a mesh shape, or after exposing the photosensitive material for forming a transparent conductive film, Development processing is performed, and further reinforcement processing is performed to form a metallic silver portion in a mesh shape.

(exposure)
In the method for producing a transparent conductive film of the present invention, pattern-like exposure is performed on an emulsion layer provided on a support. The exposure can be performed using electromagnetic waves. Examples of the electromagnetic wave include light such as visible light and ultraviolet light, and radiation such as X-rays. Furthermore, a light source having a wavelength distribution may be used for exposure, or a light source having a specific wavelength may be used.

  The method of exposing the emulsion layer in a pattern may be performed by surface exposure using a photomask or by scanning exposure using a laser beam.

(developing)
In the method for producing a transparent conductive film of the present invention, the emulsion layer is exposed and then developed (hereinafter also referred to as chemical development to distinguish it from physical development). For the chemical development, a development processing technique mainly composed of normal chemical development used for a silver salt photographic film, photographic paper, a printing plate making film, a photomask emulsion mask or the like can be used. The developer is not particularly limited as long as it is a developer mainly composed of chemical development, but a PQ developer, MQ developer, MAA developer or the like can also be used, and a lith developer such as D-85. Can be used.

  Here, “chemical development” refers to a development process in which metallic silver of an image formed by developing a latent image silver as a catalyst is formed by reducing silver ions constituting individual silver halide grains.

(Fixing)
In the present invention, fixing is performed to remove and stabilize the unexposed silver salt (silver halide grains). For fixing in the present invention, fixing techniques used for silver salt photographic film, photographic paper, film for printing plate making, emulsion mask for photomask, and the like can be used.

  In the fixing solution used in the present invention, sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, or the like can be used as a fixing agent. Aluminum sulfate, chromium sulfate, or the like can be used as a hardener for fixing. As the fixing agent preservative, sodium sulfite, potassium sulfite, ascorbic acid, erythorbic acid and the like described in the developing composition can be used, and citric acid, oxalic acid, and the like can be used.

(Reinforcement processing)
In one of the methods for producing a transparent conductive film of the present invention, the photosensitive material for forming a transparent conductive film is exposed and developed, and further, in order to improve conductivity, a reinforcing treatment is performed to form a metallic silver portion in a mesh shape. Form. Examples of the intensifying process include a physical development process and / or a plating process.

  In the present invention, for the purpose of imparting conductivity to the metal silver portion formed by the exposure and development processing, physical development and / or plating treatment for supporting the conductive metal particles on the metal silver portion is performed.

  In the present invention, physical development refers to reduction of metal ions such as silver ions with a reducing agent on metal or metal compound nuclei to precipitate metal particles. This physical phenomenon is used for instant B & W film, instant slide film, printing plate manufacturing, and the like, and the technology can be used in the present invention.

  Further, the physical development may be performed simultaneously with the development processing after exposure or separately after the development processing.

  In the present invention, the plating process can be performed using electroless plating (chemical reduction plating or displacement plating), electrolytic plating, or both electroless plating and electrolytic plating. For the electroless plating in the present invention, a known electroless plating technique can be used, for example, an electroless plating technique used in a printed wiring board or the like can be used, and the electroless plating is an electroless copper plating. Preferably there is.

  Chemical species contained in the electroless copper plating solution include copper sulfate and copper chloride, formalin and glyoxylic acid as the reducing agent, EDTA and triethanolamine as the copper ligand, and other bath stabilization and plating film Examples of the additive for improving the smoothness include polyethylene glycol, yellow blood salt, and bipyridine. Examples of the electrolytic copper plating bath include a copper sulfate bath and a copper pyrophosphate bath.

  The plating speed at the time of plating in the present invention can be performed under moderate conditions, and high-speed plating of 5 μm / hr or more is also possible. In the plating treatment, various additives such as a ligand such as EDTA can be used from the viewpoint of improving the stability of the plating solution.

(Electromagnetic wave shielding material)
The transparent conductive film of the present invention obtained by the method for manufacturing a transparent conductive film of the present invention has high conductivity and light transmittance, and is used as an electromagnetic wave shielding material with reduced interference unevenness and moire.

(Conductive metal part)
In the present invention, the electromagnetic wave shielding pattern made of the conductive metal part is formed by conducting a physical development or plating treatment on the pattern made of the metal silver part formed by the above-described exposure and development process. It is preferably formed by supporting metal particles.

  In the present invention, metallic silver is preferably formed in the exposed portion in order to increase transparency.

  In addition to the silver described above, the conductive metal particles supported on the metallic silver portion by physical development and / or plating treatment are copper, aluminum, nickel, iron, gold, cobalt, tin, stainless steel, tungsten, chromium, titanium. , Palladium, platinum, manganese, zinc, rhodium and other metals, or alloys of these in combination. From the viewpoint of conductivity, cost, etc., copper, aluminum or nickel particles are preferred. Moreover, when providing magnetic field shielding properties, it is preferable to use paramagnetic metal particles.

  In the conductive metal part, the conductive metal particles contained in the conductive metal part are preferably copper particles from the viewpoint of enhancing contrast and preventing the conductive metal part from being oxidized and fading over time. More preferably, the surface is blackened. The blackening treatment can be performed using a method performed in the printed wiring board field. For example, blackening treatment is performed by treating at 95 ° C. for 2 minutes in an aqueous solution of sodium chlorite (31 g / l), sodium hydroxide (15 g / l), and trisodium phosphate (12 g / l). Can do.

  The conductive metal part preferably contains 50% by mass or more, and more preferably 60% by mass or more of silver with respect to the total mass of the metal contained in the conductive metal part. If silver is contained in an amount of 50% by mass or more, the time required for physical development and / or plating can be shortened, productivity can be improved, and cost can be reduced.

  Furthermore, when copper and palladium are used as the conductive metal particles forming the conductive metal part, the total mass of silver, copper and palladium is 80% by mass or more based on the total mass of the metal contained in the conductive metal part. It is preferable that it is 90 mass% or more.

  Since the conductive metal portion in the present invention carries conductive metal particles, good conductivity can be obtained. For this reason, the surface resistivity of the translucent electromagnetic wave shielding film (conductive metal part) of the present invention is preferably 10Ω / □ or less, more preferably 1Ω / □ or less, and 0.5Ω / □. Most preferably:

  In the use of the translucent electromagnetic wave shielding material, the conductive metal portion preferably has a line width of 20 μm or less and a line interval of 50 μm or more. The conductive metal portion may have a portion whose line width is wider than 20 μm for the purpose of ground connection or the like. Further, from the viewpoint of making the image inconspicuous, the line width of the conductive metal part is preferably less than 18 μm, more preferably less than 15 μm, further preferably less than 14 μm, and less than 10 μm. Is more preferred, most preferably less than 7 μm.

(Light transmissive part)
In the present invention, the average transmittance in the visible light region is obtained by integrating the transmittances in the visible light region obtained by measuring the transmittance in the visible light region of 400 to 700 nm at least every 5 nm. Define what you want.

  In measurement, the measurement aperture needs to be sufficiently larger than the mesh pattern described above, and is obtained by measuring at least 100 times larger than the mesh area of the mesh.

  In the present invention, the average transmittance in the visible light region is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.

(Functional materials other than electromagnetic shielding)
The transparent conductive film of the present invention may be separately provided with a functional layer having functionality as necessary. This functional layer can have various specifications for each application. For example, as an electromagnetic shielding material for displays, the anti-reflection layer with anti-reflection function with adjusted refractive index and film thickness, non-glare layer or anti-glare layer (both have anti-glare function), and absorbs near infrared rays. Near-infrared absorbing layers made of chemical compounds and metals, layers with a color tone adjustment function that absorbs visible light in a specific wavelength range, antifouling layers with a function that easily removes dirt such as fingerprints, and scratch-resistant hardware A coating layer, a layer having an impact absorbing function, a layer having a function of preventing glass scattering when glass is broken, and the like can be provided. These functional layers may be provided on the opposite side of the silver halide grain-containing layer and the support, or may be provided on the same side.

  These functional films may be directly bonded to the PDP, or may be bonded to a transparent substrate such as a glass plate or an acrylic resin plate separately from the plasma display panel body. These functional films are called optical filters (or simply filters), and if they are for plasma displays, they are called plasma display filters.

  In order to suppress reflection of external light and suppress a decrease in contrast, an antireflection layer provided with an antireflection function contains inorganic substances such as metal oxides, fluorides, silicides, borides, carbides, nitrides and sulfides. , Vacuum deposition method, sputtering method, ion plating method, ion beam assist method, etc., a method of laminating a single layer or a multilayer, such as a method of laminating a resin having different refractive index such as acrylic resin, fluorine resin, etc. There is. Moreover, the film which gave the antireflection process can also be affixed on this filter. Further, if necessary, a non-glare layer or an anti-glare layer can be provided. For the non-glare layer or the anti-glare layer, a method of coating fine powders such as silica, melamine, acrylic, etc. into an ink and coating the surface can be used. The ink can be cured by thermal curing or photocuring. Further, a non-glare-treated or anti-glare-treated film can be pasted on the filter. Further, if necessary, a hard coat layer can be provided.

  The near-infrared absorbing layer is a layer containing a near-infrared absorbing dye such as a metal complex compound or a silver sputtered layer. Here, the silver sputter layer can cut light of 1000 nm or more from near infrared rays, far infrared rays to electromagnetic waves by alternately laminating dielectric layers and metal layers on a substrate by sputtering or the like. The dielectric layer is a transparent metal oxide such as indium oxide or zinc oxide, and the metal layer is generally silver or a silver-palladium alloy. Usually, the dielectric layer starts with 3 layers, 5 layers, 7 or 11 layers are stacked.

  A layer having a color tone adjustment function that absorbs visible light in a specific wavelength range is displayed in blue because the PDP has a characteristic that the phosphor that emits blue light emits red light in addition to blue. There is a problem that a portion to be displayed is displayed in a purplish color, and as a countermeasure against this, it is a layer that corrects colored light and contains a dye that absorbs light at around 595 nm.

  The transparent conductive film of the present invention can be used as an electromagnetic shielding material because it has good electromagnetic shielding properties and transparency. In particular, the electromagnetic wave shielding material of the present invention is a front surface of a display such as CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electroluminescence), microwave oven, electronic device, printed wiring board, etc. It can use suitably as a translucent electromagnetic wave shielding material used. Furthermore, it can be used as various conductive wiring materials such as circuit wiring.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
(Preparation of polyester support)
After drying polyethylene terephthalate pellets with an intrinsic viscosity of 0.65 dl / g at 150 ° C. for 6 hours, as a die for extrusion molding, melt extrusion at 290 ° C. using a coat hanger type T die, and applying electrostatically, about 30 ° C. The film was rapidly cooled on a cooling drum to obtain an unstretched film having a thickness of 1.1 mm. The obtained unstretched film was biaxially stretched longitudinally and laterally under the following conditions and heat-fixed, and then both ears were slit to obtain a biaxially stretched polyester support having a thickness of 100 μm.

Longitudinal stretching: Preheating roll temperature due to difference in roll peripheral speed: 78 ° C
Film temperature during stretching with infrared heater: 95 ° C
Stretch ratio: 3.3 times Lateral stretch: Stretching by stenter method Zone temperature: 100 ° C
Stretch ratio: 3.3 times Heat setting temperature: 220 ° C
(Polyester support with easy adhesion layer)
Both surfaces of the 100 μm polyester support thus obtained were subjected to a corona discharge treatment of 12 W · min / m ² , and an easy-adhesion coating solution B1 was applied to each surface to a dry film thickness of 0.1 μm. The top was subjected to a corona discharge treatment of 12 W · min / m ² , and the easy-adhesion coating solution B2 was applied to a dry film thickness of 0.06 μm. Then, heat processing was implemented at 120 degreeC for 1.5 minutes, and the polyester support body with an easily bonding layer was obtained.

<Easily adhesive coating solution B1>
Easy adhesion layer resin P-1 50g
Refractive index adjuster Z-1 listed in Table 1 Compound (UL-1) 0.2 g
Finish to 1000ml with water <Easily adhesive coating solution B2>
10g gelatin
Compound (UL-1) 0.2g
Compound (UL-2) 0.2g
Silica particles (average particle size 3μm) 0.1g
Hardener (UL-3) 1g
Finish to 1000ml with water

(Easily adhesive layer resin)
P-1: Copolymer latex liquid of 20 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, and 40 parts by mass of butyl acrylate (solid content: 30%)
(Refractive index adjusting agent)
Z-1: Tin oxide sol (synthesis of tin oxide sol)
65 g of SnCl ₄ .5H ₂ O was dissolved in 2000 ml of distilled water to obtain a homogeneous solution, which was then boiled to obtain a precipitate. The produced precipitate is taken out by decantation and washed with distilled water many times. Silver nitrate is added dropwise to distilled water in which the precipitate has been washed, and after confirming that there is no reaction of chlorine ions, distilled water is added to the washed precipitate to make a total volume of 2000 ml. To this, 40 ml of 30% aqueous ammonia was added and heated to obtain a uniform sol. Further, while adding ammonia water, the solution was concentrated by heating until the solid content concentration of SnO ₂ reached 8.3% by mass to obtain a tin oxide sol.

[Preparation of photosensitive material for forming transparent conductive film]
(Preparation of silver halide emulsion)
The following solution A was kept at 34 ° C. in a reaction vessel, and the pH was adjusted to 2.95 using nitric acid (concentration 6%) while stirring at high speed using a mixing and stirring device described in JP-A-62-2160128. It was adjusted. Subsequently, the following solution B and the following solution C were added at a constant flow rate over 8 minutes and 6 seconds using the double jet method. After completion of the addition, the pH was adjusted to 5.90 using sodium carbonate (concentration 5%), and then the following solution D and solution E were added.

(Solution A)
Alkali-treated inert gelatin (average molecular weight 100,000) 18.7g
Sodium chloride 0.31g
Solution I 1.59ml
Pure water 1246ml
(Solution B)
169.9g of silver nitrate
Nitric acid (concentration 6%) 5.89ml
Finish to 317.1 ml with pure water (Solution C)
Alkali-treated inert gelatin (average molecular weight 100,000) 5.66 g
Sodium chloride 58.8g
13.3 g of potassium bromide
Solution I 0.85ml below
Solution II below 2.72 ml
Finish to 317.1 ml with pure water.

(Solution D)
2-Methyl-4hydroxy-1,3,3a, 7-tetraazaindene 0.56 g
112.1 ml of pure water
(Solution E)
Alkali-treated inert gelatin (average molecular weight 100,000) 3.96 g
Solution I 0.40ml
128.5 ml of pure water
(Solution I)
Surfactant: 10% methanol solution of polyisopropylene polyethylene oxydisuccinate sodium salt (Solution II)
10% aqueous solution of rhodium hexachloride complex After completion of the above operation, desalting and water washing are performed using a flocculation method at 40 ° C. according to a conventional method. The pH was adjusted to 5.90 at 40 ° C., and finally a silver chlorobromide cubic grain emulsion containing 10 mol% of silver bromide and having an average grain size of 0.09 μm and a coefficient of variation of 10% was obtained.

(Solution F)
Alkali-treated inert gelatin (average molecular weight 100,000) 16.5g
Pure water 139.8ml
The silver halide emulsion was subjected to chemical sensitization at 60 ° C. for 50 minutes using 20 mg of sodium thiosulfate per mole of silver halide, and 4-hydroxy-6-methyl-1,3, after completion of chemical sensitization. 500 mg of 3a, 7-tetrazaindene (TAI) per 1 mol of silver halide and 150 mg of 1-phenyl-5-mercaptotetrazole per 1 mol of silver halide were added to obtain silver halide emulsion EM-1. In this silver halide emulsion EM-1, the volume ratio of silver halide grains to gelatin (silver halide grains / gelatin) was 0.625. Further, a dye (F-1) was added at 30 mg / m ² and a hardener (H-1) was added at a ratio of 150 mg per 1 g of gelatin to prepare an emulsion layer coating solution.

  The coating solution thus obtained was placed on one surface of the above-mentioned easily-adhesive polyester film support so that the emulsion layer dry film thickness, non-mesh film thickness, silver amount, presence or absence of surfactants, or the type described in Table 1 were obtained. After the application, an aging treatment was performed at 50 ° C. for 24 hours to prepare a photosensitive material for forming a transparent conductive film. The addition amount of the surfactant was such that the surface tension of the emulsion layer coating solution was 20 mN / m.

〔exposure〕
The obtained photosensitive material was cut into A4 size and exposed with a UV exposure device through a mesh photomask (pitch / line width = 300 μm / 5 μm).

[Chemical development]
The exposed photosensitive material is developed for 60 seconds at 25 ° C. using the following developer (DEV-1), and then fixed for 120 seconds at 25 ° C. using the following fixing solution (FIX-1). It was.

(DEV-1)
500 ml of pure water
Metol 2g
80 g of anhydrous sodium sulfite
Hydroquinone 4g
4g borax
Sodium thiosulfate 10g
Potassium bromide 0.5g
Add water to bring the total volume to 1 liter (FIX-1)
750 ml of pure water
Sodium thiosulfate 250g
Anhydrous sodium sulfite 15g
Glacial acetic acid 15ml
Potash alum 15g
Add water to bring the total volume to 1 liter [Physical development]
Next, physical development was performed at 25 ° C. for 10 minutes using the following physical developer (PDEV-1), followed by washing with water and drying.

(PDEV-1)
The following A liquid and B liquid are mixed immediately before processing (A liquid).
400ml of pure water
Citric acid 10g
Disodium hydrogen phosphate 1g
Ammonia water (28% aqueous solution) 1.2ml
Hydroquinone 3g
(Liquid B)
10 ml of pure water
0.4 g of silver nitrate
(Washing treatment and drying treatment)
The washing process was performed with tap water for 10 minutes. Moreover, the drying process was dried until it became a dry state using drying air (50 degreeC).

[Electrolytic copper plating]
Further, by using the following plating solution (PL-1), electrolytic plating was performed at 6A and 25 ° C. for 2 minutes to prepare transparent conductive films 101 to 107 having conductive metal portions made of developed silver and copper.

(PL-1)
1000ml of pure water
200 g of copper sulfate
50g of sulfuric acid
The obtained conductive metal portion of the transparent conductive film had a mesh pattern corresponding to the exposure pattern, and in each sample, the line width was 10 μm and the pitch width was 290 μm. The aperture ratio of the light transmission portion was about 93%.

[Measurement and evaluation]
Measurement of refractive index of support and easy-adhesion layer, evaluation of emulsion layer (photosensitive material for forming transparent conductive film), suitability for application, transparency of transparent conductive film, surface resistance, interference unevenness and moire by the following methods did.

(Applicability)
At the stage where the emulsion layer was applied and dried, the presence or absence of unevenness on the emulsion layer side was visually examined and evaluated according to the following criteria.

○: Unevenness is not recognized Δ: Unevenness is slightly observed ×: Unevenness is considerably recognized ××: Unevenness is uneven (plating uniformity)
The samples after the plating treatment were visually examined for unevenness and evaluated according to the following criteria.

○: Unevenness is hardly recognized Δ: Unevenness is slightly recognized (about 25% of the total area)
X: Unevenness is considerably observed (about 50% of the total area)
XX: Very uneven (80% or more of the total area)
(Transmittance)
The total transmittance in the wavelength range of 380 to 780 nm excluding the contribution of light absorption and reflection of the support of the sample having the conductive metal part and the light transmissive part obtained as described above was measured, and the conductivity The ratio with the theoretical transmittance calculated from the aperture ratio obtained by measuring the line width of the metal part was evaluated according to the following criteria.

A: Total transmittance / theoretical transmittance is 90% or more ○: Total transmittance / theoretical transmittance is 80% to less than 90% Δ: Total transmittance / theoretical transmittance is 70% to less than 80% ×: Total transmittance / Theoretical transmittance is less than 70% (Surface resistance)
The surface resistance of the conductive metal portion of the transparent conductive film was measured using a resistivity meter Loresta GP series 4-probe probe manufactured by Dia Instruments Co., Ltd., and 20 points were measured to obtain an average.

(Interference unevenness)
The sample was placed on a black board with the emulsion layer facing upward, illuminated with a 27 W three-wavelength fluorescent lamp from above, and visually checked for the presence or absence of interference unevenness, and evaluated according to the following criteria.

○: Unevenness is not recognized Δ: Unevenness is slightly observed ×: Unevenness is considerably recognized (moire)
A sample was placed on the front face of a Hitachi PDP TV and a Matsushita Electric PDP TV at a bias angle with a minimum moire, and visual sensory evaluation was performed. While observing the television screen directly, the image display surface was observed by changing the observation position with respect to the television screen at various positions such as oblique, and evaluated according to the following criteria.

○: Moire is not recognized Δ: Moire is slightly recognized ×: Moire is considerably recognized Table 1 shows the results of measurement and evaluation.

  As is clear from Table 1, the coating property of the transparent conductive film-forming photosensitive material containing the fluorine-containing surfactant having an unsaturated carbon bond of the present invention is good, and the plating uniformity is also good. It can be seen that the transparent conductive film of the present invention produced in this way satisfies high transmittance and high conductivity at the same time, and has reduced interference unevenness and moire. It can also be seen that interference unevenness is reduced when the refractive index of the easy adhesion layer is smaller than the refractive index of the support and the difference in refractive index between the easy adhesion layer and the support is within 0.1.

Claims (9)

Forming a transparent conductive film on the support having an emulsion layer containing at least silver halide and a binder, and after the exposure, developing treatment to form a metallic silver part in a mesh shape A photosensitive material for forming a transparent conductive film, wherein the emulsion layer contains a fluorine-containing surfactant having an unsaturated carbon bond. A transparent conductive film is formed by forming an emulsion layer containing at least silver halide and a binder on a support, developing a light-sensitive layer after exposure, and further performing a reinforcement treatment to form a metallic silver portion in a mesh shape. A photosensitive material for forming a transparent conductive film, wherein the emulsion layer contains a fluorine-containing surfactant having an unsaturated carbon bond. 3. The photosensitive material for forming a transparent conductive film according to claim 1, wherein the silver halide coating silver amount is 1 g / m ² or less and the dry thickness of the emulsion layer is 0.5 μm or less. . The thickness of the emulsion layer of the non-mesh part (light transmission part) of the transparent conductive film obtained by forming the metallic silver part in the mesh form is 0.1 μm or less. The photosensitive material for transparent conductive film formation of any one of these. The support has an easy-adhesion layer on the emulsion layer side, the refractive index of the easy-adhesion layer is smaller than the refractive index of the support, and the difference in refractive index between the easy-adhesion layer and the support is 0. The photosensitive material for forming a transparent conductive film according to claim 1, wherein the photosensitive material is within one. A method for producing a transparent conductive film, comprising exposing the photosensitive material for forming a transparent conductive film according to any one of claims 1 to 5 to a developing process to form a metallic silver portion in a mesh shape. A transparent conductive film characterized in that the photosensitive material for forming a transparent conductive film according to any one of claims 1 to 5 is exposed, developed, and further intensified to form a metallic silver portion in a mesh shape. A method for producing a membrane. A transparent conductive film obtained by the production method according to claim 6. An electromagnetic wave shielding material using the transparent conductive film according to claim 8.