WO2008010461A1 - film de protection électromagnétique transparent ET SON PROCÉDÉ DE FABRICATION - Google Patents

film de protection électromagnétique transparent ET SON PROCÉDÉ DE FABRICATION Download PDF

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Publication number
WO2008010461A1
WO2008010461A1 PCT/JP2007/063978 JP2007063978W WO2008010461A1 WO 2008010461 A1 WO2008010461 A1 WO 2008010461A1 JP 2007063978 W JP2007063978 W JP 2007063978W WO 2008010461 A1 WO2008010461 A1 WO 2008010461A1
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Prior art keywords
electromagnetic wave
wave shielding
transparent electromagnetic
shielding film
silver
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PCT/JP2007/063978
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English (en)
Japanese (ja)
Inventor
Kazuhiro Miyazawa
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Konica Minolta Holdings, Inc.
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Publication of WO2008010461A1 publication Critical patent/WO2008010461A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0094—Shielding materials being light-transmitting, e.g. transparent, translucent
    • H05K9/0096—Shielding materials being light-transmitting, e.g. transparent, translucent for television displays, e.g. plasma display panel

Definitions

  • the present invention relates to a transparent electromagnetic wave shielding film that shields electromagnetic waves generated from electronic devices such as mobile phones, microwave ovens, CRTs, and flat panel displays, and a method for manufacturing the same.
  • Electromagnetic wave shielding materials in which a conductive pattern is produced by performing plating or the like as a catalyst are known (see, for example, Patent Documents 7 to 9). 0 In these materials, a photosensitive silver halide emulsion is used as a support. The power to use a binder to hold on It is preferred to increase the AgZ binder ratio as much as possible to increase conductivity! /
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2004-179405
  • Patent Document 2 JP-A-5-327274
  • Patent Document 3 Japanese Patent Laid-Open No. 11-170421
  • Patent Document 4 Japanese Patent Laid-Open No. 2003-23290
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004-172041
  • Patent Document 6 Japanese Patent Laid-Open No. 2005-183059
  • Patent Document 7 Japanese Unexamined Patent Application Publication No. 2004-221564
  • Patent Document 8 Japanese Patent Application Laid-Open No. 2004-221565
  • Patent Document 9 Pamphlet of International Publication No. 01Z51276
  • the present invention has been made in view of the above problems, and its purpose is to provide a transparent electromagnetic wave shielding excellent in electromagnetic wave shielding performance, having high transparency, and having excellent durability against changes in temperature and humidity. To provide a film.
  • the inventors of the present invention have studied the method of producing a conductive mesh using a silver halide light-sensitive material while paying attention to the halogen-silver light-sensitive material.
  • the binder By designing the binder to hold the substrate on the support so that the absolute amount of the binder alone is within a certain range, it maintains durability and is resistant to changes in temperature and humidity. It was found that an excellent transparent electromagnetic wave shielding film can be obtained.
  • the object of the present invention is achieved by the following transparent electromagnetic wave shielding film.
  • a transparent electromagnetic wave shielding film produced by subjecting a photosensitive material having a layer comprising at least a photosensitive silver halide silver and a binder on a support to a development process after exposure.
  • the content of the photosensitive Harogeni ⁇ in the photosensitive material is lgZm less than 2 0. 05G / m 2 or more in terms of silver, and the amount of the binder is 2 hereinafter LOmgZm 2 or 0. 2GZm
  • LOmgZm 2 or 0. 2GZm A transparent electromagnetic wave shielding film characterized.
  • the transparent electromagnetic wave shielding film is subjected to physical development or metal plating after exposure and development, and the amount of metal applied by physical development or metal plating exposes and develops the photosensitive material.
  • the transparent electromagnetic wave shielding film according to 1 above which is 10 to 100 times in terms of mass with respect to the developed silver amount obtained by the above.
  • the transparent electromagnetic wave shielding film is characterized in that a value obtained by dividing the content of silver halide (g / m 2 ) by the average grain size of silver halide ( ⁇ m) is 6 or more and 25 or less. 3.
  • the transparent electromagnetic wave shielding film is subjected to oxidation after exposure and development. 4.
  • the transparent electromagnetic wave shielding film has an antireflection layer on the opposite side of the layer having the conductive pattern to the layer having the conductive pattern, and the protective film is formed after the antireflection layer is formed.
  • the transparent electromagnetic wave shielding film of the present invention comprises a photosensitive material having at least a layer composed of a photosensitive halogenated silver and a binder on a support.
  • the content is 0.05 g / m 2 or more and less than lg / m 2 in terms of silver, and the amount of the binder is 1 Omg / m 2 or more and 0.2 g / m 2 or less.
  • a silver halide emulsion-containing layer containing a light-sensitive silver halide silver and a binder, which will be described later, is provided on a support.
  • a film agent, a hardener, an activator and the like can be contained.
  • the effect of the present invention can be obtained when the content of the photosensitive halogenated silver is 0.05 g / m 2 or more and less than lg Zm 2 in terms of silver.
  • the content of the photosensitive halogen silver is less than 0.05 gZm 2 , it is difficult to obtain sufficient electromagnetic wave shielding performance. This is presumed to be because the amount of developed silver nuclei serving as a catalyst for the physical development or metal plating process described later is insufficient, and an effective conductive mesh is formed.
  • the photosensitive silver halide content is lgZm 2 or more, the amount of halogenated silver relative to the binder is relatively large, so that the coating becomes fragile and immediately maintains sufficient coating strength. It becomes difficult.
  • the effect of the present invention can be obtained when the binder amount of the light-sensitive material is 1 OmgZm 2 or more and 0.2 gZm 2 or less.
  • the amount of noinder is less than 1 Omg / m 2
  • the amount of halogen silver relative to the noinder becomes relatively large, so that the film becomes fragile and it is difficult to immediately maintain a sufficient film strength.
  • the Noinder amount is more than 0.2 gZ m 2 , the distance between the grains of the photosensitive halogen-molybdenum grains becomes large, so that a current silver network is formed, and an effective conductive mesh is formed.
  • the durability against changes in temperature and humidity becomes insufficient, and the effects of the present invention cannot be obtained.
  • composition of the silver halide silver grains used in the present invention is as follows: silver chloride, silver bromide, silver chlorobromide, iodine Silver bromide, silver chloroiodobromide, silver chloroiodide, etc. may have any halogen composition Force To obtain highly conductive metal silver, fine grains with high sensitivity are preferred. Silver halide grains are preferably used. If a large amount of iodine is contained, the sensitivity is high and fine particles can be obtained.
  • the contact area between the developed silver particles becomes as large as possible.
  • the smaller the size of the halogen silver silver particles the better to increase the surface area ratio, but the particles that are too small aggregate to form large agglomerates, and in that case, the contact area decreases on the contrary.
  • the average grain size of the silver halide grains is preferably 0.03 to 0.3 m, more preferably 0.01 to 0.5 m in terms of a sphere equivalent diameter.
  • the spherical equivalent diameter of a halogenated silver particle represents the diameter of a grain having a spherical shape and the same volume.
  • the average particle size of the halogenated silver particles is the temperature, pAg, pH, addition rate of the silver ion solution and the halogen solution, the particle size control agent (for example, 1 Fe-Lu 5 mercaptotetrazole, 2 —Mercaptobenzimidazole, benztriazole, tetrazaindene compounds, nucleic acid derivatives, thioether compounds, etc.) can be combined and controlled as appropriate.
  • the particle size control agent for example, 1 Fe-Lu 5 mercaptotetrazole, 2 —Mercaptobenzimidazole, benztriazole, tetrazaindene compounds, nucleic acid derivatives, thioether compounds, etc.
  • the value obtained by dividing the silver halide content (gZm 2 ) by the average grain size ( ⁇ m) of silver halide is 6 or more and 25 or less.
  • this value becomes larger than 25, and in this case, the silver halide grains slip off from the coating immediately on the edge when the film is cut. Tend to be more likely to occur.
  • this value becomes smaller than 6 and, in this case, the number of photosensitive silver halide grains in the unit area decreases. This is because it tends to decrease! /.
  • the shape of the halogen silver halide grains is not particularly limited.
  • spherical, cubic, flat plate hexagonal flat plate, triangular flat plate, quadrangular flat plate, etc.
  • octahedral shape etc. It can be in various shapes such as a 14-sided shape.
  • tabular grains having an aspect ratio of 2 or more, 4 or more, and further 8 to 16 can be preferably used.
  • particle The size distribution is not particularly limited, but a narrow distribution is preferable from the viewpoint of enhancing the transparency while maintaining high conductivity while sharply reproducing the outline of the pattern during pattern formation by exposure.
  • the particle size distribution of the halogen silver halide grains used in the light-sensitive material according to the present invention is preferably monodispersed halogen silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less.
  • the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.
  • the halogen silver halide grains used in the present invention may further contain other elements.
  • metal ions used to obtain a high contrast emulsion.
  • iron ions, rhodium ions, the first 8-10 metals ions such as ruthenium ions and Irijiu Ion preferably used because the difference between the exposed and unexposed portions in the generation of metallic silver image is likely clearly occur.
  • Transition metal ions can be added to a halogenated silver emulsion in the form of a salt complex.
  • Transition metal ions typified by rhodium ions and iridium ions can also be compounds having various ligands. Examples of such ligands include cyanide ions, halogen ions, thiocyanate ions, nitrocinole ions, water, hydroxide ions, and the like. Specific examples of the compound include potassium bromide rhodate and potassium iridate.
  • the metal compound is added before the formation of silver halide grains, during the formation of halogenated silver grains, after the formation of halogenated silver grains, etc. What is necessary is just to add in the arbitrary places in each process during physical ripening.
  • the heavy metal compound solution can be continuously formed over a part of the particle forming process.
  • Chemical sensitization in order to further improve the sensitivity, chemical sensitization performed in a photographic emulsion is performed. You can also. Chemical sensitization includes, for example, noble metal sensitization such as gold, palladium and platinum sensitization, chalcogen sensitization such as iodo sensitization with inorganic or organic compounds, and reduction sensitization such as sodium chloride tin and hydrazine. Can be used.
  • noble metal sensitization such as gold, palladium and platinum sensitization
  • chalcogen sensitization such as iodo sensitization with inorganic or organic compounds
  • reduction sensitization such as sodium chloride tin and hydrazine.
  • the silver halide grains are subjected to spectral sensitization.
  • Spectral sensitizing dyes include cyanine, carbocynin, dicarboyanine, complex cyanine, hemisyanine, styryl dye, merocyanine, complex melocyanin, holopora single dye, etc., which are used in the industry.
  • the spectral sensitizing dye can be used alone or in combination.
  • Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes.
  • any of the nuclei commonly used in cyanine dyes can be used as the basic heterocyclic ring nucleus.
  • the merocyanine dye or the complex merocyanine dye includes a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2 thoxazolidine 2,4 dione nucleus, a thiazolidine 2,4 dione nucleus, a rhodanine as a nucleus having a ketomethylene structure.
  • 5 to 6-membered heteronuclear ring nuclei such as nucleus and thiobarbituric acid nucleus can be applied.
  • sensitizing dyes may be used alone or in combination.
  • sensitizing dyes is often used for the purpose of supersensitization.
  • sensitizing dyes in a silver halide silver emulsion, they may be dispersed directly in the emulsion, or water, methanol, propanol, methyl mouthsolve, 2, 2, 3, It may be dissolved in a solvent such as 3-tetrafluoropropanol alone or in a mixed solvent and added to the L agent.
  • a solvent such as 3-tetrafluoropropanol alone or in a mixed solvent and added to the L agent.
  • an acid or a base is allowed to coexist to form an aqueous solution. 822, 135, 4, 006, 025, etc.
  • water or a hydrophilic colloid-dispersed solution may be added to the emulsion after being dissolved in a solvent substantially immiscible with water such as phenoxyethanol.
  • the dispersion may be directly dispersed in a hydrophilic colloid and the dispersion may be added to the emulsion.
  • the silver halide grains are uniformly dispersed, and the silver halide grains are supported on the support, and the adhesiveness between the silver halide emulsion-containing layer and the support.
  • a binder is used for the purpose of ensuring the above.
  • the binder that can be used in the present invention any of a water-insoluble polymer and a water-soluble polymer that are not particularly limited can be used. From the viewpoint of improving developability, a water-soluble polymer can be used. I like it.
  • hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer substances such as mono- or copolymers Can be used.
  • an ultraviolet absorber in order to avoid deterioration of the electromagnetic wave shielding film due to ultraviolet rays.
  • 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 mix
  • benzotriazoles are preferably used as ultraviolet absorbers.
  • a general formula [III 3] described in JP-A-1-250944 can be mentioned.
  • compounds described in Japanese Patent Publication No. 64-66646 are preferably used as ultraviolet absorbers.
  • UV-1L to UV-27L described in JP-A-63-187240 compounds represented by general formula [I] described in JP-A-41633, JP-A-5-
  • the compounds represented by the general formulas (1) and (II) described in Japanese Patent No. 165144 are preferably used.
  • These ultraviolet absorbers are, for example, high boiling points represented by phthalates such as dioctyl phthalate, di-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 in an organic solvent is preferably used.
  • an embodiment in which these ultraviolet absorbers are directly added to the support is also preferably used. In this case, for example, an embodiment described in JP-T-2004-531611 can also be preferably used.
  • blackening treatment from the viewpoint of preventing reflection of external light on the film surface.
  • a transparent electromagnetic wave shielding film that has undergone such blackening treatment is used in a display such as a PDP, it is possible to reduce the decrease in contrast due to reflection of external light and to make the screen color tone black when not in use. It is preferable that it can be maintained.
  • the black wrinkle processing method known methods without particular limitation can be used alone or in combination as appropriate.
  • the outermost surface of the conductive pattern when the outermost surface of the conductive pattern is also made of metallic copper, it can be immersed in an aqueous solution containing sodium chlorite, sodium hydroxide, or trisodium phosphate and oxidized, or copper pyrophosphate, A method of blackening by immersing in an aqueous solution containing potassium pyrophosphate and ammonia and performing electrolytic plating can be preferably used.
  • the outermost layer of the conductive pattern is made of a nickel-phosphorus alloy film, an acidic blackening solution containing copper (II) chloride or copper sulfate (11), nickel chloride or sulfuric acid-nickel, and hydrochloric acid.
  • the method of immersing in can be preferably used.
  • black wrinkle processing is also possible by a method of roughening the surface.
  • the blackening method using oxidation is preferred to the finer surface.
  • a method in which the photosensitive material is a high contrast is preferred.
  • a high silver salt content is used to narrow the particle size distribution.
  • a hydrazine compound is a compound having an NHNH group, and a typical one is represented by the following general formula (1).
  • each T represents an optionally substituted aryl group or heterocyclic group.
  • the aryl group represented by T includes a benzene ring or a naphthalene ring, and this ring may have a substituent.
  • a linear or branched alkyl group preferably having a carbon number of 1 To 20 methyl group, ethyl group, isopropyl group, n-dodecyl group, etc.
  • alkoxy group preferably methoxy group having 2 to 21 carbon atoms, ethoxy group etc.
  • aliphatic isylamino group preferably 2 to 21 carbon atoms
  • aromatic isylamino groups, etc. in addition to these, for example, the substituted or unsubstituted aromatic rings as described above are —CONH—, —O—, -SO NH—, — NHCONH—, —CH
  • V is a hydrogen atom, an optionally substituted alkyl group (methyl group, ethyl group, butyl, trifluoromethyl group, etc.), aryl group (phenyl group, naphthyl group), heterocyclic group (pyridyl group, piperidyl group, Pyrrolidyl group, furanyl group, thiophene group, pyrrole group and the like).
  • the hydrazine compound described above can be synthesized with reference to the description in US Pat. No. 4,269,929.
  • the hydrazine compound can be contained in the halogen-containing silver particle-containing layer, in the hydrophilic colloid layer adjacent to the halogen-containing silver particle-containing layer, or in another hydrophilic colloid layer.
  • H-1 1-trifluoromethylcarbole 2— ⁇ [4— (3-n-butylureido) phenol] ⁇ hydrazine
  • H 2 l Trifluoromethyl carboru 2- ⁇ 4- [2- (2, 4-Gee 61: 1; -Pentylphenoxy) butyramide] phenol ⁇ hydrazine
  • an amine compound or a pyridine compound can be preferably used in order to enhance the reducing action of hydrazine.
  • the amine compound that promotes the reduction action of the hydrazine compound it is particularly preferable that the molecule has at least one piperidine ring or pyrrolidine ring, at least one thioether bond, and at least two ether bonds. .
  • pyridinium compounds and phosphonium compounds can be preferably used in addition to the above-mentioned amine compounds. Since the o-um compound is positively charged, it is adsorbed on the negatively charged halogen-molybdenum grains and promotes electron injection from the developing agent at the time of image formation, thereby promoting high contrast. It is thought to do.
  • pyridinium compounds reference can be made to the bispyridium compounds disclosed in JP-A-5-53231 and JP-A-6-242534.
  • Particularly preferred pyridi-um compounds are those that are linked at the 1st or 4th position of the pyridium to form a bispyridumum! /, is there.
  • the salt chlorine ion or bromine ion is preferred as a halogen ion, and in addition, a force such as boron tetrafluoride ion, perchlorate ion, etc. Chlorine ion or 4 fluorine boron ion is preferred.
  • Hidorajini ⁇ thereof, Amini ⁇ thereof, pyrid - ⁇ beam compounds, and Tetorazoriumu compound per mol of silver halide 1 X 10- 6 ⁇ 5 X 10- 2 mol preferably tool especially 1 to contain X 10 one 4 ⁇ 2 X 10- 2 mol is preferred. It is easy to adjust the addition amount of these compounds to increase the degree of contrast ⁇ to 6 or more.
  • These compounds are used by being added to a layer containing halogenated particles or another hydrophilic colloid layer. If it is water-soluble, it is added to an aqueous solution, and if it is water-insoluble, it is added to a silver halide grain solution or hydrophilic colloid solution as a solution of an organic solvent miscible with water, such as alcohols, esters, and ketones. That's fine. Further, when it is not soluble in these organic solvents, it can be added as fine particles having a size of 0.01 to 10 / ⁇ ⁇ by a ball mill, a sand mill, a jet mill or the like.
  • a technique of solid dispersion of a dye as a photographic additive can be preferably applied.
  • a desired particle size can be obtained using a dispersing machine such as a ball mill, a planetary rotating ball mill, a vibrating ball mill, or a jet mill.
  • a surfactant is used at the time of dispersion, stability after dispersion can be improved.
  • a support for example, a cellulose ester film, a polyester film, a polycarbonate film, a polyarylate film, a polysulfone (including polyethersulfone) film, a polyester film such as polyethylene terephthalate and polyethylene naphthalate , Polyethylene film, Polypropylene film, Cellophane, Senorelose diacetate Finolem, Senorelose acetate butyrate phenolome, Polyvinylidene chloride film, Polybulol alcohol film, Ethylene butyl alcohol film, Syndiotactic polystyrene film , Polycarbonate film, norbornene resin film, polymethylpentene film, polyether ketone film, Li polyether ketone imide film, a polyamide film, a fluorine ⁇ film, a nylon film, polymethyl methacrylate Tari acetate film or an acrylic film or the like.
  • quartz glass and soda glass are also be also used to give quartz glass and soda glass.
  • cellulose triacetate film polycarbonate film, polysulfone (including polyethersulfone), and polyethylene terephthalate film are preferably used.
  • a cellulose ester film or a polyester film as the support from the viewpoints of transparency, isotropicity, adhesiveness, and the like.
  • 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.
  • the average transmittance of the plastic film or glass plate in the entire visible light region is preferably 85 to 100%, more preferably 90 to: LOO%.
  • the color tone adjusting agent the plastic film or glass plate that has been colored to such an extent that the object of the present invention is not hindered is used.
  • the average transmittance in the visible light region means that each transmittance in the visible light region determined by measuring the transmittance in the visible light region from 400 to 700 nm at least every 5 nm.
  • the rate is defined as the average value obtained by accumulating the rates.
  • the measurement parameter must be sufficiently larger than the mesh pattern described above, and is obtained by measuring at least 100 times larger than the mesh area of the mesh.
  • the thickness of the support used in the present invention is not particularly limited, but from the viewpoint of maintaining transmittance and handling, it is preferably 5 to 200 m, and preferably 30 to 150 / ⁇ ⁇ . More preferably.
  • the photosensitive material is exposed in order to form a conductive pattern by a development process described later.
  • 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 narrow wavelength distribution may be used for exposure, or a light source having a wavelength distribution may be used.
  • various light emitters that emit light in the spectral region are used as necessary.
  • a red luminescent material a green luminescent material, and a blue luminescent material may be used in combination.
  • 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.
  • mercury lamp g-line, mercury lamp i-line, etc., which favor ultraviolet lamps, are also used.
  • exposure can be performed using various laser beams.
  • monochromatic high-density light such as gas laser, light emitting diode, semiconductor laser, semiconductor laser or solid-state laser using a semiconductor laser as a pumping light source and second harmonic light source (SHG) combining nonlinear optical crystal Can be used preferably, and KrF excimer laser, ArF excimer laser, F laser, etc. can also be used.
  • a semiconductor laser In order to make the system compact and rapid, exposure should be 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. preferable. In order to design an apparatus that is particularly compact, quick, and has a long life and high stability, exposure is preferably performed using a semiconductor laser.
  • SHG second harmonic generation light source
  • the laser light source specifically, 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 for exposing the silver halide emulsion-containing layer to an image may be performed by surface exposure using a photomask or by scanning exposure using a laser beam.
  • exposure methods such as surface contact exposure, near-field exposure, reduced projection exposure, and reflection projection exposure may be used, such as condensing exposure using a lens or reflection exposure using a reflecting mirror.
  • the output of the laser may be about several tens of ⁇ W to 5W, as long as it is an amount suitable for exposing silver halide.
  • the development process is preferably a black and white development process that does not contain a color developing agent.
  • 1-phenol 3-virazolidone, 1-phenyl as a developing agent. 1, 4, dimethyl 1, 3 pyrazolidone, 1-phenyl 1, 4-methyl 4 -It can be used in combination with virazolidones such as hydroxymethyl 3 bisazolidone, 1 phenyl 4 methyl 3 bisazolidone and superadditive developing agents such as N-methylparaaminophenol sulfate.
  • a reductone compound such as ascorbic acid or isoascorbic acid in combination with the above superadditive developing agent without using hydroquinone.
  • Propanediol or the like can be used as appropriate.
  • the development processing solution used in the development processing can contain an image quality improving agent for the purpose of improving the image quality.
  • the image quality improver include nitrogen-containing heterocyclic compounds such as 1-ferro-5-mercaptotetrazole and 5-methylbenzotriazole.
  • the development processing performed after exposure includes physical development before fixing.
  • the pre-fixing physical development referred to here is a process for reinforcing developed silver by supplying silver ions other than the inside of the silver halide grains having a latent image by exposure before performing the fixing process described later. Show.
  • a specific method for supplying silver ions from the developing solution for example, a method in which silver nitrate or the like is dissolved in advance in the developing solution and silver ions are dissolved, or thiosulfuric acid is added in the developing solution.
  • Examples include a method in which a halogenated silver solvent such as sodium or ammonium thiocyanate is dissolved, and unexposed silver halide is dissolved during development to assist development of silver halide grains having a latent image. It is done.
  • a halogenated silver solvent such as sodium or ammonium thiocyanate
  • the use of a formulation in which a silver halide solvent is dissolved in advance in a developer can suppress a decrease in film transmittance due to the occurrence of capri in the unexposed area. It is preferable.
  • a fixing process is carried out for the purpose of removing and stabilizing the unexposed portions of the silver halide grains.
  • a fixer formulation used for photographic films, photographic papers and the like using silver halide grains can be used.
  • Fixing solution used in fixing process is sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, etc.
  • Aluminum sulfate, chromium sulfate, etc. can be used as a hardener for fixing.
  • sodium sulfite, potassium sulfite, ascorbic acid, erythorbic acid, etc. described in the developing solution can be used, and in addition, citrate, oxalic acid, etc. can be used. .
  • N-methyl-isothiazole-3-one N-methyl-isothiazol-5-chloro-3-one, N-methyl-isothiazole- 4,5-Dichloro-3-one, 2-Nitroe 2-Bromue 3-hydroxypropanol, 2-Methyl-4-chlorophenol, hydrogen peroxide, etc. can be used.
  • the complementary processing refers to processing for improving the conductivity by supplying a conductive material source not previously contained in the photosensitive material from the outside during or after the development processing.
  • Examples of the method include physical development or plating treatment. Physical development can be performed by immersing a photosensitive material containing a silver halide emulsion having a latent image in a processing solution containing silver ions or silver complex ions and a reducing agent. In the present invention, even when developed silver where the development start point of physical development is only the latent image nucleus becomes the physical development start point, it is defined as physical development and can be preferably used.
  • various conventionally known plating methods can be used for the plating treatment.
  • electrolytic plating and electroless plating can be carried out singly or in combination.
  • electroless plating that does not cause unevenness due to current distribution unevenness can be preferably used.
  • metals that can be used for electroless plating for example, copper, nickel, cobalt, tin, silver, gold, platinum, and other various alloys can be used. From the viewpoint of easily obtaining conductivity, it is particularly preferable to use a copper electroless plating.
  • the intensification process can be performed at any time during development, after development, before fixing, and after fixing process, but from the viewpoint of maintaining high transparency of the film, after the fixing process. Preferred to carry out.
  • it is 10 times or more and 100 times or less in terms of mass with respect to developed silver obtained by exposing and developing a metal amount-sensitive material provided by physical development or metal plating. Some embodiments are preferred. This value can be determined by quantifying the metal contained in the light-sensitive material by, for example, fluorescent X-ray analysis before and after physical development or metal plating. The amount of metal applied by physical development or metal plating
  • the conductivity tends to decrease slightly.
  • the transmittance tends to decrease due to metal deposition on unnecessary portions other than the conductive mesh pattern portion.
  • the description of physical development or metal plating means that at least one of physical development or plating treatment is performed, and both physical development and metal plating may be included. In the present invention, it is preferable to perform both physical development and metal plating.
  • Oxidation treatment allows unnecessary metal components to be ionized and dissolved and removed, and the transmittance of the film can be further increased.
  • the treatment liquid used for the oxidation treatment for example, a treatment method using an aqueous solution containing Fe (III) ions, hydrogen peroxide, persulfate, perborate, perphosphate, percarbonate, Using a treatment solution containing a conventionally known oxidant, such as a method of treatment with an aqueous solution containing peroxide such as peroxygen, rogenate, hypohalite, halogenate, or organic peroxide Can.
  • Oxidation is an aspect that is performed between the end of the development process and before the plating process. This is preferable because the transmittance can be improved efficiently in a short time, and the physical development is particularly preferable. This is a mode to be performed later.
  • a conductive mesh pattern in order to provide high translucency and high electromagnetic wave shielding performance, can be 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 is 20 m or less.
  • the interval is preferably 50 / zm or more.
  • the conductive metal part may have a part with a line width larger than 20 m for the purpose of ground connection or the like. From the viewpoint of making the image inconspicuous, the line width of the conductive metal part is preferably less than 18 ⁇ m, less than 15 ⁇ m, more preferably less than 14 m, and even more preferably less than 10 m.
  • the preferred value is less than 7 ⁇ m.
  • the conductive metal part of 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.
  • the aperture ratio of a square lattice mesh with a line width of 10 / ⁇ ⁇ and a pitch of 200 ⁇ m is 90%.
  • the halogen silver halide emulsion coated on each surface has a sensitivity at different wavelengths by spectral sensitization.
  • sensitivity By giving sensitivity to different wavelengths on the front and back surfaces, it becomes possible to create 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.
  • 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 halogenated silver particle layer. It is also preferable to set up.
  • the near-infrared ray absorbing layer may be provided on the opposite side of the support from the side where the halogen silver halide particle layer is present, or may be provided on both the side opposite to the halogen silver halide particle layer side. .
  • a near-infrared absorbing layer may be provided between the silver halide grain layer containing silver halide and the support, or a near-infrared absorbing layer may be provided on the opposite side of the support as viewed from the silver halide grain layer. Yes, the former is preferred because it can be applied to one side of the support at the same time.
  • near-infrared absorbing dyes include polymethine, phthalocyanine, naphthalocyanine, metal complex, aminium, imonium, dimonium, anthraquinone, dithiol metal complex, naphthoquinone, indole phenol , Azo, tria
  • PDP optical filter is required to have near-infrared absorptivity mainly for heat ray absorption and prevention of noise in electronic equipment.
  • a metal complex, amidium, phthalocyanine, naphthalocyanine, dim-humic dye that has a maximum absorption wavelength of 750-: L lOOnm is preferred.
  • Particularly preferred is a sulfur compound system.
  • di-moum compounds are IRG-022, IRG-040 (the trade name of Nippon Gyaku Co., Ltd.), nickel dithiol complex compound is SIR- 128, SIR-130, SIR-132, SIR-159, SIR-152, SIR-162 (above, product names manufactured by Mitsui Chemicals Co., Ltd.), phthalocyanine compounds are IR-10, IR-12 (above Commercial products such as Nippon Shokubai Co., Ltd.) can be used.
  • the near-infrared absorbing dye includes alcohol solvents such as methanol, ethanol and isopropanol, ketone solvents such as acetone, methyl ethyl ketone and methyl butyl ketone, organic solvents such as dimethyl sulfoxide, dimethylformamide, dimethyl ether and toluene.
  • alcohol solvents such as methanol, ethanol and isopropanol
  • ketone solvents such as acetone, methyl ethyl ketone and methyl butyl ketone
  • organic solvents such as dimethyl sulfoxide, dimethylformamide, dimethyl ether and toluene.
  • a colorant having a near-infrared absorbing ability is contained in the color tone correction layer, either one of the above dyes may be contained, or two or more kinds may be contained. Oh ,.
  • 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), this is used to prevent a decrease in color reproducibility due to emission of neon gas used in the PDP.
  • an embodiment containing a dye that absorbs light at around 595 nm is preferable.
  • dyes that absorb such specific wavelengths include, for example, azo, condensed azo, phthalocyanine, anthraquinone, indigo, perinone, perylene, dioxazine, and quinacridone.
  • organic pigments such as methine series, isoindolinone series, quinophthalone series, pyrrole series, thioindigo series and metal complex series, organic dyes, and inorganic pigments.
  • phthalocyanine and anthraquinone dyes are particularly preferably used because of their good weather resistance.
  • the electromagnetic wave shielding material of the present invention is used for the purpose of protecting a display screen, etc. It is preferable to provide an antireflection layer.
  • the antireflection layer metal oxides, fluorides, halides, borides, carbides, nitrides, sulfides, and other inorganic materials such as vacuum deposition, sputtering, ion plating, ion beam assist, etc.
  • a method of laminating thin films in a single layer or multiple layers, a method of laminating thin films of different refractive indexes such as acrylic resin, fluorine resin, etc. into a single layer or multiple layers can be used.
  • an antireflection layer is formed on the opposite side of the transparent electromagnetic wave shielding film with the support of the film sandwiched between the layer having the conductive pattern!
  • 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 decrease.
  • An embodiment in which the layer is formed first is preferred.
  • an aspect in which the conductive pattern layer is formed after pasting a protective film in advance Is preferred ⁇ .
  • the protective film used in the present invention is capable of using a commercially available protect film.
  • the type of pressure-sensitive adhesive used for the protective film is not particularly limited, but it is preferable to use one that does not alter the antireflection film and does not damage the antireflection film during peeling. From such a viewpoint, an acrylic or silicone adhesive is preferably used. Further, the adhesive strength is preferably 0.008-0.6NZ25mm.
  • EMP-1 In the preparation of EMP-1, the average particle size was set to 0, except that (A1 solution) and (B1 solution) were added and (C1 solution) and (D1 solution) were added at a temperature of 40 ° C. 07 ⁇ m, Halogenous silver emulsion EMP-2 with a coefficient of variation of 0.14, and an average particle size of 0.12 m, a coefficient of variation of the particle size distribution of 0.13. Of silver halide emulsion EMP-3 was obtained.
  • EMP-1 is chemically sensitized with 2. Omg of sodium thiosulfate per mol of silver halide at 40 ° C for 80 minutes, 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 to obtain a silver halide silver emulsion EM-1.
  • TAI 4-hydroxy-6-methyl-1, 3, 3a, 7-tetrazaindene
  • the silver halide emulsion was changed from EMP-1 to EMP-2 and EMP-3, and the amount of sodium thiosulfate and TAI added was adjusted to the total surface of the silver halide grains. Similarly, except for adjusting in proportion to the product, Halogenous silver emulsions EM-2 and EM-3 were obtained, respectively.
  • the silver halide emulsions EM-1 to EM-3 prepared as described above were prepared as shown in Table 1. Coating was performed so that the amount of gelatin was the same, and then drying was performed to produce photosensitive materials 101 to 117.
  • a hardener H-1: tetrakis (bulusulfol-methyl) methane
  • H-1 tetrakis (bulusulfol-methyl) methane
  • a surfactant SU-2: di (2-ethylhexyl sulfosuccinate) • sodium
  • Table 1 the amount of silver is shown as a value obtained by converting the amount of the halogeno silver emulsion used to equimolar silver.
  • Electromagnetic wave transmittance table! Specific resistance ⁇ Evaluation after forced degradation test
  • the transparent electromagnetic wave shielding films S102 to S106, SI 08 to S111, S113 and S116 satisfying the requirements of the present invention have high transmittance and low surface resistivity, and after forced degradation test It is obvious that the effect of the present invention can be obtained that the degree of deterioration of the film brittleness is small when the transmittance change of the film is small.
  • the value obtained by dividing the coating silver amount (gZm 2 ) by the particle size ( ⁇ m) is in the range of 6 to 25 [this transparent electromagnetic wave shielding Finolem S104 to S106, S108 to S111, and S113 are the same photosensitive halogen compounds.
  • the coating of the edge partial force at the time of cutting has almost no peeling and a low surface specific resistance, indicating that this is a preferred embodiment of the present invention.
  • Table 3 shows the immersion time in the Pd catalyst solution (CAT-1) and the immersion solution (PL-1) in the transparent electromagnetic wave shielding films S101, S105, and S107 produced in Example 1.
  • Transparent electromagnetic wave shielding films S201 to S209 were produced in the same manner except for changing to.
  • the amount of developed silver after the development of silver halide was completed at the stage when (DEV-1), (FIX-1) and water washing were completed. Quantitatively by X-ray fluorescence analysis, and after the processing of (PD-1), (CAT-1) and (PL-1) is completed, X-ray fluorescence analysis is performed again, and the amount of physical developed silver and copper The amount of adhesion was quantified. Using the amount of metal thus determined, the ratio of the amount of metal imparted by physical development or metal plating to the amount of developed silver obtained by exposing and developing the photosensitive material was determined as a mass ratio.
  • the amount of metal imparted by physical development and metal plating is less than 10 times in terms of mass with respect to developed silver obtained by exposing and developing the photosensitive material.
  • the transparent electromagnetic wave shielding film S201 has high transmittance and low! / Surface specific resistance, but is 10 times or more in terms of mass, compared with other transparent electromagnetic wave shielding films according to the present invention. As a result, the surface resistivity was slightly high.
  • the transparent electromagnetic wave shielding film S205 in which the amount of metal applied by physical development and metal plating is 100 times greater than the developed silver obtained by exposing and developing the photosensitive material in terms of mass is: Although high transmittance, low V, and surface specific resistance were obtained, it was less than 100 times in terms of mass, resulting in slightly lower transmittance than other transparent electromagnetic wave shielding films according to the present invention. .
  • the amount of the metal that satisfies the requirements of the present invention and is imparted by physical development and metal plating is used for the photosensitive material.
  • the transparent electromagnetic wave shielding films S105 and S202 to S204, which are 10 times to 100 times in terms of mass with respect to developed silver obtained by exposure and development processing, have particularly high transmittance and low surface resistivity. It can be seen that this is a preferred embodiment of the present invention.
  • the electromagnetic wave shielding films S208 and S209 produced using the photosensitive material 107 that does not satisfy the constituent requirements of the present invention, like S107, were found to have cracks in the coating after the forced deterioration test and were inferior in brittleness.
  • the following acid solution (OX-1) was used for 45 seconds at 45 ° C for 120 seconds between physical development and Pd catalyst treatment.
  • Transparent electromagnetic wave shielding films S301 and S302 were prepared in the same manner except that the acid-soaking treatment was performed.
  • S106, S107, S301 and S302 were prepared.
  • the plating solution (P L-1) use the following black solution (BP-1) at 80 ° C for 120 seconds.
  • Transparent electromagnetic wave shielding films S303 to S306 were produced in the same manner except that the blackening treatment was performed. Evaluation similar to Example 1 was implemented with respect to the transparent electromagnetic wave shielding films S301-S306 obtained in this way.
  • the transparent electromagnetic wave shielding film with the conductive pattern side down was placed on black paper and the opposite surface force film was observed to confirm whether metallic gloss reflection was observed. The results are shown in Table 4.
  • the transparent electromagnetic wave shielding films S301, S302, S305 and S306 subjected to the oxidation treatment can obtain particularly high transmittance and are preferable embodiments of the present invention.
  • the transparent electromagnetic wave shielding films 303 to S306 treated with black glazing are not only capable of achieving both high transmittance and low surface resistivity, but also the metal reflection gloss of the conductive pattern is inconspicuous. Sometimes the visibility is low and high quality It can be seen that the transparent electromagnetic wave shielding film is particularly preferable.
  • sensitizing dye SD-1 or SD-2 was added to each mole of silver halide 1 mol after completion of chemical sensitization and before adding TAI. Except for using ⁇ Ka ⁇ so that per 3 X 10- 4 mole in the same manner, green-sensitive silver halide emulsion EM-1G, and the red-sensitive Harogeni ⁇ emulsion EM-1R manufactured.
  • Coating was performed in the same manner as in the preparation of the photosensitive material 105 prepared in Example 1, except that the photosensitive halogenated silver halide emulsion was changed from EM-1 to EM-1G. After drying, the photosensitive material is coated on the back side of the photosensitive material using the same coating solution except that the photosensitive halogen silver emulsion is changed to EM-1G for EM-1G. Double-sided photosensitive material 401 having
  • the front and back surfaces of the support were each different.
  • an electromagnetic wave shielding layer having different properties can be obtained by preparing different electromagnetic wave shielding patterns on the front and back surfaces.
  • a plurality of films can be provided on a sheet of film, which is a preferable aspect of the present invention.
  • UV-1 1 part by mass of the UV absorber (UV-1) was mixed with 20 parts by mass of polyvinyl acetal (Esreck BM-S: Sekisui Chemical Co., Ltd.) and ethyl acetate Z
  • Photosensitive material was the same except that a polyethylene terephthalate support coated with UV — 1 at 0.2 g / m 2 after being dissolved in a methyl ethyl ketone mixed solvent (mixing ratio 2: 1) was used.
  • 501 was produced, and transparent electromagnetic wave shielding film S501 was produced using the same method as transparent electromagnetic wave shielding film S105.
  • Example 1 The same evaluation as in Example 1 was performed on the transparent electromagnetic wave shielding film S501 thus obtained.
  • light was irradiated for 24 hours at 71 X in an environment of 24 ° C 60% RH, and the ratio of the transmittance after forced deterioration to the transmittance before forced deterioration was obtained.
  • “generation of cracks after storage” was evaluated and used as a measure of durability.
  • the transparent electromagnetic wave shielding film S501 having at least one ultraviolet absorbing layer has improved durability of the coating film against light irradiation, and is a particularly preferred embodiment of the present invention. I know that there is.
  • a transparent electromagnetic wave shielding film S640 was prepared by providing an antireflection layer on the back surface of the transparent electromagnetic wave shielding film S105 produced in Example 1 by the same method as in the production of the above-described antireflection film (AR-1).
  • the transparent electromagnetic wave shielding films S601 to S604 according to the present invention all show high transmittance and low surface resistivity, and the transmittance change after the forced deterioration test is small. Although the effect of the present invention is small, the conductive pattern is particularly important.
  • the shielding films S602 and S603 are a preferable embodiment of the present invention that can provide a transparent electromagnetic wave shielding film having a good antireflection layer without causing occurrence of uneven reflection in the antireflection layer and occurrence of an antireflection function. I understand.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

L'invention concerne un film de protection électromagnétique transparent excellent en matière de performances de protection d'onde électromagnétique, de transparence élevée, et excellent en matière de durabilité malgré des changements de température et d'humidité. Ce film de protection électromagnétique transparent s'obtient par exposition et développement subséquent d'un matériau photosensible doté d'un support et d'une couche superposée contenant au moins un halogénure d'argent photosensible et un liant, la teneur en halogénure d'argent photosensible dans le matériau photosensible allant de 0,05 à moins de 1 g/m² en termes d'argent, et la quantité de liant entrant dans la fourchette de 10 mg/m2 à 0,2 g/m2.
PCT/JP2007/063978 2006-07-20 2007-07-13 film de protection électromagnétique transparent ET SON PROCÉDÉ DE FABRICATION WO2008010461A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004221565A (ja) * 2002-12-27 2004-08-05 Fuji Photo Film Co Ltd 透光性電磁波シールド膜およびその製造方法
JP2004253329A (ja) * 2003-02-21 2004-09-09 Mitsubishi Paper Mills Ltd 透明導電性フィルムの製造方法
JP2006012935A (ja) * 2004-06-23 2006-01-12 Fuji Photo Film Co Ltd 透光性電磁波シールド膜の製造方法および透光性電磁波シールド膜

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004221565A (ja) * 2002-12-27 2004-08-05 Fuji Photo Film Co Ltd 透光性電磁波シールド膜およびその製造方法
JP2004253329A (ja) * 2003-02-21 2004-09-09 Mitsubishi Paper Mills Ltd 透明導電性フィルムの製造方法
JP2006012935A (ja) * 2004-06-23 2006-01-12 Fuji Photo Film Co Ltd 透光性電磁波シールド膜の製造方法および透光性電磁波シールド膜

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