JP2008270405A - Transparent electromagnetic wave shielding film, its manufacturing method, and plasma display panel using film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent electromagnetic wave shielding film which satisfies both high optical transparency and high conductivity (electromagnetic wave shielding ability) without generating moire, and to provide its manufacturing method, and a plasma display panel using the film. <P>SOLUTION: The transparent electromagnetic wave shielding film is manufactured by way of a process for forming conductive metallic mesh by performing mesh pattern exposure in a photosensitive material to be obtained by including a layer, containing photosensitive halogenated silver particles and a binder, on a support body, and then, chemically processing and also plating-processing the photosensitive material. A specified relational expression is satisfied in the cross sectional shape of the conductive metallic mesh. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a transparent electromagnetic wave shielding film that shields electromagnetic waves generated from electronic devices such as a mobile phone, a microwave oven, a CRT, and a flat panel display, a manufacturing method thereof, and a flat panel display using the same.

  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, in electronic equipment, it is required to suppress the intensity of electromagnetic wave emission within the standard or regulation.

  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. The electromagnetic wave shielding ability can be simply expressed by a surface resistance value. A light-transmitting electromagnetic wave shielding material for PDP is required to be 10Ω / □ or less, and 2Ω / □ is required for a consumer plasma television using PDP. There is a high need for the following, more desirably, extremely high conductivity of 0.2Ω / □ 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 subjected to exposure, chemical development processing and fixing processing in a mesh pattern to form a metallic silver portion, and then conductive metal particles are supported on the metallic silver portion by physical development processing and / or plating treatment. In this method, a conductive mesh is formed, and this method has high electromagnetic shielding properties and transparency, and can further improve the moire problem. However, in the presence of panels with various pixel pitches, the moire problem has not been sufficiently solved, and it is necessary to control the line width and pitch width of the mesh lines for each pixel pitch panel. In addition, the transparency is still insufficient, and it is necessary to provide a near-infrared shielding layer and a bright line cut layer generated by excitation of a rare gas separately from the electromagnetic shielding layer. Therefore, further improvement in transmittance has been demanded as an electromagnetic wave shielding film. When the line width of the mesh line is reduced or the pitch width is increased in order to improve the moire and permeability, the electromagnetic shielding properties are deteriorated, and there are still problems in achieving both.
JP 2003-46293 A JP-A-11-26980 JP 2004-221564 A JP 2004-221565 A

  The present invention has been made in view of the above problems, and its problem is to produce a transparent electromagnetic wave shielding film that is free from moiré and satisfies both high light transmittance and high electrical conductivity (electromagnetic wave shielding ability) performances. It is to provide a method and a plasma display panel using the method.

  As a result of intensive studies to solve the above problems, the present inventor is different from the etching mesh method using the photolithography method because the shape of the conductive metal mesh in the silver salt method is formed later by the plating method. It was easy to be saddle-shaped, and the knowledge that this greatly affects the above-mentioned problem was obtained. It was also found that these problems can be solved by controlling the shape of the conductive metal mesh. That is, the said subject which concerns on this invention is solved by the following means.

1. Produced through a process of forming a conductive metal mesh by subjecting a photosensitive material comprising a layer containing photosensitive silver halide grains and a binder on a support to a mesh pattern exposure, chemical development, and further plating. The transparent electromagnetic wave shielding film, wherein the cross-sectional shape of the conductive metal mesh satisfies the following relational expression:
(Formula): 0.85 ≦ S / (a × b) ≦ 1.0
a: The length of the bottom of the cross section of the conductive metal mesh when the support is down b: The distance connecting the top and bottom of the conductive metal mesh S: The cross sectional area of the conductive metal mesh 2. The transparent electromagnetic wave shielding film according to 1 above, wherein the length a of the bottom of the cross section of the conductive metal mesh and the distance b connecting the base and top of the cross section of the conductive metal mesh satisfy the following relational expression.
(Formula): 0.3 ≦ b / a ≦ 0.6
3. 3. The transparent electromagnetic wave shielding film as described in 1 or 2 above, wherein the length a of the bottom of the cross section of the conductive metal mesh is 8 μm or more and 18 μm or less.

  4). 4. The transparent electromagnetic wave shielding film according to any one of 1 to 3 above, wherein a distance b connecting the bottom and apex of the cross section of the conductive metal mesh is 2 μm or more and 10 μm or less.

5. The length a of the base of the cross section of the conductive metal mesh, the distance b connecting the base and top of the cross section of the conductive metal mesh, and the cross sectional area S of the conductive metal mesh satisfy the following relational expression: The transparent electromagnetic wave shielding film as described in any one of 1-4.
(Formula): 0.90 ≦ S / (a × b) ≦ 1.0
6). 6. The transparent electromagnetic wave shielding film according to any one of 1 to 5, wherein after the chemical development treatment, a physical development treatment is performed and then a plating treatment is performed.

  7. 7. The transparent electromagnetic wave shielding film as described in any one of 1 to 6 above, wherein the photosensitive silver halide grains have a silver chloride content of 50 mol% or more.

  8). The silver / binder volume ratio of the silver halide grains in the layer containing the photosensitive silver halide grains and the binder is from 0.3 to 2.0, according to any one of 1 to 7 above The transparent electromagnetic wave shielding film as described.

9. The silver coating particle amount of the photosensitive silver halide grain and the layer containing the binder is 0.3 g / m ² or more and 3.0 g / m ² or less in terms of silver. The transparent electromagnetic wave shielding film as described in any one of -8.

  10. 10. The transparent electromagnetic wave shielding film according to any one of 1 to 9 above, wherein the plating treatment is electrolytic copper plating treatment, and the concentration of copper sulfate in the plating bath is 60 to 120 g / l.

  11. It is a manufacturing method of a transparent electromagnetic wave shielding film, Comprising: The transparent electromagnetic wave shielding film as described in any one of said 1-10 is manufactured, The manufacturing method of the transparent electromagnetic wave shielding film characterized by the above-mentioned.

  12 A plasma display panel using the transparent electromagnetic wave shielding film according to any one of 1 to 10 above.

  According to the above-mentioned means of the present invention, there is provided a transparent electromagnetic wave shielding film which is free from moire and simultaneously satisfies the performance of high light transmittance and high electrical conductivity (electromagnetic wave shielding ability), a manufacturing method thereof, and a plasma display panel used therefor can do.

The transparent electromagnetic wave shielding film of the present invention is a conductive metal obtained by subjecting a photosensitive material having a layer containing a photosensitive silver halide and a binder on a support to a mesh pattern exposure, chemical development, and further plating. In the transparent electromagnetic wave shielding film produced through the step of forming a mesh, the cross-sectional shape of the conductive metal mesh satisfies the following relational expression.
(Formula): 0.85 ≦ S / (a × b) ≦ 1.0
a: the length of the bottom of the cross section of the conductive metal mesh when the support is down b: the distance connecting the apex and the bottom of the conductive metal mesh S: the cross sectional area of the conductive metal mesh The “distance connecting the apex and the base” represents the shortest distance connecting the apex and the base, that is, the length of the vertical line extending from the apex to the base.

  The above features are technical features common to the inventions according to claims 1 to 12.

  Hereinafter, the present invention and its components will be described in detail.

[Cross-sectional shape of conductive metal mesh]
In the present invention, the length a of the bottom of the cross section of the conductive metal mesh, the distance b connecting the top and bottom of the conductive metal mesh, and the cross sectional area S of the conductive metal mesh are, for example, FIB (focused ion beam). After performing cross section processing by the method, a SIM image or SEM image of the mesh cross section can be taken and obtained with commercially available image analysis software (for example, LUZEX manufactured by Nireco Corporation, Image-Pro manufactured by Nippon Roper Corporation). . The calculation method of the mesh cross-sectional area S differs depending on the software specifications used. For example, the mesh cross-section is enclosed by a contour trace tool, and the area of the enclosed portion is obtained by software calculation.

  In the present invention, the conductive metal mesh is composed of developed silver formed by a chemical development process and a physical development process, and a metal such as copper or nill produced by a plating process. The bottom side of the conductive metal mesh is the length of the boundary line between the conductive metal part when the support is down and the part having no metal such as the support or gelatin undercoat layer. The distance connecting the apex and the base of the conductive metal mesh is the shortest distance between the base and the apex.

  In the present invention, the length a of the bottom of the cross section of the conductive metal mesh, the distance b connecting the top and bottom of the conductive metal mesh, and the cross sectional area S of the conductive metal mesh are 0.85 ≦ S / (a Xb) ≦ 1.0. Preferably, 0.90 ≦ S / (a × b) ≦ 1.0.

  As a means for making such a mesh shape, a plurality of factors are entangled in the silver salt method, and it is not possible to limit it to a general one, and various means can be taken. This can be achieved by a combination of the halogen composition, silver / binder volume ratio, physical development treatment, plating treatment composition, and the like. In the present invention, in order to obtain the plating shape of the present invention, it is preferable to perform a plating process after a chemical development process and then a physical development process, and the silver chloride content of the photosensitive silver halide grains is The silver / binder volume ratio of the silver halide grains in the layer composed of the photosensitive silver halide grains and the binder is preferably 0.3 or more and 2.0 or less. The plating treatment is electrolytic copper plating, and the copper sulfate concentration in the plating bath is preferably 60 to 120 g / l.

  In the present invention, in order to obtain the maximum effect of the present invention, the length b of the base of the cross section of the conductive metal mesh and the distance b connecting the base and apex of the cross section of the conductive metal mesh are 0.3 ≦ b / It is preferable that the relational expression of a ≦ 0.6 is satisfied, and the length a of the base of the cross section of the conductive metal mesh is preferably 8 μm or more and 18 μm or less, and the base and vertex of the cross section of the conductive metal mesh are defined. The connecting distance b is preferably 2 μm or more and 10 μm or less. There are several methods for achieving these. For example, it can be adjusted by the mesh line width at the time of exposure, the composition of the physical developer, the development time, the composition of the plating bath, the plating time, and the like.

[Silver halide grain emulsion-containing layer]
In the present invention, a photosensitive silver halide grain and a silver halide grain emulsion-containing layer containing a binder, which will be described later, are provided on the support. In addition to this, the silver halide grain emulsion-containing layer is a hardener. , Hardeners, activators and the like.

  In the present invention, the silver / binder volume ratio of the silver halide grains in the photosensitive silver halide grain emulsion-containing layer is preferably from 0.3 to 2.0. 0.5 to 1.0 is a more preferable embodiment. If it is smaller than 0.3, it is difficult to obtain the mesh cross-sectional shape of the present invention. If it is larger than 2.0, the binder cannot sufficiently hold the silver halide grains, and the silver halide grains are aggregated. It is not preferable because it occurs.

In the present invention, the coated silver amount of the photosensitive silver halide grain emulsion-containing layer is preferably 0.3 g / m ² or more and 3.0 g / m ² or less in terms of silver. 0.5 g / m ² or more and 2.0 g / m ² or less is a more preferable embodiment. 0.3 g / m ² it is difficult to obtain the mesh cross section smaller and the present invention is not preferable because fogging is increased permeability of 3.0 g / m ² larger than the silver halide grains is reduced.

[Silver halide grains]
The composition of the silver halide grains used in the present invention has an arbitrary halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. However, in order to obtain the effect of the present invention, the silver chloride content is preferably 50 mol% or more, and the silver chloride content is more preferably 70 mol% or more.

  In order to reduce the surface specific resistance after silver halide grains are developed to become metallic silver grains and effectively block electromagnetic waves, the contact area between developed silver grains needs to be as large as possible. For this purpose, a smaller silver halide grain size is better to increase the surface area ratio, but too small grains tend to agglomerate into large agglomerates, in which case the contact area will be reduced, so there is an optimum grain size. To do. In the present invention, the average grain size of silver halide grains is preferably from 0.01 to 0.5 μm, more preferably from 0.03 to 0.3 μm, in terms of cubic equivalent diameter. The cubic equivalent diameter of silver halide grains represents the length of one side when a volume equal to the volume of each grain is converted into a cube. The average grain size of silver halide grains is the temperature at the time of preparation of silver halide grains, pAg, pH, addition rate of silver ion solution and halogen solution, grain size control agent (for example, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, benztriazole, tetrazaindene compounds, nucleic acid derivatives, thioether compounds, etc.) can be appropriately combined and controlled.

  In the present invention, the shape of the silver halide grains is not particularly limited, and for example, spherical, cubic, flat plate (hexagonal flat plate, triangular flat plate, tetragonal flat plate, etc.), octahedron, tetrahedron It can be in various shapes such as shapes. The particle size distribution is not particularly limited, but a narrow distribution is preferable from the viewpoint of enhancing the transparency while sharply reproducing the outline of the pattern and maintaining high conductivity during pattern formation by exposure. The particle size distribution of the silver halide grains used in the light-sensitive material according to the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
(In the formula, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
The silver halide grains used in the present invention may further contain other elements. For example, in a photographic emulsion, it is also useful to dope metal ions used to obtain a high-contrast emulsion. In particular, Group 8-10 metal ions such as iron ion, rhodium ion, ruthenium ion and iridium ion are preferably used because the difference between the exposed portion and the unexposed portion tends to be clearly generated when the metal silver image is generated.

  These metal ions can be added to the silver halide grain emulsion in the form of a salt or a complex salt. 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 potassium bromide rhodate and potassium iridate.

In the present invention, the content of the metal ion compound contained in the silver halide grains, per mol of silver halide is preferably 10 ^-10 to 10 ^-2 mol / mol Ag, 10 ^-9 to 10 More preferably, it is ⁻³ mol / mol Ag.

  In order for silver halide grains to contain the above-described metal ions, the metal compound is subjected to physical ripening before formation of silver halide grains, during formation of silver halide grains, after formation of silver halide grains, etc. What is necessary is just to add in the arbitrary places in a process. Moreover, in addition, the solution of a heavy metal compound can be continuously performed over the whole or a part of particle formation process.

  In the present invention, it is preferable to perform chemical sensitization performed on a photographic emulsion in order to improve sensitivity. As chemical sensitization, for example, noble metal sensitization such as gold, palladium and platinum sensitization, chalcogen sensitization such as sulfur sensitization with inorganic sulfur or organic sulfur compounds, reduction sensitization such as tin chloride and hydrazine, etc. are used. be able to.

  The silver halide grains are preferably subjected to spectral sensitization. Preferable spectral sensitizing dyes include cyanine, carbocyanine, dicarbocyanine, complex cyanine, hemicyanine, styryl dye, merocyanine, complex merocyanine, holopolar dye, and the like. Can be used alone or in combination.

  Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic ring nucleus. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus Quinoline nuclei and the like. These nuclei may be substituted on carbon atoms.

  The merocyanine dye or the complex merocyanine dye includes a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanine nucleus as a nucleus having a ketomethylene structure. A 5- to 6-membered heterocyclic nucleus such as a thiobarbituric acid nucleus can be applied.

  These sensitizing dyes may be used alone or in combination. A combination of sensitizing dyes is often used for the purpose of supersensitization.

  In order to incorporate these sensitizing dyes in a silver halide grain emulsion, they may be dispersed directly in the emulsion, or water, methanol, propanol, methyl cellosolve, 2,2,3,3-tetra A solvent such as fluoropropanol may be dissolved alone or in a mixed solvent and added to the emulsion. Further, as described in JP-B Nos. 44-23389, 44-27555, 57-22089, etc., an acid or a base is allowed to coexist to form an aqueous solution, US Pat. No. 3,822,135, As described in US Pat. No. 4,006,025 and the like, an aqueous solution or colloidal dispersion prepared by coexisting a surfactant such as sodium dodecylbenzenesulfonate may be added to the emulsion. Further, after dissolving in a substantially immiscible solvent such as phenoxyethanol, water or a hydrophilic colloid dispersion may be added to the emulsion. As described in JP-A Nos. 53-102733 and 58-105141, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion.

〔binder〕
In the silver halide grain emulsion-containing layer according to the present invention, the silver halide grains are uniformly dispersed and the silver halide grains are supported on the support, and the adhesion between the silver halide grain emulsion-containing layer and the support is improved. A binder is used for the purpose of securing. The binder that can be used in the present invention is not particularly limited, and any of a water-insoluble polymer and a water-soluble polymer can be used. From the viewpoint of improving developability, it is preferable to use a water-soluble polymer.

  In the light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder, but if necessary, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, simple substances. Hydrophilic colloids such as synthetic hydrophilic polymer materials such as mono- or copolymers can also be used.

[Ultraviolet absorber]
In the present invention, it is preferable to use an ultraviolet absorber in order to avoid deterioration of the electromagnetic wave shielding film due to ultraviolet rays.

  As the ultraviolet absorber, known ultraviolet absorbers such as salicylic acid compounds, benzophenone compounds, benzotriazole compounds, S-triazine compounds, cyclic imino ester compounds and the like can be preferably used. Of these, benzophenone compounds, benzotriazole compounds, and cyclic imino ester compounds are preferred. As what is blended with the polyester, a cyclic imino ester compound is particularly preferable. There is no particular limitation on the layer added with these ultraviolet absorbers, but from the viewpoint of preventing deterioration of the binder used in the silver halide grain emulsion-containing layer due to ultraviolet rays, it is added directly to the silver halide grain emulsion-containing layer, or An embodiment in which the silver halide grain emulsion-containing layer is provided closer to outside light is preferred. When added to a silver halide grain emulsion-containing layer or a layer adjacent thereto, preferred ultraviolet absorbers include benzotriazoles. For example, in general formula [III-3] described in JP-A-1-250944 Compounds shown by the general formula [III] described in JP-A-64-66646, UV-1L to UV-27L described in JP-A-63-187240, and JP-A-4-1633 A compound represented by the general formula [I], a compound represented by the general formulas (I) and (II) described in JP-A No. 5-165144 is preferably used. These ultraviolet absorbers are, for example, high-boiling organic solvents represented by phthalates such as dioctyl phthalate, di-i-decyl phthalate, and dibutyl phthalate, and phosphate esters such as tricresyl phosphate and trioctyl phosphate. An embodiment in which it is added in a dispersed form is preferably used. Moreover, the aspect which adds these ultraviolet absorbers directly to a support body is also used preferably, In this case, the aspect as described, for example in Japanese translations of PCT publication No. 2004-531611 can also be used preferably.

[Support]
In the present invention, as a support, for example, a cellulose ester film, a polyester film, a polycarbonate film, a polyarylate film, a polysulfone (including polyether sulfone) film, a polyester film such as polyethylene terephthalate, polyethylene naphthalate, Polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film, polymethyl Pentene film, polyetherketone film, polyether Ton imide film, a polyamide film, a fluororesin film, a nylon film, a polymethyl methacrylate film or an acrylic film or the like. In addition to these plastic films, quartz glass, soda glass, and the like can be used.

  Of these, cellulose triacetate film, polycarbonate film, polysulfone (including polyethersulfone) and polyethylene terephthalate film are preferably used.

  In the present invention, it is particularly preferable to use a cellulose ester film or a polyester film as the support from the viewpoints of transparency, isotropic properties, adhesiveness, and the like.

  When the electromagnetic wave shielding material of the present invention is used for a display screen of a display, high transparency is required. Therefore, it is desirable that the support itself has high transparency. In this case, the average transmittance of the entire visible light region of the plastic film or glass plate is preferably 85 to 100%, more preferably 90 to 100%. Moreover, in this invention, what colored the said plastic film or glass plate to the extent which does not interfere with the objective of this invention can also be used as a color tone regulator.

  In the present invention, the average transmittance in the visible light region is the average value obtained by integrating the transmittances in the visible light region obtained by measuring the transmittance in the visible light region from 400 to 700 nm at least every 5 nm. Defined as

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

  Although there is no restriction | limiting in particular in the thickness of the support body used for this invention, It is preferable that it is 5-200 micrometers from a viewpoint of the maintenance of a transmittance | permeability, and a handleability, and it is further more preferable that it is 30-150 micrometers.

〔exposure〕
In the present invention, the photosensitive material is exposed in order to form a conductive pattern by development / compensation processing described later. Examples of the light source used for exposure include light such as visible light and ultraviolet light, radiation such as electron beam and X-ray, and ultraviolet light or near infrared light is preferably used. Further, a light source having a wavelength distribution may be used for exposure, and a light source having a narrow wavelength distribution may be used.

  Various light emitters that emit light in the spectral region are used as necessary for visible light. For example, one or more of a red light emitter, a green light emitter, and a blue light emitter are mixed and used. The spectral region is not limited to the above red, green, and blue, and phosphors that emit light in the yellow, orange, purple, or infrared region are also used. An ultraviolet lamp is also preferable, and g-line of a mercury lamp, i-line of a mercury lamp, etc. are also used.

In the present invention, exposure can be performed using various laser beams. For example, monochromatic high-density light such as a second harmonic light source (SHG) combining a solid-state laser using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a semiconductor laser as a pumping light source and a nonlinear optical crystal was used. A scanning exposure method can be preferably used, and a KrF excimer laser, an ArF excimer laser, an F ₂ laser, or the like can also be used. In order to make the system compact and quick, exposure is preferably performed using a semiconductor laser, a semiconductor laser, or a second harmonic generation light source (SHG) that combines a solid-state laser and a nonlinear optical crystal. In order to design an apparatus that is particularly compact, quick, long-life, and highly stable, exposure is preferably performed using a semiconductor laser.

  Specifically, as the laser light source, an ultraviolet semiconductor, a blue semiconductor laser, a green semiconductor laser, a red semiconductor laser, a near infrared laser, or the like is preferably used.

  The method of exposing the silver halide grain emulsion-containing layer to an image may be performed by surface exposure using a photomask or by scanning exposure using a laser beam. At this time, condensing exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as surface contact exposure, near field exposure, reduced projection exposure, and reflection projection exposure can be used. The laser output may be about several tens of μW to 5 W, as long as it is an amount suitable for sensitizing silver halide grains.

[Chemical development]
In the present invention, after the photosensitive material is exposed, chemical development processing (also simply referred to as “chemical development”) is performed. The chemical development process is preferably a so-called black and white development process that does not contain a color developing agent.

  As a chemical developing solution, in addition to hydroquinones such as hydroquinone, sodium hydroquinone sulfonate, chlorohydroquinone and the like as developing agents, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1 -Pyrazolidones such as phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and 1-phenyl-4-methyl-3-pyrazolidone and superadditive developing agents such as N-methylparaaminophenol sulfate be able to. Further, it is preferable to use a reductone compound such as ascorbic acid or isoascorbic acid in combination with the superadditive developing agent without using hydroquinone.

  Further, sodium sulfite salt or potassium sulfite salt as a preservative, sodium carbonate salt or potassium carbonate salt as a buffering agent, diethanolamine, triethanolamine, diethylaminopropanediol or the like as a development accelerator can be appropriately used in the chemical developing solution.

  The development processing solution used in the chemical development processing can contain an image quality improving agent for the purpose of improving the image quality. Examples of the image quality improver include nitrogen-containing heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole and 5-methylbenzotriazole.

  In the chemical development processing in the present invention, after the chemical development, fixing processing is performed for the purpose of removing and stabilizing unexposed silver halide grains. For the fixing treatment in the present invention, a fixer formulation used for photographic films, photographic papers and the like using silver halide grains can be used. The fixing solution used in the fixing process may use sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, or the like as a fixing agent. Aluminum sulfate, chromium sulfate, or the like can be used as a hardener for fixing. As the preservative for the fixing agent, sodium sulfite, potassium sulfite, ascorbic acid, erythorbic acid and the like described in the chemical developing solution can be used, and citric acid, oxalic acid and the like can be used.

  Furthermore, it is preferable to perform a water washing treatment after the fixing treatment. The washing water used in the present invention includes N-methyl-isothiazol-3-one, N-methyl-isothiazol-5-chloro-3-one, and N-methyl-isothiazole-4,5 as antifungal agents. -Dichloro-3-one, 2-nitro-2-bromo-3-hydroxypropanol, 2-methyl-4-chlorophenol, hydrogen peroxide and the like can be used.

[Physical development processing]
In the present invention, in order to obtain the effects of the present invention, it is preferable to perform physical development processing (also simply referred to as “physical development”) after chemical development processing. In the present invention, “physical development processing” refers to newly developed silver ions supplied from the outside in addition to developed silver produced from silver halide grains in a photosensitive material by chemical development processing, and is generated by chemical development processing. This refers to the process of reinforcing developed silver. As a specific method for supplying silver ions from the physical development processing solution, for example, a method in which silver nitrate or the like is dissolved in advance in the physical development processing solution, or silver ions are dissolved, or in the physical development processing solution, A method for enhancing development of silver halide grains having a latent image by dissolving a silver halide solvent such as sodium thiosulfate, ammonium thiocyanate, etc., and dissolving silver halide grains in an unexposed area during development. In the present invention, the former is preferable.

[Plating treatment]
In the present invention, after the chemical development process or the physical development process, a plating process is performed to further increase the conductivity.

  In the present invention, conventionally known various plating methods can be used for the plating treatment. For example, electrolytic plating and electroless plating can be carried out alone or in combination. As metals that can be used for plating, For example, copper, nickel, cobalt, tin, silver, gold, platinum, and other various alloys can be used, but in order to achieve the mesh shape and effect of the present invention, electrolytic copper sulfate plating treatment is preferable, and further plating is performed. It is preferable that the copper sulfate concentration of the bath is 60 to 120 g / l.

[Oxidation treatment]
In the present invention, it is preferable to perform an oxidation treatment after chemical development, or / and after physical development, or / and after plating. By the oxidation treatment, unnecessary metal components can be ionized and dissolved and removed, and the transmittance of the film can be further increased.

  As the treatment liquid used for the oxidation treatment, for example, a treatment method using an aqueous solution containing Fe (III) ions, or hydrogen peroxide, persulfate, perborate, perphosphate, percarbonate, perhalogenate. A treatment solution containing a conventionally known oxidant such as a method of treatment using an aqueous solution containing a peroxide such as hypohalite, halogenate, or organic peroxide can be used. The oxidation treatment is preferably performed after the chemical development treatment and before the plating treatment because the transmittance can be improved efficiently with a short time treatment, and particularly preferably the physical development treatment. This is an embodiment performed after completion.

[Blackening treatment]
In the present invention, from the viewpoint of preventing reflection of external light on the film surface, it is preferable to perform a blackening treatment after the plating treatment. When such a blackened transparent electromagnetic wave shielding film is used for a display such as a PDP, for example, it is possible to reduce the decrease in contrast due to reflection of external light and to keep the color tone of the screen when not in use high in black. This is preferable. The blackening treatment method is not particularly limited, and known methods can be used alone or in combination as appropriate. For example, when the outermost surface of the conductive pattern is made of metallic copper, a method of oxidizing by immersing in an aqueous solution containing sodium chlorite, sodium hydroxide, or trisodium phosphate, or copper pyrophosphate or pyrophosphoric acid A method of blackening by immersing in an aqueous solution containing potassium and ammonia and performing an electrolytic plating treatment can be preferably used. If the outermost layer of the conductive pattern is made of a nickel-phosphorus alloy coating, immerse it in an acidic blackening solution containing copper (II) chloride or copper (II) sulfate, nickel chloride or nickel sulfate, and hydrochloric acid. The method to do can be used preferably.

  In addition to the above-described method, the blackening treatment can be performed by a method of finely roughening the surface. However, from the viewpoint of maintaining high conductivity, oxidation is more effective than finer roughening of the surface. A blackening treatment method is preferred.

[Configuration of electromagnetic wave shielding layer]
In the present invention, in order to provide high translucency and high electromagnetic wave shielding performance, a conductive mesh pattern is formed by drawing a lattice-like fine line pattern by exposure and then performing development processing or the like. The line width of the conductive metal part (= the length of the bottom of the cross section of the conductive metal mesh) is preferably 8 μm or more and 18 μm or less as described above. The line spacing is preferably 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.

  The conductive metal portion in the present invention has an aperture ratio of preferably 85% or more, more preferably 90% or more, and most preferably 90% or more from the viewpoint of visible light transmittance. The aperture ratio is the ratio of the portion without fine lines forming the mesh to the whole. For example, the aperture ratio of a square lattice mesh having a line width of 10 μm and a pitch of 200 μm is 90%.

  In the present invention, it is also preferable to provide a photosensitive silver halide grain emulsion layer on both sides of the support and to form a conductive pattern on each. In this case, it is preferable that the silver halide grain emulsion coated on each surface has a sensitivity at different wavelengths by spectral sensitization. By giving sensitivity to different wavelengths on the front and back surfaces, it is possible to produce different conductive patterns on each surface, for example, to selectively shield against electromagnetic waves of different frequencies on the front and back surfaces. It is also possible to form a conductive pattern.

[Functional layers other than electromagnetic wave shielding layers]
When the electromagnetic wave shielding film of the present invention is used in combination with, for example, an optical filter for a plasma display panel (PDP), a near infrared absorbing layer that is a layer containing a near infrared absorbing dye under a silver halide grain layer It is also preferable to provide In some cases, the near-infrared absorbing layer may be provided on the opposite side of the support to the silver halide grain layer side, or may be provided on both the silver halide grain layer side and the opposite side. A near-infrared absorbing layer can be provided between the silver halide grain layer containing silver halide and the support, or a near-infrared absorbing layer can be provided on the opposite side of the support as viewed from the silver halide grain layer. The former is preferred because it can be applied simultaneously with one side of the support.

  Specific examples of near-infrared absorbing dyes include polymethine, phthalocyanine, naphthalocyanine, metal complex, aminium, imonium, diimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo And triallylmethane-based compounds. The PDP optical filter is required to have near-infrared absorptivity mainly for absorption of heat rays and noise prevention of electronic devices. For this purpose, a dye having a near-infrared absorbing ability having a maximum absorption wavelength of 750 to 1100 nm is preferable, and a metal complex, aminium, phthalocyanine, naphthalocyanine, diimonium, and squalium compound are particularly preferable.

  As a near-infrared absorbing dye, diimonium compounds are IRG-022, IRG-040 (above, trade names manufactured by Nippon Kayaku Co., Ltd.), nickel dithiol complex compounds are SIR-128, SIR-130, SIR-132, SIR. -159, SIR-152, SIR-162 (above, trade names manufactured by Mitsui Chemicals, Inc.), and phthalocyanine compounds use commercially available products such as IR-10, IR-12 (above, trade names of Nippon Shokubai Co., Ltd.). can do.

  The near-infrared absorbing dye may be used after being dissolved in an organic solvent such as alcohol solvents such as methanol, ethanol and isopropanol, ketone solvents such as acetone, methyl ethyl ketone and methyl butyl ketone, dimethylsulfoxide, dimethylformamide, dimethyl ether and toluene. It is preferable to apply fine particles having an average particle size of 0.01 to 10 μm with a fine particle machine, and it is preferable to use an optical density in the range of 0.05 to 3.0 at the maximum wavelength.

  In addition, when making the color tone correction | amendment layer contain the pigment | dye which has a near-infrared absorptivity, you may contain any 1 type among said pigment | dye, and may contain 2 or more types.

  When the electromagnetic wave shielding material of the present invention is used in combination with, for example, an optical filter for a plasma display panel (PDP), in order to prevent a decrease in color reproducibility due to emission lines of neon gas used for PDP, this measure is around 595 nm. The aspect containing the pigment | dye which absorbs the light of this is preferable. Specific examples of the dye that absorbs such a specific wavelength include, for example, azo, condensed azo, phthalocyanine, anthraquinone, indigo, perinone, perylene, dioxazine, quinacridone, methine, Well-known organic pigments and organic dyes such as isoindolinone-based, quinophthalone-based, pyrrole-based, thioindigo-based, and metal complex-based materials, and inorganic pigments may be mentioned. Among these, phthalocyanine-based and anthraquinone-based dyes are particularly preferably used because of good weather resistance.

  When the electromagnetic wave shielding material of the present invention is used for the purpose of protecting a display screen or the like, it is preferable to provide an antireflection layer. As the antireflection layer, inorganic materials such as metal oxides, fluorides, silicides, borides, carbides, nitrides, sulfides, etc., can be used by vacuum deposition, sputtering, ion plating, ion beam assist, etc. A method of laminating a thin film in a layer or a multilayer, a method of laminating a resin having a different refractive index such as an acrylic resin or a fluororesin into a single layer or a multilayer can be used.

  In the present invention, in the transparent electromagnetic wave shielding film, when the antireflection layer is formed on the opposite side of the layer having the conductive pattern with the support of the film interposed therebetween, the antireflection layer was first formed. An embodiment in which a protective film is later bonded and then a conductive pattern layer is formed is preferable. When the antireflection layer is formed after the conductive pattern is formed first, the efficiency of the plasma treatment and corona treatment performed to improve the adhesion between the antireflection layer and the support tends to be reduced. The embodiment in which the layer is formed first is preferred. In addition, when the antireflection layer is formed first, from the viewpoint of preventing the layer from being deteriorated by development, plating treatment, or the like, an embodiment in which a conductive pattern layer is formed after pasting a protective film in advance is preferable. .

  As the protective film used in the present invention, a commercially available protective film can be used, but from the viewpoint of facilitating coating of a photosensitive silver halide grain emulsion layer for forming a conductive pattern, The thickness of the film is preferably 10 μm or more and 100 μm or less, and particularly preferably 20 μm or more and 60 μm or less. If the thickness is less than 10 μm, the rigidity of the film is remarkably reduced, so that the work efficiency of the protection film is likely to be lowered. If the thickness is more than 100 μm, a trouble such as a winding wrinkle is likely to occur when the film is wound. is there.

  Although there is no restriction | limiting in particular in the kind of adhesive used for a protective film, The thing which does not damage an antireflection film at the time of peeling, without altering an antireflection film is used preferably. From such a viewpoint, an acrylic or silicone adhesive is preferably used. Moreover, as the adhesive force, what is 0.08-0.6N / 25mm is used preferably.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these. 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 silver halide grain emulsion EM-1]
The following solution-A was kept at 40 ° C. in a reaction vessel and adjusted to EAg = 85 mV with 1.8 N potassium bromide while stirring at high speed using a mixing stirrer described in JP-A-62-160128. . Subsequently, the following solution-B and the following solution-C were added at a constant flow rate over 19 minutes using the double jet method.

(Solution-A)
Alkali-treated inert gelatin (average molecular weight 100,000) 18.7g
Potassium bromide 0.18g
Solution-I 5.66ml
1812 ml of pure water
(Solution-B)
169.9g of silver nitrate
Finish to 555.6 ml with pure water.

(Solution-C)
Potassium bromide 140.0g
Potassium iodide 4.0g
The following solution-II 2.10 ml
The following solution-III 0.03ml
Finish to 666.7 ml with pure water.

(Solution-I)
Surfactant: 10% by mass methanol solution of polyisopropylene polyethylene oxydisuccinate sodium salt (Solution-II)
0.02 mass% aqueous solution of rhodium hexabromide complex (Solution-III)
1.0% by mass aqueous solution of potassium hexachloroiridium (IV) After the above operation, desalting and washing with water using a flocculation method were performed at 40 ° C. according to a conventional method, and Solution-D and an antibacterial agent were added. The silver iodobromide cube is well dispersed at 60 ° C., adjusted to pH 5.90 at 40 ° C., and finally contains 2 mol% of silver iodide and has an average grain size of 0.06 μm and a coefficient of variation of 10%. A grain emulsion was obtained.

(Solution-D)
18.5 g of alkali-treated inert gelatin (average molecular weight 100,000)
140.0 ml of pure water
The silver iodobromide cubic grain emulsion was chemically sensitized at 60 ° C. for 60 minutes with 28.3 mg of sodium thiosulfate per mole of silver halide, and after completion of chemical sensitization, 4-hydroxy-6-methyl- 1,3,3a, 7-tetrazaindene (TAI) was added in an amount of 500 mg per mole of silver halide and 60 mg of 1-phenyl-5-mercaptotetrazole was added to obtain a silver halide grain emulsion EM-1.

[Preparation of silver halide grain emulsion EM-2]
The following solution-E was kept at 34 ° C. in the reaction vessel, and the pH was adjusted to 2.95 with nitric acid (concentration 6%) while stirring at high speed using the same mixing and stirring device as that for adjusting EMP-1. did. Subsequently, the following solution-F and the following solution G 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-H and Solution-J were added.

(Solution-E)
Alkali-treated inert gelatin (average molecular weight 100,000) 18.7g
Sodium chloride 0.31g
The following solution-IV 1.59ml
Pure water 1246ml
(Solution-F)
169.9g of silver nitrate
Nitric acid (concentration 6%) 5.89ml
Finish to 317.1 ml with pure water.

(Solution-G)
Alkali-treated inert gelatin (average molecular weight 100,000) 5.66 g
Sodium chloride 35.9g
Potassium bromide 59.9g
Following solution-IV 0.85ml
The following solution-V 2.72 ml
Finish to 317.1 ml with pure water.

(Solution-H)
2-Methyl-4hydroxy-1,3,3a, 7-tetraazaindene 0.56 g
112.1 ml of pure water
(Solution-J)
Alkali-treated inert gelatin (average molecular weight 100,000) 3.96 g
Solution-IV 0.40ml below
128.5 ml of pure water
(Solution-IV)
Surfactant: 10% by mass methanol solution of polyisopropylene polyethylene oxydisuccinate sodium salt (Solution-V)
10% by weight aqueous solution of rhodium hexachloride complex After the above operation is completed, desalting and water washing are performed using a flocculation method at 40 ° C. according to a conventional method, and solution-K and anti-bacterial agent are added, and 60 ° C. After dispersion, the pH was adjusted to 5.90 at 40 ° C., and finally a silver chlorobromide cubic grain emulsion containing 55 mol% of silver chloride and having an average grain size of 0.09 μm and a coefficient of variation of 10% was obtained.

(Solution-K)
Alkali-treated inert gelatin (average molecular weight 100,000) 16.5g
Pure water 139.8ml
The silver chlorobromide cubic grain emulsion was subjected to chemical sensitization at 60 ° C. for 60 minutes using 56.0 mg of sodium thiosulfate per mole of silver halide, and after completion of chemical sensitization, 4-hydroxy-6-methyl- 500 mg of 1,3,3a, 7-tetrazaindene (TAI) per mol of silver halide and 100 mg of 1-phenyl-5-mercaptotetrazole were added to obtain a silver halide grain emulsion EM-2.

[Preparation of silver halide grain emulsion EM-3]
In the preparation of the silver halide grain emulsion EM-2, a salt having an average grain size of 0.09 μm containing 90 mol% of silver chloride and a coefficient of variation of 10% was used except that the solution-G was changed to the following solution-L. Silver bromide cubic grain emulsion EM-3 was obtained.

(Solution-G)
Alkali-treated inert gelatin (average molecular weight 100,000) 5.66 g
Sodium chloride 58.8g
13.3 g of potassium bromide
Following solution-IV 0.85ml
The following solution-V 2.72 ml
Finish to 317.1 ml with pure water.

[Production of photosensitive materials 101 to 109]
Silver halide particle emulsions EM-1 to EM-3 prepared as described above on a polyethylene terephthalate film support having a thickness of 180 μm provided with a subbing layer are silver / gelatin (binder) as shown in Table 1. Coating was performed so that the volume ratio and the coating silver amount were achieved, followed by drying to prepare photosensitive materials 101 to 109. In the preparation of each photosensitive material, a hardener (2,4-dichloro-6-hydroxy-1,3,5-s-triazine sodium salt) was added at a ratio of 50 mg / g gelatin. did. Further, as a coating aid, a surfactant (SU-2: di (2-ethylhexyl) sulfosuccinate / sodium) was added to adjust the surface tension. In Table 1, the volume of silver and the amount of silver were determined by converting the amount of silver halide grain emulsion used to equimolar silver.

[Preparation of transparent electromagnetic wave shielding film S101]
The photosensitive material 101 manufactured as described above is exposed using an ultraviolet lamp through a lattice-like photomask having a line width of 5 μm and an interval between lines of 240 μm, and then the following chemical development processing. After developing for 60 seconds at 25 ° C. using the liquid (DEV-1), fixing processing was performed for 120 seconds at 25 ° C. using the following fixing processing solution (FIX-1), followed by washing with water. .
(DEV-1: Chemical development processing solution)
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: fixing processing solution)
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.

Subsequently, after being immersed in a 10% hydrochloric acid solution for 1 minute, a copper sulfate electroplating treatment was performed for 12 minutes at 25 ° C. under a current density of 2 A / dm ² using the following plating treatment solution (PL-1). Transparent electromagnetic wave shielding film S101 was produced.

(PL-1: plating solution)
80 g of copper sulfate pentahydrate
180 g of sulfuric acid
Chlorine 40ppm
Top Lucina 380H (Okuno Pharmaceutical) 5.0ml
Add water to bring the total volume to 1 liter.

[Preparation of transparent electromagnetic wave shielding film S102]
In the production of the transparent electromagnetic wave shielding film S101, after chemical development-fixing-water washing treatment, physical development treatment at 25 ° C. for 480 seconds is performed using the following physical development processing solution (PD-1), and then water washing treatment is performed. A transparent electromagnetic wave shielding film S102 was prepared in the same manner except that the time for plating (PL-1) was 10 minutes.

(PD-1: Physical development processing solution)
800ml of pure water
Citric acid 7.9g
Hydroquinone 7.7g
Silver nitrate 0.8g
Disodium hydrogen phosphate 1.0g
1.2% 28% ammonia water
[Preparation of transparent electromagnetic wave shielding film S103]
A transparent electromagnetic wave shielding film S103 was produced in the same manner as in the production of the transparent electromagnetic wave shielding film S102 except that the photosensitive material 101 was changed to 102.

[Preparation of transparent electromagnetic wave shielding film S104]
In the production of the transparent electromagnetic wave shielding film S103, the plating solution (PL-1) was changed to the following plating solution (PL-2), and the copper sulfate electrolysis was performed for 4 minutes at 25 ° C. under a current density of 5 A / dm ^2. A transparent electromagnetic wave shielding film S104 was produced in the same manner except that plating was performed.

(PL-2: Plating solution)
200 g of copper sulfate pentahydrate
70g of sulfuric acid
Chlorine 20ppm
Top Lucina 380H (Okuno Pharmaceutical) 5.0ml
Add water to bring the total volume to 1 liter.

[Preparation of transparent electromagnetic wave shielding films S105 to S111]
Transparent electromagnetic wave shielding films S105 to S111 were produced in the same manner except that the photosensitive material 102 was changed to 103 to 109 in the production of the transparent electromagnetic wave shielding film S103.

[Evaluation of transparent electromagnetic wave shielding films S101 to S111]
The following evaluation was performed on each of the transparent electromagnetic wave shielding films S101 to S111 having the conductive metal mesh portion obtained as described above.

(Measurement of mesh cross section)
Take a mesh cross-section SIM image using the FIB device SMI2050 (Seiko Instruments Co., Ltd.) and mesh analysis using the image analysis software LUZEX (Nireco Co., Ltd.), the length of the bottom of the mesh cross section, mesh The distance connecting the apex and the bottom and the cross-sectional area of the mesh were measured.

(Measurement of surface resistivity)
The surface resistivity was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Dia Instruments Co., Ltd.).

(Measurement of transmittance)
The transmittance was measured using a spectrophotometer (Hitachi spectrophotometer U-3210: manufactured by Hitachi, Ltd.).

(Moire evaluation)
An electromagnetic wave shielding film was installed on the front surface of the Hitachi PDP TV and the Matsushita Electric PDP TV at a bias angle with minimum moire, and visual sensory evaluation was performed. While observing the television screen directly, the image display surface was observed while changing the observation position with respect to the television screen to various positions such as oblique. In all cases, the case where moire was not manifested was evaluated as ◯, the level at which moire was slightly observed was evaluated as Δ, and the sample where moire was actualized was evaluated as ×.

  The contents and evaluation results of the transparent electromagnetic wave shielding film are shown in Tables 1 and 2.

  As is apparent from Table 2, it can be seen that the sample satisfying the conductive metal mesh shape of the present invention has no moiré and satisfies both high light transmittance and high conductivity (electromagnetic wave shielding ability) performance at the same time. .

Example 2
[Preparation of transparent electromagnetic wave shielding films S201 to S206]
In the production of the transparent electromagnetic wave shielding film S105 of Example 1, transparent electromagnetic wave shielding films S201 to S206 were produced in the same manner except that the plating (PL-1) time was changed as shown in Table 2.

  For each of the transparent electromagnetic wave shielding films S201 to S206 having the conductive metal mesh portion obtained as described above, measurement of mesh cross-sectional shape, surface specific resistance, transmittance, and evaluation of moire as in Example 1. Went. Table 3 shows the contents and evaluation results of the transparent electromagnetic wave shielding film.

  As is apparent from Table 3, the length a of the bottom of the cross section of the conductive metal mesh and the distance b connecting the base and top of the cross section of the conductive metal mesh satisfy the relational expression of 0.3 ≦ b / a ≦ 0.5. In addition, samples S105 and S202 in which the length of the bottom of the cross section of the conductive metal mesh is 8 μm or more and 18 μm or less, and the distance b connecting the bottom and the apex of the cross section of the conductive metal mesh is 2 μm or more and 10 μm or less. It can be seen that ˜S205 is a more preferable form for exhibiting the effects of the present invention.

Conceptual diagram showing a cross section of conductive metal mesh

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent electromagnetic wave shielding film 2 Filled part: Development silver area | region produced | generated by chemical development process and physical development process 3 Diagonal part: Metal area | region carry | supported by plating process 4 Photosensitive silver halide particle containing layer 5 Support body a Bottom Length b Distance between top and bottom S Cross section of conductive metal mesh

Claims (12)

Produced through a process of forming a conductive metal mesh by subjecting a photosensitive material comprising a layer containing photosensitive silver halide grains and a binder on a support to a mesh pattern exposure, chemical development, and further plating. A transparent electromagnetic wave shielding film, wherein the cross-sectional shape of the conductive metal mesh satisfies the following relational expression:
(Formula): 0.85 ≦ S / (a × b) ≦ 1.0
a: Length of the base of the cross section of the conductive metal mesh when the support is down b: Distance connecting the apex and the base of the conductive metal mesh S: Cross section of the conductive metal mesh 2. The transparent electromagnetic wave shielding film according to claim 1, wherein the length a of the bottom of the cross section of the conductive metal mesh and the distance b connecting the base and top of the cross section of the conductive metal mesh satisfy the following relational expression.
(Formula): 0.3 ≦ b / a ≦ 0.6 The transparent electromagnetic wave shielding film according to claim 1 or 2, wherein the length a of the bottom of the cross section of the conductive metal mesh is 8 µm or more and 18 µm or less. The transparent electromagnetic wave shielding film according to any one of claims 1 to 3, wherein a distance b connecting the bottom and the apex of the cross section of the conductive metal mesh is 2 µm or more and 10 µm or less. The length a of the bottom of the cross section of the conductive metal mesh, the distance b connecting the base and top of the cross section of the conductive metal mesh, and the cross sectional area S of the conductive metal mesh satisfy the following relational expression. Item 5. The transparent electromagnetic wave shielding film according to any one of Items 1 to 4.
(Formula): 0.90 ≦ S / (a × b) ≦ 1.0 The transparent electromagnetic wave shielding film according to any one of claims 1 to 5, wherein after the chemical development treatment, a physical development treatment is performed and then a plating treatment is performed. The transparent electromagnetic wave shielding film according to any one of claims 1 to 6, wherein a silver chloride content of the photosensitive silver halide grains is 50 mol% or more. 8. The silver / binder volume ratio of the silver halide grains in the layer containing the photosensitive silver halide grains and the binder is 0.3 or more and 2.0 or less. The transparent electromagnetic wave shielding film described in 1. The coated silver amount of the silver halide grains in the layer containing the photosensitive silver halide grains and the binder is 0.3 g / m ² or more and 3.0 g / m ² or less in terms of silver. The transparent electromagnetic wave shielding film according to any one of 1 to 8. The transparent electromagnetic wave shielding film according to claim 1, wherein the plating treatment is an electrolytic copper plating treatment, and the copper sulfate concentration in the plating bath is 60 to 120 g / l. It is a manufacturing method of a transparent electromagnetic wave shielding film, Comprising: The transparent electromagnetic wave shielding film as described in any one of Claims 1-10 is manufactured, The manufacturing method of the transparent electromagnetic wave shielding film characterized by the above-mentioned. A plasma display panel using the transparent electromagnetic wave shielding film according to any one of claims 1 to 10.

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