WO2007077898A1 - Film conducteur et son procede de production, film de blindage electromagnetique et son procede de production, et ecran a plasma - Google Patents

Film conducteur et son procede de production, film de blindage electromagnetique et son procede de production, et ecran a plasma Download PDF

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Publication number
WO2007077898A1
WO2007077898A1 PCT/JP2006/326153 JP2006326153W WO2007077898A1 WO 2007077898 A1 WO2007077898 A1 WO 2007077898A1 JP 2006326153 W JP2006326153 W JP 2006326153W WO 2007077898 A1 WO2007077898 A1 WO 2007077898A1
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Prior art keywords
film
silver
conductive film
layer
conductive
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PCT/JP2006/326153
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English (en)
Japanese (ja)
Inventor
Hideaki Nomura
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Fujifilm Corporation
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Publication of WO2007077898A1 publication Critical patent/WO2007077898A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/022—Electroplating of selected surface areas using masking means
    • 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 conductive film and a manufacturing method thereof. More specifically, the present invention relates to a method for producing a conductive film having both homogeneous and high conductivity and excellent translucency. The present invention also relates to a transparent electromagnetic shielding film and a transparent electrode using the obtained conductive film.
  • displays such as CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electric mouth luminescence), FED (field emission display), microwave oven, electronic Also related to equipment.
  • the conductive film obtained by the present invention is also used for imaging semiconductor elements and printed wiring boards.
  • EMI Electro-Magnetic Interference
  • translucent electromagnetic shielding material for PDP is preferably 2.5 ⁇ Zsq or less for consumer plasma television using PDP, 1.5 ⁇ Zsq or less, more preferably 0.l QZsq or less ⁇ Conductivity is required.
  • a transmittance of approximately 70% or more is required for CRT, whereas a transmittance of 80% or more is desired for PDP.
  • a shielding material in which conductive fibers are made into a mesh for example, a shielding material in which conductive fibers are made into a mesh;
  • Various methods have been proposed so far, such as a method of forming a mesh of a metal thin film by etching using a photolithography method.
  • Silver halide light-sensitive materials have been widely used in the past as photographic films such as color negative films, black and white negative films, movie films, and color reversal films, and photographic printing papers such as color paper and black and white photographic paper. If this material is used, patterned metallic silver can be obtained by a simple process using a photographic method by pattern exposure and development. This metallic silver uses conductivity depending on the composition of the photosensitive material and the development method. It is possible.
  • Patent Document 1 discloses a method of forming a conductive metal silver thin film pattern by a silver salt diffusion transfer method in which silver is deposited on a physical development nucleus in the 1960s.
  • Patent Document 2 discloses that a uniform silver thin film without light transmission obtained by using the same silver salt diffusion transfer method has a microwave attenuation function.
  • Non-Patent Document 1 and Patent Document 3 describe a method of applying this principle to an instant black-and-white slide film and simply performing exposure and development to form a conductive pattern.
  • Patent Document 4 discloses a method for forming a conductive silver film that can be used as a display electrode for a plasma display based on the principle of the silver salt diffusion transfer method.
  • the conductive metallic silver film obtained by such a method has insufficient translucency for image display and image forming elements, and images of displays such as CRTs and PDPs. display The ability to shield the electromagnetic wave radiated from the surface without disturbing the image display was also insufficient.
  • Patent Document 5 describes the production of a light-transmitting electromagnetic wave shielding material in which a silver salt photosensitive material is used to form a pattern by development, and then the developed silver is further stuck or physically developed.
  • a method has been proposed. Although this method has an improvement effect on the above-mentioned problems, it is easy to cause uneven plating (uneven electrolysis) because the developed silver has high resistance or the power supply from the power supply roller to the developed photosensitive material is not always smooth. .
  • the uniformity in conductivity and translucency is caused by local fluctuations in the metal deposition rate on the developed silver. It turned out to be damaged. There is a need for means to achieve both transparency and conductivity.
  • Patent Document 1 Japanese Patent Publication No. 42-23746
  • Patent Document 2 Japanese Patent Publication No. 43-12862
  • Patent Document 3 Pamphlet of International Publication No.01Z51276
  • Patent Document 4 Japanese Unexamined Patent Publication No. 2000-149773
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004-221564
  • Non-Patent Document 1 Analytical 'Chemistry, Published 2000, No. 72, 645
  • the present invention has been made in view of such circumstances, and an object of the present invention is to conduct electroplating on a patterned developed silver obtained by pattern exposure and development of a silver halide silver photographic material. This is to reduce unevenness in the electrolytic plating process in the method for forming a conductive film.
  • a conductive film having high conductivity in particular, a light-transmitting conductive film having both high conductivity and high light-transmitting property, in particular, high electromagnetic shielding properties and high transparency.
  • Another object is to provide an electromagnetic shielding film having the same, and to provide a production method in which these films can be mass-produced at low cost and the electromagnetic shielding ability is not deteriorated even when mass-produced.
  • an electromagnetic wave shielding film having high translucency and high conductivity to be equipped in a display device such as a PDP.
  • the present inventors have found that electrodeposition unevenness is prominent in the early stage of the plating process, and as the plating bath becomes more fatigued, It was found that the decrease in translucency increases for the amount. Furthermore, it was also found that when the photosensitive material is subjected to a pre-bath treatment with a hardening solution prior to immersion of the developed photosensitive material in a plating solution, unevenness of electrodeposition is suppressed. Based on these findings, the present invention has been completed by devising a series of processing steps including development “pre-plating bath” electroplating that ensures conductivity and translucency.
  • the present invention is as follows.
  • a conductive film comprising a conductive functional part including a conductive metal part and a light-transmitting part on a support, and the swelling ratio of the light-transmitting part is 180% or less .
  • a method of producing a conductive film comprising a hardening step of reacting a hardening solution with the surface of the film having a surface resistance of 1 to: ⁇ .
  • (6) The conductive film according to (5), wherein the film is a halogenated silver photographic light-sensitive material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support. Production method.
  • the hardener is a compound selected from the group consisting of formaldehyde, bivalyl aldehyde, dartal aldehyde, sputum aldehyde, potash alum, chromium alum, and aluminum sulfate.
  • a method for producing a conductive film is a compound selected from the group consisting of formaldehyde, bivalyl aldehyde, dartal aldehyde, sputum aldehyde, potash alum, chromium alum, and aluminum sulfate.
  • the electromagnetic wave shielding film wherein the electromagnetic wave shielding film produced by the method for producing a conductive film according to any one of (5) to (8) has a surface resistance of 2.5 ⁇ Zsq or less. .
  • An electroplating treatment step for subjecting the metallic silver part of the film subjected to the hardening step to an electroplating treatment
  • the film quality of the silver salt-containing layer can be strengthened by crosslinking or the like in the hardening step, and even when the electrolytic plating process is performed, the generation of scratches can be suppressed, and uneven electrodeposition in the electrolytic plating process is prevented. be able to.
  • the hardener is a compound selected from formaldehyde, bivalyl aldehyde, dartal aldehyde, ⁇ aldehyde, potash alum, chromium alum, and aluminum sulfate (13) to ( The method for producing a conductive film according to any one of 18).
  • An optical filter for a plasma display panel comprising the electromagnetic wave shielding film according to (11) or (12).
  • An optical filter for a plasma display panel comprising an electromagnetic wave shielding film obtained by the production method according to any one of (13) to (24).
  • a plasma display panel comprising the optical filter according to (26) or (27).
  • a plasma television comprising an electromagnetic wave shielding film obtained by the production method according to any one of (13) to (24).
  • a surface resistance of 1 to: L 000 ⁇ A process for producing a conductive film, characterized by subjecting the film surface of the Z mouth to a pretreatment with a dura solution continuously followed by electroplating.
  • a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer containing a halogenated silver emulsion layer on a support, which is continuously developed and applied to a metallic silver portion formed by the developing process.
  • a method for producing a conductive film that is subjected to electrolytic plating treatment is characterized in that a pretreatment with a hardening solution is performed immediately before the electrolytic plating treatment is applied to a developed silver halide photosensitive material.
  • a method for producing a membrane is characterized in that a pretreatment with a hardening solution is performed immediately before the electrolytic plating treatment is applied to a developed silver halide photosensitive material.
  • a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer including a halogenated silver emulsion layer on a support is developed to form a metallic silver portion, and a hard film is formed on the metallic silver portion.
  • a method for producing an electromagnetic wave shielding film comprising sequentially performing a solution treatment and an electrolytic plating treatment.
  • the photosensitive material Prior to immersing the developed photosensitive material in a plating solution, the photosensitive material is pre-bathed with a hardening solution.
  • a conductive film of the present invention which is characterized in that it is processed, unevenness in the plating process can be reduced. Therefore, it is possible to form a conductive film having a uniform and high conductivity and a high translucency at the same time, and an electromagnetic wave shielding film with a fine line pattern excellent in EMI shielding properties can be obtained.
  • the conductive film is used as a transparent electrode for an image sensor unit of a display device or an imaging semiconductor element of an image recording element
  • the electromagnetic wave shield film is used as a member for preventing an electromagnetic wave disturbance of the image element unit.
  • FIG. 1 is a schematic diagram showing an example of an electrolytic plating bath suitably used in the present invention.
  • FIG. 2 is a schematic view showing an example of a conductive film of the present invention.
  • Electrolytic plating section 28 Rogeny silver emulsion layer
  • the method for producing a conductive film of the present invention includes a hardening step in which a hardening solution is reacted with the surface of a film having a surface resistance of 1 to 5 ⁇ / mouth. More specifically, an exposed portion and an unexposed portion are exposed by exposing a photosensitive material having an emulsion layer containing a photosensitive silver halide salt on a support, and performing development processing and preferably fixing processing continuously. Forming a metallic silver part and a light-transmitting part in each of the parts, and then conducting a pre-bath treatment of the developed photosensitive material with a hard film solution, followed by an electrolytic plating process, and an apparatus for producing a conductive film And the invention of application of the conductive film. In the present invention, it is preferable to perform a pre-bath treatment (hardening step) with a hardening solution immediately before the developed silver is immersed in the electrolytic plating solution.
  • the pre-bath treatment with the hardening solution uniformly deposits metal on the developed silver to suppress uneven deposition, and also reduces the adhesion of development stains to the translucent part.
  • the task to do is achieved.
  • “continuous” means that the photosensitive material to be processed is continuously conveyed (that is, the process flow is continuous), and is not necessarily developed, plated. It does not mean that it is continuous! /, Without interrupting processes such as processing!
  • “immediately before the development silver is immersed in the electrolytic plating solution” means that after the treatment with the hardening solution, the plating solution treatment process is entered without interposing other processes. It doesn't mean a long gap.
  • Mesh-like silver produced by simply developing a patterned silver halide photographic light-sensitive material is fine, filamentous silver (or ultrafine, discrete spherical silver) and has very poor electrical conductivity (usually Surface resistance is 1 ⁇ : L000 ⁇ Higuchi).
  • the inventor has electrolyzed metal on patterned developed silver to increase conductivity.
  • the metal film obtained in this way has an electrolysis unevenness due to non-uniformity of deposition, and the uniformity of the conductive film is found. Lack. Increasing the electrolysis time or strengthening the electrolysis conditions will increase the conductivity, but the material will also become soiled and the translucency will be impaired.
  • a means for applying the hardening solution to the photosensitive material before immersing the photosensitive material carrying developed silver in the plating solution is adopted, non-uniformity of electrodeposition is reduced, and photosensitive material contamination is also reduced. As a result, the conductivity is increased while maintaining the translucency, and the above-mentioned drawbacks can be solved.
  • the pre-curing treatment of the photosensitive material is preferably a bathing treatment in the hardening solution in the front tub or a coating treatment with a coating device! /, But any other method in which the hardening solution contacts the surface of the photosensitive material.
  • the hardening agent in the hardening solution used in the present invention is preferably a compound having an action of hardening gelatin, and details thereof will be described later.
  • the concentration in the dura mater solution may be any concentration as long as the desired effect is exhibited, but is preferably 0.005 to 1. OmolZL.
  • the surface tension is preferably lower than that of water, and if it is 60 mNZm or less, the effect increases. Further details of the dura solution will be described later.
  • a known electroplating process can be used, which is covered with a noder and is usually of non-uniform shape and non-uniform thickness. For this reason, the conductivity of filamentary silver with insufficient conductivity is enhanced, and the light transmittance and exposure of the unexposed area can be improved by pretreatment with a hardening solution before the developed sample enters the plating solution. It is possible to form a conductive film that is excellent in both the conductivity of the part.
  • the “transmittance” of the light-transmitting part in the present invention refers to the transmittance 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 light-transmitting part is preferably 90% or more, more preferably 95% or more, more preferably 97% or more, and even more preferably 98% or more. It is most preferably 99% or more.
  • a binder can be used for the purpose of supporting the conductive film of the present invention.
  • the binder it is preferable to use a water-soluble polymer that can be used as a binder for a water-insoluble polymer and a water-soluble polymer.
  • binder examples include polysaccharides such as gelatin, polybutyl alcohol (PVA), polyvinylpyrrolidone (PVP), starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, Examples include polyacrylic acid, polyalginic acid, polyhyaluronic acid, carboxycellulose, and the like. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group.
  • the content of the noinda is not particularly limited, and can be appropriately determined as long as dispersibility and adhesion can be exhibited.
  • the AgZ binder mass ratio is preferably 3 or more, more preferably 4.5 or more and 12 or less, and most preferably 6 or more and 10 or less. Further, gelatin is the most preferable type of binder.
  • the conductive film of the present invention is characterized in that the swelling ratio of the light transmitting portion is 180% or less.
  • the swelling rate is defined as follows. That is, measure the layer thickness (a) when dried and the layer thickness (b) after 1 minute immersion in distilled water at 25 ° C,
  • the film thickness of the emulsion layer is measured by observing the cross section of the sample with a scanning electron microscope.
  • the film thickness after swelling is measured by observing the cross section of the sample after freeze-drying the swollen sample with liquid nitrogen using a scanning electron microscope.
  • the swelling ratio of the light transmitting part layer is preferably 150% or less, more preferably 130% or less.
  • the swelling ratio may be 50% or more from the viewpoint of suppressing the decrease in the amount of liquid in the film during the plating process and suppressing the decrease in the plating rate. It is preferable.
  • the swelling rate can be controlled by the type, addition amount, and pH of the hardening agent in the hardening treatment.
  • the swelling rate is defined in the final form as an electromagnetic wave shielding film. That is, the swelling rate defined in the present invention is a value after the electrolytic plating process. Any value can be used for the swelling ratio of the photosensitive material before processing, which will be described later. ⁇ Conductive film and its manufacturing method ⁇
  • a silver halide film having a silver halide emulsion layer on a support is exposed and developed to form a metallic silver portion, and the metallic silver is formed.
  • a hardening process in which a hardening solution containing a hardening agent is reacted on the surface of the film, and an electroplating process in which the metallic silver portion of the film subjected to the hardening process is subjected to an electroplating process.
  • a process for producing a conductive film in which a hardening solution containing a hardening agent is reacted on the surface of the film, and an electroplating process in which the metallic silver portion of the film subjected to the hardening process is subjected to an electroplating process.
  • the present inventors presume this reason as follows. Since the silver halide emulsion layer has a small amount of hardener in the silver halide silver emulsion layer, its film quality is weak, and scratches are easily generated during the electroplating process, causing uneven electrodeposition.
  • the film quality of the silver salt-containing layer can be strengthened by crosslinking or the like in the hardening step, and even when the electrolytic plating process is performed, the generation of scratches can be suppressed, and uneven electrodeposition in the electrolytic plating process is prevented. be able to.
  • the silver halide emulsion layer preferably contains a silver halide silver and a binder (preferably gelatin).
  • a silver halide silver preferably contains a silver halide silver and a binder (preferably gelatin).
  • the content ratio of silver (Ag) and binder (B) in the silver halide emulsion layer is within the range of the following formula (1). It is preferable that it exists in.
  • the volume ratio of AgZ binder is 1Z4 or more.
  • the hardener is a compound having a function of hardening gelatin in order to obtain a sufficient effect in the hardening treatment.
  • formaldehyde, pinolylaldehyde, dartalaldehyde U, Aldehyde, Potassium alum, Chromium alum, and Aluminum sulfate power Daltar aldehyde or aluminum sulfate particularly preferred to be a selected compound.
  • the hardening solution contains 0.0005 to 1. OOOmolZL of a hardening agent, and it is preferable that the hardening solution contains a compound having a swelling inhibiting action.
  • a plastic film, a plastic plate, a glass plate, or the like can be used as the support of the photosensitive material used in the production method of the present invention.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate
  • polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene and EVA
  • Bulu resin such as vinyl and poly vinylidene
  • PEEK polyether ether ketone
  • PSF polysulfone
  • PSS polyether sulfone
  • PC polycarbonate
  • polyamide polyimide
  • acrylic resin Fats triacetyl cellulose (TAC), etc.
  • the plastic film is preferably a polyethylene terephthalate film and Z or triacetyl cellulose (TAC) from the viewpoints of transparency, heat resistance, ease of handling and cost! /.
  • TAC triacetyl cellulose
  • the electromagnetic wave shielding material for display is required to be transparent, it is desirable that the support has high transparency.
  • the total visible light transmittance of the plastic film or plastic plate is preferably 70 to 100%, more preferably 85 to 100%, and particularly preferably 90 to 100%.
  • the plastic film and the plastic plate that are colored to the extent that they do not interfere with the object of the present invention can also be used.
  • the plastic film and plastic plate in the present invention can be used as a single layer, but can also be used as a multilayer film in which two or more layers are combined.
  • a glass plate is used as the support in the present invention
  • the kind thereof is not particularly limited.
  • tempered glass having a tempered layer on the surface. Tempered glass is compared to non-tempered glass There is a high possibility that damage can be prevented. Further, the tempered glass obtained by the air cooling method is preferable from the viewpoint of safety because the broken piece is small and the end face is not sharp even if it is broken.
  • a protective layer may be provided on the emulsion layer described later.
  • the term “protective layer” refers to a layer that can be used as gelatin and a high-molecular polymer, and also has a photosensitivity in order to exhibit the effect of preventing scratches and improving mechanical properties. Formed in the emulsion layer. It is preferable that the protective layer is not provided in the case of performing the sticking treatment.
  • the thickness is preferably 0.2 / z m or less.
  • the formation method of the protective layer coating method is not particularly limited, and a known coating method can be appropriately selected.
  • the photosensitive material used in the production method of the present invention may contain a known dye in the emulsion layer for the purpose of dyeing or the like.
  • the light-sensitive material used in the production method of the present invention preferably has an emulsion layer (silver salt-containing layer) containing a silver salt as an optical sensor on a support.
  • the emulsion layer in the present invention may contain a dye, a binder, a solvent and the like, if necessary, in addition to the silver salt.
  • the light-sensitive material may contain a dye at least in the emulsion layer.
  • the dye is contained in the emulsion layer as a filter dye or for various purposes such as prevention of irradiation.
  • the dye may contain a solid disperse dye.
  • Examples of the dye preferably used in the present invention include dyes represented by general formula (FA), general formula (FA1), general formula (FA2), and general formula (FA3) described in JP-A-9-179243. Specifically, compounds F1 to F34 described in the publication are preferable. Also, ( ⁇ -2) to ( ⁇ -24) described in JP-A-7-152112, (III-5) to (III-18) described in JP-A-7-152112, and JP-A-7-152112. The described (IV-2) to (IV-7) are also preferably used.
  • a solid fine particle dispersed dye to be decolored during development or fixing is described in JP-A-3-138640.
  • examples include cyanine dyes, pyrylium dyes and amino dyes.
  • dyes that do not decolorize at the time of processing cyanine dyes having a carboxyl group described in JP-A-9-96891, cyanine dyes that do not contain an acidic group described in JP-A-8-245902, and JP-A-8-333519 Lake type cyanine dyes described in Japanese Laid-Open Patent Publication No. 1-266536, cyanopolar dyes described in Japanese Patent Laid-Open No.
  • the dye may contain a water-soluble dye.
  • water-soluble dyes include oxonol dyes, benzylidene dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and benzylidene dyes are useful in the present invention.
  • Specific examples of water-soluble dyes that can be used in the present invention include British Patent Nos. 584, 609, 1, 177, 429, Japanese Patent Publication Nos. 48-85130, 49-99620, 49-114420 gazette, 52-20822 gazette, 59-154439 gazette, 59-208548 gazette, U.S.
  • the content of the dye in the emulsion layer is preferably 0.01 to 10% by mass with respect to the total solid content, from the viewpoint of preventing irradiation and the like, and from the viewpoint of lowering sensitivity due to an increase in the amount of added calories. 1-5 mass% is further more preferable.
  • Examples of the silver salt used in the present invention include inorganic silver salts such as halogenated silver. Book In the invention, it is preferable to use halogenated silver having excellent characteristics as an optical sensor.
  • halogenated silver for functioning as an optical sensor. It is used in silver salt photographic film, photographic paper, printing plate making film, emulsion mask for photomask, etc. relating to halogenated silver.
  • the technique can also be used in the present invention.
  • the halogen element contained in the silver halide may be any of chlorine, bromine, iodine and fluorine, or a combination thereof.
  • halogen silver containing mainly AgCl, AgBr and Agl is preferably used, and halogen silver containing mainly AgBr and AgCl is preferably used. More preferred are silver chlorobromide, silver bromide, silver iodochlorobromide and silver iodobromide, and most preferred is silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride. Used.
  • halogenated silver mainly composed of AgBr means silver halide in which the molar fraction of bromide ions in the silver halide composition is 50% or more.
  • the silver halide silver grains mainly composed of AgBr may contain iodide ions and chloride ions in addition to bromide ions.
  • Silverogenated silver is in the form of a solid grain, and from the viewpoint of image quality of the patterned metal silver layer formed after exposure and development processing, the average grain size of halogenated silver is 0 in sphere equivalent diameter. It is preferably 1 to 1000 ⁇ (1 / ⁇ ), more preferably 0.1 to 100 nm, and even more preferably 1 to 50 nm.
  • the spherical equivalent diameter of a halogenated silver particle is a diameter of a particle having a spherical shape and the same volume.
  • the shape of the silver halide grains is not particularly limited.
  • various shapes such as a spherical shape, a cubic shape, a flat plate shape (hexagonal flat plate shape, triangular flat plate shape, quadrangular flat plate shape, etc.), octahedral shape, tetrahedral shape, etc.
  • the cubic shape and the tetrahedron shape are preferable.
  • the silver halide grains can have a uniform internal and surface layer, or they can be different. Moreover, you may have the localized layer from which a halogen composition differs in a particle
  • the silver halide emulsion which is a coating solution for the emulsion layer used in the present invention, is a photographic Emulsion Chemistry (The Forcal by Chimie etPhysique Photographique (Paul Montel3 ⁇ 4: flJ, 1967 ⁇ ) by P. Glafkides, G. F. Dufin. Press, 1966), VL Zelikman et al, Making and Coating Photographic Emulsion (The ForcalPress, 1964), and the like.
  • the silver halide emulsion may be prepared by any of an acidic method and a neutral method, and a method of reacting a soluble silver salt with a soluble halogen salt may be a one-side mixing method. Any of a simultaneous mixing method, a combination thereof, and the like may be used.
  • a method for forming silver particles a method of forming particles in the presence of excess silver ions (so-called back mixing method) can also be used.
  • a method of keeping pAg constant in a liquid phase in which halogenated silver is formed that is, a so-called controlled double jet method can be used.
  • halogenated silver solvent such as ammonia, thioether or tetrasubstituted thiourea. More preferred as such a method is a tetrasubstituted thiourea compound, which is described in JP-A-53-82408 and JP-A-55-77737.
  • Preferred thiourea compounds include tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. Amount of Harogeni ⁇ solvent type and particle size of interest of the compound to be used, different forces Harogeni ⁇ per mole 10- 5 to 10- 2 mol by halogen composition are preferred.
  • the silver halide emulsion used for forming the emulsion layer in the present invention is preferably a monodispersed emulsion ⁇ (standard deviation of grain size) Z (average grain size)
  • the coefficient of variation represented by X100 is preferably 20% or less, more preferably 15% or less, and most preferably 10% or less.
  • the silver halide emulsion used in the present invention may be a mixture of a plurality of types of silver halide emulsions having different grain sizes.
  • the silver halide silver emulsion used in the present invention may contain a metal belonging to Group VIII or Group VIIB.
  • a metal belonging to Group VIII or Group VIIB in particular, in order to achieve high contrast and low capri, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, an iron compound, an osmium compound, a rhenium compound, and the like.
  • These compounds are compounds having various ligands, and examples of such ligands include cyanide ions, cyanogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions, and such pseudohalogens.
  • organic molecules such as ammonia, amines (such as methylamine and ethylenediamine), heterocyclic compounds (such as imidazole, thiazole, 5-methylthiazole, mercaptoimidazole), urea, and thiourea can be exemplified.
  • rhodium compound a water-soluble rhodium compound can be used.
  • water-soluble rhodium compounds include rhodium halide ( ⁇ ) compounds, hexachlororhodium (III) complex salts, pentachloroacorodium complex salts, tetrachlorodiacorodium complex salts, hexabromorhodium ( ⁇ ) complex salts, Xamin rhodium (III) complex salt, trioxalato rhodium ( ⁇ I) complex salt, K Rh Br and the like.
  • iridium compound examples include hexachrome iridium complex salts such as K IrCl Cl,
  • Hexabromoiridium complex salts Hexabromoiridium complex salts, hexammine iridium complex salts, pentachloro-trosyl iridium complex salts and the like.
  • ruthenium compound examples include hexaclonal ruthenium, pentachloro-trosyl ruthenium, K [Ru (CN)] and the like.
  • iron compounds examples include potassium hexanoate ( ⁇ ) and ferrous thiocyanate. I can get lost.
  • Examples of the ruthenium compounds and osmium compounds include water-soluble complex salts described in JP-A-63-2042, JP-A-1-285941, JP-A-2-20852, JP-A-2-20855, and the like. It is done.
  • a silver halide containing Pd (II) ions and Z or Pd metal can also be preferably used.
  • Pd may be uniformly distributed in the halogen silver halide grains, but is preferably contained in the vicinity of the surface layer of the halogen silver halide grains.
  • Pd is “contained in the vicinity of the surface layer of the silver halide grain” when the surface force of the halogenated silver grain is within 50 nm in the depth direction, and the palladium content is higher than that of the other layers. Means to have a layer.
  • Such silver halide grains can be prepared by adding Pd during the formation of silver halide grains. After adding 50% or more of the total amount of silver ions and halogen ions, Pd Is preferably added. It is also preferable to add Pd (II) ions to the surface layer of halogenated silver by adding them at the post-ripening stage.
  • Pd-containing halogenated silver particles increase the speed of physical development and electroless plating, increase the production efficiency of the desired electromagnetic shielding material, and contribute to the reduction of production costs.
  • Pd is a well-known force used as an electroless plating catalyst
  • Pd can be unevenly distributed on the surface layer of silver halide grains, so that it is possible to save extremely expensive Pd. .
  • Te content of Pd ions and / or Pd metal contained in Harogeni ⁇ is 10- 4-0 of silver halide, with respect to the number of moles of silver. 5 mol Z moles Ag is preferable, and 0.01 to 0.3 mol Z mol Ag is more preferable.
  • Examples of the Pd compound used include PdCl and Na PdCl.
  • chemical sensitization performed with a photographic emulsion can be performed in order to further improve the sensitivity as an optical sensor.
  • Chemical sensitization methods include sulfur sensitization, selenium sensitization, tellurium sensitization, chalcogen sensitization, noble metal sensitization such as gold sensitization, and reduction sensitization. it can. These are used alone or in combination.
  • sulfur sensitizing method and gold sensitizing method sulfur sensitizing method and selenium sensitizing method and gold sensitizing method
  • sulfur sensitizing method and tellurium sensitizing method sulfur sensitizing method and tellurium sensitizing method.
  • a combination of sensitivity and gold sensitization is preferred.
  • the sulfur sensitization is usually performed by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C or higher for a predetermined time.
  • a sulfur sensitizer known compounds can be used.
  • various sulfur compounds such as thiosulfate, thioureas, and thiazoles can be used. , Rhodons, etc. can be used.
  • Preferred sulfur compounds are thiosulfate and thiourea compounds.
  • selenium sensitizer used for the selenium sensitization known selenium compounds can be used.
  • unstable selenium compound compounds described in JP-B-44-15748, JP-A-43-13489, JP-A-4-109240, JP-A-4-324855 and the like can be used.
  • the tellurium sensitizer used in the tellurium sensitizer is a compound that forms silver telluride presumed to be a sensitization nucleus on the surface or inside of a silver halide silver grain.
  • the described compounds can be used. Particularly preferred are compounds represented by the general formulas (11), (III) and (IV) in JP-A-5-313284.
  • the conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45. ⁇ 85 ° C.
  • Examples of the noble metal sensitizer include gold, platinum, noradium, iridium, and the like. Gold sensitization is particularly preferable. Specific examples of gold sensitizers used for gold sensitization include salt and gold acid, potassium chromate orate, potassium thiothiocyanate, gold sulfide, tiodarcos gold (1), tiomannose gold ( I) and the like, can be used per mole 10- 7-10 moles silver halide. A cadmium salt, a sulfite salt, a lead salt, a thallium salt, etc. may coexist in the halogen-silver emulsion used in the present invention in the process of halogen-silver particle formation or physical ripening.
  • reduction sensitization can be used.
  • reduction sensitizer stannic salts, amines, formamidinesulfinic acid, silane compounds, and the like can be used.
  • a thiosulfonic acid compound may be added to the above-described halogenated silver emulsion by the method described in European Published Patent (EP) 293917.
  • the silver halide emulsion used in the preparation of the light-sensitive material used in the present invention may be only one type, or two or more types (for example, those having different average grain sizes, those having different halogen compositions, and different crystal habits). , Different chemical sensitization conditions, and different sensitivity). In particular, in order to obtain high contrast, it is preferable to apply an emulsion with higher sensitivity as it is closer to the support as described in JP-A-6-324426.
  • the silver salt-containing layer provided on the support is exposed.
  • Exposure can be performed using electromagnetic waves. Examples of electromagnetic waves include light such as visible light and ultraviolet light, and radiation such as X-rays. Further, for the exposure, a light source having a specific wavelength or a light source having a wavelength distribution may be used.
  • Examples of the light source include scanning exposure using a cathode ray (CRT).
  • CRT cathode ray
  • a cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy.
  • various light emitters that emit light in the spectral region are used as necessary. For example, one or more of 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.
  • a cathode ray tube that emits white light by mixing these light emitters is often used. UV lamps are also good Mercury lamp g-line and mercury lamp i-line are also used.
  • exposure can be performed using various laser beams.
  • the exposure in the present invention is performed by using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light emitting source (SHG) that combines a solid state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal.
  • a scanning exposure method using monochromatic high-density light such as KrF excimer laser, ArF excimer laser, or F 2 laser can also be used.
  • the exposure is preferably performed using a semiconductor laser, a semiconductor laser, or a second harmonic generation light source (SHG) that combines a solid-state laser and a nonlinear optical crystal.
  • SHG second harmonic generation light source
  • exposure is preferably performed using a semiconductor laser.
  • a blue semiconductor laser with a wavelength of 430 to 460 nm (presented by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001), a semiconductor laser (oscillation) LiNbO SH with a waveguide inversion domain structure
  • Approx. 530nm green laser, wavelength 685nm red semiconductor laser (Hitachi type No. HL6738MG), wavelength 650nm red semiconductor laser (Hitachi type No. HL6501MG), etc., are preferably used. It is done.
  • the method of exposing the silver salt-containing layer in a pattern may be performed by surface exposure using a photomask or by scanning exposure using a laser beam. At this time, exposure methods such as contact exposure, proximity exposure, reduced projection exposure, and reflection projection exposure may be used, which may be refractive exposure using a lens or reflection exposure using a reflecting mirror.
  • development processing is further performed.
  • the development processing can be performed by a normal development processing technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion layer, and the like.
  • development processing negative development processing and reversal development processing can be selected.
  • chemical development or physical development in the aspect of the present invention, exactly, dissolution physical development
  • “chemical development” and “dissolved physical development” have the meanings commonly used in the industry. For example, Shinichi Kikuchi “Photochemistry” (Kyoritsu Publishing Co., Ltd., 1955) Published), CEK Mees, “The Theory of Photographic Processes, 4th ed.”, 373-377 (Mcmillan, 1977flJ) [This is explained!
  • the chemical developer there is no particular limitation on the chemical developer as long as the developed silver can be obtained, it may be a black-and-white developer or a color developer (it does not need to develop color), but a black-and-white developer is preferred.
  • black and white developer PQ developer, MQ developer, MAA developer (methol ascorbic acid developer), etc. can also be used.
  • CN-16, CR-56, CP45X Developers such as FD-3, Papitol, KODAK's prescription C-41, E-6, RA-4, D-72, or the developer included in the kit, and D-19, D-8 5
  • a lith developer or a high-contrast positive developer known by a prescription name such as D-8 can also be used.
  • each of the above developing solutions contains thiosulfate (sodium salt, ammonium salt, etc.) or thiocyanate (sodium salt, ammonium salt, etc.) as a halogenated silver solubilizer.
  • thiosulfate sodium salt, ammonium salt, etc.
  • thiocyanate sodium salt, ammonium salt, etc.
  • a metal silver portion preferably a butter-shaped metal silver portion is formed by performing the above exposure and development treatment, and a light transmissive portion described later is formed.
  • a force capable of using any of the above-described developers preferably a black-and-white developer.
  • a color developing agent or a black-and-white developing agent is preferable, and an ascorbic acid developing agent or a dihydroxybenzene developing agent can be used particularly preferably.
  • Ascorbic acid-based developing agents include ascorbic acid, isoascorbic acid and erythorbic acid and salts thereof (Na salt, etc.), but sodium erythorbate is also preferred in terms of cost.
  • dihydroxybenzene-based developing agents examples include hydroquinone, black mouth hydroquinone, isopropyl hydroquinone, methyl hydroquinone, and hyde mouth quinone monosulfonate. Hydroquinone is particularly preferred.
  • the ascorbic acid developing agent, dihydroxybenzene developing agent may be used in combination with an auxiliary developing agent that exhibits superadditivity, and it does not have to be fouled.
  • the ascorbic acid developing agent is dihydroxyben.
  • auxiliary developing agents that exhibit superadditivity with Zen-based developing agents include 1-phenol and 1-3 pyrazolidones and P-aminophenols.
  • 1-Fue-Lu 3-Virazolidone or a derivative thereof used as an auxiliary developing agent specifically includes 1-Fu-Lu 3-Virazolidone, 1-Fu-Lu 4, 4 Dimethyl-3- virazolidone 1 phenyl 4 methyl 4 hydroxymethyl 3 virazolidone.
  • P-aminophenol auxiliary developing agents examples include N-methyl p-aminophenol, ⁇ -aminophenol, N— (j8-hydroxyethyl) p-aminophenol, and N— (4-hydroxyphenol) glycine. Of these, N-methyl-paminophenol is preferred.
  • the dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol Z liter, but in the present invention, it is particularly preferably used in an amount of 0.23 mol Z liter or more. More preferably, it is in the range of 0.23 to 0.6 mol Z liter.
  • the former is 0.23 to 0.6 mol Z liter, more preferably 0.23 to 0.3. It is preferable to use 5 monolet / lit nore, the latter being less than 0.06 monolet / lit nore, more preferably 0.03 mol Z liter to 0.003 mol Z liter.
  • the bathing potential of the developer is determined mainly by the developing agent and PH, which is a total of the oxidation-reduction properties of the components of the developer.
  • a preferred redox potential is baser than 290 mVvs SCE, more preferably baser than 320 mVvsSCE, and more preferably baser than 340 mVvsSCE.
  • the above-mentioned preference is given, and the pH is adjusted according to the type of the selected developing agent. Is done by.
  • a preferable pH value is 0 to 2, preferably 0.5 to 1.5 higher than the pK value of the developing agent, and is appropriately selected according to the type of the developing agent.
  • both the development starter that is, the mother liquor charged as a new solution in the developing tank
  • the development replenisher are each 0.1 mol of hydroxide solution per liter of solution. It preferably has a pH buffering capacity such that the increase in pH when sodium is calorie is 0.5 or less.
  • developer As a method for confirming that the image replenisher development replenisher (hereinafter sometimes referred to as “developer” together) has this pH buffering capacity, the development start replenisher that is the test target is not used.
  • a buffer As a method of imparting the above properties to the development initiator and the development replenisher, it is preferable to use a buffer.
  • the buffer include carbonates, boric acid described in JP-A-62-286259, saccharides (eg saccharose), oximes (eg acetooxime), phenols described in JP-A-60-93433. (For example, 5-sulfosalicylic acid), triphosphate (for example, sodium salt, potassium salt) and the like can be used, and carbonate and boric acid are preferably used.
  • the amount of the above-mentioned buffer (especially carbonate) is preferably 0.25 or more / Lit or more, and 0.25 ⁇ : L 5 mono / Lit power is particularly preferred! / ⁇ .
  • the pH of the development initiator is 9.0 to 11.0, particularly preferably 9.5 to 10.7.
  • the pH of the developer replenisher and the developer in the developer tank during continuous processing are also in this range.
  • the alkali agent used for setting the pH usual water-soluble inorganic alkali metal salts (for example, sodium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate) can be used.
  • the amount of developer replenisher added in the developer is 645. Less than milliliters, preferably 30 to 484 milliliters, especially 100 to 484 milliliters.
  • the development replenisher may have the same composition as the development starter, but has a higher concentration than the starter by an amount commensurate with compensation for the components consumed in development. It is preferable that
  • additives usually used for the developer used for developing the light-sensitive material in the present invention (hereinafter, both the development starter and the development replenisher may be simply referred to as "developer") (For example, a preservative and a chelating agent) can be contained.
  • a preservative sulfurous acid Sulphites such as sodium, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite and sodium formaldehyde bisulfite are listed.
  • the sulfite is preferably used in an amount of 0.20 mol Z liters or more, more preferably 0.3 mol Z liters or more. If used in a large amount, it may cause silver stains in the developer.
  • the upper limit is preferably 1.2 mol Z liter. Particularly preferred is 0.35 to 0.7 mole Z liter.
  • ascorbic acid derivatives may be used in small amounts in combination with sulfites as preservatives for dihydroxybenzene developing agents.
  • the ascorbic acid derivative is the same as the ascorbic acid as the developing agent described above, and includes ascorbic acid and its stereoisomer erythorbic acid and its alkali metal salt thorium and potassium salt). To do.
  • sodium erythorbate is preferably used in terms of material cost.
  • the amount of the ascorbic acid derivative added is preferably in the range of 0.03 to 0.12 in terms of molar ratio with respect to the dihydroxybenzene developing agent, particularly preferably in the range of 0.05 to 10.10. .
  • the developer does not contain a boron compound.
  • additives that can be used in the developer include: development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and dimethylformamide; A development accelerator such as alkanolamine such as amine and triethanolamine, imidazole or a derivative thereof, a mercapto compound, an indazole compound, a benzotriazole compound, and a benzoimidazole compound. (black pepper) May be included as an inhibitor.
  • development inhibitors such as sodium bromide and potassium bromide
  • organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and dimethylformamide
  • a development accelerator such as alkanolamine such as amine and triethanolamine, imidazole or a derivative thereof, a mercapto compound, an indazole compound, a benzotriazole compound, and a benzoimidazole compound. (black pepper) May be included as an inhibitor.
  • benzoimidazole compounds include 5—-troindazole, 5 p-trobenzoylaminoindazole, 1-methyl-5-troindazole, 6-nitroindazole, 3-methyl-5--.
  • the content of these benzoimidazole compounds is usually from 0.01 to LOmmol, more preferably from 0.1 to 2mmol per liter of the developer.
  • organic / inorganic chelating agents can be used in combination in the developer.
  • Examples of the inorganic chelating agent that can be used include sodium tetrapolyphosphate and sodium hexametaphosphate.
  • organic chelating agent organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used.
  • organic carboxylic acids examples include acrylic acid, oxalic acid, malonic acid, succinic acid, dartaric acid, adipic acid, pimelic acid, succinic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decandi power norlevonic acid, undecandi power norlevonic acid.
  • aminopolycarboxylic acid examples include iminoniacetic acid, ditrimethyl triacetic acid, ditrimethyl tripropionic acid, ethylenediamine monohydroxyethyl triacetic acid, ethylenediammine tetraacetic acid, glycol ether tetraacetic acid, 1, 2-Diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol etherdiaminetetraacetic acid, and other JP-A-52-25632, 55-67747, 57-
  • JP-A-52-25632 Japanese Patent No. 102624 and Japanese Patent Publication No. 53-40900
  • the ⁇ Ka ⁇ these chelating agents preferably the developing solution per liter, 1 X 10- 4 ⁇ 1 X
  • the compounds described in JP-A-61-267759 can be used as a dissolution aid in the developer.
  • the developer may contain a color toning agent, a surfactant, an antifoaming agent, a hardening agent, and the like as necessary.
  • the development processing temperature and time are interrelated, and the force determined in relation to the total processing time.
  • the development temperature is preferably about 20 ° C to about 50 ° C, more preferably 25 to 45 ° C.
  • the development time is preferably 5 seconds to 2 minutes, more preferably 7 seconds to 1 minute 30 seconds.
  • the developer is concentrated and diluted at the time of use, that is, as a liquid concentrated developer. It is also preferable to supply the above. In order to concentrate the developer, it is effective to salt the salt component contained in the developer.
  • concentration of developer is a common expression in the industry and means “concentration”, and does not mean “concentration” by evaporation under reduced pressure or the like.
  • a fixing process is preferably performed for the purpose of removing and stabilizing the silver salt in the unexposed portion, but the fixing process may be omitted in the present invention.
  • the current image processing is performed by dissolution physical development
  • the unexposed silver halide is generally dissolved and disappeared during the current image process.
  • the development is performed with a chemical development type development formula, it is preferable to increase the transparency of the unexposed area, that is, the translucent area, by the fixing process.
  • the fixing process is not necessarily performed after the development process, and may be performed after an electrolytic plating process described later.
  • the fixing process in the present invention is a conventional fixing process technique used for color photography, black and white silver salt photographic film, photographic paper, printing plate film, X-ray photographic film, photomask emulsion mask, and the like. Can be used.
  • Preferable components of the fixing solution used in the fixing step include the following.
  • fixing agents such as sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, etc., if necessary, tartaric acid, citrate, darconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, darcoheptanoic acid, tyrone and their salts
  • a preservative such as a pH buffering agent such as ethylenediamine amine acetic acid, diethylenetriaminepentaacetic acid, ditrimethyl triacetic acid and salts thereof.
  • boric acid is not included.
  • Examples of the fixing agent for the fixing solution used in the present invention include sodium thiosulfate and ammonium thiosulfate.
  • Ammonium thiosulfate is preferable from the viewpoint of fixing speed, but in recent years the conservation of the natural environment has been improved.
  • View power Sodium thiosulfate may be used in view of water quality control of total nitrogen content.
  • the amount of these known fixing agents used can be varied as appropriate and is generally from about 0.1 to about 2 moles Z liter. Particularly preferred is 0.2 to 1.5 mol Z liter.
  • the fixer contains a hardener (eg, a water-soluble Minum compounds), preservatives (eg, sulfites, bisulfites), pH buffers (eg, acetic acid), pH adjusters (eg, ammonia, sulfuric acid), chelating agents, surfactants, wetting agents, constants
  • a hardener eg, a water-soluble Minum compounds
  • preservatives eg, sulfites, bisulfites
  • pH buffers eg, acetic acid
  • pH adjusters eg, ammonia, sulfuric acid
  • chelating agents eg, ammonia, sulfuric acid
  • surfactant examples include anionic surfactants such as sulfates and sulfones, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740.
  • anionic surfactants such as sulfates and sulfones
  • polyethylene surfactants such as polyethylene surfactants
  • amphoteric surfactants described in JP-A-57-6740.
  • a known antifoaming agent may be added to the fixing solution.
  • Examples of the wetting agent include alkanolamine and alkylene glycol.
  • Examples of the fixing accelerator include thiourea derivatives described in Japanese Patent Publication Nos. 45-35754, 58-122535, and 58-122536; alcohols having triple bonds in the molecule; Examples include thioether compounds described in US Pat. No. 4126459; mesoionic compounds described in JP-A-4-229860, and compounds described in JP-A-2-44355 may be used.
  • Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citrate, oxalic acid, maleic acid, glycolic acid and adipic acid, boric acid, phosphate and sulfite.
  • Inorganic buffers such as can be used.
  • the pH buffer acetic acid, tartaric acid, and sulfite are preferably used.
  • the pH buffer is used for the purpose of preventing the pH of the fixing agent from rising due to the introduction of the developer, and is preferably 0.01 to: L 0 mol Z liter, more preferably 0.02 to 0.6. Use about mol Z liters.
  • the pH of the fixing solution is preferably 4.0 to 8.0 force S, particularly preferably 4.5 to 7.5.
  • water-soluble halides are alkali metal bromides and iodides and ammonium bromide and iodide, and preferred alkali metal salts are sodium and potassium salts.
  • the total amount of water-soluble halide added is 0.035 to 0.5 monole / L, more preferably 0.05 to 0.4 monole / L. It is particularly preferred that water-soluble halides contain water-soluble compounds such as potassium chloride, sodium chloride, and sodium ammonia. The amount of the additive is 0.005 to 0.05 mol / L.
  • water-soluble halides are used in the plating process following the fixing process.
  • it has the effect of increasing the metal deposition rate, and the effect of iodine ions is particularly great.
  • Examples of the hardener in the fixing solution of the present invention include water-soluble aluminum salts and chromium salts.
  • a preferable compound as the hardener is a water-soluble aluminum salt, and examples thereof include aluminum chloride, aluminum sulfate, potash and vane.
  • the preferred amount of added calories of the above hardener is 0.01 monole to 0.2 monole / lit nore, more preferably 0.03 to 0.08 mol Z liter.
  • the fixing processing temperature and time in the fixing step are related to each other, and are determined in relation to the total processing time.
  • 5 to 40 at 30 to 60 ° C. It has the activity of completing the fixing of the unexposed portion of the halogen silver halide grains in seconds.
  • Preferred ⁇ Fixing temperature is 30 ° C-60 ° C, more preferably 35-55 ° C.
  • the fixing time is 5 to 40 seconds, more preferably 7 to 30 seconds.
  • the replenishing amount of the fixing solution more preferably 1600MlZm 2 or less preferably fixture 70 OmlZm 2 or less with respect to the processing of the photosensitive material.
  • the concentration of the replenisher is set to a concentration that compensates for consumption during processing under the specified replenishment amount.
  • the photosensitive material that has been subjected to development and fixing processing is washed or stabilized after the plating process described below or after the development or fixing process and after the plating process. (It is also called processing).
  • the amount of washing water (or stabilizing solution replenishment amount) is usually 20 liters or less per lm 2 of photosensitive material, and a replenishing amount of 3 liters or less (including 0). It can also be performed with water). For this reason, not only water saving processing is possible, but piping for installing an automatic processor can be eliminated.
  • a multi-stage countercurrent method for example, two-stage, three-stage, etc. has been known for a long time.
  • the photosensitive material after fixing is gradually processed in a normal direction, that is, in contact with the fixing solution in the order of V and processing solution. Therefore, it is washed with water for further efficiency. Further, when washing with a small amount of water, it is more preferable to provide a squeeze roller and crossover roller washing tank described in JP-A-63-18350 and 62-287252. In addition, the environmental load associated with wastewater pollution, which is a problem when washing with small amounts of water, is reduced. For reduction, various oxidant additions and filter filtration may be combined.
  • a part or all of the overflow solution of the washing bath or stable bathing power generated by replenishing the washing bath or the stable bath with the water subjected to the prevention means according to the treatment can also be used for a processing solution having fixing ability, which is a previous processing step.
  • a water-soluble surfactant or antifoaming agent is added to prevent unevenness of water bubbles, which is likely to occur when washing with a small amount of water, and to prevent the treatment agent component adhering to the Z or squeeze roller from being transferred to the treated film.
  • the dye adsorbent described in JP-A-63-163456 is added to the water washing tank. May be installed.
  • the compounds described in JP-A-2-201357, JP-A-2-132435, JP-A-1102553, and JP-A No. 46-44446 are disclosed. May be used as the final bath of the light-sensitive material.
  • metal compounds such as ammonia compounds, Bi, A1, fluorescent brighteners, various chelating agents, membrane pH regulators, hardeners, bactericides, fungicides, alkanolamines, A surfactant can also be added.
  • Water used in the water washing or stabilization process is sterilized with tap water, deionized water, halogen, UV germicidal lamps, various oxidizing agents (such as ozone, hydrogen peroxide, and chlorate). It is preferred to use fresh water. Further, washing water containing the compounds described in JP-A-4-39 652 and JP-A-5-241309 may be used.
  • the bath temperature and time in the water washing treatment or stable temperature are preferably 0 to 50 ° C. and 5 seconds to 2 minutes.
  • a processing solution such as a developing solution or a fixing solution used in the present invention
  • a packaging material having low oxygen permeability described in JP-A-61-73147.
  • the replenishment amount it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment tank with air.
  • the roller-conveying type automatic developing machine those described in US Pat. Nos. 30,257,795 and 3,545971 can be used.
  • the roller transport type processor also has four process powers of development, fixing, washing and drying, other processes (for example, The stop process) is not excluded, but it is most preferable to follow these four processes. Further, instead of the washing step, four steps by a stable step may be used.
  • the mass of the metallic silver contained in the exposed portion after the development processing is based on the mass of silver contained in the exposed portion before the exposure. It is preferred that the content is 50% by mass or more. Further preferred is 80% by mass or more. If the mass of the silver contained in the exposed part is contained in the exposed part before exposure! /, It is preferable if it is 50% by mass or more with respect to the mass of silver because high conductivity can be obtained! / ,.
  • the gradation after development processing in the present invention is not particularly limited, but is preferably more than 4.0.
  • the conductivity of the conductive metal portion can be increased while keeping the transparency of the light transmissive portion high.
  • means for setting the gradation to 4.0 or more include the aforementioned doping of rhodium ions and iridium ions.
  • the development processing agent and the fixing processing agent in the present invention are solid agents, the same results as in the liquid agent can be obtained. From the viewpoint of storage stability and the like, a solid processing agent is preferable. The following describes the solid processing agent.
  • solid preparation in the present invention known forms (powder, granules, granules, lumps, tablets, compactors, briquettes, plates, rods, pastes, etc.) can be used. These solid agents may be coated with a water-soluble coating agent or film in order to separate components that react with each other upon contact, or the components that react with each other may be separated by forming a plurality of layers. You may use these together.
  • a component that does not react even when contacted may be sandwiched between components that react with each other, and processed into tablets, prickets, etc.
  • a similar layer structure may be used for packaging. These methods are disclosed in, for example, JP-A-61-259921, 4-16841, 4-78848, 5-93991 and the like.
  • the bulk density of the solid processing agent is preferably 0.5 to 6. Og / cm 3, especially the tablet 1.0 to 5. Og / cm 3 is preferably 0.5 to 1. 5 g / cm 3 is preferred.
  • any known method can be used.
  • JP-A-61-259921, JP-A-4-15641, JP 4-16841, 4-32837, 4-78848, 5-93991, JP-A-5-93991 4-85533, 4-85534, 4-85535, 5-134362, 5-197070, 5-204098, 5-22436 1 Reference can be made to 6-138604, 6-138605, 8-286329, and the like.
  • rolling granulation method extrusion granulation method, compression granulation method, disintegration granulation method, stirring granulation method, spray drying method, dissolution coagulation method, pre-ketting method, roller compaction Ting method or the like can be used.
  • the solubility of the solid agent in the present invention can be adjusted by changing the surface state (smooth, porous, etc.), partially changing the thickness, or forming a hollow donut shape. Furthermore, it is possible to take a plurality of shapes in order to give different solubility to a plurality of granules or to match the solubility of materials having different solubility. Further, it may be a multi-layer granulated product having different compositions on the surface and inside.
  • the packaging material of the solid agent a material having a low oxygen and moisture permeability is preferable.
  • a known material such as a bag shape, a cylindrical shape, or a box shape can be used. JP-A 6-242585 to 6-242588, 6-247432, 6-247448, 6-301 189, 7-5664, 7-5666
  • a foldable shape as disclosed in Japanese Patent Publication Nos. 7-7669.
  • screw caps, pull tops, aluminum seals may be attached to the processing agent outlet, or the packaging materials may be heat sealed, but other known materials may be used. I do not. Furthermore, it is preferable to recycle or loose waste packaging materials for environmental conservation!
  • a method for dissolving and replenishing the solid processing agent of the present invention a known method without particular limitation can be used. These methods include, for example, a dissolving device having a stirring function. A method for dissolving and replenishing a certain amount in a place, a method for dissolving in a dissolving device having a dissolving part and a part for stocking the finished liquid as described in JP-A-9-80718, and replenishing from the stock part, As disclosed in JP-A-5-119454, JP-A-6-19102, and JP-A-7-261357, a processing agent is introduced into a circulation system of an automatic processor to dissolve and replenish, and a dissolution tank is provided.
  • any other known method can be used, such as a method of adding a processing agent and dissolving it in accordance with the processing of the photosensitive material by the built-in automatic processor.
  • the processing agent may be input manually or as described in JP-A-9-138495 and automatically opened and automatically added by a dissolving apparatus or an automatic developing machine having an open mechanism. The latter is preferable from the viewpoint of the working environment.
  • the method for producing a conductive film of the present invention is characterized by having a hardening process for reacting a hardening solution on the surface of the film.
  • a treatment with a hardening solution can be performed prior to electroplating, and the effect of improving the uniformity of subsequent plating and suppressing the contamination of the photosensitive material can be obtained by performing this hardening solution treatment.
  • the hardener contained in the hardener solution should be any compound that increases gelatin film hardenability in an aqueous solvent, preferably formaldehyde, bivalyl aldehyde, dartal aldehyde, sputum aldehyde, potash alum, Chromium alum, mucochloric acid, glycoxal, 1,2-dihydroxypyridines, diglycolaldehyde, 2,4-dichroic — 6-hydroxy-1-s-triazines such as s-triazine, crotonaldehyde, boric acid, Examples include sodium nitrate, paraformaldehyde, and aluminum sulfate.
  • the hardener is dartalaldehyde or aluminum sulfate.
  • the concentration of the hardener is preferably 0.005-1. OmolZL, more preferably 0.01 to 1. OmolZL, and most preferably 0.05 to 0.8 molZL.
  • the solvent of the dura mater solution is an aqueous solvent mainly composed of water, and is water or an aqueous electrolyte solution. It is preferable.
  • a compound having a swelling inhibiting action it is preferable to add a compound having a swelling inhibiting action to the dura solution.
  • a compound having a swelling inhibiting action Specifically, NaCl, NaBr, KI, KC1, LiCl, NaCIO, Na SO, CH CO Na, CH CO K
  • Umu salt, etc. may be added.
  • Particularly preferred as a swelling inhibitor is Na 2 SO.
  • the immersion time in the dura mater solution of the present invention is preferably 2 seconds to 10 minutes, more preferably 5 seconds to 5 minutes.
  • the temperature of the dura mater solution of the present invention is preferably 15 ° C to 60 ° C, more preferably 25 ° C to 55 ° C.
  • an electrolytic plating process is carried out for supporting the conductive metal particles on the metal silver portion.
  • the electrolytic plating process is carried out after the development process, after the fixing process after the development process, or after the development process or after the washing process or the rinsing substitute for the washing process.
  • stage the electrolytic plating is performed can be selected as appropriate.
  • electrolytic plating is more preferable than non-electrolytic plating in that it can be performed under mild electrolyte conditions (high stability) that does not cause metal deposition in the unexposed areas.
  • high-speed plating is also possible.
  • various additives such as a ligand such as EDTA can be used from the viewpoint of increasing the stability of the plating solution.
  • the metal species used for electroplating are the same as those described in the section on electroless plating, and the preferred metal species are also the same. Copper and silver plating are particularly preferable.
  • the electrolytic solution can dissolve the metal compound of the metal to be plated at the required concentration, and is low enough to be suitable for electrolysis. Solution resistance (contact resistance with developed silver as an electrode, current resistance of the electrolyte) As long as (total) can be secured, any of them can be used. Accordingly, although it is appropriately selected according to the metal compound to be used, since the metal to be plated is generally copper, silver or the like, an aqueous solution of an inorganic acid such as sulfuric acid, hydrochloric acid or nitric acid is preferred.
  • silver and copper can easily form an ammine complex or a hydroxyamino complex.
  • Hydroxyl-ammonium ammonia water
  • alkanolamine aqueous solution preferably ethanolamine, methethanolamine, or triethanolamine aqueous solution. I like it!
  • the concentration of acids, hydroxides, alkanolamines used in these electrolytes is 0.1 mol ZL to 10 mol ZL, preferably 0.2 mol ZL to 8 mol ZL, particularly preferably. Is 0.25 mol ZL to 5 mol ZL.
  • the metal compound of the plating metal is 0.05 mol ZL to 10 monolayer / L, preferably ⁇ or 0.07 monolayer / L to 5 monolayer / L, and particularly preferably 0.25 to 0.1 mol / L to 3 mol ZL. .
  • the temperature of the plating solution in electrolytic plating is preferably 10 ° C to 60 ° C, more preferably 20 ° C to 50 ° C, and particularly preferably 25 ° C to 45 ° C.
  • the charge time is a force that can be adjusted as appropriate to obtain the desired metal coating thickness. 10 seconds to 600 seconds, preferably 20 seconds to 450 seconds, particularly preferably 30 seconds to 300 seconds. ) Adjust the liquid composition and temperature.
  • a preferable metal compound and plating solution composition for example, in the case of copper plating, one containing 30 to 300 gZL of copper sulfate pentahydrate and 30 to 300 g / L of sulfuric acid can be used.
  • a neutral or acidic aqueous solution or ammoniacal alkaline aqueous solution containing 30 to 300 g ZL of silver nitrate can be used.
  • nickel plating it is possible to use one containing sulfuric acid-nickel, nickel hydrochloride, and in the case of silver plating, those containing cyanogen silver.
  • an additive such as a surfactant, a sulfur compound, or a nitrogen compound may be added to the plating solution.
  • a plating apparatus for suitably carrying out the plating treatment according to the present invention is a reel for feeding (see FIG. It is preferable that the film sequentially drawn out from (not shown) is fed into an electroplating bath and the film after plating is wound up on a reel for reeling out (not shown).
  • Fig. 1 shows an example of an electrolytic plating bath suitably used for the plating treatment according to the present invention.
  • the electroplating apparatus 10 shown in FIG. 1 is capable of continuously plating a long film 16.
  • the arrow indicates the transport direction of the film 16.
  • the electrolytic plating apparatus 10 includes an electrolytic tank 11 that stores a plating solution 15.
  • a pair of anode plates 13 are disposed in parallel in the electrolytic cell 11, and a pair of guide rollers 14 are rotatably disposed in parallel with the anode plate 13 inside the anode plate 13.
  • the guide roller 14 is movable in the vertical direction, so that the processing time for the film 16 can be adjusted.
  • a pair of feed rollers (force swords) 12 a and 12 b for guiding the film 16 to the electrolytic cell 11 and supplying a current to the film 16 are rotatably arranged. Further, above the electrolytic cell 11, a liquid draining roller 17 is rotatably disposed below the power supply roller 12b on the outlet side.
  • the anode plate 13 is connected to a positive terminal of a power supply device (not shown) via an electric wire (not shown), and the power supply rollers 12a and 12b are connected to a negative terminal of the power supply device (not shown). Yes.
  • the film 16 is set in a state where it is wound around a supply reel (not shown), and the film 16 is placed so that the surface on which the film 16 should be formed contacts the power supply rollers 12a and 12b. It is wound around a conveyance roller (not shown).
  • a voltage is applied to the anode plate 13 and the feed rollers 12a and 12b, and the film 16 is conveyed while being in contact with the feed rollers 12a and 12b.
  • the film 16 is introduced into the electrolytic cell 11 and immersed in the plating solution 15 to form a copper plating.
  • the plating solution 15 adhering to the film 16 is wiped off and collected in the electrolytic cell 11. This is repeated in a plurality of electrolytic baths, and finally washed with water, and then wound around a reel (not shown).
  • the conveyance speed of the film 16 is set in the range of 1 to 30 mZ.
  • the conveying speed of the film 16 is preferably in the range of 1 to: LOmZ, and more preferably in the range of 2 to 5 mZ.
  • the number of electrolytic plating baths is not particularly limited, but 2-10 baths are preferred, and 3-6 baths are more preferred. Good.
  • the applied voltage is preferably in the range of 0.5 to L00V, and more preferably in the range of 1 to 60V.
  • the feeding rollers 12a and 12b be in contact with the entire surface of the film (80% or more of the contact area is substantially in electrical contact).
  • the thickness of the conductive metal part to be attached by the above-mentioned staking treatment is preferable because the viewing angle of the display is widened as it is thinner as an electromagnetic shielding material for the display. In addition, thin films are required for the demand for higher density for the use of conductive wiring materials. From this point of view, the thickness of the plated conductive metal force layer is preferably less than 9 m, more preferably less than 0.1 m and less than 5 ⁇ m, more preferably less than force S. More preferably, it is 1 m or more and less than 3 ⁇ m.
  • FIG. 2 shows an example of the conductive film of the present invention.
  • a conductive film 21 shown in FIG. 2 has a conductive functional layer 22 on a support 23.
  • the conductive functional layer 22 contains a silver halide emulsion layer 28.
  • a metal silver portion can be formed by performing exposure 'development processing or the like on the exposed portion 24, and a conductive metal portion can be formed by applying electrolytic plating in order to further increase the conductivity.
  • the unexposed part 25 becomes a light-transmitting part (for example, made of gelatin).
  • the metal silver part after the development process and the conductive metal part formed after the staking process are preferably subjected to an acid bath treatment.
  • an acid bath treatment for example, when a metal is slightly deposited on the light transmissive part, the metal can be removed, and the light transmissive part can be almost 100% transparent.
  • oxidation treatment examples include known methods using various oxidizing agents such as Fe (III) ion treatment.
  • the oxidation treatment can be carried out after the exposure and development treatment of the silver salt-containing layer or after the plating treatment, and may be carried out after the development treatment and after the plating treatment.
  • the metallic silver portion after the exposure and development treatment is further treated with a solution containing Pd.
  • Pd may be divalent palladium ion or metallic palladium. This treatment can accelerate the electroless plating speed.
  • the conductive metal part is formed by carrying the metal silver part formed by the above-described exposure and development processes so as to carry conductive metal particles on the metal silver part.
  • Metal silver may be formed in an exposed area, or may be formed in an unexposed area by using an auto-positive material as a photosensitive material, or by using reversal development for development processing. In the present invention, it is preferable to form metallic silver in the exposed portion in order to increase transparency.
  • the conductive metal supported on the metal part in addition to the above-mentioned silver and copper, aluminum, nickel, iron, gold, conol, tin, stainless steel, tungsten, chromium, titanium, palladium, platinum, manganese And particles of metals such as zinc and rhodium, or alloys obtained by combining these metals.
  • the conductive metal is preferably copper, aluminum or nickel particles.
  • the conductive metal contained in the conductive metal part is copper. It is more preferable that the surface is blackened at least on the surface.
  • the black wrinkle treatment can be performed using a method used in the printed wiring board field. For example, blackening treatment can be performed by treating for 2 minutes at 95 ° C in an aqueous solution of sodium chlorite (31 gZD, sodium hydroxide (15 gZD, trisodium phosphate (12 gZD)).
  • the conductive metal part preferably contains 50% by mass or more of silver, more preferably 60% by mass or more, based on the total mass of the metal contained in the conductive metal part. . If silver is contained in an amount of 50% by mass or more, the time required for the plating treatment can be shortened, the productivity can be improved, and the cost can be reduced. Furthermore, when copper and palladium are used as the conductive metal particles forming the conductive metal part, the total mass of silver, copper and palladium is 80% by mass with respect to the total mass of the metal contained in the conductive metal part. Preferably, it is 90% by mass or more.
  • the surface resistance value of the electromagnetic wave shielding film (conductive metal part) of the present invention is preferably 10 3 Q Zsq or less, and more preferably 2.5 ⁇ / sq or less. More preferably, it is 5 ⁇ Zsq or less.
  • a triangle such as an equilateral triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid, etc.
  • geometric figures are preferably geometric figures that combine (positive) n-gons, circles, ellipses, stars, etc., such as quadrilaterals, (regular) hexagons, (positive) octagons, etc. More preferably, it is mesh-like.
  • the triangular shape is the most effective, but if the line width of the visible light is the same (positive), the larger the n number of n-squares, the higher the aperture ratio increases and the visible light transmission Is advantageous.
  • the shape of the said electroconductive metal part is not specifically limited, Arbitrary shapes can be suitably determined according to the objective.
  • the conductive metal portion preferably has a line width of 40 ⁇ m or less and a line spacing of 50 / z m or more.
  • the conductive metal part may have a part with a line width wider than 20 m for purposes such as ground connection.
  • the line width of the conductive metal part is preferably less than 40 ⁇ m, more preferably less than 35 m, and even more preferably less than 30 m. U, most preferred to be less than 25 ⁇ m.
  • the conductive metal portion in the present invention preferably has an aperture ratio of 85% or more, more preferably 90% or more, and even more preferably 95% or more. Is most preferred.
  • the aperture ratio is the percentage of the mesh without fine lines. For example, the aperture ratio of a square mesh with a line width of 10 ⁇ m and a pitch of 200 ⁇ m is 90%.
  • the “light transmissive part” in the present invention means a part having transparency other than the conductive metal part in the electromagnetic wave shielding film.
  • the transmittance of the light transmissive part is 90% or more, preferably 90% or more, preferably represented by the minimum value of the transmittance in the wavelength region of 380 to 780 nm excluding the light absorption and reflection contributions of the support. 95% or more, more preferably 97% or more, even more preferably 98% or more, most preferably 99% or more
  • the light-transmitting portion has substantially no physical development nucleus from the viewpoint of improving the transmittance.
  • the present invention does not require diffusion after dissolving unexposed halogenated silver and converting it to a soluble silver complex compound. It is preferred that it has substantially no development nuclei.
  • substantially free of physical development nuclei means that the abundance of physical development nuclei in the light-transmitting part is in the range of 0 to 5%.
  • the light-transmitting portion in the present invention is formed together with the metallic silver portion by exposing and developing the silver salt-containing layer.
  • the light transmissive portion is preferably subjected to an acid treatment after the development treatment, and further after a physical treatment or a staking treatment.
  • the dry film thickness of the light-transmitting part is preferably 2.0 m or less.
  • the light-transmitting part has water-soluble polymer power.
  • the thickness of the support in the electromagnetic wave shielding film of the present invention is preferably 5 to 200 / zm, more preferably 30 to 150 / ⁇ ⁇ . If it is in the range of 5 to 200 m, the desired visible light transmittance can be obtained and it can be easily handled.
  • the thickness of the metallic silver portion provided on the support before the plating treatment can be appropriately determined according to the coating thickness of the silver salt-containing layer coating applied on the support.
  • the thickness of the metallic silver part is preferably 30 m or less, more preferably 20 m or less, and even more preferably 0.01 to 9 ⁇ m. 0.05 to 5 ⁇ m Most preferably m.
  • the metallic silver part is a pattern.
  • the thickness of the conductive metal part is thin for use as an electromagnetic shielding material for displays. It is preferable because the viewing angle of the display is widened. In addition, as the use of conductive wiring materials, thin films that require high density are required. From this point of view, the thickness of the layer having the conductive metal force carried on the conductive metal part is preferably less than 9 m, more preferably 0.1 ⁇ m or more and less than 5 ⁇ m. It is more preferably 0.1 m or more and less than 3 ⁇ m.
  • a metal silver portion having a desired thickness is formed by controlling the coating thickness of the above-described silver salt-containing layer, and the thickness of the layer made of conductive metal particles can be freely controlled by the staking treatment. Even an electromagnetic wave shielding film having a thickness of less than 5 / zm, preferably less than 3 m, can be easily formed.
  • the present invention supports a pattern containing only a necessary amount of conductive metal. Since it can be provided on the body, it is sufficient to use only the minimum amount of metal, which is advantageous in terms of both reducing manufacturing costs and reducing the amount of metal waste.
  • the electromagnetic wave shielding film of the present invention is separately used in combination with a functional layer having functionality as necessary.
  • This functional layer can have various specifications for each application.
  • an antireflection layer provided 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 near infrared rays.
  • Near-infrared absorbing layer made of a compound or metal that absorbs light, a layer with a color tone adjustment function that absorbs visible light in a specific wavelength range, an antifouling layer with a function that easily removes dirt such as fingerprints, and scratches It is possible to provide a hard coat layer that is difficult, a layer having an impact absorbing function, a layer having a function of preventing glass scattering when glass is broken, and the like.
  • 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 bonded to a transparent substrate such as a glass plate or an acrylic resin plate separately from the plasma display panel main body which may be directly bonded to the PDP.
  • These functional films are called optical filters (or simply filters).
  • the antireflection layer provided with the antireflection function suppresses reflection of outside light and reduces contrast.
  • inorganic materials such as metal oxides, fluorides, halides, borides, carbides, nitrides, and sulfides can be formed in a single layer by vacuum deposition, sputtering, ion plating, ion beam assist, etc.
  • there are a method of laminating in multiple layers a method of laminating resins having different refractive indexes, such as acrylic resin and fluorine resin, in a single layer or multiple layers.
  • a film that has been subjected to anti-reflection treatment can be attached to the filter.
  • a non-glare layer or an anti-glare layer can be provided.
  • a method of coating fine particles of silica, melamine, acrylic, etc. into an ink and coating the surface can be used.
  • the ink can be cured by heat curing or photocuring.
  • a non-glare-treated or anti-glare-treated film can be pasted on the filter.
  • a node 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.
  • the silver sputtered layer can cut light of 1000 nm or more from near infrared rays, far infrared rays to electromagnetic waves by alternately laminating a dielectric layer and a metal layer 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, and usually three layers starting from the dielectric layer. Laminate 5 layers, 7 layers or 11 layers.
  • a layer having a color tone adjusting function that absorbs visible light in a specific wavelength range has a characteristic that a PDP emits red light although the amount of phosphor that emits blue is small in addition to blue.
  • a PDP emits red light although the amount of phosphor that emits blue is small in addition to blue.
  • the portion that should be displayed in blue is displayed in a color in which purple is strong, and as a countermeasure against this, it is a layer that corrects colored light and contains a dye that absorbs light at around 595 nm.
  • the electromagnetic wave shielding film obtained by the production method of the present invention has good electromagnetic wave shielding properties and permeability, and therefore can be used as a transparent electromagnetic wave shielding material. Furthermore, it can be used as various conductive wiring materials such as circuit wiring.
  • the electromagnetic wave shielding film of the present invention is used in the front of displays such as CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electricular luminescence), microwave ovens, electronic equipment, printed wiring boards, etc. It can be suitably used as an electromagnetic shielding film used in a panel.
  • CTR cathode ray tube
  • PDP plasma display panel
  • liquid crystal liquid crystal
  • EL electric luminescence
  • microwave ovens electronic equipment
  • printed wiring boards etc. It can be suitably used as an electromagnetic shielding film used in a panel.
  • the conductive film of the present invention typified by an electromagnetic wave shielding film and a conductive film will be described with respect to additional components other than those described above.
  • an electromagnetic shielding film or conductive film for example, a transparent electrode
  • an optical filter for example, a liquid crystal display panel, a plasma display panel, other image display grat panels, or an imaging semiconductor integrated circuit such as a CCD.
  • an imaging semiconductor integrated circuit such as a CCD.
  • the adhesive used in the present invention preferably has a refractive index of 1.40-1.70. This is a relationship between the refractive index of the adhesive and the transparent substrate such as a plastic film used in the present invention, and the difference is reduced to prevent the visible light transmittance from being lowered. 40-1.70 is good with little decrease in visible light transmittance.
  • the adhesive used in the present invention shows fluidity, and it is preferably an adhesive which flows by heating or pressing tool particularly, the following heating or LKgfZcm 2 or more pressure 200 ° C
  • An adhesive is preferred.
  • the electromagnetic wave shielding adhesive film according to the present invention in which a conductive layer is embedded in the adhesive layer is allowed to flow and adhere to the display or plastic plate as the adherend. can do . Since it can flow, the electromagnetic wave shielding adhesive film can be easily adhered to an adherend having a curved surface or a complicated shape by laminating or pressure forming, particularly pressure forming.
  • the softening temperature of the adhesive is preferably 200 ° C. or lower.
  • the environment used is usually less than 80 ° C, so the softening temperature of the adhesive layer is preferably 80 ° C or higher, and the workability that is preferred is 80-120 ° C. preferable.
  • the softening temperature is the temperature at which the viscosity is 10 12 boise or less (10 13 Pa's or less). Usually, at that temperature, flow is recognized within a time of 1 to LO seconds.
  • Typical examples of the adhesive that flows by heating or pressurization as described above include the following thermoplastic resins.
  • polyisoprene 1.521
  • polybutene 1.513
  • urethane acrylate, epoxy acrylate, and polyether acrylate are excellent in terms of adhesiveness.
  • epoxy acrylate include 1,6 hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allylic alcohol.
  • An acid adduct is mentioned.
  • a polymer having a hydroxyl group in the molecule, such as epoxy acrylate, is effective in improving adhesion.
  • These copolymerized resins can be used in combination of two or more as required.
  • the softness temperature of the polymer used as the adhesive is preferably 200 ° C or less, and more preferably 150 ° C or less, in terms of handling ability. Since the environment in which the electromagnetic wave shielding adhesive film is used is usually 80 ° C or lower, the softening temperature of the adhesive layer is most preferably 80 to 120 ° C in view of processability. On the other hand, it is preferable to use a polymer having a mass average molecular weight (measured using a standard polystyrene calibration curve by gel permeation chromatography, the same shall apply hereinafter) of 500 or more. If the molecular weight is 500 or less, the cohesive force of the adhesive composition is too low, and the adhesion to the adherend may be reduced.
  • the adhesive used in the present invention may contain additives such as diluents, plasticizers, antioxidants, fillers, colorants, ultraviolet absorbers and tackifiers, as necessary.
  • the thickness of the adhesive layer is more preferably 10 to 80 m, particularly preferably 20 to 50 ⁇ m, more than the thickness of the conductive layer.
  • the adhesive covering the geometric figure has a refractive index difference of 0.14 or less with respect to the transparent plastic substrate.
  • the difference in refractive index between the adhesive layer and the adhesive covering the geometric figure is 0.14 or less. This is because if the refractive index of the transparent plastic substrate and the adhesive or the refractive index of the adhesive and the adhesive layer are different, the visible light transmittance is lowered, and if the difference in refractive index is 0.14 or less, it is visible. The decrease in light transmittance is small and good.
  • polyisoprene 1.521
  • polybutene 1.5125
  • poly 1,3 butadiene l.
  • polyoxyethylene l.4563
  • the transparent plastic substrate is an acrylic resin
  • epoxy acrylate, urea acrylate, polyether acrylate, polyester acrylate and the like can also be used as the copolymer resin of acrylic resin and non-acrylic resin.
  • Epoxy acrylate and polyether acrylate are particularly excellent in terms of adhesiveness.
  • Examples of epoxy acrylate include 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and aryl alcohol diglycidyl ether.
  • Epoxy acrylate is effective in improving adhesion because it has a hydroxyl group in the molecule, and these copolymerized resins can be used in combination of two or more as required.
  • the polymer that is the main component of the adhesive has a mass average molecular weight of 1,000 or more. When the molecular weight is 1,000 or less, the cohesive force of the composition is too low, and the adhesion to the adherend is reduced.
  • Adhesive curing agents include amines such as triethylenetetramine, xylenediamine, diaminodimethane, phthalic anhydride, maleic anhydride, dodecyl succinic anhydride, anhydrous pyromellitic acid, benzophenone anhydride tetracarboxylic acid, etc. Acid anhydrides, diaminodiphenylsulfone, tris (dimethylaminomethyl) phenol, polyamide resin, dicyandiamide, ethylmethylimidazole and the like can be used. These may be used alone or in combination of two or more.
  • the addition amount of these crosslinking agents is selected in the range of 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polymer. If the amount of addition is less than 0.1 parts by mass, curing may be insufficient, and if it exceeds 50 parts by mass, excessive crosslinking may occur, which may adversely affect adhesion.
  • the adhesive resin composition used in the present invention may contain additives such as diluents, plasticizers, antioxidants, fillers and tackifiers, as necessary. Then, the resin composition of this adhesive is used to cover a part or the entire surface of the base material of the constituent material provided with a geometric figure drawn with a conductive material on the surface of the transparent plastic base material.
  • the adhesive film according to the present invention is formed after coating, solvent drying, and heat curing.
  • the adhesive film having electromagnetic shielding properties and transparency obtained as described above can be directly attached to a display such as CRT, PDP, liquid crystal, and EL with an adhesive of the adhesive film, or an acrylic plate, a glass plate, etc. Affixed to a plate or sheet for use as a display.
  • this adhesive film is used in the same manner as described above for windows and casings for looking inside measuring devices, measuring devices and manufacturing devices that generate electromagnetic waves.
  • it will be installed on the windows of buildings and automobile windows where there is a risk of electromagnetic interference from radio towers and high voltage lines. It is preferable to provide a ground wire on the geometrical figure drawn with the conductive material.
  • the translucent part on the transparent plastic substrate has intentional irregularities to improve adhesion, or light is scattered on the surface to transfer the back surface shape of the conductive material.
  • transparency is impaired, when a resin having a refractive index close to that of the transparent plastic substrate is smoothly applied to the uneven surface, irregular reflection is suppressed to a minimum and transparency is exhibited.
  • geometrical shapes drawn with conductive materials on transparent plastic substrates have very small line widths, so they are not visible to the naked eye.
  • the pitch is sufficiently large, so it appears that transparency appears.
  • the pitch of the geometric figure is sufficiently small compared to the wavelength of the electromagnetic wave to be shielded, it is considered that excellent shielding properties are exhibited.
  • an ethylene-acetate butyl having a high heat-fusibility is used as a transparent base film.
  • a film of heat fusible resin such as copolymer resin or ionomer resin alone or laminated with other resin film
  • the lamination is usually performed by a dry lamination method using an adhesive layer.
  • the adhesive constituting the adhesive layer include acrylic resin, polyester resin, polyurethane resin, polybulal alcohol resin, butyl chloride, Z-acetate copolymer resin, and ethylene-acetate copolymer resin.
  • a thermosetting resin such as an ionizing radiation curable resin (such as an ultraviolet curable resin, an electron beam curable resin).
  • the electromagnetic wave shielding sheet of the above publication refers to a functional layer described as “electromagnetic wave shielding film” in the present invention.
  • the surface of the display is made of glass, so the adhesive can be used to attach a transparent plastic film and a glass plate.
  • Problems occur such as the image being distorted and the display color appearing different from the original display.
  • the problem of bubbles and peeling occurs when the adhesive peels off from the plastic film or glass plate. This phenomenon may occur on both the plastic film side and the glass plate side, and peeling occurs on the side with weaker adhesion. Therefore, it is necessary that the adhesive force between the pressure-sensitive adhesive and the plastic film or glass plate is high. Specifically, it adheres to transparent plastic film and glass plate.
  • the adhesive strength with the adhesive layer is at least lOgZcm at 80 ° C! /.
  • an adhesive that exceeds 2000 gZcm may not be preferable because it makes the bonding work difficult. However, it can be used without problems if no significant problems occur. Furthermore, it is also possible to install a paper (separator) so that the part does not unnecessarily come into contact with other parts when facing the transparent plastic film of the adhesive.
  • the adhesive is preferably transparent. Specifically, the total light transmittance is preferably 70% or more, more preferably 80% or more, and most preferably 85 to 92%. Furthermore, it is preferable that haze is low. Specifically, 0 to 3% is preferable, and 0 to 1.5% is more preferable.
  • the pressure-sensitive adhesive used in the present invention is preferably colorless so as not to change the original display color of the display. However, even if the resin itself is colored, it can be regarded as virtually colorless if the pressure-sensitive adhesive is thin. Similarly, this is not within this range when intentionally coloring as described later.
  • Examples of the pressure-sensitive adhesive having the above-mentioned properties include acrylic resin, a 1-year-old refin resin, vinyl acetate resin, acrylic copolymer resin, urethane resin, epoxy resin, Examples thereof include a vinyl chloride-based resin, a vinyl chloride-based resin, an ethylene butyl acetate-based resin, a polyamide-based resin, and a polyester-based resin. Of these, acrylic resin is preferred. Even when the same coagulant is used, the pressure-sensitive adhesive properties can be reduced by reducing the addition amount of the cross-linking agent, adding a tackifier, or changing the molecular end groups when the pressure-sensitive adhesive is synthesized by the polymerization method. It is also possible to improve.
  • the thickness of the pressure-sensitive adhesive layer is preferably about 5 to 50 ⁇ m.
  • the thickness is preferably reduced within the above range. Specifically, it is about 1-20 / ⁇ ⁇ .
  • the display color of the display itself is not changed and the transparency is within the above range as described above, Even if it exceeds the above range,
  • the optical filter according to the present invention can be provided with a peelable protective film.
  • the protective film may be provided on one side or both sides of the optical filter.
  • an optical filter is used by laminating sheets having effects such as strengthening the outermost surface, imparting antireflection properties, imparting antifouling properties, etc.
  • the protective film needs to be peeled off in the case of such further lamination. Therefore, it is desirable that the protective film is laminated so as to be peelable.
  • the peel strength when the protective film is laminated on the conductive metal part is preferably 5mNZ25mm width to 5NZ25mm width, more preferably 10mNZ25mm width to 100mNZ2 5mm width. If it is less than the lower limit, it is easy to peel off, and the protective film may be peeled off during handling or inadvertent contact. If the upper limit is exceeded, a large force is required for peeling.
  • the mesh-like conductive metal part may peel off from the transparent substrate film (or from the adhesive layer), which is also not preferable.
  • the protective film laminated on the transparent substrate film side can withstand the etching conditions, for example, it should not be eroded during immersion for several minutes by an etching solution of about 50 ° C, particularly its alkaline component. It is desirable or in the case of dry etching, it should be able to withstand a temperature condition of about 100 ° C.
  • the coating liquid adheres to the opposite surface of the laminated body, so that the photosensitive solution is etched during the etching process. It is preferable that the adhesive of the photosensitive resin is obtained so that the photosensitive resin does not peel off and drift in the etching solution.
  • the etching solution iron chloride, copper chloride, etc. It is preferable to have durability that resists contamination by the etching solution, or that resists erosion or contamination by a resist removal solution such as an alkaline solution.
  • polyethylene resin which is a polyolefin resin, polypropylene resin, polyester resin such as polyethylene terephthalate resin
  • a resin film such as polycarbonate resin or acrylic resin
  • a corona discharge treatment to the surface which is the outermost surface when applied to a laminate, or to laminate an easy adhesion layer.
  • acrylic acid ester-based, rubber-based, or silicone-based ones can be used as the pressure-sensitive adhesive constituting the protective film.
  • the above-described protective film material and adhesive material can also be applied as they are to the protective film applied to the conductive metal part side, so different protective films can be used. However, the same material can be used as both protective films.
  • the electromagnetic wave shielding film according to the present invention may be blackened.
  • the black wrinkle process is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-188576.
  • the blackened layer formed by the blackening treatment can impart antireflection properties in addition to the antifungal effect.
  • the black layer can be formed by, for example, a Co—Cu alloy plating, and by providing the black layer on the conductive metal portion, reflection of the surface can be prevented.
  • a chromate treatment may be performed thereon as an antifungal treatment.
  • the chromate treatment is performed by dipping in a solution containing chromic acid or dichromate as a main component and drying to form an anti-fouling film. If necessary, it can be performed on one or both sides of the conductive metal part.
  • a commercially available chromate-treated copper foil or the like may be used.
  • the configuration shown in JP-A-11-266095 may be used. That is, after the first black layer is provided on the conductive metal portion and the electrolytic plating is performed on the first black layer, the second black layer is further formed on the plating. It is a configuration with layers. In order to perform electroplating on the first black layer, at least the first black layer must be conductive.
  • the conductive black layer can be formed using a conductive metal compound, for example, a compound such as nickel (Ni), zinc (Zn), copper (Cu), or the like. It can be formed using an electrodepositing ionic polymer material such as an electrodeposition coating material.
  • a method for providing a black glazed layer is known (see, for example, Fig. 5 of JP-A-11 266095).
  • a transparent support with conductive metal parts formed in an electrolyte containing blackening material The body may be immersed and plated by an electrochemical plating method.
  • the electrolyte bath containing the above blackening material can be a black tanning bath containing nickel sulfate as a main component, and is also commercially available. Black tanning baths can be used in the same way. Specifically, for example, Shimizu Co., Ltd.
  • black tanning bath (trade name, Nobrau SNC, Sn—Ni alloy system), Nippon Steel Industry Black tanning bath manufactured by Co., Ltd. (trade name, Nitsuka Black, Sn—Ni alloy), Black tanning bath manufactured by Metal Chemical Co., Ltd. (trade name, Evo--Chromium 85 series, Cr-based) Etc.
  • various black tanning baths such as Zn-based, Cu-based and others can be used as the black tanning bath.
  • the conductive mesh is applied to form a conductive mesh pattern, and then a second black layer is formed thereon.
  • the metal with an electric field is Cu
  • HS hydrogen sulfide
  • CuS copper sulfide
  • the blackening agent for the second blackening layer it can be easily manufactured using a sulfate compound, and there are many types of commercially available treatment agents. Yes, for example, using the brand name 'Copa-Black CuO, CuS, selenium-based Copa-Black No. 65, etc. (made by Isolate Chemical Laboratory), brand name' Ebonol C Special (made by Meltex Co., Ltd.), etc. can do.
  • the functional film (C) is anti-reflective (AR: anti-reflection) to suppress external light reflection or mirror image. It is necessary to have a function of anti-glare (AG: anti-glare) or anti-reflection / anti-glare (ARAG) having both characteristics to prevent the reflection of the image. If the visible light reflectance of the display filter surface is low, contrast and the like can be improved by preventing reflection only.
  • the functional film having antireflection has an antireflection film.
  • the refractive index is 1.5 or less, preferably 1.4 or less
  • the fluorine-based transparent high A thin film of molecular resin, magnesium fluoride, silicon-based oxalate-silicon-silicon, etc., formed with a single layer with an optical film thickness of, for example, 1Z4 wavelength, metal oxides, fluorides, halides with different refractive indexes Nitro There are two or more layers of thin films of inorganic compounds such as chemical compounds and sulfates, or organic compounds such as silicon-based resin, acrylic resin, and fluorine-based resin, but it is not limited to these. ! /
  • the visible light reflectance of the surface of the functional film (C) having antireflection properties is 2% or less, preferably 1.3% or less, and more preferably 0.8% or less.
  • the functional film having anti-glare property has an anti-glare film that is transparent to visible light having a surface state with minute irregularities of about 0.1 ⁇ m-lO ⁇ m.
  • An ink obtained by dispersing particles of an inorganic compound or an organic compound such as a silicon compound, melamine, or acrylic is applied on a substrate and cured. The average particle size of the particles is 1-40 / ⁇ ⁇ .
  • the above-described methods can also provide anti-glare properties by applying the above thermosetting type or photo-curing type resin to a substrate and pressing and curing a mold having a desired dalos value or surface state. It is not limited to.
  • the haze of the functional film having antiglare property is 0.5% or more and 20% or less, preferably 1% or more and 10% or less. If the haze is too small, the antiglare property is insufficient, and if the haze is too large, the transmitted image sharpness tends to be low.
  • the functional film has a hard coat property.
  • the hard coat film include thermosetting or photocuring type resin such as acrylic type resin, silicon type resin, melamine type resin, urethane type resin, alkyd type resin, fluorine type resin.
  • the type and formation method are not particularly limited!
  • the thickness of these films is about 1-50 / ⁇ ⁇ .
  • the pencil hardness according to JIS ( ⁇ -5400) is at least ⁇ , preferably 2 ⁇ , and more preferably 3 ⁇ or more.
  • the anti-static treatment may be required for the display filter because dust may adhere to it due to electrostatic charging, or it may be discharged and receive an electric shock when it comes into contact with the human body. Therefore, in order to impart antistatic ability, the functional film may be conductive. In this case, the required electrical conductivity is 10 11 ⁇ Good if it is below.
  • the method for imparting conductivity include a method of containing an antistatic agent in the film and a method of forming a conductive layer (antistatic layer).
  • Specific examples of the antistatic agent include the trade name Pelestat (manufactured by Sanyo Kasei Co., Ltd.), the trade name of electro slipper (manufactured by Kao Corporation), and the like.
  • the conductive layer examples include known transparent conductive films such as ITO, and conductive films in which conductive ultrafine particles such as ITO ultrafine particles and tin oxide ultrafine particles are dispersed.
  • the hard coat film, the antireflection film and the antiglare film preferably have a conductive film or contain conductive fine particles.
  • the functional film (C) has an antifouling property! /, Because it can be easily removed when it is smudged or smudged.
  • Those having antifouling property are those having non-wetting properties against water and Z or fats and oils, and examples thereof include fluorine compounds and key compounds.
  • Specific examples of the fluorine-based antifouling agent include trade name OPTOOL (manufactured by Daikin) and the like, and examples of the key compound include trade name Takata Quantum (manufactured by Nippon Oil & Fats Co., Ltd.).
  • the functional film preferably has an ultraviolet-cutting property for the purpose of preventing deterioration of a dye or a polymer film described later.
  • Examples of the functional film having an ultraviolet cutting property include a method of adding an ultraviolet absorber to the above-described polymer film described later and an ultraviolet absorbing film.
  • the display filter When the display filter is used in a temperature / humidity environment that is higher than normal temperature and humidity, the dye described later deteriorates due to the moisture that has passed through the film, or in the adhesive used for bonding or pasting.
  • the functional film has gas barrier properties because moisture may aggregate at the mating interface and become cloudy, or the tackifier in the adhesive may phase separate and precipitate due to the influence of moisture. And preferred.
  • the water vapor permeability of the functional film is less than or equal to lOgZm 2 ⁇ day, preferably Is preferably 5 gZm 2 ⁇ day or less.
  • the polymer film, the conductive mesh layer, the functional film, and, if necessary, a transparent molded product to be described later are bonded together via an arbitrary pressure-sensitive adhesive or adhesive transparent to visible light.
  • adhesives or adhesives include acrylic adhesives, silicone adhesives, Examples include urethane adhesives, polyvinyl butyral adhesives (PVB), ethylene vinyl acetate adhesives (EVA), polybutyl ether, saturated amorphous polyester, melamine resin, etc. It may be in the form of a liquid or liquid.
  • the pressure-sensitive adhesive is preferably a pressure-sensitive adhesive sheet. Bonding is performed by laminating each member after applying the sheet-like adhesive material or after applying the adhesive.
  • Liquid materials are adhesives that harden when left at room temperature or heated after coating and bonding.
  • the coating method include a bar coating method, a reverse coating method, a gravure coating method, a die coating method, and a roll coating method, and are selected in consideration of the type of adhesive, viscosity, coating amount, and the like.
  • the thickness of the layer is not particularly limited, but is 0.5 m to 50 ⁇ m, preferably 1 ix m to 30 m. It is preferable that the surface on which the pressure-sensitive adhesive layer is formed and the surface to be bonded are previously improved in wettability by easy adhesion coating or corona discharge treatment.
  • the above-mentioned adhesive or adhesive transparent to visible light is referred to as a translucent adhesive.
  • a light-transmitting pressure-sensitive adhesive layer is particularly used.
  • the translucent adhesive material used for the translucent adhesive material layer it is important that the same force as described above can sufficiently fill the concave portion of the conductive mesh layer. If the thickness of the conductive mesh layer is too thin, a gap will be formed due to insufficient embedding, and bubbles will be swallowed into the recess, resulting in a turbid display filter with poor transparency. On the other hand, if it is too thick, problems such as an increase in the cost for producing the adhesive material and a poor handling of the members occur.
  • the thickness of the translucent adhesive is preferably (d-2) to (d + 30) ⁇ m! /.
  • the visible light transmittance of the display filter is preferably 30 to 85%. More preferably, it is 35 to 70%. If it is less than 30%, the luminance is too low and visibility is deteriorated. Also, if the visible light transmittance of the display filter is too high, the display contrast cannot be improved.
  • the visible light transmittance in the present invention is calculated according to JIS (R-3106) from the wavelength dependence of the transmittance in the visible light region.
  • the functional film when the functional film is bonded onto the conductive mesh layer via the light-transmitting adhesive layer, air bubbles may be trapped in the recesses, which may become cloudy and insufficient in translucency.
  • the gas that has entered between the members at the time of bonding can be defoamed or solid-dissolved in an adhesive material, thereby eliminating turbidity and improving translucency.
  • the pressure treatment may be performed in the state of the above configuration or in the state of the display filter of the present invention.
  • Examples of the pressurizing method include a method in which a laminate is sandwiched between flat plates, a press method, a method of passing between press rolls while pressurizing, and a method of pressurizing in a pressurizing container, but are not particularly limited. .
  • the method of pressurizing in a pressure vessel is preferable because pressure is uniformly applied to the entire laminate and there is no unevenness of pressurization, and more than one laminate can be processed at a time.
  • An autoclave device can be used as the pressurized container.
  • the pressure is about 0.2 MPa to 2 MPa, preferably 0.4 to 1.3 MPa.
  • the pressurization time varies depending on the pressurization conditions and is not particularly limited. However, if the pressure is too long, the processing time is increased and the cost is increased. Therefore, the holding time must be 6 hours or less under appropriate pressurization conditions. Is preferred. In particular, in the case of a pressurized container, it is preferable to hold for about 10 minutes to 3 hours after reaching the set pressure.
  • the fluidity of the translucent adhesive is temporarily increased, making it easy to degas bubbles that have been squeezed, and the bubbles are more likely to dissolve in the adhesive.
  • the heating condition is not particularly limited due to the heat resistance of each member constituting the display filter, which is about room temperature to 80 ° C.
  • the pressurizing process or the pressurizing and heating process is preferable because it can improve the adhesion after bonding between the respective members constituting the display filter.
  • a conductive mesh layer of a polymer film is formed, and a translucent adhesive layer is provided on the other main surface.
  • the specific example of the translucent adhesive material used for the translucent adhesive material layer is as above-mentioned, and is not specifically limited.
  • the thickness is not particularly limited, but is 0.5 m to 50 ⁇ m, preferably 1 ⁇ m to 30 ⁇ m. It is preferable that the surface on which the light-transmitting pressure-sensitive adhesive layer is formed and the surface to be bonded are previously improved in wettability by an easy adhesion treatment such as an easy adhesion coat or a corona discharge treatment.
  • a release film may be formed on the translucent adhesive layer. Ie at least Functional film z Translucent adhesive layer z Conductive mesh layer z Polymer film z Translucent adhesive layer) Z release film.
  • the release film is obtained by coating silicone or the like on the main surface of the polymer film in contact with the adhesive material layer.
  • the display filter of the present invention is mainly used for the purpose of blocking electromagnetic waves generated from various display cameras.
  • a preferred example is a plasma display filter.
  • the display filter of the present invention since the plasma display generates intense near-infrared rays, the display filter of the present invention has no practical problem, and it is necessary to cut not only electromagnetic waves but also near-infrared rays to the level.
  • the transmittance in the wavelength region 800 to 1000 nm needs to be 25% or less, preferably 15% or less, and more preferably 10% or less.
  • the display filter used in the plasma display is required to have a transmission color of-neutral gray or blue gray. This is also the power that the light emission characteristics and contrast of the plasma display need to be maintained or improved, and that whites with a slightly higher color temperature than standard whites may be preferred.
  • a color plasma display has insufficient color reproducibility, and it is preferable to selectively reduce unnecessary light emission from the phosphor or discharge gas which is the cause.
  • the emission spectrum of red display shows several emission peaks ranging from 580 nm to 700 nm, and the red emission is close to orange due to the emission peak on the relatively strong V and short wavelength side, and the color purity is improved. ! / There is a problem that becomes a thing.
  • These optical properties can be controlled by using a dye.
  • near-infrared absorbers can be used for near-infrared cuts, and dyes that selectively absorb unnecessary luminescence can be used to reduce unnecessary luminescence.
  • the color tone of the filter can also be made suitable by using a dye having an appropriate absorption in the visible region.
  • a method of containing a dye (1) at least one kind of dye and a polymer film or a resin board mixed with a transparent resin, (2) at least one kind of dye, a resin Or Resin monomer z A polymer film or resin plate that is dispersed and dissolved in a thick resin solution of organic solvent, and prepared by casting method. (3) At least one pigment, organic resin and organic binder In addition to the solvent, one or more of a paint, a coating on a polymer film or a resin board, and (4) a transparent adhesive containing at least one pigment can be selected. It is not limited.
  • inclusion as used in the present invention means that it is contained in the inside of a layer such as a substrate or a coating film or an adhesive material, and of course, is applied to the surface of the substrate or layer.
  • the above-mentioned dye is a general dye or pigment having a desired absorption wavelength in the visible region, or a near-infrared absorber, and the kind thereof is not particularly limited, and examples thereof include anthraquinone and phthalocyanine. , Methine, azomethine, oxazine, imonium, azo, styryl, coumarin, porphyrin, dibenzofuranone, diketopyrrolopyrrole, rhodamine, xanthene, pyromethene, dithiol, dithio Examples thereof include organic dyes that are generally commercially available, such as minimum compounds. The type 'concentration' is determined by the absorption wavelength of the dye 'absorption coefficient, the transmission characteristics required for the display filter-transmittance, and the type of the medium or coating to be dispersed' thickness. Absent.
  • the dye does not deteriorate significantly due to decomposition at 80 ° C, for example. It is suitable to have. In addition to heat resistance, some dyes have poor light resistance. If the plasma display emits light or the ultraviolet rays of the outside light are deteriorated by visible light, the material containing the ultraviolet absorber does not transmit the ultraviolet rays, so that the deterioration of the dye caused by the ultraviolet rays is reduced. In particular, it is important to use a dye that does not significantly deteriorate due to ultraviolet rays or visible light.
  • two or more kinds of dyes having different absorption wavelengths may be contained in one medium or a coating film, or a medium containing a dye.
  • the body may have two or more coating films.
  • the above methods (1) to (4) containing a dye include a high molecular film (A) containing a dye, a functional film containing a dye (C), and a dye.
  • the translucent adhesive (D1), translucent adhesive (D2), and other translucent adhesives or adhesives containing pigments used for laminating are in one or more forms of the present invention. Can be used as a display filter.
  • the dyes are easily deteriorated by ultraviolet rays.
  • Ultraviolet rays that display filters receive under normal use conditions are included in external light such as sunlight. Therefore, in order to prevent the deterioration of the dye by ultraviolet rays, at least one layer selected from the layer containing the dye itself and the layer on the human side that receives external light from the layer has a layer having an ultraviolet cutting ability. It is preferable that For example, when the polymer film (A) contains a pigment, the translucent pressure-sensitive adhesive layer and Z or the functional film contain a UV absorber or have a functional film having an ultraviolet cutting ability. The pigment can be protected from ultraviolet rays contained in outside light.
  • the transmittance in the ultraviolet region shorter than the wavelength of 380 nm is 20% or less, preferably 10% or less, more preferably 5% or less.
  • the functional film having the ultraviolet power function may be a coating film containing an ultraviolet absorber or an inorganic film that reflects or absorbs ultraviolet light.
  • Conventionally known UV absorbers such as benzotriazoles and benzophenones can be used, and their type 'concentration is dispersibility or solubility in the medium to be dispersed or dissolved' solubility, absorption wavelength 'absorption coefficient, It is determined by the thickness and is not particularly limited.
  • the layer or film having the ability to cut off ultraviolet rays has little absorption in the visible light region and does not significantly reduce the visible light transmittance or exhibit a color such as yellow.
  • a functional film containing a dye if a layer containing a dye is formed, a polymer film that is better if the film or functional film on the human side of the layer has UV-cutting ability contains the dye. If you want to have a functional film or functional layer that has the ability to cut off UV rays on the person side of the film, it is fine.
  • the dye may be deteriorated by contact with a metal.
  • dye it is still more preferable to arrange
  • the dye-containing layer is a functional film, a polymer film, or a translucent adhesive layer.
  • U which is particularly preferred to be a translucent adhesive layer.
  • the display filter of the present invention comprises a polymer film (A), a conductive mesh layer (B), a functional film (C), a translucent adhesive (D1), and a translucent adhesive (D2 ) Are configured in the order of (C) / (D1) / (B) / (A) / (D2), and preferably a conductive mesh comprising a conductive mesh layer (B) and a polymer film (A).
  • the film and functional film are bonded with a translucent adhesive (D1), and the main surface of the polymer film (A) opposite to the conductive mesh layer (B) is translucent adhesive (D2). Is attached.
  • the functional film (C) is attached to the person side
  • the translucent adhesive (D2) is attached to the display side.
  • a method of using the display filter of the present invention by providing it on the front surface of the display, a method of using it as a front filter plate using a transparent molded product (E) described later as a support, a transparent surface of the display is used.
  • a method of using it by attaching it through a light-sensitive adhesive (D2).
  • D2 light-sensitive adhesive
  • the filter for display is relatively easy to install, and the mechanical strength is improved by the support, which is suitable for protecting the display.
  • Examples of the transparent molded product include a glass plate and a translucent plastic plate. From the standpoint of mechanical strength, lightness, and resistance to cracking, a plastic plate is preferred, but a thermal stability glass plate with little deformation due to heat and the like can also be suitably used.
  • Specific examples of plastic plates include acrylic resin such as poly (methyl methacrylate) (PMMA), polycarbonate resin, and transparent ABS resin. However, these are not limited to these resins. Absent. In particular, PMMA can be suitably used because of its high transparency in a wide wavelength region and high mechanical strength.
  • the thickness of the plastic plate is not particularly limited as long as it has sufficient mechanical strength and rigidity to maintain flatness without bending. ⁇ About 10mm.
  • the glass is preferably a semi-tempered glass plate or a tempered glass plate that has been subjected to chemical strengthening or air-cooling strengthening to add mechanical strength.
  • the thickness is preferably about 1 to 4 mm, but is not particularly limited.
  • the transparent molded product can be subjected to various known pretreatments necessary before bonding the film, and a display filter. Colored frame printing such as black may be applied to the peripheral portion.
  • the composition of the display filter when using a transparent molded product is at least a functional film (C) Z light-transmitting adhesive (Dl) Z conductive mesh layer (B) Z polymer film (A) Z Translucent adhesive (D2) Z transparent molded product (E). Further, even if the functional film (C) is provided on the main surface opposite to the surface to be bonded to the translucent adhesive (D2) of the transparent molded product (E) through the translucent adhesive layer. good. In this case, it is not necessary to have the same configuration as the functional film (C) provided on the human side.For example, in the case of having an antireflection function, the back surface reflection of the display filter having the support is performed. Can be reduced.
  • a functional film (C2) such as an antireflection film may be formed on the main surface opposite to the surface to be bonded to the transparent adhesive (D2) of the same transparent molded product (E).
  • the functional film (C2) can be installed on the display with the human side facing, but as described above, the layer having the ability to cut off ultraviolet rays is placed on the human layer from the dye-containing layer and the dye-containing layer. U, preferred to install.
  • a window-like electromagnetic wave shielding filter having a translucent conductive layer is installed like the display filter of the present invention.
  • the electromagnetic wave is absorbed in the conductive layer and then induces an electric charge, the electric charge is not released by taking the ground.
  • the display filter becomes an antenna again, the electromagnetic wave is oscillated and the electromagnetic wave shielding ability is obtained. Decreases. Therefore, the display filter and the ground part of the display body must be in electrical contact.
  • the above-mentioned translucent adhesive material (D1) and functional film (C) need to be formed on the conductive mesh layer (B) leaving a conductive part capable of establishing external force conduction. is there.
  • the shape of the conducting portion is not particularly limited, but it is important that there is no gap for electromagnetic wave leakage between the display filter and the display body. Therefore, it is preferable that the conduction part is provided continuously at the peripheral part of the conductive mesh layer (B). That is, it is preferable that the conductive portion is provided in a frame shape except for the central portion which is the display portion of the display.
  • the conductive portion may be a mesh pattern layer or a pattern layer that is not patterned, for example, a solid layer of metal foil, but the electrical contact with the ground portion of the display body is good. In order to achieve this, it is preferable that the conductive portion be patterned like a metal foil solid layer.
  • the conductive part is not patterned, such as a solid metal foil, and if Z or the mechanical strength of the conductive part is sufficiently strong, the conductive part can be used as an electrode as it is. It is.
  • an electrode on the conducting part it is preferable to form an electrode on the conducting part to protect the conducting part and to make good electrical contact with the earth part when Z or the conducting part is a mesh pattern layer.
  • the shape of the electrode is not particularly limited, but it is preferable that the electrode is formed so as to cover all the conductive portions.
  • the material used for the electrode is composed of a single substance or two or more of silver, copper, nickel, aluminum, chromium, iron, zinc, carbon, etc. in terms of conductivity, contact resistance and adhesion to the transparent conductive film.
  • An alloy, a synthetic resin and a single substance or a mixture of these alloys, or a paste that also has a mixture force between a borosilicate glass and these single substances or an alloy can be used. Conventionally known methods can be employed for printing and coating the paste.
  • Commercially available conductive tape can also be suitably used.
  • the conductive tape is conductive on both sides, and a single-sided adhesive type and a double-sided adhesive type using a carbon-dispersed conductive adhesive can be suitably used.
  • the thickness of the electrode is also not particularly limited, but is about several / zm to several mm.
  • a display filter having excellent optical characteristics which can maintain or improve the image quality without significantly impairing the luminance of the plasma display.
  • there is a possibility of harming the health of the plasma display and it has excellent electromagnetic shielding ability to block electromagnetic waves.
  • a display filter having excellent weather resistance can be provided at low cost.
  • the first and second undercoat layers having the following composition were applied to both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 m).
  • Polystyrene fine particles (average particle size 3 ⁇ ) 0.05g
  • Colloidal silica (Snowtex ZL: particle size 70 ⁇ : L 00 m manufactured by Nissan Chemical Co., Ltd.)
  • This coating solution was applied at a drying temperature of 170 ° C for 2 minutes so that the dry film thickness was 0.1 l / z m.
  • Hexacloammonium rhodate ammonium (0.001% NaCl 20% aqueous solution) 7ml
  • Hexaclo oral iridium (III) potassium (0.005% KC1 20% aqueous solution) and hexachloro oral iridium ammonium (0.001% NaC 120% aqueous solution) used in the 3rd liquid are powdered with KC1 20% aqueous solution and NaC 120% respectively. It was dissolved in an aqueous solution and prepared by heating at 40 ° C for 120 minutes.
  • the plate was washed with water by the floating method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the ionic precipitation agent 1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide precipitated. Next, about 3 liters of the supernatant was removed (first water wash). After adding 3 liters of distilled water, sulfuric acid was added until the silver halide settled. Again 3 liters of the supernatant was removed (second water wash). The same operation as the second washing was repeated once more (third washing) to complete the washing and desalting process.
  • the coating solution for each layer was adjusted for viscosity by adding a thickener represented by the following structure (Z).
  • the sample used in the present invention formed a knock layer and an antistatic layer having the following composition.
  • 1,3-Divinylsulfonyl-2-propanol 60mg / m 'Polymethylmethalate fine particles (average particle size 6.5m) 30mg / m' Liquid paraffin / 8mg, m Compound (Cpd-7) 120mg / m 'Nitric acid Calcium 20mg / m Preservative (Proxel) 12mgZ
  • the antistatic layer and the back layer were coated in the order of the antistatic layer and the back layer in the order of the curtain coater method while simultaneously adding a hardener solution, and a cold air set zone (5 ° C).
  • a hardener solution and a cold air set zone (5 ° C).
  • the coating solution showed a sufficient setting property.
  • both sides were simultaneously dried in the drying zone. In this way, sample (1-1) was prepared.
  • the obtained sample (1-1) had an applied silver amount of 7.6 g / m 2 , an Ag / gelatin mass ratio of the emulsion layer of 6.9, a swelling ratio of 209%, and the product of the Ag / gelatin mass ratio and the swelling ratio was 13.2. It was a photosensitive material having an emulsion layer as the uppermost layer.
  • the swelling ratio of the emulsion layer was determined as follows. That is, by observing a section of the dried sample with a scanning electron microscope, the thickness (a) of the emulsion layer at the time of drying is obtained, immersed in distilled water at 25 ° C for 1 minute, and then freeze-dried with liquid nitrogen. By observing the slice of the sample with a scanning electron microscope, the film thickness (b) of the emulsion layer during swelling was determined, and the swelling ratio was calculated by the following equation.
  • a running process (until the cumulative replenishment amount of the developer became three times the tank capacity) was performed with the processing steps and processing solutions shown below.
  • Black and white development processing (temperature 30 ° C, time 40 seconds), fixing processing (temperature 30 ° C, time 40 seconds), hardening processing (temperature 30 ° C, time 40 seconds) for the exposed silver halide film
  • an electroplating treatment was applied to the halogenated silver film that had been subjected to the hardening process. It was divided into times.
  • an antifouling treatment was performed to obtain a conductive film.
  • composition of each treatment solution is as follows.
  • dartal aldehyde was used as the additive for hardening.
  • a comparative example there were also used a case where no additive was added without adding dartalaldehyde, and a case where sulfuric acid was used without containing dartalaldehyde.
  • the swelling rate of the obtained conductive film was determined as follows. That is, by observing a section of the light-transmitting part at the time of drying with a scanning electron microscope, the film thickness (a) of the light-transmitting part layer at the time of drying was obtained, and after being immersed in distilled water at 25 ° C for 1 minute.
  • the thickness (b) of the light-transmitting part layer at the time of swelling was determined by observing a piece of the sample freeze-dried with liquid nitrogen with a scanning electron microscope, and the swelling ratio was calculated by the following equation.
  • the sample after the running treatment was visually evaluated according to the following four steps.
  • ⁇ ⁇ ⁇ 'Vertical gymra is a force that is barely acceptable.
  • Example 1 and Comparative Examples 1 and 2 were sampled.
  • the sampled photosensitive materials of Example 1 and Comparative Examples 1 and 2 were cut into 35 mm ⁇ 45 mm, and the surface resistance was measured.
  • Lorestar GP MCP-T600 / ASP probe manufactured by Mitsubishi Chemical was used for the surface resistance.
  • Table 2 shows the measurement results of the surface resistance of the photosensitive materials of Example 1 and Comparative Examples 1 and 2.
  • Example 1 As shown in Table 1, in Example 1 in which dartalaldehyde was added as a hardener, it was found that uneven stripes were suppressed and plating uniformity was improved.
  • Example 1 The same procedure as in Example 1 was performed, except that the pretreatment of Example 1 was changed to the following prescription. As a result, similar to Example 1, good results were obtained.
  • Sample (3-1) to (3-4) were obtained by adjusting the amount of hardener (Cpd-7) added and the amount of gelatin applied to sample (1-1) of Example 1. These samples were used for the same evaluation as in Example 1 except that the conditions for the dura treatment were changed. The results obtained are shown in Table 3.
  • the dry film thickness of the light-transmitting part obtained was obtained by observing a section of the light-transmitting part during drying with a scanning electron microscope to obtain the film thickness (a) of the light-transmitting part layer during drying. It was.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

La présente invention concerne un procédé pour réduire les variations de plaquage et la contamination d'un matériau photosensible pendant un procédé de plaquage électrolytique lorsqu'un matériau photosensible en halogénure d'argent est soumis à une exposition et au développement de motifs et puis au plaquage électrolytique. Elle concerne aussi un film conducteur, en particulier un film de blindage électromagnétique ayant en même temps une conductivité uniforme et élevée et un facteur de transmission lumineuse élevé, qui est produit par le procédé décrit ci-dessus. Elle concerne en outre un affichage d'image comprenant un tel film. L'invention concerne de manière spécifique un procédé pour former un film conducteur, qui se caractérise en ce qu'il comprend une phase de durcissement de film lors de laquelle une surface de film ayant une résistivité en surface de 1-1000 Ω/□ est faite réagir à une solution de durcissement de film. Elle concerne également de manière spécifique un film conducteur et un film de blindage électromagnétique obtenus par un tel procédé, ainsi qu'un affichage d'image comprenant un tel film.
PCT/JP2006/326153 2005-12-28 2006-12-27 Film conducteur et son procede de production, film de blindage electromagnetique et son procede de production, et ecran a plasma WO2007077898A1 (fr)

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JP2005-379199 2005-12-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011131500A (ja) * 2009-12-24 2011-07-07 Fujifilm Corp 導電膜形成用感光材料、及び導電膜の製造方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6147010A (ja) * 1984-08-13 1986-03-07 東レ株式会社 被覆透明導電パネル
JPH06161016A (ja) * 1992-07-07 1994-06-07 Eastman Kodak Co 写真材料の硬化方法及び硬化用組成物
JP2002083518A (ja) * 1999-11-25 2002-03-22 Sumitomo Metal Mining Co Ltd 透明導電性基材とその製造方法並びにこの透明導電性基材が適用された表示装置、および透明導電層形成用塗液とその製造方法
JP2004127719A (ja) * 2002-10-02 2004-04-22 Nippon Hoso Kyokai <Nhk> 透明導電性フィルム及び表示装置
JP2004221564A (ja) * 2002-12-27 2004-08-05 Fuji Photo Film Co Ltd 透光性電磁波シールド膜の製造方法及び透光性電磁波シールド膜
JP2005183059A (ja) * 2003-12-17 2005-07-07 Mitsubishi Paper Mills Ltd 透明導電性フィルムの製造方法。
JP2006332459A (ja) * 2005-05-27 2006-12-07 Fujifilm Holdings Corp 導電性金属膜形成用感光材料、導電性金属膜の製造方法、導電性金属膜、及びプラズマディスプレイパネル用透光性電磁波シールド膜
JP2006336099A (ja) * 2005-06-06 2006-12-14 Fujifilm Holdings Corp めっき処理方法、透光性導電性膜、及び透光性電磁波シールド膜
JP2007095408A (ja) * 2005-09-28 2007-04-12 Mitsubishi Paper Mills Ltd 導電性材料およびその製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6147010A (ja) * 1984-08-13 1986-03-07 東レ株式会社 被覆透明導電パネル
JPH06161016A (ja) * 1992-07-07 1994-06-07 Eastman Kodak Co 写真材料の硬化方法及び硬化用組成物
JP2002083518A (ja) * 1999-11-25 2002-03-22 Sumitomo Metal Mining Co Ltd 透明導電性基材とその製造方法並びにこの透明導電性基材が適用された表示装置、および透明導電層形成用塗液とその製造方法
JP2004127719A (ja) * 2002-10-02 2004-04-22 Nippon Hoso Kyokai <Nhk> 透明導電性フィルム及び表示装置
JP2004221564A (ja) * 2002-12-27 2004-08-05 Fuji Photo Film Co Ltd 透光性電磁波シールド膜の製造方法及び透光性電磁波シールド膜
JP2005183059A (ja) * 2003-12-17 2005-07-07 Mitsubishi Paper Mills Ltd 透明導電性フィルムの製造方法。
JP2006332459A (ja) * 2005-05-27 2006-12-07 Fujifilm Holdings Corp 導電性金属膜形成用感光材料、導電性金属膜の製造方法、導電性金属膜、及びプラズマディスプレイパネル用透光性電磁波シールド膜
JP2006336099A (ja) * 2005-06-06 2006-12-14 Fujifilm Holdings Corp めっき処理方法、透光性導電性膜、及び透光性電磁波シールド膜
JP2007095408A (ja) * 2005-09-28 2007-04-12 Mitsubishi Paper Mills Ltd 導電性材料およびその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011131500A (ja) * 2009-12-24 2011-07-07 Fujifilm Corp 導電膜形成用感光材料、及び導電膜の製造方法

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