JP2008041738A - Light transparency electromagnetic wave shielding film, its manufacturing method, and plasma display panel employing it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method capable of obtaining a light transparency electromagnetic wave shielding film, satisfying the performance of high light transmitting property and a high conductivity at the same time without increasing process and inexpensively; and further, to provide a light transparency electromagnetic wave shielding film manufactured by the manufacturing method, and a plasma display panel employing it. <P>SOLUTION: The light transparency electromagnetic wave shielding film is manufactured by a method wherein a sensitive material having a light sensitive layer containing light sensitive silver salt particles on a supporting body is exposed, and fixing treatment is applied after applying physical development process to form a conductive metal and a light transmitting part. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a translucent electromagnetic wave shielding film. Furthermore, it is related with the translucent electromagnetic wave shielding film manufactured using the method, and a plasma display panel 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. In addition, near infrared rays are also emitted at this time, which causes malfunction of an operation element such as a remote controller. 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 light-sensitive material to provide a thin line pattern of a conductive mesh in a large amount at a low cost (for example, see Patent Document 3).

In this method, the photosensitive material is exposed to conductive mesh in the form of a mesh to form a metallic silver portion, and then conductive metal particles are supported on the metallic silver portion by physical development and / or plating treatment. Although it is a method of forming a mesh, there has been a problem of a decrease in light transmittance of a light transmitting portion after physical development and / or plating treatment. In order to improve the light transmission, it is necessary to add a process for removing the conductive metal particles in the light transmission part by an oxidation process, and an increase in manufacturing cost is a problem.
JP 2003-46293 A JP-A-11-26980 JP 2004-221564 A

  The present invention has been made in view of the above-mentioned problems, and its problem is to reduce the cost of a translucent electromagnetic wave shielding film that simultaneously satisfies the performances of high light transmittance and high electrical conductivity (electromagnetic wave shielding ability) without increasing the number of steps. And providing a light-transmitting electromagnetic wave shielding film produced by the production method and a plasma display panel using the same.

  As a result of intensive studies by the present inventors, the Fe (III) ion treatment is carried out by performing the fixing treatment after performing at least one of the physical development processing and the plating treatment instead of performing the fixing treatment immediately after the development processing. Acquired knowledge that a light-transmitting electromagnetic wave shielding film having a high light transmittance of the light transmitting portion can be obtained without increasing the number of steps for removing the deposit on the light transmitting portion such as oxidation treatment using various oxidizing agents. It was.

  This is mainly due to the silver halide grains and the metal fine particles adhering to the silver halide grains in the light transmitting portion, and the light transmittance is reduced because they are removed by the fixing process. It is interpreted that a highly translucent electromagnetic shielding film can be obtained.

  The fixing process is to make insoluble silver halide grains complex ionized with sodium thiosulfate or ammonium thiosulfate so as to be water-soluble so that they can be removed by washing with water.

  Since it does not affect the metallic silver portion other than the silver halide grains and the conductive metal particles, it does not affect the conductivity of the conductive metal portion, that is, the electromagnetic wave shielding property.

  Although a method for improving the light transmittance by dissolving the light-transmitting part deposit by oxidation treatment is known, the conductive metal part is also removed at the same time as the light-transmitting part deposit. This is undesirable.

  That is, the said subject which concerns on this invention is solved by the following means.

  1. It is characterized by forming a conductive metal portion and a light transmitting portion by exposing a photosensitive material having a photosensitive layer containing photosensitive silver salt particles on a support, performing a physical development process and then performing a fixing process. A method for producing a translucent electromagnetic wave shielding film.

  2. A photosensitive material having a photosensitive layer containing photosensitive silver salt particles is exposed on a support, subjected to a physical development process and then a chemical development process to form a conductive metal part and a light transmission part. 2. The method for producing a translucent electromagnetic wave shielding film as described in 1 above, wherein a fixing treatment is performed.

  3. 3. The method for producing a translucent electromagnetic wave shielding film as described in 1 or 2 above, wherein plating treatment is performed after the physical development treatment and before the fixing treatment.

  4). A photosensitive material having a photosensitive layer containing photosensitive silver salt particles on the support is exposed and subjected to a chemical development process to form a metallic silver part and a light transmission part. Any one of the above 1 to 3 having a conductive metal part in which conductive metal particles are supported on the metal silver part by performing at least one of the plating processes and then performing a fixing process. A method for producing a translucent electromagnetic wave shielding film according to claim 1.

  5. A translucent electromagnetic wave shielding film produced by the method for producing a translucent electromagnetic wave shielding film according to any one of 1 to 4 above.

  6). 6. A plasma display panel using the translucent electromagnetic wave shielding film as described in 5 above.

  According to the present invention, there is provided a manufacturing method capable of obtaining a light-transmitting electromagnetic wave shielding film satisfying both high light transmittance and high conductivity at a low cost without increasing the number of steps, and the transmittance manufactured by the manufacturing method. An optical electromagnetic shielding film and a plasma display panel using the same can be provided.

  In the method for producing a translucent electromagnetic wave shielding film of the present invention, a photosensitive material having a photosensitive layer containing photosensitive silver salt particles is exposed on a support, and a fixing process is performed after at least a physical development process. A conductive metal part and a light transmission part are formed.

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

[Support]
In the present invention, a plastic film, a plastic plate, glass or the like can be used as the 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 still more 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.

[Photosensitive layer]
In the photosensitive material according to the present invention, a photosensitive layer containing photosensitive silver salt particles is provided on a support as an optical sensor. The photosensitive layer can contain a binder, a solvent and the like in addition to the photosensitive silver salt particles.

<Photosensitive silver salt particles>
Examples of the photosensitive silver salt particles used in the present invention include inorganic silver salt particles such as silver halide particles and organic silver salt particles such as silver acetate, but silver halide particles having excellent characteristics as an optical sensor are used. It is preferable. The silver halide grains preferably used in the present invention will be further described.

  In the present invention, techniques conventionally used in various silver salt photographic light-sensitive materials using silver halide grains 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, iodine and fluorine, or a combination thereof.

  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. Incidentally, the sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and a spherical shape.

  The shape of the silver halide grains is not particularly limited. For example, the shape can be various shapes such as a spherical shape, a cubic shape, a flat plate shape (hexagon flat plate shape, a triangular flat plate shape, a quadrangular flat plate shape, etc.), an octahedron shape, and a tetrahedron shape. 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 to obtain 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.

  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.

<Binder>
In the photosensitive layer according to the present invention, the binder can be used for the purpose of uniformly dispersing silver salt particles and assisting the adhesion between the silver salt-containing layer and the support. In the present invention, both a water-insoluble polymer and a water-soluble polymer can be used as a binder, but a water-soluble polymer is preferably used.

  Examples of the binder include gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch and other polysaccharides, cellulose and derivatives thereof, polyethylene oxide, polyvinylamine, chitosan, polylysine, polyacrylic acid, polyalginic acid, polyhyaluron. Examples include acids and carboxycellulose. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group.

  The content of the binder contained in the photosensitive layer according to the present invention is not particularly limited, and can be appropriately determined within a range in which dispersibility and adhesion can be exhibited. The content of the binder in the photosensitive layer is preferably 1/4 to 100, more preferably 1/2 to 2 in terms of Ag / binder volume ratio. It is preferable that the photosensitive layer contains a binder in an Ag / binder volume ratio of 1/4 or more because the metal particles can easily come into contact with each other in the physical development and / or plating treatment step, and high conductivity can be obtained. .

<Solvent>
The solvent that can be used in the preparation of the coating solution for the photosensitive layer 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.

[exposure]
In the present invention, the photosensitive layer provided on the support is exposed. 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 for exposing the photosensitive layer in a pattern may be performed by surface exposure using a photomask or by scanning exposure using a laser beam.

[Chemical development]
In the present invention, it is preferable to perform chemical development after exposing the photosensitive layer. The chemical development processing can be performed using a development processing technique mainly composed of normal chemical development used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask and the like. 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.

[Physical development and plating]
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, it is possible to carry the conductive metal particles on the metallic part only by physical development or plating treatment, but it is also possible to carry the conductive metal particles on the metallic silver part by further combining physical development and plating treatment. it can.

  The “physical development processing” in the present invention means that metal ions such as silver ions in a soluble metal salt-containing solution are reduced with a reducing agent on metal or metal compound nuclei to precipitate metal particles. This physical development processing is used for instant B & W film, instant slide film, printing plate production, and the like, and the technology can be used in the present invention.

  In the present invention, for the plating treatment, electroless plating (chemical reduction plating or displacement plating), electrolytic plating, or both electroless plating and electrolytic plating can be used. For the electroless plating in the present invention, a known electroless plating technique can be used.

  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, etc., as well as stabilization of the bath 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 rate during the plating treatment 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.

[Fixing process]
In the present invention, a fixing process for removing and stabilizing the unexposed silver salt (silver halide grains) is performed. For the fixing process in the present invention, a fixing process technique used for a silver salt photographic film, photographic paper, a printing plate-making film, a photomask emulsion mask, or 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.

[Conductive metal part]
In the present invention, the conductive metal portion is formed by supporting the conductive metal particles on the metal silver portion by subjecting the metal silver portion formed by the exposure and development processing described above to physical development or plating treatment.

  The surface resistance value of the translucent electromagnetic wave shielding film (conductive metal portion) of the present invention is preferably 10Ω / sq or less, more preferably 2Ω / sq or less, and 0.2Ω / sq or less. Most preferred.

  From the viewpoint of making the conductive metal portion in the present invention unnoticeable, the line width of the conductive metal portion is preferably less than 30 μm, more preferably less than 20 μm, and most preferably less than 15 μm. .

  The conductive metal portion in the present invention preferably has an aperture ratio of 85% or more, more 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%.

[Light transmissive part]
The light transmissive part in the present invention means a part having transparency other than the conductive metal part in the light transmissive electromagnetic wave shielding film.

  The transmittance in the light transmissive part is indicated by the minimum value of the transmittance in the wavelength region of 380 to 780 nm excluding the contribution of light absorption and reflection of the support.

  The transmittance of the present invention is preferably 85% or more, and more preferably 90% or more.

[Functional films other than electromagnetic shielding]
In the present invention, a functional layer having functionality may be separately provided as necessary. This functional layer can have various specifications for each application. For example, as an electromagnetic shielding material for displays, an antireflection layer with an antireflection function with an adjusted refractive index and film thickness, a non-glare layer or an antiglare layer (both have a glare prevention function), and absorbs near infrared rays. Near-infrared absorbing layer made of a compound or metal that absorbs visible light in a specific wavelength range, anti-smudge layer with a function that easily removes dirt such as fingerprints, and hard to scratch 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 salt-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 main body. These functional films are called optical filters (or simply 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. 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.

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Example 1
(Preparation of photosensitive material)
Preparation of seed emulsion-1 Seed emulsion-1 was prepared as follows.

Solution A1
Ossein gelatin 24.2g
9657ml water
Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml
Potassium bromide 10.8g
114ml of 10% nitric acid
Solution B1
2.5 mol / L silver nitrate aqueous solution 2825 ml
Solution C1
Potassium bromide (diluted to 2825 ml with water) 841 g
Solution D1
1.75 mol / L potassium bromide aqueous solution The following silver potential control amount: 464 each of solution B1 and solution C1 in solution A1 using a mixing stirrer shown in JP-B-58-58288 and 58-58289 at 42 ° C. .3 ml was added by the simultaneous mixing method in 1.5 minutes, and nucleation was performed.

  After the addition of the solution B1 and the solution C1 was stopped, the temperature of the mixed solution was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with 3% KOH, and then again the solution B1 and the solution C1 was added by a simultaneous mixing method at a flow rate of 55.4 ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 is +8 mV using the solution D1. And +16 mV.

  After completion of the addition, the pH was adjusted to 6 with 3% KOH, and immediately desalted and washed with water. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.064 μm. It was confirmed with an electron microscope that the diameter (in terms of circle diameter) was 0.595 μm. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

Preparation of Em-1 Tabular silver halide grain emulsion Em-1 was prepared using seed emulsion-1 and the following four solutions.

Solution A2
Ossein gelatin 34.03g
Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 2.25 ml
Seed emulsion-1 1.218 mol equivalent Finished to 3150 ml with water.

Solution B2
Potassium bromide (finish to 3644 ml with water) 1734 g
Solution C2
Silver nitrate (finish to 4165 ml with water) 2478 g
Solution D2
A fine grain emulsion consisting of 3% by weight gelatin and silver iodide grains (average grain size 0.05μm) ^*
Equivalent to 0.080 mol (*) An aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide in 6.64 l of a 5.0 mass% gelatin aqueous solution containing 0.06 mol of potassium iodide. 2 l each was added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After particle formation, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

  In the reaction vessel, the solution A2 was vigorously stirred while maintaining the temperature at 60 ° C., and a part of the solution B2, a part of the solution C2, and half of the solution D2 were added by the simultaneous mixing method over 5 minutes. Half of the remaining amount of solution B2 and solution C2 is added over 37 minutes, and then part of solution B2, part of solution C2 and the rest of solution D2 are added over 15 minutes, and finally solution B2 And the entire remaining amount of C2 was added over 33 minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.8 throughout. Here, the addition rate of the solution B2 and the solution C2 was changed in a function manner with respect to time so as to match the critical growth rate.

  Further, the solution D2 was added in an amount corresponding to 0.15 mol% with respect to the total silver amount to perform halogen substitution. After completion of the addition, the emulsion was cooled to 40 ° C., and 1800 ml of an aqueous solution of 13.8% (mass) modified gelatin modified with phenylcarbamoyl group (substitution rate 90%) as an aggregating polymer agent was added and stirred for 3 minutes. . Thereafter, a 56% (mass) aqueous solution of acetic acid was added to adjust the pH of the emulsion to 4.6, the mixture was stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation. Thereafter, 9.0 l of 40 ° C. distilled water was added, and the supernatant was drained after standing with stirring. Further, 11.25 l of distilled water was added, and after stirring and standing, the supernatant was drained. Subsequently, an aqueous gelatin solution and an aqueous 10% (mass) sodium carbonate solution were added to adjust the pH to 5.80, stirred at 50 ° C. for 30 minutes, and redispersed. After redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

  When the obtained silver halide grain emulsion was observed with an electron microscope, it was found to be a flat plate having an average grain size of 1.11 μm, an average thickness of 0.25 μm, an average aspect ratio of about 4.5, and a grain size distribution of 18.1%. It was a silver halide grain. The average distance between twin planes is 0.020 μm, and the ratio of the distance between twin planes to the thickness is 5 or more and 97% (number) of grains of all tabular silver halide grains, 10 or more grains. 49% and 15 or more particles accounted for 17%.

  Next, after the emulsion Em-1 was heated to 60 ° C., a predetermined amount of spectral sensitizing dye was added as a solid fine particle dispersion, and then adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate were mixed. An aqueous solution and a dispersion of triphenylphosphine selenide were added, and after 60 minutes, a silver iodide fine grain emulsion was added, followed by ripening for a total of 2 hours. At the end of aging, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

  In addition, said additive and its addition amount (per mol of AgX) are shown below.

5,5'-Dichloro-9-ethyl-3,3'-di- (sulfopropyl)
-Oxacarbocyanine sodium salt anhydride 2.0 mg
5,5'-di- (butoxycarbonyl) -3,3'-di- (4-sulfobutyl)
-Benzimidazolocarbocyanine sodium salt anhydrate 120 mg
Adenine 15mg
Potassium thiocyanate 95mg
Chloroauric acid 2.5mg
Sodium thiosulfate 2.0mg
Triphenylphosphine selenide 0.4mg
Silver iodide fine particles 280mg
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI)
500mg
A solid fine particle dispersion of spectral sensitizing dye was prepared by the following method. That is, it was obtained by adding a predetermined amount of a spectral sensitizing dye to water previously adjusted to 27 ° C. and stirring with a high-speed stirrer (dissolver) at 3.500 rpm for 30 to 120 minutes.

  A dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., stirred, and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of 25% by weight aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed at a dispersion blade peripheral speed of 40 m / sec for 30 minutes at 50 ° C. with a high-speed stirring disperser having a dissolver having a diameter of 10 cm. Thereafter, the ethyl acetate was removed while rapidly stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3% by mass or less. Thereafter, this dispersion was diluted with pure water to make 80 kg. A portion of the dispersion thus obtained was collected and used in the above experiments.

  The average iodide content on the outermost surface of the silver halide grains contained in the silver halide grain emulsion Em-1 by the addition of the silver iodide fine grains was about 4 mol%.

  Next, the following additives were added to the emulsion Em-1 thus sensitized to prepare a photosensitive layer coating solution. At the same time, a protective layer coating solution was also prepared.

  Next, the photosensitive layer coating solution and the protective layer coating solution were simultaneously applied on one side of the undercoated polyethylene terephthalate film base (thickness: 175 μm) so as to have the following predetermined coating amount and dried. .

Photosensitive layer The following various additives were added to the emulsion Em-1 obtained above.

2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine
5 mg / m ²
t-Butyl-catechol 130 mg / m ²
Polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ²
Styrene-maleic anhydride copolymer 80 mg / m ²
Sodium polystyrene sulfonate 80mg / m ²
Trimethylolpropane 350mg / m ²
Diethylene glycol 50mg / m ²
Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ²
1,3-dihydroxybenzene-4-ammonium sulfonate 500 mg / m ²
2-Mercaptobenzimidazole-5-sulfonic acid sodium salt 5 mg / m ²
_{n-C 4 H 9 OCH 2} CH (OH) CH 2 N (CH 2 COOH) 2 350mg / m 2
Colloidal silica 0.5g / m ²
Dextrin (average molecular weight 1000) 0.2 g / m ²
However, the gelatin was adjusted to 1.0 g / m ² .

Protective layer Gelatin 0.8g / m ²
Matting agent made of polymethyl methacrylate (Area average particle size 7.0 μm) 50 mg / m ²
Formaldehyde 20mg / m ²
2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt
10 mg / m ²
Bis-vinylsulfonylmethyl ether 36 mg / m ²
Polyacrylamide (average molecular weight 10,000) 0.1 g / m ²
Sodium polyacrylate 30mg / m ²
Polysiloxane 20mg / m ²
_{C 9 F 19 -O- (CH 2} CH 2 O) 11 -H 3mg / m 2
_{C 8 F 17 SO 2 N (} C 3 H 7) - (CH 2 CH 2 O) 15 -H 2mg / m 2
_{C 8 F 17 SO 2 N (} C 3 H 7) - (CH 2 CH 2 O) 4 - (CH 2) 4 SO 3 Na
1mg / m ²
〔exposure〕
The photosensitive layer coating solution and the protective layer coating solution are coated on PET, and the dried coating film is exposed with a high-pressure mercury lamp through a lattice-like photomask (line / space = 195 μm / 5 μm (pitch 200 μm)). .

[Chemical development]
Using a commercially available developer for monochrome light-sensitive materials (Ecostage developer: manufactured by Konica Minolta Co., Ltd.), development treatment was performed at 27 ° C. for 30 seconds and rinsed with pure water.

[Physical development processing]
Physical developer (mixture obtained by mixing a solution obtained by dissolving 6 g of citric acid and 10 g of hydroquinone in 1000 ml of water and a solution obtained by dissolving 10 g of silver nitrate in 300 ml of water immediately before the physical development treatment.) Was developed at 20 ° C. for 10 minutes and rinsed with pure water.

[Plating treatment]
Plating solution (containing copper sulfate 0.06 mol / L, formalin 0.22 mol / L, triethanolamine 0.12 mol / L, polyethylene glycol 100 ppm, yellow blood salt 50 ppm, α, α′-bipyridine 20 ppm, The electroless copper plating treatment was performed at 45 ° C. using an electroless Cu plating solution having a pH of 12.5.

[Fixing]
Using a commercially available fixing solution for monochrome light-sensitive materials (Ecostage fixing solution: manufactured by Konica Minolta Co., Ltd.), the fixing treatment was performed at 27 ° C. for 5 minutes and rinsed with pure water.

  The line width of the conductive metal part of the sample having the conductive metal part and the light transmissive part obtained as described above was measured to determine the aperture ratio, and the surface resistance value was measured.

(Surface resistance)
The surface resistance value was measured by using a resistivity meter Loresta GP manufactured by Dia Instruments.

(Transmittance)
As described above, the transmittance of the light transmissive part was measured as the minimum value of the transmittance in the wavelength region of 380 to 780 nm excluding the contribution of light absorption and reflection of the support.

  An evaluation result is shown in Table 1 with the data of a comparative example.

Note that the processing order after exposure was changed as follows.
A: exposure / chemical development / physical development / fixing B: exposure / chemical development / plating / fixing C: exposure / physical development / chemical development / fixing D: exposure / chemical development / fixing / plating Clear from the results shown in Table 1 As described above, according to the production method of the present invention, a translucent electromagnetic wave shielding film satisfying both high transmittance and high electrical conductivity (electromagnetic wave shielding ability) performance can be obtained without increasing the number of steps. As a result, a large amount of translucent electromagnetic wave shielding film can be produced at low cost.

Claims (6)

It is characterized by forming a conductive metal portion and a light transmitting portion by exposing a photosensitive material having a photosensitive layer containing photosensitive silver salt particles on a support, performing a physical development process and then performing a fixing process. A method for producing a translucent electromagnetic wave shielding film. A photosensitive material having a photosensitive layer containing photosensitive silver salt particles is exposed on a support, subjected to a physical development process and then a chemical development process to form a conductive metal part and a light transmission part. The method for producing a translucent electromagnetic wave shielding film according to claim 1, wherein fixing treatment is performed. The method for producing a translucent electromagnetic wave shielding film according to claim 1, wherein the plating treatment is performed after the physical development treatment and before the fixing treatment. A photosensitive material having a photosensitive layer containing photosensitive silver salt particles on the support is exposed and subjected to a chemical development process to form a metallic silver part and a light transmission part. The metal silver part has a conductive metal part supporting conductive metal particles by performing at least one of the plating processes and thereafter performing a fixing process. The manufacturing method of the translucent electromagnetic wave shielding film as described in any one of Claims. A translucent electromagnetic wave shielding film produced by the method for producing a translucent electromagnetic wave shielding film according to claim 1. A plasma display panel using the translucent electromagnetic wave shielding film according to claim 5.