WO2007077898A1 - Conductive film and method for producing same, electromagnetic shielding film and method for producing same, and plasma display panel - Google Patents

Conductive film and method for producing same, electromagnetic shielding film and method for producing same, and plasma display panel 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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French (fr)
Japanese (ja)
Inventor
Hideaki Nomura
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Fujifilm Corporation
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Publication of WO2007077898A1 publication Critical patent/WO2007077898A1/en

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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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Abstract

Disclosed is a method for reducing plating variations and contamination of a photosensitive material during an electrolytic plating process when a silver halide photosensitive material is subjected to a pattern exposure, development and then to electrolytic plating. Also disclosed is a conductive film, particularly an electromagnetic shielding film having uniform and high conductivity and high light transmittance at the same time, which is produced by the above-described method. Further disclosed is an image display comprising such a film. Specifically disclosed is a method for forming a conductive film, which is characterized by comprising a film-hardening step wherein a film surface having a surface resistivity of 1-1000 Ω/□ is reacted with a film-hardening solution. Also specifically disclosed are a conductive film and electromagnetic shielding film obtained by such a method, and an image display comprising such a film.

Description

明 細 書  Specification
導電性膜、その製造方法、電磁波シールド膜、その製造方法及びプラズ マディスプレイパネノレ  Conductive film, method for producing the same, electromagnetic wave shielding film, method for producing the same, and plasma display panel
技術分野  Technical field
[0001] 本発明は、導電性膜及びその製造方法に関する。さらに詳しく説明すると均質で高 い導電性と優れた透光性を併せ有する導電性膜の製造方法に関する。また、得られ た導電性膜を利用した透明性電磁波シールド膜及び透明電極に関する。さらに該電 磁波シールド膜や透明電極を装備した CRT (陰極線管）、 PDP (プラズマディスプレ ィパネル）、液晶、 EL (エレクト口ルミネッセンス）、 FED (フィールドェミッションデイス プレイ)などのディスプレイ、電子レンジ、電子機器などにも関する。  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. In addition, 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.
また、本発明によって得られる導電性膜はこれらの画像表示素子のほかに撮像用 半導体素子やプリント配線板などにも用いられる。  In addition to these image display elements, the conductive film obtained by the present invention is also used for imaging semiconductor elements and printed wiring boards.
背景技術  Background art
[0002] 近年、各種の電気設備や電子応用設備の利用の増加に伴い、電磁波障害 (Elect ro— Magnetic Interference : EMI)が急増している。 EMIは、電子、電気機器の 誤動作、障害の原因になるほか、これらの装置のオペレーターにも健康障害を与え ることが指摘されている。このため、電子'電気機器の電磁波放出の強さを規格又は 規制内に抑えることが要求されて 、る。  [0002] In recent years, electromagnetic interference (Electro-Magnetic Interference: EMI) has increased rapidly with the increase in the use of various types of electrical equipment and electronic application equipment. In addition to causing malfunctions and failures of electronic and electrical equipment, EMI has been pointed out to cause health problems for operators of these devices. For this reason, it is required to suppress the electromagnetic wave emission intensity of electronic and electrical equipment within the standard or regulation.
[0003] 上記 EMIの対策のために電磁波をシールドする方法が種々提案され、用いられて いるが、 CRT、 PDPなどに適用する場合には、電磁波シールド能にカ卩えて画面に表 示される画像や文字等を視認する必要があるため、透明性も要求される。  [0003] Various methods for shielding electromagnetic waves have been proposed and used for EMI countermeasures, but when applied to CRT, PDP, etc., images displayed on the screen in consideration of electromagnetic shielding performance Therefore, transparency is also required.
[0004] 特に、 PDPは、 CRT等と比較すると多量の電磁波を発生するため、より強い電磁 波シールド能が求められており、 CRT用の透光性電磁波シールド材料に必要な表 面抵抗値は凡そ 300 Ω Zsq以下であるのに対し、 PDP用の透光性電磁波シールド 材料では、 2. 5 Ω Zsq以下であることが好ましぐ PDPを用いた民生用プラズマテレ ビにおいては、 1. 5 Ω Zsq以下とすることが求められ、より望ましくは 0. l QZsq以
Figure imgf000002_0001
ヽ導電性が要求されて ヽる。 透明性に関しても、 CRT用として凡そ 70%以上の透過率が要求されているのに対 して、 PDP用として 80%以上の透過率が望まれている。 [0004] In particular, since PDP generates a larger amount of electromagnetic waves than CRT, etc., stronger electromagnetic shielding ability is required, and the surface resistance value required for translucent electromagnetic shielding materials for CRT is While it is approximately 300 Ω Zsq or less, translucent electromagnetic shielding material for PDP is preferably 2.5 Ω Zsq or less for consumer plasma television using PDP, 1.5 Ω Zsq or less, more preferably 0.l QZsq or less
Figure imgf000002_0001
ヽ Conductivity is required. In terms of transparency, a transmittance of approximately 70% or more is required for CRT, whereas a transmittance of 80% or more is desired for PDP.
[0005] 上記の問題を解決するための開口部を有する金属メッシュを利用して電磁波シー ルド性と透明性とを両立させる材料'方法として、例えば導電性繊維をメッシュにした シールド材、無電解めつき触媒を印刷法で格子状パターンとして印刷してそのバタ ーンに無電解めつきを行う方法、無電解めつき触媒含有フォトレジストをメッシュ状に パターン形成させてその上に無電解めつきする方法、フォトリソグラフィ一法でエッチ ング加工して金属薄膜のメッシュを形成する方法、など多様な方法がこれまで提案さ れている。し力しながら、これらの方法は、製造工程は煩雑かつ複雑で生産コストが 高価になる、格子模様の交点部等で線幅が不均一になる、モアレが生じる、あるいは 透光性と導電性の一方又は両方が不足する、などの問題がある。  [0005] As a method of 'a material that achieves both electromagnetic shielding properties and transparency by using a metal mesh having an opening for solving the above-mentioned problem, for example, a shielding material in which conductive fibers are made into a mesh; A method in which a plating catalyst is printed as a grid pattern by electroless printing and electroless plating is applied to the pattern, and a non-electrolytic plating catalyst-containing photoresist is formed into a mesh pattern and electroless plating is applied on the pattern. 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. However, in these methods, the manufacturing process is complicated and complicated, and the production cost is expensive, the line width is uneven at the intersection of the lattice pattern, etc., moire occurs, or translucency and conductivity. There is a problem that one or both of them are insufficient.
[0006] その改善手段として、銀塩感光材料を用いた導電性金属銀パターンを形成する方 法が提案されている。  [0006] As a means for improving this, a method of forming a conductive metal silver pattern using a silver salt photosensitive material has been proposed.
銀塩感光材料は、カラーネガフィルム、黒白ネガフィルム、映画用フィルム、カラーリ バーサルフィルム等の写真フィルム、カラーペーパー、黒白印画紙などの写真用印 画紙等として従来カゝら広く用いられているが、この材料を利用すればパターン露光と 現像による写真的方法によって簡易なプロセスでパターン状の金属銀を得ることがで き、この金属銀は、感光材料の構成や現像方法次第では導電性を利用することが可 能である。 1960年代に物理現像核に銀を沈着させる銀塩拡散転写法によって導電 性金属銀薄膜パターンを形成する方法が、特許文献 1に開示されている。また同様 の銀塩拡散転写法を利用して得た光透過性のない均一な銀薄膜がマイクロ波減衰 機能を有することが特許文献 2に開示されている。この原理をインスタント黒白スライ ドフィルムに適用して簡便に露光'現像を行って導電性パターンを形成する方法が、 非特許文献 1及び特許文献 3に記載されている。また、銀塩拡散転写法の原理によ つて、プラズマディスプレイ用の表示電極に利用可能な導電性の銀膜を形成する方 法が特許文献 4に記載されて 、る。  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. Further, 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.
[0007] しカゝしながら、このような方法で得た導電性金属銀膜は、画像表示や画像形成素子 用としては透光性が不十分であり、また CRTや PDPなどのディスプレイの画像表示 面から放射される電磁波を、画像表示を妨害せずに、遮蔽する能力も不十分であつ た。 [0007] However, 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.
また、高い導電性を得ることも困難で、導電性を高めるために厚い銀膜を得ようとす ると、透明性が損なわれる問題があった。したがって、上記銀塩拡散転写法や物理 現像法をそのまま用いても、電子ディスプレイ機器の画像表示面力ゝらの電磁波をシ 一ルドするのに好適な、光透過性と導電性の優れた透光性電磁波シールド材料は 得ることができな力つた。  In addition, it is difficult to obtain high conductivity, and there is a problem that transparency is impaired when a thick silver film is obtained to increase conductivity. Therefore, even if the above silver salt diffusion transfer method or physical development method is used as it is, it is suitable for shielding electromagnetic waves such as image display surface strength of electronic display devices, and has excellent light transmission and conductivity. The photoelectromagnetic shielding material was unobtainable.
また、銀塩拡散転写法や物理現像法を用いないで、通常の市販のネガフィルムと ネガ型現像処理を利用したのでは、導電性と透明性を両立させる点にぉ 、て一層不 利であり、 CRTや PDPの透光性電磁波シールド材料として利用するには不十分なも のであった。  In addition, using a commercially available negative film and a negative development process without using the silver salt diffusion transfer method or the physical development method is more disadvantageous in terms of achieving both conductivity and transparency. Therefore, it was insufficient for use as a light-transmitting electromagnetic shielding material for CRT and PDP.
[0008] このようなことから、特許文献 5には、銀塩感光材料を用いて現像によりパターン形 成した後、現像銀にさらにめつき又は物理現像処理を加える透光性電磁波シールド 材料の製造方法が提案されるに至った。この方法は、上記問題に対して改善効果は 見られるが、現像銀が高抵抗性であるためか給電ローラーから現像済み感光材料へ の給電が必ずしも円滑でなぐメツキむら (電解むら）が起こり易い。とくにめつきの初 期課程で、また現像済みフィルムを連続搬送しながらめっきする連続処理方式にお いて、現像銀上への金属の沈積速度の局部的変動によって導電性や透光性の均一 性が損われることが判った。さらなる透明性と導電性の両立させる手段が求められて いる。  [0008] For this reason, 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. . In particular, in the initial process of plating, and in the continuous processing method in which the developed film is plated while continuously transporting the film, 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.
[0009] 特許文献 1：特公昭 42— 23746号公報  [0009] Patent Document 1: Japanese Patent Publication No. 42-23746
特許文献 2：特公昭 43— 12862号公報  Patent Document 2: Japanese Patent Publication No. 43-12862
特許文献 3 :国際公開第 01Z51276号パンフレット  Patent Document 3: Pamphlet of International Publication No.01Z51276
特許文献 4 :特開 2000— 149773号公報  Patent Document 4: Japanese Unexamined Patent Publication No. 2000-149773
特許文献 5 :特開 2004— 221564号公報  Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-221564
非特許文献 1 :アナリティカル 'ケミストリー（Analytical Chemistry)、 2000年発刊、第 7 2卷、 645項  Non-Patent Document 1: Analytical 'Chemistry, Published 2000, No. 72, 645
発明の開示 発明が解決しょうとする課題 Disclosure of the invention Problems to be solved by the invention
[0010] 本発明は、かかる事情に鑑みなされたものであり、本発明の目的は、ハロゲンィ匕銀 写真感光材料をパターン露光と現像を行って得たパターン状現像銀上にさらに電解 めっきする導電性膜形成方法において電解めつき工程で生じるメツキムラを低減する ことである。また、メツキムラを解決して、高い導電性を有する導電性膜、とりわけ高い 導電性と高 ヽ透光性とを同時に有する透光性導電性膜、中でも高 ヽ電磁波シールド 性と高い透明性とを同時に有する電磁波シールド膜を提供すること、並びにそれらの 膜の安価で大量生産可能で、かつ大量製造しても電磁波シールド能が劣化しな 、 製造方法を提供することである。さらに、 PDPをはじめとするディスプレイ装置などに 装備させる高透光性と高導電性を具備する電磁波シールド膜を提供することである。 課題を解決するための手段  [0010] 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. In addition, by solving the unevenness of the plating, 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. Furthermore, it is to provide an electromagnetic wave shielding film having high translucency and high conductivity to be equipped in a display device such as a PDP. Means for solving the problem
[0011] 本発明者らは、微細な現像銀表面への電着過程を詳細に検討した結果、電着ムラ は、メツキ過程の初期に顕著に生じること、めっき浴の疲労が進むと電着量の割に透 光性の低下が増大することが判った。さらに現像済み感光材料のメツキ液への浸漬 に先行して該感光材料を硬膜溶液で前浴処理すると電着ムラは抑止されることも判 明した。これらの知見に基づいて導電性と透光性が確保される現像'めっき前浴 '電 解めつきを含む一連の処理工程を案出して本発明を完成するに至った。 [0011] As a result of detailed examination of the electrodeposition process on the fine developed silver surface, 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.
[0012] 本発明は以下のとおりである。  [0012] The present invention is as follows.
(1) 支持体上に、導電性金属部及び光透過性部を含む導電性機能層とを有し、 前記光透過性部の膨潤率が 180%以下であることを特徴とする導電性膜。  (1) 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 .
(2) 前記導電性膜の表面抵抗が 2. 5 Ω /sq以下であり、かつ Z又は前記光透過 性部の透過率が 95%以上であることを特徴とする（1)に記載の導電性膜。  (2) The conductive film according to (1), wherein the surface resistance of the conductive film is 2.5 Ω / sq or less, and the transmittance of Z or the light transmissive part is 95% or more. Sex membrane.
(3) 前記光透過性部の乾燥膜厚が 2. 0 μ m以下であることを特徴とする（1)また は（2)に記載の導電性膜。  (3) The conductive film according to (1) or (2), wherein the dry thickness of the light-transmitting portion is 2.0 μm or less.
(4) 前記光透過性部が実質的に水溶性ポリマー力 なることを特徴とする（1)〜（ 3)の 、ずれかに記載の導電性膜。  (4) The conductive film according to any one of (1) to (3), wherein the light-transmitting portion has substantially a water-soluble polymer force.
(5) 表面抵抗が 1〜： ίΟΟΟ Ω Ζ口のフィルムの表面に硬膜溶液を反応させる硬膜 工程を有することを特徴とする導電性膜の製造方法。 (6) 前記フィルムが支持体上にハロゲン化銀乳剤層を含む少なくとも 1層の親水 性コロイド層を有するハロゲンィ匕銀写真感光材料であることを特徴とする（5)に記載 の導電性膜の製造方法。 (5) 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: ΟΟΟΟΟΟΩ. (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.
(7) 前記硬膜溶液が、硬膜剤を含有し、該硬膜剤がゼラチンを硬膜する作用を有 する化合物であることを特徴とする（5)または (6)に記載の導電性膜の製造方法。 (7) The conductive film according to (5) or (6), wherein the hardening solution contains a hardening agent, and the hardening agent has a function of hardening gelatin. A method for producing a membrane.
(8) 前記硬膜剤が、ホルムアルデヒド、ビバリルアルデヒド、ダルタルアルデヒド、 琥珀アルデヒド、カリ明ばん、クロム明ばん、および硫酸アルミニウム力 選択される 化合物であることを特徴とする（7)に記載の導電性膜の製造方法。 (8) 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.
(9) (5)〜（8)の 、ずれかに記載の導電性膜の製造方法によって得られたことを 特徴とする導電性膜。  (9) A conductive film obtained by the method for producing a conductive film according to any one of (5) to (8).
(10) (5)〜（8)の 、ずれかに記載の導電性膜の製造方法によって製造されたこと を特徴とする電磁波シールド膜。  (10) An electromagnetic wave shielding film produced by the method for producing a conductive film according to any one of (5) to (8).
(11) (5)〜（8)のいずれかに記載の導電性膜の製造方法によって製造された電磁 波シールド膜の表面抵抗が 2. 5 Ω Zsq以下であることを特徴とする電磁波シールド 膜。  (11) 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 Ω Zsq or less. .
(12) 表面抵抗が 1. 5 Ω /sq以下であることを特徴とする（11)に記載の電磁波シ 一ルド膜。  (12) The electromagnetic shielding film according to (11), wherein the surface resistance is 1.5 Ω / sq or less.
(13) 支持体上にハロゲンィ匕銀乳剤層を有するハロゲンィ匕銀フィルムを露光して 現像し、金属銀部を形成する現像工程と、  (13) a development step of exposing and developing a halogenated silver film having a halogenated silver emulsion layer on a support to form a metallic silver portion;
前記金属銀部が形成されたフィルムの表面に、硬膜剤を含有する硬膜溶液を反応 させる硬膜工程と、  A hardening step of reacting a hardening solution containing a hardening agent on the surface of the film on which the metallic silver portion is formed;
前記硬膜工程が施されたフィルムの金属銀部に対し、電解めつき処理を施す電解 めっき処理工程と、  An electroplating treatment step for subjecting the metallic silver part of the film subjected to the hardening step to an electroplating treatment;
を有する導電性膜の製造方法。 The manufacturing method of the electroconductive film which has this.
本発明の製造方法では、フィルム表面を硬膜溶液で前浴処理することで、電解め つき処理工程における電着ムラが抑止され、得られる導電性膜の表面抵抗が十分に 低減できる。このように得られる導電性膜の表面抵抗が十分に低減できる理由は定 かではないが、本発明者らはこの理由を以下のように推定する。上記ハロゲン化銀乳 剤層は、ハロゲンィ匕銀乳剤層の硬膜剤の含有量が少ないため、その膜質が弱く電解 めっき処理の際に傷が発生し易ぐ電着ムラの原因になる。しかし、本発明では、硬 膜工程により銀塩含有層の膜質を架橋などにより強化でき、電解めつき処理が施さ れても傷の発生を抑制でき、電解めつき処理における電着ムラを防止することができ る。 In the production method of the present invention, by pre-bathing the film surface with a hardening solution, uneven electrodeposition in the electrolytic plating process is suppressed, and the surface resistance of the resulting conductive film can be sufficiently reduced. Although the reason why the surface resistance of the conductive film thus obtained can be sufficiently reduced is not clear, the present inventors presume this reason as follows. Silver halide milk Since the agent layer has a small amount of hardener in the silver halide silver halide emulsion layer, its film quality is weak, and scratches are easily generated during the electroplating process, causing uneven electrodeposition. However, in the present invention, 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.
(14) 前記ハロゲンィ匕銀乳剤層がハロゲンィ匕銀及びバインダーを含有することを 特徴とする（13)に記載の導電性膜の製造方法。  (14) The method for producing a conductive film as described in (13), wherein the silver halide silver halide emulsion layer contains silver halide silver and a binder.
(15) 前記ハロゲンィ匕銀乳剤層における銀 (Ag)及びバインダー (B)の含有質量 比が下記式（1)の範囲にあることを特徴とする（14)に記載の導電性膜の製造方法。  (15) The method for producing a conductive film according to (14), wherein a content ratio of silver (Ag) and binder (B) in the halogenated silver emulsion layer is in the range of the following formula (1): .
AgZB = 3〜15 (1)  AgZB = 3 to 15 (1)
(16) AgZバインダー体積比が 1Z4以上の銀塩含有層を用いることを特徴とす る（14)または（15)に記載の導電性膜の製造方法。  (16) The method for producing a conductive film as described in (14) or (15), wherein a silver salt-containing layer having an AgZ binder volume ratio of 1Z4 or more is used.
(17) 前記バインダーがゼラチンであることを特徴とする（14)〜（16)のいずれか に記載の導電性膜の製造方法。  (17) The method for producing a conductive film as described in any one of (14) to (16), wherein the binder is gelatin.
(18) 前記硬膜剤がゼラチンを硬膜する作用を有する化合物であることを特徴と する（13)〜（17)の 、ずれかに記載の導電性膜の製造方法。  (18) The method for producing a conductive film according to any one of (13) to (17), wherein the hardener is a compound having a function of hardening gelatin.
(19) 前記硬膜剤が、ホルムアルデヒド、ビバリルアルデヒド、ダルタルアルデヒド、 琥珀アルデヒド、カリ明ばん、クロム明ばん、および硫酸アルミニウム力 選択される 化合物であることを特徴とする（13)〜（18)の ヽずれかに記載の導電性膜の製造方 法。  (19) 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).
(20) 前記硬膜剤がダルタルアルデヒド又は硫酸アルミニウムであることを特徴と する（13)〜（19)の 、ずれかに記載の導電性膜の製造方法。  (20) The method for producing a conductive film according to any one of (13) to (19), wherein the hardener is dartalaldehyde or aluminum sulfate.
(21) 前記硬膜溶液が硬膜剤を 0.005〜1.000mol/L含有することを特徴とする（13 )〜（20)の 、ずれかに記載の導電性膜の製造方法。  (21) The method for producing a conductive film according to any one of (13) to (20), wherein the hardening solution contains a hardening agent in an amount of 0.005 to 1.000 mol / L.
(22) 前記硬膜溶液がさらに膨潤抑制作用のある化合物を含有することを特徴と する（13)〜（21)の 、ずれかに記載の導電性膜の製造方法。  (22) The method for producing a conductive film according to any one of (13) to (21), wherein the dura mater solution further contains a compound having a swelling-inhibiting action.
(23) 露光部に前記金属銀部を形成し、未露光部に光透過性部を形成することを 特徴とする（13)〜（22)の ヽずれかに記載の導電性膜の製造方法。 (24) 前記光透過性部が実質的に物理現像核を有しないことを特徴とする（13) 〜（23)の 、ずれかに記載の導電性膜の製造方法。 (23) The method for producing a conductive film according to any one of (13) to (22), wherein the metal silver portion is formed in the exposed portion and the light transmissive portion is formed in the unexposed portion. . (24) The method for producing a conductive film according to any one of (13) to (23), wherein the light-transmitting portion has substantially no physical development nucleus.
(25) (13)〜（24)のいずれかに記載の製造方法により得られることを特徴とする 、導電性金属部及び光透過性部を有するプラズマディスプレイパネル用電磁波シー ルド膜。  (25) An electromagnetic shielding film for a plasma display panel having a conductive metal portion and a light transmissive portion, which is obtained by the production method according to any one of (13) to (24).
(26) (11)又は（12)に記載の電磁波シールド膜を有することを特徴とするプラズ マディスプレイパネル用光学フィルター。  (26) An optical filter for a plasma display panel, comprising the electromagnetic wave shielding film according to (11) or (12).
(27) (13)〜（24)のいずれかに記載の製造方法により得られた電磁波シールド 膜を有することを特徴とするプラズマディスプレイパネル用光学フィルター。  (27) 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).
(28) (26)又は（27)に記載の光学フィルターを有することを特徴とするプラズマ ディスプレイパネル。  (28) A plasma display panel comprising the optical filter according to (26) or (27).
(29) (13)〜（24)のいずれかに記載の製造方法により得られた電磁波シールド 膜を有することを特徴とするプラズマテレビ。  (29) A plasma television comprising an electromagnetic wave shielding film obtained by the production method according to any one of (13) to (24).
(30) 表面抵抗が 1〜： L 000 Ω Z口のフィルム表面に連続して硬膜溶液による前 処理を施したのち電解めつきを施すことを特徴とする導電性膜の製造方法。  (30) A surface resistance of 1 to: L 000 Ω 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.
(31) 支持体上にハロゲンィ匕銀乳剤層を含む少なくとも 1層の親水性コロイド層を 有するハロゲン化銀写真感光材料に連続して現像処理と該現像処理によって形成さ れた金属銀部への電解めつき処理を施す導電性膜の製造方法にぉ ヽて、現像処理 済みハロゲン化銀感光材料に電解めつき処理を施す直前に硬膜溶液による前処理 を施すことを特徴とするの導電性膜の製造方法。  (31) 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.
(32) 前記硬膜溶液中の硬膜剤がゼラチンを硬膜する作用を有する化合物である ことを特徴とする上記 (30)または (31)に記載の導電性膜の製造方法。  (32) The method for producing a conductive film as described in (30) or (31) above, wherein the hardening agent in the hardening solution is a compound having a function of hardening gelatin.
(33) 支持体上にハロゲンィ匕銀乳剤層を含む少なくとも 1層の親水性コロイド層を 有するハロゲン化銀写真感光材料に現像処理を施して金属銀部を形成し、該金属 銀部に硬膜溶液処理と電解めつき処理を順次施すことを特徴とする電磁波シールド 膜の製造方法。  (33) 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.
発明の効果 The invention's effect
現像済み感光材料のメツキ液への浸漬に先行して該感光材料を硬膜溶液で前浴 処理することを特徴とする本発明の導電性膜の製造方法によれば、電解めつき工程 で生じるメツキムラを低減することができる。したがって、均質かつ高い導電性と高い 透光性とを同時に有する導電性膜を形成することが可能であり、 EMIシールド性に 優れた細線のパターンの電磁波シールド膜も得られる。 Prior to immersing the developed photosensitive material in a plating solution, the photosensitive material is pre-bathed with a hardening solution. According to the method for producing 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.
上記導電性膜は、ディスプレイ機器の画像素子ユニットや画像記録素子の撮像用 半導体素子用の透明電極として、電磁波シールド膜は、上記画像素子ユニットの電 磁波障害防止用部材として用いられる。特に被処理感光材料を連続的に電解めつき する本発明の製造方法では、めっきムラの抑止効果、メツキ液の疲労が少なぐ電磁 波シールド能を劣化させることなく透光性部の現像汚れ防止効果が顕著に向上し、 膜を安価に大量生産できる。  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, and the electromagnetic wave shield film is used as a member for preventing an electromagnetic wave disturbance of the image element unit. In particular, in the manufacturing method of the present invention in which the photosensitive material to be processed is continuously electrolyzed, the effect of suppressing plating unevenness, the fatigue of the plating solution is reduced, and the electromagnetic wave shielding ability is reduced. The effect is remarkably improved and the membrane can be mass-produced at low cost.
図面の簡単な説明  Brief Description of Drawings
[0014] [図 1]本発明に好適に用いられる電解めつき槽の一例を示す模式図である。 [0014] FIG. 1 is a schematic diagram showing an example of an electrolytic plating bath suitably used in the present invention.
[図 2]本発明の導電性膜の一例を示す模式図である。  FIG. 2 is a schematic view showing an example of a conductive film of the present invention.
符号の説明  Explanation of symbols
[0015] 10 電解めつき装置 [0015] 10 Electrolytic plating apparatus
11 電解槽  11 Electrolysis tank
12a, 12b 給電ローラ  12a, 12b Feed roller
13 アノード板  13 Anode plate
14 ガイドローラ  14 Guide roller
16 フィルム  16 films
17 液きりローラ  17 Liquid roller
21 導電性膜  21 Conductive film
22 導電性機能層  22 Conductive functional layer
23 支持体  23 Support
24 露光部 (金属銀部）  24 Exposure part (Metal silver part)
25 未露光部  25 Unexposed area
26 電解めつき処理部  26 Electrolytic plating section
27 電解めつき処理部 28 ノ、ロゲンィ匕銀乳剤層 27 Electrolytic plating section 28 Rogeny silver emulsion layer
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0016] 以下に、本発明の導電性膜の製造方法および透光性導電膜の中でも特に電磁波 シールド膜について詳細に説明するが、半導体素子などの透明電極に用いる現像 銀由来の導電性膜もこれに準拠して製造することができる。 [0016] In the following, the method for producing a conductive film of the present invention and the electromagnetic wave shielding film among the translucent conductive films will be described in detail. However, a conductive film derived from developed silver used for a transparent electrode such as a semiconductor element is also described. It can be manufactured according to this.
なお、本明細書において「〜」は、その前後に記載される数値を下限値および上限 値として含む意味として使用される。  In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.
[0017] <本発明の特徴 > <Features of the present invention>
本発明の導電性膜の製造方法は、表面抵抗が 1〜： ίΟΟΟ Ω /口のフィルムの表面 に硬膜溶液を反応させる硬膜工程を有する。より具体的には、支持体上に感光性ハ ロゲン化銀塩を含有する乳剤層を有する感光材料を露光し、連続的に、現像処理と 好ましくは定着処理を施すことによって露光部および未露光部に、それぞれ金属銀 部および光透過性部を形成し、次 、でこの現像済み感光材料を硬膜溶液で前浴処 理してから電解めつき処理を施す導電性膜の製造方法、装置、及び上記導電性膜 の適用の発明である。本発明では、現像銀の電解メツキ液への浸漬の直前に、硬膜 溶液による前浴処理 (硬膜工程)を行うことが好ま ヽ。  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 Ω / 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.
この硬膜溶液による前浴処理によって現像銀への金属電析が均一に行われて電 着ムラが抑止され、また透光性部への現像汚れの付着も低減されて、本発明の目的 とする課題が達成される。  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.
なお、念のために付言するなら、上記において、「連続的」とは、被処理感光材料が 連続搬送される（つまり工程の流れが連続している）ことを指しており、必ずしも現像、 めっき処理などの工程が中断されることなく、連続して!/、ることを指すものではな!/、。 また、「現像銀の電解メツキ液への浸漬の直前」とは硬膜溶液で処理したのち、他の 工程を差し挟むことなくそのままめっき液処理の工程に入ることを意味しており、時間 的な間隔をさすものではな 、。パターン露光したハロゲンィ匕銀写真感光材料を単に 現像処理することによって生じたメッシュ状の銀は細 、フィラメント状銀 (又は超微粒 子で離散的な球状銀)であって導電性が極めて乏しい (通常表面抵抗が 1〜： L000 Ω Ζ口）。本発明者は、導電性を増大させるには金属をパターン状現像銀上に電解 メツキによって電析させることが効果的であることを見出した力 し力しながら、このよう にして得た金属膜は沈積の不均一性に由来する電解ムラがあって導電性膜の均一 性に欠ける。電解時間を長くしたり、電解条件を強化すると導電性の増加は認められ るが、感材汚れも発生して透光性が損なわれる。本発明では、現像銀を担持した感 光材料をメツキ液に浸漬させる前に硬膜溶液を感光材料に適用する手段を採用する と電着の不均一が低減され、感材汚れも減少して、その結果透光性を維持したまま 導電性が増加して、上記の欠点を解決できることに基 、て 、る。 As a reminder, in the above, “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! In addition, “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 Ω 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. In the present invention, if 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.
感光材料の前硬膜処理の形態は、前浴槽による硬膜溶液への浸浴処理、あるいは 塗布装置による塗りつけ処理が好まし!/、が、そのほか硬膜溶液が感材表面に接触す る任意の手段を用いることができる。本発明に用いる硬膜溶液中の硬膜剤は、ゼラチ ンを硬膜する作用を有する化合物であることが好ましいが、その詳細は後述する。硬 膜溶液中の濃度は、目的の効果が発現する限り、如何なる濃度でもよいが、 0. 005 〜1. OmolZLであることが好ましい。表面張力は、水より低い場合が好ましぐさらに は 60mNZm以下であると効果が増加する。硬膜溶液の更なる詳細は、後述する。  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 following means can be used. 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.
[0018] 現像処理と好ましくは定着処理に続く電解めつき処理は、公知の電解めつき処理を 用いることができ、これによつてノインダ一に覆われて通常不均一形状と不均一太さ のために導電性が不十分なフィラメント状銀の導電性が強化され、さらに現像済み試 料のメツキ液への浸入の前に硬膜溶液で前処理することによって未露光部の透光性 と露光部の導電性とがともに優れた導電性膜を形成することができる。 [0018] For the electroplating process that follows the development process and preferably the fixing process, 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.
以下、本発明を構成する要素について順次詳細に説明する。  Hereinafter, the elements constituting the present invention will be sequentially described in detail.
[0019] 《導電性膜》 [0019] << conductive film >>
本発明における光透過性部の「透過率」とは、支持体の光吸収及び反射の寄与を 除いた 380〜780nmの波長領域における透過率の最小値で示される透過率を指し 、（透光性電磁波シールド材料の透過率) Z (支持体の透過率） X 100 (%)で表され る。光透過性部の透過率は 90%以上であることが好ましぐ 95%以上であることがよ り好ましぐ 97%以上であることがさらに好ましぐ 98%以上であることがさらにより好 ましぐ 99%以上であることが最も好ましい。  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 conductive electromagnetic shielding material) Z (the transmittance of the support) X 100 (%). 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.
<バインダー > 本発明の導電性膜を担持する目的でバインダーを用いることができる。本発明にお V、て上記バインダーとしては、非水溶性ポリマーおよび水溶性ポリマーの 、ずれもバ インダーとして用いることができる力 水溶性ポリマーを用いることが好まし!/、。 <Binder> A binder can be used for the purpose of supporting the conductive film of the present invention. In the present invention, as 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.
上記バインダーとしては、例えば、ゼラチン、ポリビュルアルコール（PVA)、ポリビ -ルピロリドン (PVP)、澱粉等の多糖類、セルロースおよびその誘導体、ポリエチレ ンオキサイド、ポリサッカライド、ポリビニルァミン、キトサン、ポリリジン、ポリアクリル酸 、ポリアルギン酸、ポリヒアルロン酸、カルボキシセルロース等が挙げられる。これらは 、官能基のイオン性によって中性、陰イオン性、陽イオン性の性質を有する。  Examples of the binder 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.
ノインダ一の含有量は、特に限定されず、分散性と密着性を発揮し得る範囲で適 宜決定することができる。本発明において、 AgZバインダー質量比率が 3以上である ことが好ましぐ 4. 5以上 12以下であることがより好ましぐ 6以上 10以下であることが 最も好ましい。また、バインダーの種類としてはゼラチンが最も好ましい。  The content of the noinda is not particularly limited, and can be appropriately determined as long as dispersibility and adhesion can be exhibited. In the present invention, 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.
<膨潤率> <Swelling rate>
本発明の導電性膜は、光透過性部の膨潤率が 180%以下であることを特徴とする 。本発明において、膨潤率は以下のように定義する。すなわち、乾燥時の層膜厚 (a) および、 25°Cの蒸留水に 1分間浸潰した後の層膜厚 (b)を測定し、  The conductive film of the present invention is characterized in that the swelling ratio of the light transmitting portion is 180% or less. In the present invention, 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,
膨潤率 (%) = 100 X ( (b)— (a) ) / (a)  Swell rate (%) = 100 X ((b) — (a)) / (a)
とする。ここで乳剤層膜厚の測定は、試料の断面を走査型電子顕微鏡で観察するこ とによって測定する。膨潤後の膜厚は、膨潤した試料を液体窒素により凍結乾燥した 後の試料断面を走査型電子顕微鏡で観察することにより測定する。本発明において 、光透過性部層の膨潤率は 150%以下が好ましぐ 130%以下がより好ましい。本発 明にお ヽて膨潤率に下限は無 、が、めっき処理における膜中の液の取り込み量の 低下抑制、めっき速度の低下抑制等の観点から、膨潤率は 50%以上であることが好 ましい。本発明において、膨潤率の制御は硬膜処理における硬膜剤の種類、添加量 、 pHによって制御可能である。 And Here, 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. In the present invention, the swelling ratio of the light transmitting part layer is preferably 150% or less, more preferably 130% or less. In the present invention, there is no lower limit to the swelling ratio, but 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. In the present invention, the swelling rate can be controlled by the type, addition amount, and pH of the hardening agent in the hardening treatment.
なお、本発明で規定して 、る膨潤率は電磁波シールド膜としての最終形態での規 定である。すなわち、本発明で規定している膨潤率は電解めつき処理工程後の値で ある。後述する処理前の感光材料の膨潤率に関しては如何なる値でも構わな 、。 《導電性膜とその製造法》 As defined in the present invention, 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》
本発明の導電性膜の製造方法は、支持体上にハロゲン化銀乳剤層を有するハロ ゲン化銀フィルムを露光して現像し、金属銀部を形成する現像工程と、前記金属銀 が形成されたフィルムの表面に、硬膜剤を含有する硬膜溶液を反応させる硬膜工程 と、前記硬膜工程が施されたフィルムの金属銀部に対し、電解めつき処理を施す電 解めつき処理工程と、を有する導電性膜の製造方法である。  In the method for producing a conductive film of the present invention, 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. And a process for producing a conductive film.
本発明の製造方法では、フィルム表面を硬膜溶液で前浴処理することで、電解め つき処理工程における電着ムラが抑止され、得られる導電性膜の表面抵抗が十分に 低減できる。このように得られる導電性膜の表面抵抗が十分に低減できる理由は定 かではないが、本発明者らはこの理由を以下のように推定する。上記ハロゲン化銀乳 剤層は、ハロゲンィ匕銀乳剤層の硬膜剤の含有量が少ないため、その膜質が弱く電解 めっき処理の際に傷が発生し易ぐ電着ムラの原因になる。しかし、本発明では、硬 膜工程により銀塩含有層の膜質を架橋などにより強化でき、電解めつき処理が施さ れても傷の発生を抑制でき、電解めつき処理における電着ムラを防止することができ る。  In the production method of the present invention, by pre-bathing the film surface with a hardening solution, uneven electrodeposition in the electrolytic plating process is suppressed, and the surface resistance of the resulting conductive film can be sufficiently reduced. Although the reason why the surface resistance of the conductive film thus obtained can be sufficiently reduced is not clear, 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. However, in the present invention, 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.
上記ハロゲン化銀乳剤層はハロゲンィ匕銀及びバインダー (好ましくはゼラチン)を含 有することが好ましい。また本発明にかかる導電性膜では、その表面抵抗を十分にて 低減するために、ハロゲン化銀乳剤層における銀 (Ag)及びバインダー (B)の含有質 量比が下記式（1)の範囲にあることが好ましい。  The silver halide emulsion layer preferably contains a silver halide silver and a binder (preferably gelatin). In the conductive film according to the present invention, in order to sufficiently reduce the surface resistance, 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.
AgZB = 3〜15 (1)  AgZB = 3 to 15 (1)
またハロゲンィ匕銀乳剤層は、その表面抵抗を十分にて低減するために、 AgZバイ ンダ一体積比が 1Z4以上とすることが好ま 、。  In addition, in order to sufficiently reduce the surface resistance of the silver halide silver emulsion layer, it is preferable that the volume ratio of AgZ binder is 1Z4 or more.
本発明の製造方法では、硬膜処理で十分な効果を得るために、硬膜剤がゼラチン を硬膜する作用を有する化合物であることが好ましぐ例えば、ホルムアルデヒド、ピ ノリルアルデヒド、ダルタルアルデヒド、琥珀アルデヒド、カリ明ばん、クロム明ばん、 および硫酸アルミニウム力 選択される化合物であることが好ましぐダルタルアルデ ヒド又は硫酸アルミニウムであることが特に好ま U、。このような化合物を硬膜剤として 使用することで、ハロゲンィ匕銀乳剤層の表面のゼラチンの架橋密度をさらに向上させ ることができ、ハロゲンィ匕銀乳剤層の硬膜ィ匕に特に有効である。 In the production method of the present invention, it is preferable that the hardener is a compound having a function of hardening gelatin in order to obtain a sufficient effect in the hardening treatment. For example, 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. By using such a compound as a hardener, the crosslink density of gelatin on the surface of the halogenated silver emulsion layer can be further improved. It is particularly effective for the hardening of a halogenated silver emulsion layer.
なお、硬膜溶液は、硬膜剤を 0. 005〜1. OOOmolZL含有することが好ましぐさ らに膨潤抑制作用のある化合物を含有することが好ましい。  In addition, it is preferable that 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.
[0021] [感光材料 (ノ、ロゲンィ匕銀フィルム） ] [0021] [Sensitive material (No, Rogeny silver film)]
く支持体〉  <Support>
本発明の製造方法に用いられる感光材料の支持体としては、プラスチックフィルム 、プラスチック板、およびガラス板などを用いることができる。  As the support of the photosensitive material used in the production method of the present invention, a plastic film, a plastic plate, a glass plate, or the like can be used.
上記プラスチックフィルムおよびプラスチック板の原料としては、例えば、ポリエチレ ンテレフタレート（PET)、およびポリエチレンナフタレートなどのポリエステル類；ポリ エチレン（PE)、ポリプロピレン（PP)、ポリスチレン、 EVAなどのポリオレフイン類；ポリ 塩化ビニル、ポリ塩ィ匕ビユリデンなどのビュル系榭脂；その他、ポリエーテルエーテル ケトン（PEEK)、ポリサルホン（PSF)、ポリエーテルサルホン（PES)、ポリカーボネー ト（PC)、ポリアミド、ポリイミド、アクリル榭脂、トリァセチルセルロース (TAC)などを用 いることがでさる。  Examples of the raw material for the plastic film and plastic plate include 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; other polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin Fats, triacetyl cellulose (TAC), etc. can be used.
本発明においては、透明性、耐熱性、取り扱いやすさおよび価格の点から、上記プ ラスチックフィルムはポリエチレンテレフタレートフィルム及び Z又はトリァセチルセル ロース (TAC)であることが好まし!/、。  In the present invention, 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! /.
[0022] ディスプレイ用の電磁波シールド材では透明性が要求されるため、支持体の透明 性は高 、ことが望ま 、。この場合におけるプラスチックフィルムまたはプラスチック板 の全可視光透過率は 70〜100%が好ましぐさらに好ましくは 85〜100%であり、特 に好ましくは 90〜 100%である。また、本発明では、前記プラスチックフィルムおよび プラスチック板として本発明の目的を妨げない程度に着色したものを用いることもでき る。 [0022] Since the electromagnetic wave shielding material for display is required to be transparent, it is desirable that the support has high transparency. In this case, the total visible light transmittance of the plastic film or plastic plate is preferably 70 to 100%, more preferably 85 to 100%, and particularly preferably 90 to 100%. In the present invention, 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.
本発明におけるプラスチックフィルムおよびプラスチック板は、単層で用いることもで きるが、 2層以上を組み合わせた多層フィルムとして用いることも可能である。  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.
[0023] 本発明における支持体としてガラス板を用いる場合、その種類は特に限定されない 力 ディスプレイ用電磁波シールド膜の用途として用いる場合、表面に強化層を設け た強化ガラスを用いることが好ましい。強化ガラスは、強化処理していないガラスに比 ベて破損を防止できる可能性が高い。さらに、風冷法により得られる強化ガラスは、 万一破損してもその破 ¾片が小さぐかつ端面も鋭利になることはないため、安全 上好ましい。 [0023] When a glass plate is used as the support in the present invention, the kind thereof is not particularly limited. When used as an electromagnetic wave shielding film for a force display, it is preferable to use 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.
[0024] く保護層〉  [0024] Ku protective layer>
本発明に用いられる感光材料は、後述する乳剤層上に保護層を設けても良い。本 発明にお 1、て「保護層」とは、ゼラチンや高分子ポリマーと 、つたノインダ一力もなる 層を意味し、擦り傷防止や力学特性を改良する効果を発現するために感光性を有す る乳剤層に形成される。上記保護層はめつき処理する上では設けない方が好ましぐ 設けるとしても薄い方が好ましい。その厚みは 0. 2 /z m以下が好ましい。  In the light-sensitive material used in the present invention, a protective layer may be provided on the emulsion layer described later. In the present invention, 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.
上記保護層の塗布方法の形成方法は特に限定されず、公知の塗布方法を適宜選 択することができる。  The formation method of the protective layer coating method is not particularly limited, and a known coating method can be appropriately selected.
尚、本発明の製造方法に用いられる感光材料は、染色等の目的で乳剤層に公知 の染料を含んで 、てもよ 、。  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.
[0025] <乳剤層 > [0025] <Emulsion layer>
本発明の製造方法に用いられる感光材料は、支持体上に、光センサーとして銀塩 を含む乳剤層（銀塩含有層）を有するのが好ましい。本発明における乳剤層には、銀 塩のほか、必要に応じて、染料、バインダー、溶媒等を含有することができる。  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.
<染料 >  <Dye>
感光材料には、少なくとも乳剤層に染料が含まれてもよい。染料は、フィルター染料 として若しくはィラジェーシヨン防止その他種々の目的で乳剤層に含まれる。上記染 料としては、固体分散染料を含有してよい。本発明に好ましく用いられる染料として は、特開平 9— 179243号公報記載の一般式 (FA)、一般式 (FA1)、一般式 (FA2 )、一般式 (FA3)で表される染料が挙げられ、具体的には同公報記載の化合物 F1 〜F34が好ましい。また、特開平 7— 152112号公報記載の（Π— 2)〜（Π— 24)、特 開平 7— 152112号公報記載の（III 5)〜（III— 18)、特開平 7— 152112号公報 記載の（IV— 2)〜 (IV— 7)等も好ましく用いられる。  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, (Π-2) to (Π-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.
[0026] このほか、本発明に使用することができる染料としては、現像または定着の処理時 に脱色させる固体微粒子分散状の染料としては、特開平 3— 138640号公報記載の シァニン染料、ピリリウム染料およびアミ-ゥム染料が挙げられる。また、処理時に脱 色しない染料として、特開平 9— 96891号公報記載のカルボキシル基を有するシァ ニン染料、特開平 8 - 245902号公報記載の酸性基を含まな 、シァニン染料および 同 8— 333519号公報記載のレーキ型シァニン染料、特開平 1— 266536号公報記 載のシァニン染料、特開平 3— 136038号公報記載のホロポーラ型シァニン染料、 特開昭 62— 299959号公報記載のピリリウム染料、特開平 7— 253639号公報記載 のポリマー型シァニン染料、特開平 2— 282244号公報記載のォキソノール染料の 固体微粒子分散物、特開昭 63— 131135号公報記載の光散乱粒子、特開平 9 5 913号公報記載の Yb3+化合物および特開平 7 - 113072号公報記載の ITO粉末 等が挙げられる。また、特開平 9— 179243号公報記載の一般式 (F1)、一般式 (F2 )で表される染料で、具体的には同公報記載の化合物 F35〜F112も用いることがで きる。 [0026] In addition, as a dye that can be used in the present invention, 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. Further, as 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. 3-136038, pyrylium dyes described in Japanese Patent Laid-Open No. 62-299959, Polymer type cyanine dye described in JP-A-7-253639, solid fine particle dispersion of oxonol dye described in JP-A-2-282244, light scattering particle described in JP-A-63-131135, JP-A-9 5913 Examples thereof include Yb 3+ compounds described above and ITO powders described in JP-A-7-113072. Further, dyes represented by general formula (F1) and general formula (F2) described in JP-A-9-179243, specifically, compounds F35 to F112 described in the same publication can also be used.
[0027] また、上記染料としては、水溶性染料を含有することができる。このような水溶性染 料としては、ォキソノール染料、ベンジリデン染料、メロシアニン染料、シァニン染料 およびァゾ染料が挙げられる。中でも本発明においては、ォキソノール染料、へミオ キソノール染料およびべンジリデン染料が有用である。本発明に用い得る水溶性染 料の具体例としては、英国特許 584, 609号明細書、同 1, 177, 429号明細書、特 開昭 48— 85130号公報、同 49— 99620号公報、同 49— 114420号公報、同 52— 20822号公報、同 59— 154439号公報、同 59— 208548号公報、米国特許 2, 27 4, 782号明細書、同 2, 533, 472号明細書、同 2, 956, 879号明細書、同 3, 148 , 187号明細書、同 3, 177, 078号明細書、同 3, 247, 127号明細書、同 3, 540, 887号明細書、同 3, 575, 704号明細書、同 3, 653, 905号明細書、同 3, 718, 4 27号明細書に記載されたものが挙げられる。  [0027] The dye may contain a water-soluble dye. Such 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. Patent 2,274,782, Gazette 2,533,472, No. 2, 956, 879, No. 3, 148, 187, No. 3, 177, 078, No. 3, 247, 127, No. 3, 540, 887, Examples thereof include those described in JP 3,575,704, 3,653,905, and 3,718,427.
[0028] 上記乳剤層中における染料の含有量は、ィラジェーシヨン防止などの効果と、添カロ 量増加による感度低下の観点から、全固形分に対して 0. 01〜10質量％が好ましく 、0. 1〜5質量％がさらに好ましい。  [0028] 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.
[0029] く銀塩〉  [0029] Ku-silver salt>
本発明で用いられる銀塩としては、ハロゲンィ匕銀などの無機銀塩が挙げられる。本 発明にお 、ては、光センサーとしての特性に優れるハロゲンィ匕銀を用いることが好ま しい。 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.
[0030] 本発明で好ましく用いられるハロゲンィ匕銀について説明する。  [0030] The halogen silver used preferably in the present invention will be described.
本発明では、光センサーとして機能させるためにハロゲンィ匕銀を使用することが好 ましぐハロゲンィ匕銀に関する銀塩写真フィルムや印画紙、印刷製版用フィルム、フォ トマスク用ェマルジヨンマスク等で用いられる技術は、本発明にお 、ても用いることが できる。  In the present invention, it is preferable to use 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.
[0031] 上記ハロゲン化銀に含有されるハロゲン元素は、塩素、臭素、ヨウ素およびフッ素 のいずれであってもよぐこれらを組み合わせでもよい。例えば、 AgCl、 AgBr、 Agl を主体としたハロゲンィ匕銀が好ましく用いられ、さらに AgBrや AgClを主体としたハロ ゲンィ匕銀が好ましく用いられる。より好ましくは、塩臭化銀、臭化銀、沃塩臭化銀、沃 臭化銀であり、最も好ましくは、塩化銀 50モル％以上を含有する塩臭化銀、沃塩臭 化銀が用いられる。  [0031] The halogen element contained in the silver halide may be any of chlorine, bromine, iodine and fluorine, or a combination thereof. For example, 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.
[0032] 尚、ここで、 「AgBr (臭化銀)を主体としたハロゲンィ匕銀」とは、ハロゲン化銀組成中 に占める臭化物イオンのモル分率が 50%以上のハロゲン化銀を 、う。この AgBrを 主体としたハロゲンィ匕銀粒子は、臭化物イオンのほかに沃化物イオン、塩化物イオン を含有していてもよい。  Here, “halogenated silver mainly composed of AgBr (silver bromide)” 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.
[0033] ノヽロゲン化銀は固体粒子状であり、露光、現像処理後に形成されるパターン状金 属銀層の画像品質の観点からは、ハロゲンィ匕銀の平均粒子サイズは、球相当径で 0 . 1〜1000ηπι(1 /ζ πι)であることが好ましぐ 0. l〜100nmであることがより好ましく 、 l〜50nmであることがさらに好ましい。  [0033] 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 ηπι (1 / ζππ), more preferably 0.1 to 100 nm, and even more preferably 1 to 50 nm.
尚、ハロゲンィ匕銀粒子の球相当径とは、粒子形状が球形の同じ体積を有する粒子 の直径である。  The spherical equivalent diameter of a halogenated silver particle is a diameter of a particle having a spherical shape and the same volume.
[0034] ハロゲン化銀粒子の形状は特に限定されず、例えば、球状、立方体状、平板状 (6 角平板状、三角形平板状、 4角形平板状など)、八面体状、 14面体状など様々な形 状であることができ、立方体、 14面体が好ましい。  [0034] The shape of the silver halide grains is not particularly limited. For example, 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.
ハロゲン化銀粒子は内部と表層が均一な相力 なって 、ても異なって 、てもよ 、。 また粒子内部或いは表面にハロゲン組成の異なる局在層を有していてもよい。 [0035] 本発明に用いられる乳剤層用塗布液であるハロゲンィ匕銀乳剤は、 P. Glafkides著 Chimie etPhysique Photographique (Paul Montel¾:flJ, 1967^) , G. F . Dufin著 Photographic Emulsion Chemistry (The Forcal Press刊、 19 66年)、 V. L. Zelikman et al著 Making and Coating Photographic E mulsion (The ForcalPress刊、 1964年）などに記載された方法を用いて調製する ことができる。 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 | grain inside or the surface. [0035] 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 Montel¾: 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.
[0036] すなわち、上記ハロゲン化銀乳剤の調製方法としては、酸性法、中性法等のいず れでもよぐ又、可溶性銀塩と可溶性ハロゲン塩とを反応させる方法としては、片側混 合法、同時混合法、それらの組み合わせなどのいずれを用いてもよい。  That is, 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.
また、銀粒子の形成方法としては、粒子を銀イオン過剰の下において形成させる方 法 (いわゆる逆混合法)を用いることもできる。さらに、同時混合法の一つの形式とし てハロゲンィ匕銀の生成される液相中の pAgを一定に保つ方法、すなわち、いわゆる コントロールド.ダブルジェット法を用いることもできる。  Further, as 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. Further, as one type of the simultaneous mixing method, 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.
またアンモニア、チォエーテル、四置換チォ尿素等のいわゆるハロゲンィ匕銀溶剤を 使用して粒子形成させることも好ましい。係る方法としてより好ましくは四置換チォ尿 素化合物であり、特開昭 53— 82408号、同 55— 77737号各公報に記載されている 。好ましいチォ尿素化合物はテトラメチルチオ尿素、 1, 3—ジメチルー 2—イミダゾリ ジンチオンが挙げられる。ハロゲンィ匕銀溶剤の添加量は用いる化合物の種類および 目的とする粒子サイズ、ハロゲン組成により異なる力 ハロゲンィ匕銀 1モルあたり 10— 5 〜 10— 2モルが好ましい。 It is also preferable to form grains using a so-called 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匕銀solvent type and particle size of interest of the compound to be used, different forces Harogeni匕銀per mole 10- 5 to 10- 2 mol by halogen composition are preferred.
[0037] 上記コントロールド ·ダブルジェット法およびハロゲンィ匕銀溶剤を使用した粒子形成 方法では、結晶型が規則的で粒子サイズ分布の狭 ヽハロゲンィ匕銀乳剤を作るのが 容易であり、本発明に好ましく用いることができる。  [0037] In the controlled double jet method and the grain forming method using a halogenated silver solvent, it is easy to produce a halogenated silver emulsion having a regular crystal type and a narrow grain size distribution. It can be preferably used.
また、粒子サイズを均一にするためには、英国特許第 1, 535, 016号明細書、特 公昭 48— 36890号広報、同 52— 16364号公報に記載されているように、硝酸銀や ハロゲンィ匕アルカリの添加速度を粒子成長速度に応じて変化させる方法や、英国特 許第 4, 242, 445号明細書、特開昭 55— 158124号公報に記載されているように 水溶液の濃度を変化させる方法を用いて、臨界飽和度を越えな 、範囲にぉ 、て早く 銀を成長させることが好ましい。本発明における乳剤層の形成に用いられるハロゲン 化銀乳剤は単分散乳剤が好ましぐ { (粒子サイズの標準偏差) Z (平均粒子サイズ）In order to make the grain size uniform, as described in British Patent No. 1,535,016, JP-B-48-36890, JP-B-52-16364, silver nitrate or halogenated silver is used. The method of changing the alkali addition rate according to the particle growth rate, or changing the concentration of the aqueous solution as described in British Patent No. 4,242,445, JP-A-55-158124 Using the method, the critical saturation is not exceeded, and the range is quickly reached. It is preferred to grow silver. 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)
} X 100で表される変動係数が 20%以下、より好ましくは 15%以下、最も好ましくは 1 0%以下であることが好まし 、。 } The coefficient of variation represented by X100 is preferably 20% or less, more preferably 15% or less, and most preferably 10% or less.
[0038] 本発明に用いられるハロゲンィ匕銀乳剤は、粒子サイズの異なる複数種類のハロゲ ン化銀乳剤を混合してもよ 、。  [0038] 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.
[0039] 本発明に用いられるハロゲンィ匕銀乳剤は、 VIII族、 VIIB族に属する金属を含有し てもよい。特に、高コントラストおよび低カプリを達成するために、ロジウム化合物、イリ ジゥム化合物、ルテニウム化合物、鉄化合物、オスミウム化合物、レニウム化合物など を含有することが好ましい。これら化合物は、各種の配位子を有する化合物であって よぐ配位子として例えば、シアンィ匕物イオンゃノヽロゲンイオン、チオシアナ一トイオン 、ニトロシルイオン、水、水酸化物イオンなどや、こうした擬ハロゲン、アンモニアのほ 力 アミン類 (メチルァミン、エチレンジァミン等）、ヘテロ環化合物 (イミダゾール、チ ァゾール、 5—メチルチアゾール、メルカプトイミダゾールなど）、尿素、チォ尿素等の 、有機分子を挙げることができる。  [0039] The silver halide silver emulsion used in the present invention may contain 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. Further, 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.
また、高感度化のためには K [Fe (CN) ) ^>K [Ru (CN)〕、K [Cr (CN)〕のごと  For higher sensitivity, K [Fe (CN)) ^> K [Ru (CN)], K [Cr (CN)]
4 6 4 6 3 6 き六シァノ化金属錯体のドープが有利に行われる。  4 6 4 6 3 6 Doping of a metal hexasyanide complex is advantageously performed.
[0040] 上記ロジウム化合物としては、水溶性ロジウム化合物を用いることができる。水溶性 ロジウム化合物としては、例えば、ハロゲン化ロジウム（ΠΙ)化合物、へキサクロロロジ ゥム（III)錯塩、ペンタクロロアコロジウム錯塩、テトラクロロジアコロジウム錯塩、へキ サブロモロジウム（ΠΙ)錯塩、へキサァミンロジウム（III)錯塩、トリオキザラトロジウム（Π I)錯塩、 K Rh Br等が挙げられる。 [0040] As the rhodium compound, a water-soluble rhodium compound can be used. Examples of water-soluble rhodium compounds include rhodium halide (ΠΙ) compounds, hexachlororhodium (III) complex salts, pentachloroacorodium complex salts, tetrachlorodiacorodium complex salts, hexabromorhodium (ΠΙ) complex salts, Xamin rhodium (III) complex salt, trioxalato rhodium (ΠI) complex salt, K Rh Br and the like.
3 2 9  3 2 9
[0041] 上記イリジウム化合物としては、 K IrCl Cl等のへキサクロ口イリジウム錯塩、  [0041] Examples of the iridium compound include hexachrome iridium complex salts such as K IrCl Cl,
2 6、 K Ir  2 6, K Ir
3 6  3 6
へキサブロモイリジウム錯塩、へキサアンミンイリジウム錯塩、ペンタクロロ-トロシルイ リジゥム錯塩等が挙げられる。  Hexabromoiridium complex salts, hexammine iridium complex salts, pentachloro-trosyl iridium complex salts and the like.
上記ルテニウム化合物としては、へキサクロ口ルテニウム、ペンタクロロ-トロシルル テ-ゥム、 K [Ru (CN)〕等が挙げられる。  Examples of the ruthenium compound include hexaclonal ruthenium, pentachloro-trosyl ruthenium, K [Ru (CN)] and the like.
4 6  4 6
上記鉄化合物としては、へキサシァノ鉄 (π)酸カリウム、チォシアン酸第一鉄が挙 げられる。 Examples of the iron compounds include potassium hexanoate (π) and ferrous thiocyanate. I can get lost.
[0042] 上記ルテニウム化合物、ォスミニゥム化合物は特開昭 63— 2042号公報、特開平 1 — 285941号公報、同 2— 20852号公報、同 2— 20855号公報等に記載された水 溶性錯塩が挙げられる。  [0042] 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.
[0043] これらの化合物の添力卩量はハロゲン化銀 1モル当り 10— ω〜10— 2モル Zモル Agであ ることが好ましぐ 10— 9〜： L0— 3モル/モル Agであることがさらに好ましい。 [0043]添力卩量silver halide per mole of 10-omega to 10-2 mol Z mol Ag der Rukoto is preferred instrument 10 9 ~ of these compounds: L0- 3 mol / mol Ag More preferably it is.
[0044] その他、本発明では、 Pd (II)イオンおよび Zまたは Pd金属を含有するハロゲン化 銀も好ましく用いることができる。 Pdはハロゲンィ匕銀粒子内に均一に分布していても よいが、ハロゲンィ匕銀粒子の表層近傍に含有させることが好ましい。ここで、 Pdが「ノヽ ロゲン化銀粒子の表層近傍に含有する」とは、ハロゲンィ匕銀粒子の表面力も深さ方 向に 50nm以内にぉ 、て、他層よりもパラジウムの含有率が高 、層を有することを意 味する。  In addition, in the present invention, 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. Here, 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.
このようなハロゲンィ匕銀粒子は、ハロゲン化銀粒子を形成する途中で Pdを添加する ことにより作製することができ、銀イオンとハロゲンイオンとをそれぞれ総添加量の 50 %以上添加した後に、 Pdを添加することが好ましい。また Pd (II)イオンを後熟時に添 加するなどの方法でハロゲンィ匕銀表層に存在させることも好ま U、。  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.
この Pd含有ハロゲンィ匕銀粒子は、物理現像や無電解めつきの速度を速め、所望の 電磁波シールド材の生産効率を上げ、生産コストの低減に寄与する。 Pdは、無電解 めっき触媒としてよく知られて用いられている力 本発明では、ハロゲン化銀粒子の 表層に Pdを偏在させることが可能なため、極めて高価な Pdを節約することが可能で ある。  These 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 In the present invention, Pd can be unevenly distributed on the surface layer of silver halide grains, so that it is possible to save extremely expensive Pd. .
[0045] 本発明にお 、て、ハロゲンィ匕銀に含まれる Pdイオンおよび/または Pd金属の含有 率は、ハロゲン化銀の、銀のモル数に対して 10— 4〜0. 5モル Zモル Agであることが 好ましく、 0. 01〜0. 3モル Zモル Agであることがさらに好ましい。 [0045] Contact with the present invention, Te, content of Pd ions and / or Pd metal contained in Harogeni匕銀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.
使用する Pd化合物の例としては、 PdClや、 Na PdCl等が挙げられる。  Examples of the Pd compound used include PdCl and Na PdCl.
4 2 4  4 2 4
[0046] 本発明では、さらに光センサーとしての感度を向上させるため、写真乳剤で行われ る化学増感を施すこともできる。化学増感の方法としては、硫黄増感、セレン増感、テ ルル増感等カルコゲン増感、金増感などの貴金属増感、還元増感等を用いることが できる。これらは、単独または組み合わせて用いられる。上記化学増感の方法を組み 合わせて使用する場合には、例えば、硫黄増感法と金増感法、硫黄増感法とセレン 増感法と金増感法、硫黄増感法とテルル増感法と金増感法などの組み合わせが好 ましい。 In the present invention, 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. When a combination of the above chemical sensitization methods is used, for example, 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. A combination of sensitivity and gold sensitization is preferred.
[0047] 上記硫黄増感は、通常、硫黄増感剤を添加して、 40°C以上の高温で乳剤を一定 時間攪拌することにより行われる。上記硫黄増感剤としては公知の化合物を使用す ることができ、例えば、ゼラチン中に含まれる硫黄ィ匕合物のほか、種々の硫黄化合物 、例えば、チォ硫酸塩、チォ尿素類、チアゾール類、ローダ-ン類等を用いることが できる。好ましい硫黄化合物は、チォ硫酸塩、チォ尿素化合物である。硫黄増感剤 の添加量は、化学熟成時の pH、温度、ハロゲンィ匕銀粒子の大きさなどの種々の条 件の下で変化し、ハロゲン化銀 1モル当り 10— 7〜： LO— 2モルが好ましぐより好ましくは 1 0一5〜 10— 3モノレである。 [0047] 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. As the sulfur sensitizer, known compounds can be used. For example, in addition to sulfur compounds contained in gelatin, 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. The addition amount of the sulfur sensitizer, pH during chemical ripening, temperature, changes in various conditions under such size of Harogeni匕銀particles, per mol of silver halide 10- 7 ~: LO- 2 more preferably mole preferably tool 1 0 one 5 to 10-3 Monore.
[0048] 上記セレン増感に用いられるセレン増感剤としては、公知のセレン化合物を用いる ことができる。上記不安定型セレン化合物としては特公昭 44— 15748号公報、同 43 — 13489号公報、特開平 4— 109240号公報、同 4— 324855号公報等に記載の 化合物を用いることができる。  [0048] As the selenium sensitizer used for the selenium sensitization, known selenium compounds can be used. As the 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.
[0049] 上記テルル増感剤に用いられるテルル増感剤は、ハロゲンィ匕銀粒子表面または内 部に、増感核になると推定されるテルル化銀を生成せしめる化合物である。具体的に は、ジャーナル'ォブ'ケミカル'ソサイァティ一'ケミカル 'コミュニケーション (J. Che m. Soc. Chem. Commun. ) 635 (1980)、 ibid 1102 (1979)、 ibid 645 (197 9)などに記載の化合物を用いることができる。特に特開平 5— 313284号公報中の 一般式 (11)、 （III)、（IV)で示される化合物が好ましい。  [0049] 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. Specifically, in the journal 'Ob' Chemical 'Society' Chemical 'Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid 1102 (1979), ibid 645 (197 9), etc. The described compounds can be used. Particularly preferred are compounds represented by the general formulas (11), (III) and (IV) in JP-A-5-313284.
[0050] 本発明で用いることのできるセレン増感剤およびテルル増感剤の使用量は、使用 するハロゲンィ匕銀粒子、化学熟成条件等によって変わるが、一般にハロゲンィ匕銀 1モ ル当たり 10— 8〜： L0— 2モル、好ましくは 10— 7〜： L0— 3モル程度を用いる。本発明における 化学増感の条件としては特に制限はないが、 pHとしては 5〜8、 pAgとしては 6〜11 、好ましくは 7〜 10であり、温度としては 40〜95°C、好ましくは 45〜85°Cである。 [0050] The amount of the selenium sensitizer and a tellurium sensitizer that can be used in the present invention, Harogeni匕銀particles used, but the chemical ripening condition and the like and, generally Harogeni匕銀1 molar per 10- 8 ~: L0- 2 moles, preferably 10- 7 ~: L0- 3 moles is used. 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.
[0051] また、上記貴金属増感剤としては、金、白金、ノラジウム、イリジウム等が挙げられ、 特に金増感が好ましい。金増感に用いられる金増感剤としては、具体的には、塩ィ匕 金酸、カリウムクロ口オーレート、カリウムォーリチオシァネート、硫化金、チォダルコ一 ス金（1)、チォマンノース金（I)などが挙げられ、ハロゲン化銀 1モル当たり 10— 7〜10 モル程度を用いることができる。本発明に用いるハロゲンィ匕銀乳剤にはハロゲンィ匕銀 粒子の形成または物理熟成の過程においてカドミウム塩、亜硫酸塩、鉛塩、タリウム 塩などを共存させてもよい。 [0051] 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.
[0052] また、本発明においては、還元増感を用いることができる。還元増感剤としては第 ースズ塩、アミン類、ホルムアミジンスルフィン酸、シラン化合物などを用いることがで きる。上記ハロゲンィ匕銀乳剤は、欧州公開特許 (EP) 293917に示される方法により 、チォスルホン酸ィ匕合物を添加してもよい。本発明に用いられる感光材料の作製に 用いられるハロゲンィ匕銀乳剤は、 1種だけでもよいし、 2種以上 (例えば、平均粒子サ ィズの異なるもの、ハロゲン組成の異なるもの、晶癖の異なるもの、化学増感の条件 の異なるもの、感度の異なるもの）の併用であってもよい。中でも高コントラストを得る ためには、特開平 6— 324426号公報に記載されているように、支持体に近いほど高 感度な乳剤を塗布することが好ま U、。  [0052] In the present invention, reduction sensitization can be used. As the 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.
[0053] [露光]  [0053] [Exposure]
本発明では、支持体上に設けられた銀塩含有層の露光を行う。露光は、電磁波を 用いて行うことができる。電磁波としては、例えば、可視光線、紫外線などの光、 X線 などの放射線等が挙げられる。さらに露光には波長分布を有する光源を利用してもよ ぐ特定の波長の光源を用いてもよい。  In the present invention, 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.
[0054] 上記光源としては、例えば、陰極線 (CRT)を用いた走査露光を挙げることができる 。陰極線管露光装置は、レーザーを用いた装置に比べて、簡便でかつコンパクトで あり、低コストになる。また、光軸や色の調整も容易である。画像露光に用いる陰極線 管には、必要に応じてスペクトル領域に発光を示す各種発光体が用いられる。例え ば、赤色発光体、緑色発光体、青色発光体のいずれか 1種又は 2種以上が混合され て用いられる。スペクトル領域は、上記の赤色、緑色及び青色に限定されず、黄色、 橙色、紫色或いは赤外領域に発光する蛍光体も用いられる。特に、これらの発光体 を混合して白色に発光する陰極線管がしばしば用いられる。また、紫外線ランプも好 ましぐ水銀ランプの g線、水銀ランプの i線等も利用される。 [0054] Examples of the light source include scanning exposure using a cathode ray (CRT). 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. As the cathode ray tube used for image exposure, 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. In particular, 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.
[0055] また本発明では、露光は種々のレーザービームを用いて行うことができる。例えば、 本発明における露光は、ガスレーザー、発光ダイオード、半導体レーザー、半導体レ 一ザ一又は半導体レーザーを励起光源に用いた固体レーザーと非線形光学結晶を 組合わせた第二高調波発光光源 (SHG)等の単色高密度光を用いた走査露光方式 を好ましく用いることができ、さらに KrFエキシマレーザー、 ArFエキシマレーザー、 F 2レーザー等も用いることができる。システムをコンパクトで、安価なものにするためにIn the present invention, exposure can be performed using various laser beams. For example, 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. To make the system compact and inexpensive
、露光は、半導体レーザー、半導体レーザーあるいは固体レーザーと非線形光学結 晶を組合わせた第二高調波発生光源 (SHG)を用いて行うことが好ま 、。特にコン パクトで、安価、さらに寿命が長ぐ安定性が高い装置を設計するためには、露光は 半導体レーザーを用いて行うことが好まし 、。 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. In particular, in order to design a compact, inexpensive, long-life, highly stable device, exposure is preferably performed using a semiconductor laser.
[0056] レーザー光源としては、具体的には、波長 430〜460nmの青色半導体レーザー（ 2001年 3月の第 48回応用物理学関係連合講演会で日亜化学発表)、半導体レー ザ一 (発振波長約 1060nm)を導波路状の反転ドメイン構造を有する LiNbOの SH  [0056] Specifically, as the laser light source, 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
3 Three
G結晶により波長変換して取り出した約 530nmの緑色レーザー、波長約 685nmの 赤色半導体レーザー（日立タイプ No. HL6738MG)、波長約 650nmの赤色半導 体レーザー（日立タイプ No. HL6501MG)などが好ましく用いられる。 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.
[0057] 銀塩含有層をパターン状に露光する方法は、フォトマスクを利用した面露光で行つ てもよいし、レーザービームによる走査露光で行ってもよい。この際、レンズを用いた 屈折式露光でも反射鏡を用いた反射式露光でもよぐコンタクト露光、プロキシミティ 一露光、縮小投影露光、反射投影露光などの露光方式を用いることができる。  [0057] 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.
[0058] [現像処理]  [0058] [Development processing]
本発明では、銀塩含有層を露光した後、さらに現像処理が行われる。現像処理は、 銀塩写真フィルムや印画紙、印刷製版用フィルム、フォトマスク用ェマルジヨン塗層 等に用いられる通常の現像処理の技術を用いることができる。  In the present invention, after the silver salt-containing layer is exposed, 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.
現像処理は、ネガ型現像処理および反転現像処理の!/、ずれの現像を選択すること もできる。また、化学現像、物理現像 (本発明の態様では正確には溶解物理現像)の いずれで行ってもよい。 ここで ヽぅ化学現像及び溶解物理現像は、当業界で通常用いられて ヽる用語どお りの意味であり、写真化学の一般教科書、例えば菊地真一著「写真化学」（共立出版 社、 1955刊行）、 C. E. K. Mees編「The Theory of Photographic Process es, 4th ed.」373— 377頁（Mcmillan社、 1977flJ行）【こ解説されて!ヽる。 For development processing, negative development processing and reversal development processing can be selected. Further, chemical development or physical development (in the aspect of the present invention, exactly, dissolution physical development) may be used. Here, “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!
化学現像液にっ 、ては現像銀が得られる限り、黒白現像液であってもカラー現像 液 (発色しなくてもよい)であってもよぐ特に限定はしないが、黒白現像液が好ましく 、黒白現像液としては PQ現像液、 MQ現像液、 MAA現像液 (メトール.ァスコルビン 酸現像液)等を用いることもでき、例えば、富士フィルム社指定処方の CN— 16、 CR — 56、 CP45X、 FD— 3、パピトール、 KODAK社指定処方の C— 41、 E— 6、 RA —4、 D— 72などの現像液、又はそのキットに含まれる現像液、また、 D— 19、 D-8 5、 D— 8などの処方名で知られるリス現像液や硬調ポジ現像液を用いることもできる 。溶解物理現像の態様においては、上記の各現像液にハロゲンィ匕銀溶解剤としてチ ォ硫酸塩 (ナトリウム塩、アンモ-ゥム塩など)ゃチオシアン酸塩 (ナトリウム塩、アンモ -ゥム塩など）を添加すればよぐ D— 19、 D— 85、 D— 8、 D— 72などの高活性型 現像液に添加することが好まし ヽ。  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. As black and white developer, PQ developer, MQ developer, MAA developer (methol ascorbic acid developer), etc. can also be used. For example, 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. In the embodiment of dissolution physical development, 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. Should be added to highly active developers such as D-19, D-85, D-8, and D-72.
本発明では、上記の露光及び現像処理を行うことにより金属銀部、好ましくはバタ ーン状金属銀部が形成されると共に、後述する光透過性部が形成される。  In the present invention, 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.
<現像液組成及び現像処理工程 > <Developer composition and development process>
本発明においては、前記した現像液のいずれをも用いることができる力 好ましくは 黒白現像液である。現像主薬としてはカラー現像主薬や黒白系現像主薬が好ましく 、とくに好ましくはァスコルビン酸系現像主薬ゃジヒドロキシベンゼン系現像主薬を用 いることができる。ァスコルビン酸系現像主薬としてはァスコルビン酸、イソァスコルビ ン酸ゃエリソルビン酸やその塩 (Na塩等）などがあげられるがコストの点力もエリソル ビン酸 Naが好ましい。ジヒドロキシベンゼン系現像主薬としてはハイドロキノン、クロ口 ハイドロキノン、イソプロピルハイドロキノン、メチルハイドロキノン、ハイド口キノンモノス ルホン酸塩などが挙げられる力 特にハイドロキノンが好ましい。ァスコルビン酸系現 像主薬ゃジヒドロキシベンゼン系現像主薬は特に超加成性を示す補助現像主薬と 併用してもよ ヽがしなくても良!ヽ。上記ァスコルビン酸系現像主薬ゃジヒドロキシベン ゼン系現像主薬と超加成性を示す補助現像主薬としては、 1—フエ-ル一 3 ピラゾ リドン類や P ァミノフエノール類が挙げられる。 In the present invention, a force capable of using any of the above-described developers, preferably a black-and-white developer. As the developing agent, 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. Examples of dihydroxybenzene-based developing agents 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. Examples of auxiliary developing agents that exhibit superadditivity with Zen-based developing agents include 1-phenol and 1-3 pyrazolidones and P-aminophenols.
[0060] 補助現像主薬として用いられる 1—フエ-ルー 3—ビラゾリドンまたはその誘導体と しては、具体的に、 1—フエ-ルー 3—ビラゾリドン、 1—フエ-ルー 4, 4 ジメチルー 3 -ビラゾリドン、 1 フエニル 4 メチル 4 ヒドロキシメチル 3 ビラゾリドンな どがある。 [0060] 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.
上記 P -ァミノフエノール系補助現像主薬としては、 N メチル p ァミノフエノー ル、 ρ ァミノフエノール、 N— ( j8—ヒドロキシェチル） p ァミノフエノール、 N— (4 ーヒドロキシフエ-ル）グリシン等がある力 なかでも N—メチルー p ァミノフエノール が好ましい。  Examples of P-aminophenol auxiliary developing agents include N-methyl p-aminophenol, ρ-aminophenol, N— (j8-hydroxyethyl) p-aminophenol, and N— (4-hydroxyphenol) glycine. Of these, N-methyl-paminophenol is preferred.
ジヒドロキシベンゼン系現像主薬は、通常 0. 05〜0. 8モル Zリットルの量で用いら れるのが好ましいが、本発明においては、 0. 23モル Zリットル以上で使用するのが 特に好ましい。さらに好ましくは、 0. 23〜0. 6モル Zリットルの範囲である。またジヒ ドロキシベンゼン類と 1 フエ-ル 3 ビラゾリドン類若しくは ァミノフエノール類 との組合せを用いる場合には、前者を 0. 23〜0. 6モル Zリットル、さらに好ましくは 0 . 23〜0. 5モノレ/リットノレ、後者を 0. 06モノレ/リットノレ以下、さらに好ましくは 0. 03 モル Zリットル〜 0. 003モル Zリットルの量で用いるのが好ましい。  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. When a combination of dihydroxybenzenes and 1-phenol 3 bisazolidones or aminophenols is used, 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.
現像液の浸浴電位すなわち酸化還元電位は、現像液の構成成分の酸化還元性の 総合されたものである力 主として現像主薬と PHによって定まる。好ましい酸化還元 電位は、 290mVvsSCEよりも卑であり、より好ましくは一 320mVvsSCEよりも卑であ り、さらに好ましくは、一 340mVvsSCEよりも卑である。 The bathing potential of the developer, that is, the oxidation-reduction potential, 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.
現像液の酸ィ匕還元電位を本発明に好ましい 290mVvsSCEよりも卑とするには、上 記の好ま 、現像主薬として挙げた主薬を用い、選択した現像主薬の種類に応じて pHを調整することによって行われる。好ましい pH値は現像主薬の pK値よりも 0〜2、 好ましくは 0. 5〜1. 5高い側であり、現像主薬の種類に応じて適宜選択される。  In order to make the acid / acid reduction potential of the developer lower than the preferable 290 mV vs SCE of the present invention, 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.
[0061] 本発明にお ヽては、現像開始液 (すなわち現像槽に新液として充填される母液)お よび現像補充液の双方が、それぞれ液 1リットルに 0. 1モルの水酸ィ匕ナトリウムをカロ えたときの pH上昇が 0. 5以下である pH緩衝能を有することが好ましい。使用する現 像開始液な ヽし現像補充液 (以下両者を併せて現像液と呼ぶこともある）がこの pH 緩衝能を有することを確かめる方法としては、試験対象の現像開始液な ヽし現像補 充液の pHを 10. 5に合わせ、ついでこの液 1リットルに水酸化ナトリウムを 0. 1モル添 加し、この際の液の pH値を測定し、 pH値の上昇が 0. 5以下であれば上記に規定し た pH緩衝能を有すると判定する。本発明の製造方法では、特に、上記試験を行った 時の pH値の上昇が 0. 4以下である現像開始液および現像補充液を用いることが好 ましい。 [0061] In the present invention, both the development starter (that is, the mother liquor charged as a new solution in the developing tank) and 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. Current to use 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. Adjust the pH of the solution to 10.5, then add 0.1 mol of sodium hydroxide to 1 liter of this solution, measure the pH value of the solution, and if the increase in pH value is 0.5 or less Judged to have the pH buffering capacity specified above. In the production method of the present invention, it is particularly preferable to use a development starting solution and a development replenisher whose pH value rises to 0.4 or less when the above test is performed.
[0062] 現像開始液および現像補充液に上記の性質を与える方法としては、緩衝剤を使用 することが好ましい。上記緩衝剤としては、炭酸塩、特開昭 62— 186259号公報に 記載のホウ酸、特開昭 60— 93433号公報に記載の糖類 (例えばサッカロース）、ォ キシム類 (例えばァセトォキシム）、フエノール類 (例えば 5—スルホサリチル酸）、第 3 リン酸塩 (例えばナトリウム塩、カリウム塩)などを用いることができ、好ましくは炭酸塩 、ホウ酸が用いられる。上記緩衝剤（特に炭酸塩)の使用量は、好ましくは、 0. 25モ ノレ/リットノレ以上であり、 0. 25〜： L 5モノレ/リットノレ力特に好まし!/ヽ。  [0062] As a method of imparting the above properties to the development initiator and the development replenisher, it is preferable to use a buffer. Examples of 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! / ヽ.
[0063] 本発明においては、上記現像開始液の pHが 9. 0〜11. 0であることが好ましぐ 9 . 5〜10. 7の範囲であることが特に好ましい。上記現像補充液の pHおよび連続処 理時の現像タンク内の現像液の pHもこの範囲である。 pH設定のために用いるアル カリ剤には通常の水溶性無機アルカリ金属塩 (例えば水酸ィ匕ナトリウム、水酸化力リウ ム、炭酸ナトリウム、炭酸カリウム)を用いることができる。  [0063] In the present invention, it is particularly preferable that 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. As 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.
[0064] 本発明の光透過性導電膜や電磁波シールド膜の製造方法にお!ヽて、感光材料 1 平方メートルを処理する際に、現像液中の現像補充液の添加量 (補充量）は 645ミリ リットル以下、好ましくは 30〜484ミリリットル、特に 100〜484ミリリットルである。現像 補充液は、現像開始液と同一の組成を有していてもよいが、現像で消費される成分 につ 、て消費量を補償するに見合う量だけ開始液よりも高 、濃度を有して 、ることが 好ましい。  [0064] In the process for producing a light-transmitting conductive film or electromagnetic wave shielding film of the present invention, when processing 1 square meter of photosensitive material, the amount of developer replenisher added in the developer (replenishment amount) 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
[0065] 本発明で感光材料を現像処理する際の現像液 (以下、現像開始液および現像補 充液の双方をまとめて単に「現像液」という場合がある）には、通常用いられる添加剤 (例えば、保恒剤、キレート剤）を含有することができる。上記保恒剤としては亜硫酸 ナトリウム、亜硫酸カリウム、亜硫酸リチウム、亜硫酸アンモ-ゥム、重亜硫酸ナトリウ ム、メタ重亜硫酸カリウム、ホルムアルデヒド重亜硫酸ナトリウムなどの亜硫酸塩が挙 げられる。該亜硫酸塩は、 0. 20モル Zリットル以上用いられることが好ましぐさらに 好ましくは 0. 3モル Zリットル以上用いられる力 多量添加すると現像液中の銀汚れ の原因になることがあるので、その上限は 1. 2モル Zリットルとするのが望ましい。特 に好ましくは、 0. 35〜0. 7モル Zリットルである。また、ジヒドロキシベンゼン系現像 主薬の保恒剤として、亜硫酸塩と併用してァスコルビン酸誘導体を少量使用してもよ い。ここでァスコルビン酸誘導体とは、前記した現像主薬としてのァスコルビン酸と同 じであり、ァスコルビン酸、および、その立体異性体であるエリソルビン酸やそのアル カリ金属塩けトリウム、カリウム塩)などを包含する。上記ァスコルビン酸誘導体として は、エリソルビン酸ナトリウムを用いることが素材コストの点で好ましい。上記ァスコル ビン酸誘導体の添カ卩量はジヒドロキシベンゼン系現像主薬に対して、モル比で 0. 03 〜0. 12の範囲が好ましぐ特に好ましくは 0. 05-0. 10の範囲である。上記保恒剤 としてァスコルビン酸誘導体を使用する場合には現像液中にホウ素化合物を含まな いことが好ましい。 [0065] 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. As the 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. In addition, ascorbic acid derivatives may be used in small amounts in combination with sulfites as preservatives for dihydroxybenzene developing agents. Here, 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. As the ascorbic acid derivative, 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. . When an ascorbic acid derivative is used as the preservative, it is preferable that the developer does not contain a boron compound.
上記以外に現像剤に用いることのできる添加剤としては、臭化ナトリウム、臭化カリ ゥムの如き現像抑制剤；エチレングリコール、ジエチレングリコール、トリエチレングリコ ール、ジメチルホルムアミドの如き有機溶剤；ジエタノールァミン、トリエタノールァミン 等のアルカノールァミン、イミダゾールまたはその誘導体等の現像促進剤や、メルカ プト系化合物、インダゾール系化合物、ベンゾトリアゾール系化合物、ベンゾイミダゾ ール系化合物をカプリ防止剤または黒ポッ (black pepper)防止剤として含んでもよ い。上記べンゾイミダゾール系化合物としては、具体的に、 5— -トロインダゾール、 5 p -トロべンゾィルァミノインダゾール、 1ーメチルー 5 -トロインダゾール、 6— ニトロインダゾール、 3—メチルー 5— -トロインダゾール、 5— -トロべンズイミダゾー ル、 2—イソプロピル— 5 -トロべンズイミダゾール、 5 -トロべンズトリァゾール、 4 一〔（2 メルカプト 1, 3, 4ーチアジアゾールー 2 ィル）チォ〕ブタンスルホン酸ナ トリウム、 5 アミノー 1, 3, 4 チアジアゾールー 2 チオール、メチルベンゾトリアゾ ール、 5 メチルベンゾトリァゾール、 2 メルカプトべンゾトリアゾールなどを挙げるこ とができる。これらべンゾイミダゾール系化合物の含有量は、通常、現像液 1リットル 当り 0. 01〜： LOmmolであり、より好ましくは、 0. l〜2mmolである。 In addition to the above, 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. Specific examples of the benzoimidazole compounds include 5—-troindazole, 5 p-trobenzoylaminoindazole, 1-methyl-5-troindazole, 6-nitroindazole, 3-methyl-5--. Troindazole, 5--trobens imidazole, 2-isopropyl-5-trobens imidazole, 5-trobenstriazole, 4 1 [(2 mercapto 1, 3, 4-thiadiazol-2 yl) thio] butanesulfone Examples include sodium acid, 5 amino-1, 3, 4 thiadiazole-2 thiol, methylbenzotriazole, 5 methylbenzotriazole, and 2 mercaptobenzotriazole. You can. 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.
[0067] さらに上記現像液中には、各種の有機 ·無機のキレート剤を併用することができる。 Furthermore, various organic / inorganic chelating agents can be used in combination in the developer.
上記無機キレート剤としては、テトラポリリン酸ナトリウム、へキサメタリン酸ナトリウム等 を用いることができる。一方、上記有機キレート剤としては、主に有機カルボン酸、アミ ノポリカルボン酸、有機ホスホン酸、ァミノホスホン酸および有機ホスホノカルボン酸を 用!/、ることができる。  Examples of the inorganic chelating agent that can be used include sodium tetrapolyphosphate and sodium hexametaphosphate. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used.
上記有機カルボン酸としては、アクリル酸、シユウ酸、マロン酸、コハク酸、ダルタル 酸、アジピン酸、ピメリン酸、コハク酸、ァゼライン酸、セバチン酸、ノナンジカルボン 酸、デカンジ力ノレボン酸、ゥンデカンジ力ノレボン酸、マレイン酸、ィタコン酸、リンゴ酸 、クェン酸、酒石酸等を挙げることができるがこれらに限定されるものではない。  Examples of the above organic carboxylic acids 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. , Maleic acid, itaconic acid, malic acid, citrate, tartaric acid and the like, but are not limited thereto.
[0068] 上記アミノポリカルボン酸としては、イミノニ酢酸、二トリ口三酢酸、二トリ口三プロピオ ン酸、エチレンジァミンモノヒドロキシェチル三酢酸、エチレンジァミン四酢酸、グリコ ールエーテル四酢酸、 1, 2—ジァミノプロパン四酢酸、ジエチレントリアミン五酢酸、 トリエチレンテトラミン六酢酸、 1, 3—ジアミノー 2—プロパノール四酢酸、グリコール エーテルジァミン四酢酸、その他特開昭 52— 25632号、同 55— 67747号、同 57— 102624号の各公報、および特公昭 53— 40900号公報等に記載の化合物を挙げ ることがでさる。 [0068] Examples of the aminopolycarboxylic acid 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- The compounds described in each publication of Japanese Patent No. 102624 and Japanese Patent Publication No. 53-40900 can be mentioned.
[0069] これらキレート剤の添カ卩量としては、現像液 1リットル当り好ましくは、 1 X 10— 4〜1 X [0069] The添Ka卩量these chelating agents, preferably the developing solution per liter, 1 X 10- 4 ~1 X
10— 1モノレ、より好ましく ίま 1 X 10— 3〜1 X 10— 2モノレである。 10 1 Monore, more preferably ί or 1 X 10 3 to 1 X 10- 2 Monore.
[0070] さらに、現像液中に溶解助剤として特開昭 61— 267759号公報記載の化合物を用 いることができる。さらに現像液には、必要に応じて色調剤、界面活性剤、消泡剤、 硬膜剤等を含んでもよい。現像処理温度および時間は相互に関係し、全処理時間と の関係において決定される力 一般に現像温度は約 20°C〜約 50°Cが好ましぐ 25 〜45°Cがさらに好ましい。また、現像時間は 5秒〜 2分が好ましぐ 7秒〜 1分 30秒が さらに好ましい。  [0070] Furthermore, the compounds described in JP-A-61-267759 can be used as a dissolution aid in the developer. Further, 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. Generally, 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.
[0071] 現像液の搬送コスト節減、包装材料コスト節減、省スペース等の目的から、現像液 を濃縮ィ匕し、使用時に希釈して用いるようにする態様、すなわち液体濃縮現像剤とし て供給する態様も好ましい。現像液の濃縮化のためには、現像液に含まれる塩成分 をカリウム塩ィ匕することが有効である。なお、ここでいう「現像液の濃縮化」とは当業界 の慣用表現であって、「濃厚化」を意味するものであって、減圧蒸発などによる「濃縮 」を意味するものではない。 [0071] For the purpose of reducing developer transport cost, packaging material cost, space saving, etc., 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. Here, “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.
[0072] [定着処理]  [0072] [Fixing treatment]
現像処理に続いて好ましくは未露光部分の銀塩を除去して安定化させる目的で定 着処理が行われるが、本発明においては定着処理を省略することもできる。とくに現 像処理が溶解物理現像によって行われる場合には、未露光部のハロゲン化銀は現 像過程でかなり溶解され、消滅しているのが一般的である。しカゝしながら、現像が化 学現像型の現像処方で行われる場合には、定着処理によって未露光部すなわち透 光性部の透明度を増大させることが好ま U、。  Subsequent to the development process, 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. In particular, when the current image processing is performed by dissolution physical development, the unexposed silver halide is generally dissolved and disappeared during the current image process. However, when 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.
定着処理は、必ずしも現像処理に続いて行う必要はなぐ後述する電解メツキ工程 の後に行ってもよい。  The fixing process is not necessarily performed after the development process, and may be performed after an electrolytic plating process described later.
本発明における定着処理は、カラー写真用や黒白銀塩写真フィルム、印画紙、印 刷製版用フィルム、 X線写真フィルム用、フォトマスク用ェマルジヨンマスク等に用い られる通常の定着処理の技術を用いることができる。  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.
[0073] 上記定着工程で使用する定着液の好ましい成分としては、以下が挙げられる。  [0073] Preferable components of the fixing solution used in the fixing step include the following.
すなわち、チォ硫酸ナトリウム、チォ硫酸アンモ-ゥム、チォシアン酸カリウムなどの 定着剤、必要により酒石酸、クェン酸、ダルコン酸、ホウ酸、イミノジ酢酸、 5—スルホ サリチル酸、ダルコヘプタン酸、タイロン及びこれらの塩などの pH緩衝剤ゃ保恒剤、 エチレンジァミン四酢酸、ジエチレントリアミン五酢酸、二トリ口三酢酸及びこれらの塩 などの硬水軟化剤等を含むことが好ましい。ただし、近年の環境保護の観点からは、 ホウ酸は含まれな 、方が好ま ヽ。本発明に用いられる定着液の定着剤としてはチ ォ硫酸ナトリウム、チォ硫酸アンモ-ゥムなどが挙げられ、定着速度の点からはチォ 硫酸アンモ-ゥムが好ましいが、近年の自然環境保全の観点力 全窒素量の水質規 制に鑑みてチォ硫酸ナトリウムが使われてもよい。これら既知の定着剤の使用量は適 宜変えることができ、一般には約 0. 1〜約 2モル Zリットルである。特に好ましくは、 0 . 2〜1. 5モル Zリットルである。定着液には所望により、硬膜剤（例えば水溶性アル ミニゥム化合物）、保恒剤（例えば、亜硫酸塩、重亜硫酸塩）、 pH緩衝剤（例えば、酢 酸)、 pH調整剤 (例えば、アンモニア、硫酸)、キレート剤、界面活性剤、湿潤剤、定 着促進剤を含むことができる。 In other words, 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 It is preferable to include a preservative such as a pH buffering agent such as ethylenediamine amine acetic acid, diethylenetriaminepentaacetic acid, ditrimethyl triacetic acid and salts thereof. However, from the viewpoint of environmental protection in recent years, 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. If desired, 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 An adhesion promoter can be included.
上記界面活性剤としては、例えば硫酸ィ匕物、スルホンィ匕物などのァニオン界面活 性剤、ポリエチレン系界面活性剤、特開昭 57— 6740号公報記載の両性界面活性 剤などが挙げられる。また、上記定着液には、公知の消泡剤を添加してもよい。  Examples of the surfactant include anionic surfactants such as sulfates and sulfones, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. A known antifoaming agent may be added to the fixing solution.
上記湿潤剤としては、例えば、アルカノールァミン、アルキレングリコールなどが挙 げられる。また、上記定着促進剤としては、例えば特公昭 45— 35754号、同 58— 1 22535号、同 58— 122536号の各公報に記載のチォ尿素誘導体；分子内に 3重結 合を持つアルコール；米国特許 US第 4126459号明細書記載のチォエーテル化合 物；特開平 4— 229860号公報記載のメソイオンィ匕合物などが挙げられ、特開平 2— 44355号公報記載の化合物を用いてもよい。また、上記 pH緩衝剤としては、例えば 酢酸、リンゴ酸、こはく酸、酒石酸、クェン酸、シユウ酸、マレイン酸、グリコール酸、ァ ジピン酸などの有機酸や、ホウ酸、リン酸塩、亜硫酸塩などの無機緩衝剤が使用でき る。上記 pH緩衝剤として好ましくは、酢酸、酒石酸、亜硫酸塩が用いられる。ここで p H緩衝剤は、現像液の持ち込みによる定着剤の pH上昇を防ぐ目的で使用され、好 ましくは 0. 01〜： L 0モル Zリットル、より好ましくは 0. 02〜0. 6モル Zリットル程度 用いる。定着液の pHは 4. 0〜8. 0力 S好ましく、特に好ましくは 4. 5〜7. 5の範囲で ある。  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. As the pH buffer, acetic acid, tartaric acid, and sulfite are preferably used. Here, 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.
本発明では、迅速定着が可能なように定着液を高活性にするために水溶性ハライ ドを添加することが好ましい。好ましい水溶性ノヽライドは、アルカリ金属の臭化物及び よう化物ならびに臭化アンモ-ゥム及びよう化アンモ-ゥムであり、好ましいアルカリ 金属塩は、ナトリウム塩及びカリウム塩である。水溶性ハライドの全添加量は、 0. 035 〜0. 5モノレ/ Lであり、より好ましくは 0. 05〜0. 4モノレ/ Lである。水溶性ハライドの中 には、ようィ匕カリウム、ようィ匕ナトリウム、ようィ匕アンモ-ゥムなどの水溶性ようィ匕物が含 まれていることが特に好ましぐその場合の水溶性ようィ匕物の添加量は 0. 005〜0. 0 5モル/ Lである。  In the present invention, it is preferable to add a water-soluble halide in order to make the fixing solution highly active so that rapid fixing is possible. Preferred 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.
水溶性ハライドは、 pAgを高く調整することに加えて定着工程に続くめっき工程に おいて金属析出速度を高める作用を有しており、特によう素イオンの効果が大きい。 In addition to adjusting pAg to a high level, water-soluble halides are used in the plating process following the fixing process. In particular, it has the effect of increasing the metal deposition rate, and the effect of iodine ions is particularly great.
[0075] 本発明の定着液中の硬膜剤としては、水溶性アルミニウム塩、クロム塩が挙げられ る。上記硬膜剤として好ましい化合物は、水溶性アルミニウム塩であり、例えば塩ィ匕 アルミニウム、硫酸アルミニウム、カリ明バンなどが挙げられる。上記硬膜剤の好まし い添カロ量は 0. 01モノレ〜 0. 2モノレ/リットノレであり、さらに好ましくは 0. 03〜0. 08モ ル Zリットルである。 [0075] 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.
[0076] 上記定着工程における定着処理温度および時間は、相互に関係し、全処理時間と の関係において決定される力 本発明の高活性の迅速定着液では、 30〜60°Cで 5 〜40秒で未露光部のハロゲンィ匕銀粒子の定着を完了させる活性を有する。好ま ヽ 定着温度は 30°C〜60°Cであり、 35〜55°Cがさらに好ましい。また、定着時間は 5秒 〜40秒力 子ましく、 7秒〜 30秒がさらに好まし 、。  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. In the highly active rapid fixing solution of the present invention, 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 は Fixing temperature is 30 ° C-60 ° C, more preferably 35-55 ° C. Also, the fixing time is 5 to 40 seconds, more preferably 7 to 30 seconds.
定着液の補充量は、感光材料の処理量に対して 1600mlZm2以下が好ましぐ 70 OmlZm2以下がさらに好ましい。補充液の濃度は、定められた補充量のもとで処理 中の消費を補償するに見合う濃度に設定される。 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.
[0077] [水洗処理、安定化処理など]  [0077] [Washing treatment, stabilization treatment, etc.]
現像、定着処理を施した感光材料は、続いて、又は次に述べるめっき処理の後に、 あるいは、現像、定着処理後とめっき処理後の両方で、水洗処理や安定化処理 (水 洗代替安定化処理とも言う）を施されるのが好ま 、。上記水洗処理または安定化処 理においては、水洗水量 (又は安定化液補充量）は通常感光材料 lm2当り、 20リット ル以下で行われ、 3リットル以下の補充量 (0も含む、すなわちため水水洗)で行うこと もできる。このため、節水処理が可能となるのみならず、自動現像機設置の配管を不 要とすることができる。水洗水の補充量を少なくする方法としては、古くから多段向流 方式 (例えば 2段、 3段など）が知られている。この多段向流方式を本発明の製造方 法に適用した場合、定着後の感光材料は徐々に正常な方向、即ち定着液で汚れて V、な 、処理液の方向に順次接触して処理されて 、くので、さらに効率のょ 、水洗が なされる。また、水洗を少量の水で行う場合は、特開昭 63— 18350号、同 62— 287 252号各公報などに記載のスクイズローラー、クロスオーバーローラーの洗浄槽を設 けることがより好ましい。また、少量水洗時に問題となる廃水汚濁に係る環境負荷低 減のためには、種々の酸化剤添加やフィルター濾過を組み合わせてもよい。さらに、 上記方法においては、水洗浴または安定ィ匕浴に防黴手段を施した水を、処理に応じ て補充することによって生じた水洗浴または安定ィ匕浴力ものオーバーフロー液の一 部または全部を、特開昭 60— 235133号公報に記載されているようにその前の処理 工程である定着能を有する処理液に利用することもできる。また、少量水洗時に発生 し易い水泡ムラ防止および Zまたはスクイズローラーに付着する処理剤成分が処理 されたフィルムに転写することを防止するために、水溶性界面活性剤や消泡剤を添 カロしてちょい。 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). In the above washing treatment or stabilization treatment, 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. As a method for reducing the replenishment amount of flush water, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time. When this multi-stage counter-current method is applied to the production method of the present invention, 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. Further, in the above method, 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. As described in JP-A-60-235133, it can also be used for a processing solution having fixing ability, which is a previous processing step. In addition, 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. Hey.
[0078] また、上記水洗処理または安定ィ匕処理にお!、ては、感光材料から溶出した染料に よる汚染防止に、特開昭 63— 163456号公報に記載の色素吸着剤を水洗槽に設置 してもよい。また、水洗処理に続いて安定ィ匕処理においては、特開平 2— 201357号 、同 2— 132435号、同 1 102553号、特開日召 46— 44446号の各公報に記載のィ匕 合物を含有した浴を、感光材料の最終浴として使用してもよい。この際、必要に応じ てアンモ-ゥム化合物、 Bi、 A1などの金属化合物、蛍光増白剤、各種キレート剤、膜 pH調節剤、硬膜剤、殺菌剤、防かび剤、アルカノールァミンや界面活性剤を加える こともできる。水洗工程または安定ィ匕工程に用いられる水としては水道水のほか脱ィ オン処理した水やハロゲン、紫外線殺菌灯や各種酸化剤 (オゾン、過酸化水素、塩 素酸塩など)等によって殺菌された水を使用することが好ましい。また、特開平 4— 39 652号、特開平 5— 241309号公報記載の化合物を含む水洗水を使用してもよい。 水洗処理または安定ィ匕温度における浴温度および時間は 0〜50°C、 5秒〜 2分であ ることが好ましい。  [0078] Further, in the water washing treatment or the stable water treatment, for the purpose of preventing contamination by the dye eluted from the photosensitive material, the dye adsorbent described in JP-A-63-163456 is added to the water washing tank. May be installed. In addition, in the stable water treatment following the water washing treatment, 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. At this time, if necessary, 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.
[0079] 本発明に用いられる現像液や定着液等の処理液の保存には、特開昭 61— 73147 号公報に記載された酸素透過性の低い包材で保存することが好ましい。また、補充 量を低減する場合には処理槽の空気との接触面積を小さくすることによって液の蒸 発、空気酸ィ匕を防止することが好ましい。ローラー搬送型の自動現像機については 米国特許 US第 3025779号明細書、同第 3545971号明細書などに記載されてい るものも用いることができる。また、ローラー搬送型プロセッサ一は現像、定着、水洗 および乾燥の四工程力もなることが好ましぐ本発明においても、他の工程 (例えば、 停止工程)を除外しないが、この四工程を踏襲するのが最も好ましい。また、水洗ェ 程の代わりに安定ィ匕工程による四工程でも構わない。 [0079] For storage of a processing solution such as a developing solution or a fixing solution used in the present invention, it is preferable to store with a packaging material having low oxygen permeability described in JP-A-61-73147. Further, when reducing 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. As the roller-conveying type automatic developing machine, those described in US Pat. Nos. 30,257,795 and 3,545971 can be used. Also, in the present invention where it is preferable that 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.
[0080] 本発明に適用される前記ハロゲン化銀感光材料である限り、現像処理後の露光部 に含まれる金属銀の質量は、露光前の露光部に含まれていた銀の質量に対して 50 質量％以上の含有率であることが好ましぐ 80質量％以上であることがさらに好まし V、。露光部に含まれる銀の質量が露光前の露光部に含まれて!/、た銀の質量に対し て 50質量％以上であれば、高 、導電性を得ることができるため好まし!/、。  [0080] As long as the silver halide light-sensitive material is applied to the present invention, 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! / ,.
[0081] 本発明における現像処理後の階調は、特に限定されるものではないが、 4. 0を超 えることが好ましい。現像処理後の階調が 4. 0を超えると、光透過性部の透明性を高 く保ったまま、導電性金属部の導電性を高めることができる。階調を 4. 0以上にする 手段としては、例えば、前述のロジウムイオン、イリジウムイオンのドープが挙げられる  The gradation after development processing in the present invention is not particularly limited, but is preferably more than 4.0. When the gradation after development processing exceeds 4.0, the conductivity of the conductive metal portion can be increased while keeping the transparency of the light transmissive portion high. Examples of means for setting the gradation to 4.0 or more include the aforementioned doping of rhodium ions and iridium ions.
[0082] 本発明における現像処理剤および定着処理剤は固形剤にしても液剤同様の結果 が得られる。保存安定性等の観点力 は、固形処理剤が好ましい。以下に固形処理 剤に関する記述を行う。 [0082] Even if 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.
本発明における固形剤は、公知の形態 (粉状、粒状、顆粒状、塊状、錠剤、コンパ クタ一、ブリケット、板状、棒状、ペースト状など）が使用できる。これらの固形剤は、接 触して互いに反応する成分を分離するために、水溶性のコーティング剤やフィルムで 被覆してもよいし、複数の層構成にして互いに反応する成分を分離してもよぐこれら を併用してもよい。  As the 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.
[0083] 被覆剤、造粒助剤には公知のものが使用できる力 ポリビュルピロリドン、ポリェチ レンダリコール、ポリスチレンスルホン酸、ビュル系化合物が好ましい。この他、特開 平 5— 45805号公報第 2欄の 48行〜第 3欄の 13行目が参考にできる。  [0083] The ability to use known coating agents and granulation aids Polyburylpyrrolidone, polyethylene glycol, polystyrene sulfonic acid, and bull compounds are preferred. In addition, JP-A-5-45805, column 2, line 48 to column 3, line 13 can be referred to.
[0084] 複数の層構成にする場合は、接触しても反応しない成分を互いに反応する成分の 間にはさんだ構成にして錠剤やプリケット等に加工してもよいし、公知の形態の成分 を同様の層構成にして包装してもよい。これらの方法は、たとえば特開昭 61— 2599 21号公報、同 4— 16841号公報、同 4— 78848号公報、同 5— 93991号公報等に 示されている。 [0085] 固形処理剤の嵩密度は、 0. 5〜6. Og/cm3が好ましぐ特に錠剤は 1. 0〜5. Og /cm3が好ましぐ顆粒は 0. 5〜1. 5g/cm3が好ましい。 [0084] In the case of a plurality of layers, 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. [0085] 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.
[0086] 本発明に用いることができる固形処理剤の製法は、公知のいずれの方法を用いる ことができる。たとえば、特開昭 61— 259921号公報、特開平 4— 15641号公報、特 開平 4— 16841号公報、同 4— 32837号公報、同 4— 78848号公報、同 5— 93991 号公報、特開平 4— 85533号公報、同 4— 85534号公報、同 4— 85535号公報、同 5— 134362号公報、同 5— 197070号公報、同 5— 204098号公報、同 5— 22436 1号公報、同 6— 138604号公報、同 6— 138605号公報、同 8— 286329号公報等 を参考にすることができる。  [0086] As a method for producing a solid processing agent that can be used in the present invention, any known method can be used. For example, 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.
[0087] より具体的には転動造粒法、押し出し造粒法、圧縮造粒法、解砕造粒法、撹拌造 粒法、スプレードライ法、溶解凝固法、プリケッティング法、ローラーコンパクティング 法等を用いることができる。  [0087] More specifically, 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.
[0088] 本発明における固形剤は、表面状態 (平滑、多孔質等)や部分的に厚みを変えたり 、中空状のドーナツ型にしたりして溶解性を調節することもできる。さらに、複数の造 粒物に異なった溶解性を与えたり、溶解性の異なる素材の溶解度を合わせるために 、複数の形状をとることも可能である。また、表面と内部で組成の異なる多層の造粒 物でもよい。  [0088] 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.
[0089] 固形剤の包材は、酸素および水分透過性の低い材質が好ましぐ包材の形状は袋 状、筒状、箱状などの公知のものが使用できる。また、特開平 6— 242585号公報〜 同 6— 242588号公報、同 6— 247432号公報、同 6— 247448号公報、同 6— 301 189号公報、同 7— 5664号公報、同 7— 5666号公報〜同 7— 5669号公報に開示 されているような折り畳み可能な形状にすることも、廃包材の保管スペース削減のた めには好ましい。これらの包材は、処理剤の取り出し口にスクリューキャップや、プル トップ、アルミシールをつけたり、包材をヒートシールしてもよいが、このほかの公知の ものを使用してもよぐ特に限定はしない。さらに環境保全上、廃包材をリサイクルま たはリュースすることが好まし!/、。  [0089] As the packaging material of the solid agent, a material having a low oxygen and moisture permeability is preferable. As the packaging material, 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 In order to reduce the storage space for waste packaging materials, it is also preferable to use a foldable shape as disclosed in Japanese Patent Publication Nos. 7-7669. For these packaging materials, 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!
[0090] 本発明の固形処理剤の溶解および補充の方法としては特に限定はなぐ公知の方 法を使用することができる。これらの方法としてはたとえば、撹拌機能を有する溶解装 置で一定量を溶解し補充する方法、特開平 9— 80718号公報に記載されているよう な溶解部分と完成液をストックする部分とを有する溶解装置で溶解し、ストック部から 補充する方法、特開平 5— 119454号公報、同 6— 19102号公報、同 7— 261357 号公報に記載されているような自動現像機の循環系に処理剤を投入して溶解 '補充 する方法、溶解槽を内蔵する自動現像機で感光材料の処理に応じて処理剤を投入 し溶解する方法などがある力 このほかの公知のいずれの方法を用いることもできる。 また処理剤の投入は、人手で行ってもよいし、特開平 9— 138495号公報に記載さ れて!ヽるような開封機構を有する溶解装置や自動現像機で自動開封、自動投入して もよぐ作業環境の点からは後者が好ましい。具体的には取り出し口を突き破る方法 、はがす方法、切り取る方法、押し切る方法や、特開平 6— 19102号公報、同 6— 95 331号公報に記載の方法などがある。 [0090] As 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. Further, 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. Specifically, there are a method of breaking through the take-out port, a peeling method, a cutting method, a pushing method, and the methods described in JP-A-6-19102 and JP-A-6-95331.
[硬膜溶液による前処理] [Pretreatment with dura solution]
本発明の導電性膜の製造方法は、フィルムの表面に硬膜溶液を反応させる硬膜ェ 程を有することを特徴とする。また、電解めつきに先立って硬膜溶液による処理を行う ことができ、この硬膜溶液処理を行うことにより、その後のメツキの均一性向上と感材 汚れの抑止の効果が得られる。  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. In addition, 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.
本発明にお！ヽて硬膜溶液に含まれる硬膜剤は、水性溶媒中でゼラチン膜硬化性 を増加させる任意の化合物であるのが好ましぐホルムアルデヒド、ビバリルアルデヒ ド、ダルタルアルデヒド、琥珀アルデヒド、カリ明ばん、クロム明ばん、ムコクロル酸、グ リオキザール、 1, 2—ジヒドロキシピリジン類、ジグリコールアルデヒド、 2, 4ージクロ口 — 6—ヒドロキシ一 s -トリァジンなどのヒドロキシ一 s -トリアジン類、クロトンアルデヒド 、ホウ酸、ぼう硝、パラホルムアルデヒド、硫酸アルミニウムなどが挙げられ、中でも好 ましくはホルムアルデヒド、ビバリルアルデヒド、グルタルアルデヒド、琥珀アルデヒド、 カリ明ばん、クロム明ばん、硫酸アルミニウム力 選択される化合物であることが好ま しい。硬膜剤はより好ましくは、ダルタルアルデヒドまたは硫酸アルミニウムである。 硬膜剤の濃度は、 0. 005-1. OmolZLであることが好ましぐより好ましくは 0. 01 〜1. OmolZLであり、 0. 05〜0. 8molZLであることが最も好ましい。  In the present invention! 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. Among them, formaldehyde, bivalyl aldehyde, glutaraldehyde, sputum aldehyde, potash alum, chromium alum, and aluminum sulfate are preferred. That's right. More preferably, 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.
硬膜溶液の溶媒は、水を主体とする水性溶媒であり、水または電解質水溶液であ ることが好ましい。 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.
また、硬膜溶液には膨潤抑制作用のある化合物を添加することが好ましい。具体的 には、 NaCl, NaBr, KI, KC1, LiCl, NaCIO , Na SO , CH CO Na, CH CO K  In addition, it is preferable to add a compound having a swelling inhibiting action to the dura solution. Specifically, NaCl, NaBr, KI, KC1, LiCl, NaCIO, Na SO, CH CO Na, CH CO K
4 2 4 3 2 3 2 4 2 4 3 2 3 2
, CH CO NH , (NH ) SOの塩、などが挙げられる。水溶性塩のカチオン部として, CH 2 CO 3 NH 4, (NH 2) SO salt, and the like. As cation part of water-soluble salt
3 2 4 4 2 4 3 2 4 4 2 4
テトラエチルアンモ -ゥム力テトラプチルアンモ-ゥム，ァ-オン部としてハライドィォ ン，過塩素イオン，トシラートイオン，テトラフルォロホウ酸イオン，へキサフルォロリン 酸イオン等を組み合わせた第四級アンモ-ゥム塩、などを添加してもよい。膨潤抑制 剤としてとくに好ましいのは Na SOである。  Tetraethylammonium force, tetraptylammonium, quaternary ammonia combined with halide, perchlorate ion, tosylate ion, tetrafluoroborate ion, hexafluorophosphate ion, etc. Umu salt, etc. may be added. Particularly preferred as a swelling inhibitor is Na 2 SO.
2 4  twenty four
本発明の硬膜溶液への浸漬時間は、好ましくは 2秒〜 10分であり、より好ましくは 5 秒〜 5分である。  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.
本発明の硬膜溶液の温度は、好ましくは 15°C〜60°Cであり、より好ましくは 25°C〜 55°Cである。  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.
[0092] [電解めつき処理] [0092] [Electrolytic plating process]
本発明では、前記露光及び現像処理により形成された金属銀部に導電性を付与 する目的で、前記金属銀部に導電性金属粒子を担持させるための電解めつき処理 を行う。  In the present invention, for the purpose of imparting conductivity to the metal silver portion formed by the exposure and development processing, an electrolytic plating process is carried out for supporting the conductive metal particles on the metal silver portion.
本発明において、電解めつき処理は、現像処理に続いて、又は現像処理後定着処 理を行ったのち、あるいは現像処理後又は現像処理後の水洗や水洗代替リンスの後 に行われる。いずれの段階で電解めつきを行うかは適宜選択できる。ただし、硬膜処 理はめつき処理に先立って行われることが好まし!/、。  In the present invention, 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. In which stage the electrolytic plating is performed can be selected as appropriate. However, it is preferable to perform the dura mating process prior to the mating process!
[0093] (電解めつき） [0093] (Electrolytic plating)
本発明において電解めつきは、未露光部に金属沈積が生じない緩や力な電解液 条件 (安定性が高い)で行うことができる点で無電解めつきよりも好ましぐさらに 5 mZhr以上の高速めつきも可能である。めっき処理において、めっき液の安定性を高 める観点からは、例えば、 EDTAなどの配位子など種々の添加剤を用いることができ る。  In the present invention, 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. In the plating treatment, various additives such as a ligand such as EDTA can be used from the viewpoint of increasing the stability of the plating solution.
電解めつきに用いられてめっきされる金属種は、無電解めつきの項で述べた金属 種と同じであり、好ましい金属種も同じである。特に銅及び銀めつきが好ましい。 [0094] 電解液は、めっきされる金属の金属化合物を必要濃度に溶解できて、電解に適し た十分に低!、液抵抗 (電極である現像銀との接触抵抗、電解液の通電抵抗の合計） が確保できる限り、いずれでも用いることができる。したがって、用いられる金属化合 物に応じて適宜選択されるが、一般にめつき対象金属が銅、銀などであるので、硫酸 、塩酸、硝酸などの無機酸の水溶液が好ましい。また、銀、銅がアンミン錯体ゃヒドロ キシァミノ錯体を形成し易いこと力 水酸ィ匕アンモ-ゥム（アンモニア水）、アルカノー ルァミン水溶液、好ましくはエタノールァミン、ジェエタノールァミンあるいはトリェタノ ールァミン水溶液も好まし!/、。 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. [0094] 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. In addition, 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!
これらの電解液の酸、水酸ィ匕アンモ-ゥム、アルカノールァミン類の使用濃度は、 0 . 1モル ZL〜10モル ZL、好ましくは 0. 2モル ZL〜8モル ZL〜、特に好ましくは 0 . 25モル ZL〜5モル ZLである。また、めっき金属の金属化合物 0. 05モル ZL〜1 0モノレ/ L、好ましく ίま 0. 07モノレ/ L〜5モノレ/ L、特に好ましく ίま 0. 1モル/ L〜3 モル ZLである。  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. In addition, the metal compound of the plating metal is 0.05 mol ZL to 10 monolayer / L, preferably ί or 0.07 monolayer / L to 5 monolayer / L, and particularly preferably 0.25 to 0.1 mol / L to 3 mol ZL. .
電解めつきにおけるめっき液の温度は 10°C〜60°Cが好ましぐ 20°C〜50°Cがより 好ましぐ 25°C〜45°Cであるのが特に好ましい。電荷時間は、目的の金属被覆厚み が得られるように適宜調節できる力 10秒〜 600秒、好ましくは 20秒〜 450秒、特に 好ましくは 30秒〜 300秒となるように印加電圧 (許容範囲内で）、液組成や温度を調 整する。  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.
好ましい金属化合物とめっき液組成の例としては、例えば銅めつきの場合は、硫酸 銅五水塩を 30〜300gZL、硫酸を 30〜300g/Lを含むものを用いることができる。 銀めつきの場合は、硝酸銀を 30〜300gZL含む中性乃至酸性水溶液やアンモニア 性アルカリ水溶液を用いることができる。なお、ニッケルめっきの場合は、硫酸-ッケ ル、塩酸ニッケル、銀めつきの場合はシアンィ匕銀などを含むものを用いることができる 。また、めっき液には、界面活性剤、硫黄化合物、窒素化合物等の添加剤を添加し ても良い。  As an example of 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. In the case of silver plating, a neutral or acidic aqueous solution or ammoniacal alkaline aqueous solution containing 30 to 300 g ZL of silver nitrate can be used. In the case of 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. In addition, an additive such as a surfactant, a sulfur compound, or a nitrogen compound may be added to the plating solution.
[0095] 本発明における電解めつきの態様の典型例を以下によって説明する力 本発明は これに限定されるものではない。本発明に係るめっき処理を好適に実施するための めっき装置は、公知の装置と同様に、フィルムが巻き付けられた繰り出し用リール（図 示せず)から順次繰り出されたフィルムを電解めつき槽に送り込み、めっき後のフィル ムを卷取り用リール（図示せず）に順次巻き取る構成となって 、ることが好ま 、。 [0095] The power to explain a typical example of the embodiment of electroplating in the present invention is as follows. The present invention is not limited to this. 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).
[0096] 図 1に本発明に係るめっき処理に好適に用いられる電解めつき槽の一例を示す。こ の図 1に示す電解めつき装置 10は、長尺のフィルム 16に連続してめっき処理を施す ことができるものである。矢印はフィルム 16の搬送方向を示している。電解めつき装 置 10は、めっき液 15を貯留する電解槽 11を備えている。電解槽 11内には、一対の アノード板 13が平行に配設され、アノード板 13の内側には、一対のガイドローラ 14 がアノード板 13と平行に回動可能に配設されている。ガイドローラ 14は垂直方向に 移動可能で、これによりフィルム 16のめつき処理時間を調整できる。 [0096] 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.
[0097] 電解槽 11の上方には、フィルム 16を電解槽 11に案内するとともにフィルム 16に電 流を供給する給電ローラ (力ソード） 12a, 12bがそれぞれ一対回転自在に配設され ている。また、電解槽 11の上方には、出口側の給電ローラ 12bの下方に液切りローラ 17が回動可能に配設されている。 Above the electrolytic cell 11, 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.
アノード板 13は、電線（図示せず)を介して電源装置（図示せず)のプラス端子に接 続され、給電ローラ 12a, 12bは、電源装置（図示せず)のマイナス端子に接続されて いる。  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.
[0098] フィルム 16を繰り出しリール（図示せず）に巻かれた状態でセットして、フィルム 16 のめつきを形成すべき側の面が給電ローラ 12a, 12bと接触するように、フィルム 16を 搬送ローラ（図示せず）に巻き掛ける。  [0098] 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).
アノード板 13および給電ローラ 12a, 12bに電圧を印加し、フィルム 16を給電ロー ラ 12a, 12bに接触させながら搬送する。フィルム 16を電解槽 11に導入し、めっき液 15に浸せきして銅めつきを形成する。液切りローラ 17間を通過する際に、フィルム 16 に付着しためっき液 15拭い取り、電解槽 11に回収する。これを複数の電解めつき槽 で繰り返し、最後に水洗した後、卷取りリール（図示せず）に巻き取る。  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. When passing between the liquid draining rollers 17, 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).
フィルム 16の搬送速度は、 l〜30mZ分の範囲で設定される。フィルム 16の搬送 速度は、好ましくは、 1〜： LOmZ分の範囲であり、より好ましくは、 2〜5mZ分の範囲 である。  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.
[0099] 電解めつき槽の数は、特に限定されないが、 2〜10槽が好ましぐ 3〜6槽がより好 ましい。 [0099] The number of electrolytic plating baths is not particularly limited, but 2-10 baths are preferred, and 3-6 baths are more preferred. Good.
印加電圧は、 0. 5〜： L00Vの範囲であることが好ましぐ 1〜60Vの範囲であること 力 り好ましい。  The applied voltage is preferably in the range of 0.5 to L00V, and more preferably in the range of 1 to 60V.
給電ローラ 12a, 12bはフィルム全面 (接触している面積のうちの実質的に電気的 に接触して ヽる部分が 80%以上）と接触して ヽることが好ま ヽ。  It is preferable that 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).
[0100] 上記めつき処理によりめつきされる導電性金属部の厚さは、ディスプレイの電磁波 シールド材の用途としては、薄いほどディスプレイの視野角が広がるため好ましい。さ らに、導電性配線材料の用途としては、高密度化の要請力も薄膜ィ匕が要求される。こ のような観点から、めっきされた導電性金属力もなる層の厚さは、 9 m未満であるこ と力 S好ましく、 0. 1 m以上 5 μ m未満であること力 Sより好ましく、 0. 1 m以上 3 μ m 未満であることがさらに好ましい。  [0100] 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 μm, more preferably less than force S. More preferably, it is 1 m or more and less than 3 μm.
[0101] 図 2に本発明の導電性膜の一例を示す。図 2に示す導電性膜 21は支持体 23上に 導電性機能層 22を有する。導電性機能層 22はハロゲン化銀乳剤層 28を含有して いる。例えば、露光部 24に露光'現像処理等を行うことにより、金属銀部を形成する ことができ、さらに導電性を高めるため、電解めつきを施すことにより導電性金属部を 形成することができる。なお、一例として、電解めつき処理部 26に Cuを電解めつきし 、電解めつき処理部 27に Niを電解めつきする態様などがある。未露光部 25は光透 過性部（一例としては、ゼラチンからなるもの）となる。  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. For example, 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. . As an example, there is a mode in which Cu is electrolytically attached to the electrolytic plating treatment part 26 and Ni is electrolytically attached to the electrolytic plating treatment part 27. The unexposed part 25 becomes a light-transmitting part (for example, made of gelatin).
[0102] [酸化処理]  [0102] [Oxidation treatment]
本発明では、現像処理後の金属銀部、並びにめつき処理後に形成される導電性金 属部には、好ましくは酸ィ匕処理が行われる。酸化処理を行うことにより、例えば、光透 過性部に金属が僅かに沈着していた場合に、該金属を除去し、光透過性部の透過 性をほぼ 100%にすることができる。  In the present invention, 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. By performing the oxidation 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.
酸化処理としては、例えば、 Fe (III)イオン処理など、種々の酸化剤を用いた公知の 方法が挙げられる。酸化処理は、銀塩含有層の露光及び現像処理後、あるいはめつ き処理後に行うことができ、さらに現像処理後とめっき処理後のそれぞれで行っても よい。  Examples of the oxidation treatment 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.
[0103] 本発明では、さらに露光及び現像処理後の金属銀部を、 Pdを含有する溶液で処 理することもできる。 Pdは、 2価のパラジウムイオンであっても金属パラジウムであって もよ 、。この処理により無電解めつき速度を促進させることができる。 [0103] In the present invention, the metallic silver portion after the exposure and development treatment is further treated with a solution containing Pd. You can also Pd may be divalent palladium ion or metallic palladium. This treatment can accelerate the electroless plating speed.
[0104] [導電性金属部] [0104] [Conductive metal part]
次に、本発明における導電性金属部につ!、て説明する。  Next, the conductive metal portion in the present invention will be described.
本発明では、導電性金属部は、前述した露光及び現像処理により形成された金属 銀部をめつき処理することにより前記金属銀部に導電性金属粒子を担持させることに より形成される。  In the present invention, 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.
金属銀は、露光部に形成させる場合と、感光材料としてオートポジ材料を用いたり、 現像処理に反転現像を用 、るなどによって未露光部に形成させると場合がある。本 発明においては、透明性を高めるために露光部に金属銀を形成させることが好まし い。  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.
前記金属部に担持させる導電性金属としては、上述した銀、銅のほか、アルミ-ゥ ム、ニッケル、鉄、金、コノ ルト、スズ、ステンレス、タングステン、クロム、チタン、パラ ジゥム、白金、マンガン、亜鉛、ロジウムなどの金属、又はこれらを組み合わせた合金 の粒子を挙げることができる。導電性、価格等の観点から導電性金属は、銅、アルミ ニゥム又はニッケルの粒子であることが好ましい。また、磁場シールド性を付与する場 合、導電性金属として常磁性金属を用いることが好ま 、。  As 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. From the viewpoint of conductivity, cost, etc., the conductive metal is preferably copper, aluminum or nickel particles. In addition, when providing magnetic field shielding properties, it is preferable to use a paramagnetic metal as the conductive metal.
[0105] 上記導電性金属部において、コントラストを高くし、かつ導電性金属部が経時的に 酸化され退色されるのを防止する観点からは、導電性金属部に含まれる導電性金属 は銅であることが好ましぐ少なくともその表面が黒ィ匕処理されたものであることがさら に好ましい。黒ィ匕処理は、プリント配線板分野で行われている方法を用いて行うこと ができる。例えば、亜塩素酸ナトリウム（31gZD、水酸ィ匕ナトリウム（15gZD、リン酸 三ナトリウム（12gZDの水溶液中で、 95°Cで 2分間処理することにより黒化処理を行 うことができる。 [0105] From the viewpoint of increasing the contrast in the conductive metal part and preventing the conductive metal part from being oxidized and discolored over time, 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)).
[0106] 上記導電性金属部は、該導電性金属部に含まれる金属の全質量に対して、銀を 5 0質量％以上含有することが好ましぐ 60質量％以上含有することがさらに好ましい。 銀を 50質量％以上含有すれば、めっき処理に要する時間を短縮し、生産性を向上 させ、かつ低コストとすることができる。 さらに、導電性金属部を形成する導電性金属粒子として銅及びパラジウムが用いら れる場合、銀、銅及びパラジウムの合計の質量が導電性金属部に含まれる金属の全 質量に対して 80質量％以上であることが好ましぐ 90質量％以上であることがさらに 好ましい。 [0106] 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.
[0107] 本発明における導電性金属部は、導電性金属粒子を担持するため良好な導電性 が得られる。このため、本発明の電磁波シールド膜 (導電性金属部）の表面抵抗値は 、 103 Q Zsq以下であることが好ましぐ 2. 5 Ω /sq以下であることがより好ましぐ 1. 5 Ω Zsq以下であることがさらに好ましい。 [0107] Since the conductive metal portion in the present invention carries conductive metal particles, good conductivity can be obtained. For this reason, 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 Ω / sq or less. More preferably, it is 5 Ω Zsq or less.
[0108] 本発明の導電性金属部は、透光性電磁波シールド材料としての用途である場合、 正三角形、二等辺三角形、直角三角形などの三角形、正方形、長方形、菱形、平行 四辺形、台形などの四角形、（正)六角形、（正)八角形などの (正) n角形、円、楕円 、星形などを組み合わせた幾何学図形であることが好ましぐこれらの幾何学図形か らなるメッシュ状であることがさらに好まし 、。 EMIシールド性の観点からは三角形の 形状が最も有効であるが、可視光透過性の観点力もは同一のライン幅なら (正) n角 形の n数が大きいほど開口率が上がり可視光透過性が大きくなるので有利である。 なお、導電性配線材料の用途である場合、前記導電性金属部の形状は特に限定 されず、目的に応じて任意の形状を適宜決定することができる。  [0108] When the conductive metal portion of the present invention is used as a light-transmitting electromagnetic wave shielding material, a triangle such as an equilateral triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid, etc. These 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. From the viewpoint of EMI shielding properties, 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. In addition, when it is a use of an electroconductive wiring material, the shape of the said electroconductive metal part is not specifically limited, Arbitrary shapes can be suitably determined according to the objective.
[0109] 透光性電磁波シールド材料の用途にお!、て、上記導電性金属部の線幅は 40 μ m 以下、線間隔は 50 /z m以上であることが好ましい。また、導電性金属部は、アース接 続などの目的においては、線幅は 20 mより広い部分を有していてもよい。また画像 を目立たせなくする観点からは、導電性金属部の線幅は 40 μ m未満であることが好 ましぐ 35 m未満であることがより好ましぐ 30 m未満であることがさらに好ましぐ 25 μ m未満であることが最も好ま U、。  [0109] For use as a light-transmitting electromagnetic wave shielding material, the conductive metal portion preferably has a line width of 40 μm or less and a line spacing of 50 / z m or more. In addition, the conductive metal part may have a part with a line width wider than 20 m for purposes such as ground connection. Also, from the viewpoint of making the image inconspicuous, the line width of the conductive metal part is preferably less than 40 μm, more preferably less than 35 m, and even more preferably less than 30 m. U, most preferred to be less than 25 μm.
[0110] 本発明における導電性金属部は、可視光透過率の点から開口率は 85%以上であ ることが好ましぐ 90%以上であることがさらに好ましぐ 95%以上であることが最も好 ましい。開口率とは、メッシュをなす細線のない部分が全体に占める割合であり、例え ば、線幅 10 μ m、ピッチ 200 μ mの正方形の格子状メッシュの開口率は、 90%であ る。 [0111] [光透過性部] [0110] From the viewpoint of visible light transmittance, 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 μm and a pitch of 200 μm is 90%. [0111] [Light transmissive part]
本発明における「光透過性部」とは、電磁波シールド膜のうち導電性金属部以外の 透明性を有する部分を意味する。光透過性部における透過率は、前述のとおり、支 持体の光吸収及び反射の寄与を除いた 380〜780nmの波長領域における透過率 の最小値で示される透過率が 90%以上、好ましくは 95%以上、さらに好ましくは 97 %以上であり、さらにより好ましくは 98%以上であり、最も好ましくは 99%以上である  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. As described above, 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
[0112] 光透過性部は、透過性を向上させる観点から実質的に物理現像核を有しないこと が好ましい。本発明は、従来の銀錯塩拡散転写法とは異なり、未露光のハロゲンィ匕 銀を溶解し、可溶性銀錯化合物に変換させた後、拡散させる必要がないため、光透 過性部には物理現像核を実質的に有しな 、ことが好ま 、。 [0112] It is preferable that the light-transmitting portion has substantially no physical development nucleus from the viewpoint of improving the transmittance. Unlike the conventional silver complex salt diffusion transfer method, 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.
ここに、「実質的に物理現像核を有しない」とは、光透過性部における物理現像核 の存在率が 0〜5%の範囲であることを!、う。  Here, “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%.
[0113] 本発明における光透過性部は、前記銀塩含有層を露光及び現像処理することによ り、金属銀部と共に形成される。光透過性部は、透過性を向上させる観点から、前記 現像処理後、さらには物理処理又はめつき処理後に酸ィ匕処理を行うことが好ましい。  [0113] 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. From the viewpoint of improving the transmittance, 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.
[0114] 光透過性部の乾燥膜厚は 2. 0 m以下であることが好ましい。また、光透過性部 は水溶性ポリマー力もなることが好まし 、。  [0114] The dry film thickness of the light-transmitting part is preferably 2.0 m or less. In addition, it is preferable that the light-transmitting part has water-soluble polymer power.
[0115] [電磁波シールド膜の層構成]  [0115] [Layer structure of electromagnetic shielding film]
本発明の電磁波シールド膜における支持体の厚さは、 5〜200 /z mであることが好 ましぐ 30〜150 /ζ πιであることがさらに好ましい。 5〜200 mの範囲であれば所望 の可視光の透過率が得られ、かつ取り扱!/、も容易である。  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 / ζ πι. 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.
[0116] めっき処理前の支持体上に設けられる金属銀部の厚さは、支持体上に塗布される 銀塩含有層用塗料の塗布厚みに応じて適宜決定することができる。金属銀部の厚さ は、 30 m以下であることが好ましぐ 20 m以下であることがより好ましぐ 0. 01〜 9 μ mであることがさらに好ましぐ 0. 05〜5 μ mであることが最も好ましい。また、金 属銀部はパターン状であることが好ま U、。  [0116] 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 μm. 0.05 to 5 μm Most preferably m. In addition, it is preferable that the metallic silver part is a pattern.
[0117] 導電性金属部の厚さは、ディスプレイの電磁波シールド材の用途としては、薄いほ どディスプレイの視野角が広がるため好ましい。さらに、導電性配線材料の用途とし ては、高密度化の要請力 薄膜ィ匕が要求される。このような観点から、導電性金属部 に担持された導電性金属力もなる層の厚さは、 9 m未満であることが好ましぐ 0. 1 μ m以上 5 μ m未満であることがより好ましぐ 0. 1 m以上 3 μ m未満であることがさ らに好ましい。 [0117] 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 μm or more and less than 5 μm. It is more preferably 0.1 m or more and less than 3 μm.
本発明では、上述した銀塩含有層の塗布厚みをコントロールすることにより所望の 厚さの金属銀部を形成し、さらにめつき処理により導電性金属粒子からなる層の厚み を自在にコントロールできるため、 5 /z m未満、好ましくは 3 m未満の厚みを有する 電磁波シールド膜であっても容易に形成することができる。  In the present invention, 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.
[0118] なお、従来のエッチングを用いた方法では、金属薄膜の大部分をエッチングで除 去、廃棄する必要があつたが、本発明では必要な量だけの導電性金属を含むパター ンを支持体上に設けることができるため、必要最低限の金属量だけを用いればよぐ 製造コストの削減及び金属廃棄物の量の削減という両面から利点がある。 [0118] In the conventional method using etching, most of the metal thin film needs to be removed by etching and discarded, but 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.
[0119] [電磁波シールド膜以外の機能性膜]  [0119] [Functional films other than electromagnetic shielding films]
本発明の電磁波シールド膜は、必要に応じて、別途、機能性を有する機能層と組 合わせて用いられる。この機能層は、用途ごとに種々の仕様とすることができる。例え ば、ディスプレイ用電磁波シールド材用途としては、屈折率や膜厚を調整した反射防 止機能を付与した反射防止層や、ノングレアー層またはアンチグレアー層（共にぎら つき防止機能を有する）、近赤外線を吸収する化合物や金属からなる近赤外線吸収 層、特定の波長域の可視光を吸収する色調調節機能をもった層、指紋などの汚れを 除去しやすい機能を有した防汚層、傷のつき難いハードコート層、衝撃吸収機能を 有する層、ガラス破損時のガラス飛散防止機能を有する層などを設けることができる 。これらの機能層は、銀塩含有層と支持体とを挟んで反対側の面に設けてもよぐさ らに同一面側に設けてもよい。  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. For example, as an electromagnetic shielding material for displays, 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.
これらの機能性膜は PDPに直接貼合してもよぐプラズマディスプレイパネル本体と は別に、ガラス板やアクリル榭脂板などの透明基板に貼合してもよい。これらの機能 性膜を光学フィルター（または単にフィルター）と呼ぶ。  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).
[0120] 反射防止機能を付与した反射防止層は、外光の反射を抑えてコントラストの低下を 抑えるために、金属酸化物、フッ化物、ケィ化物、ホウ化物、炭化物、窒化物、硫ィ匕 物等の無機物を、真空蒸着法、スパッタリング法、イオンプレーティング法、イオンビ ームアシスト法等で単層あるいは多層に積層させる方法、アクリル榭脂、フッ素榭脂 等の屈折率の異なる榭脂を単層あるいは多層に積層させる方法等がある。また、反 射防止処理を施したフィルムを該フィルター上に張り付けることもできる。また必要で あればノングレアー層またはアンチグレアー層を設けることもできる。ノングレアー層 やアンチグレアー層は、シリカ、メラミン、アクリル等の微粉体をインキ化して、表面に コーティングする方法等を用いることができる。インキの硬化は熱硬化あるいは光硬 化等を用いることができる。また、ノングレア処理またはアンチグレア処理をしたフィル ムを該フィルター上に張り付けることもできる。更に必要で有ればノヽードコート層を設 けることちでさる。 [0120] The antireflection layer provided with the antireflection function suppresses reflection of outside light and reduces contrast. In order to suppress this, 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. Alternatively, 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. In addition, a film that has been subjected to anti-reflection treatment can be attached to the filter. If necessary, a non-glare layer or an anti-glare layer can be provided. For the non-glare layer and the anti-glare layer, 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. Further, a non-glare-treated or anti-glare-treated film can be pasted on the filter. If necessary, a node coat layer can be provided.
[0121] 近赤外線吸収層は、金属錯体化合物等の近赤外線吸収色素を含有する層、また は、銀スパッタ層等である。ここで銀スパッタ層とは、誘電体層と金属層を基材上に交 互にスパッタリング等で積層させることで、近赤外線、遠赤外線から電磁波まで 1000 nm以上の光をカットすることもできる。誘電体層としては酸化インジウム、酸化亜鉛等 の透明な金属酸ィ匕物等であり、金属層としては銀あるいは銀—パラジウム合金が一 般的であり、通常、誘電体層よりはじまり 3層、 5層、 7層あるいは 11層程度積層する。  [0121] The near-infrared absorbing layer is a layer containing a near-infrared absorbing dye such as a metal complex compound or a silver sputtered layer. Here, the silver 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.
[0122] 特定の波長域の可視光を吸収する色調調節機能をもった層は、 PDPが青色を発 光する蛍光体が青色以外に僅かであるが赤色を発光する特性を有しているため、青 色に表示されるべき部分が紫が力つた色で表示されるという問題があり、この対策とし て発色光の補正を行う層であり、 595nm付近の光を吸収する色素を含有する。  [0122] 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. However, there is a problem that 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.
[0123] 本発明の製造方法で得られる電磁波シールド膜は、良好な電磁波シールド性及び 透過性を有するため、透過性電磁波シールド材料として用いることができる。さらに、 回路配線などの各種の導電性配線材料として用いることができる。特に本発明の電 磁波シールド膜は、 CRT (陰極線管）、 PDP (プラズマディスプレイパネル）、液晶、 E L (エレクト口ルミネッセンス）などのディスプレイ前面、電子レンジ、電子機器、プリント 配線板など、特にプラズマディスプレイパネルで用いられる電磁波シールド膜として 好適に用いることができる。 [0124] [その他の導電性膜の構成要素] [0123] 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. In particular, 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. [0124] [Other conductive film components]
電磁波シールド膜や導電性膜で代表される本発明の導電性膜について、さらに上 記した以外の付帯構成要素につ!、て述べる。  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.
(1)接着剤層  (1) Adhesive layer
電磁波シールド膜や導電性膜 (例えば透明電極)が、光学フィルターや、液晶表示 板、プラズマディスプレーパネル、その他の画像表示グラットパネル、あるいは CCD に代表される撮像用半導体集積回路などに組み込まれる際には、接着層を介して接 合される。  When an electromagnetic shielding film or conductive film (for example, a transparent electrode) is incorporated in an optical filter, a liquid crystal display panel, a plasma display panel, other image display grat panels, or an imaging semiconductor integrated circuit such as a CCD. Are bonded via an adhesive layer.
[0125] 本発明で用いる接着剤の屈折率は 1. 40-1. 70のものを使用することが好ましい 。これは本発明で使用するプラスチックフィルム等の透明基材と接着剤の屈折率との 関係で、その差を小さくして、可視光透過率が低下するのを防ぐためであり、屈折率 が 1. 40-1. 70であると可視光透過率の低下が少なく良好である。  [0125] 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.
[0126] 本発明で用いられる接着剤は、また、加熱または加圧により流動する接着剤である ことが好ましぐ特に、 200°C以下の加熱または lKgfZcm2以上の加圧により流動性 を示す接着剤であることが好ましい。このような接着剤を用いることにより、この接着剤 の層に導電層が埋設されている本発明おける電磁波シールド性接着フィルムを被着 体であるディスプレイやプラスチック板に接着剤層を流動させて接着することができる 。流動できるので電磁波シールド性接着フィルムを被着体にラミネートや加圧成形、 特に加圧成形により、また曲面、複雑形状を有する被着体にも容易に接着することが できる。このためには、接着剤の軟ィ匕温度が 200°C以下であると好ましい。電磁波シ 一ルド性接着フィルムの用途から、使用される環境が通常 80°C未満であるので接着 剤層の軟化温度は、 80°C以上が好ましぐ加工性力も 80〜120°Cが最も好ましい。 軟化温度は、粘度が 1012ボイズ以下（1013Pa's以下）になる温度のことで、通常その 温度では 1〜： LO秒程度の時間のうちに流動が認められる。 [0126] 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. By using such an adhesive, 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. For this purpose, the softening temperature of the adhesive is preferably 200 ° C. or lower. Due to the use of electromagnetic shielding adhesive films, 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.
[0127] 上記のような加熱または加圧により流動する接着剤としては、主に以下に示す熱可 塑性榭脂が代表的なものとしてあげられる。たとえば天然ゴム (屈折率 n=1.52)、ポリイ ソプレン (n=1.521)、ポリ 1, 2 ブタジエン (n=l.50)、ポリイソブテン (n=1.505〜1.51) 、ポリブテン (n=1.513)、ポリ 2 へプチルー 1, 3 ブタジエン (n=l.50)、ポリ 2 t ーブチルー 1, 3 ブタジエン (n=l.506)、ポリ 1, 3 ブタジエン (n=1.515)などの（ジ )ェン類、ポリオキシエチレン (n=l.456)、ポリオキシプロピレン (n=l.450)、ポリビュルェ チルエーテル (n=l .454)、ポリビュルへキシルエーテル (n=l .459)、ポリビュルブチルェ 一テル (n=l.456)などのポリエーテル類、ポリビュルアセテート (n=l.467)、ポリビュルプ 口ピオネート (n=l.467)などのポリエステル類、ポリウレタン (n=1.5〜1.6)、ェチルセル口 ース (n=1.479)、ポリ塩化ビュル (n=1.54〜1.55)、ポリアクリロニトリル (n=1.52)、ポリメタ タリロニトリル (n=l.52)、ポリスルホン (n=l.633)、ポリスルフイド (n=1.6)、フエノキシ榭脂（ n=1.5〜1.6)、ポリェチルアタリレート (n=1.469)、ポリブチルアタリレート (n=1.466)、ポリ 2 ェチルへキシルアタリレート (n=l .463)、ポリ t ブチルアタリレート (n=l .464)、 ポリ 3 エトキシプロピルアタリレート (n=l.465)、ポリオキシカノレポ-ノレテトラメチレン (n=1.465)、ホ。リメチルアタリレート (n=1.472〜1.480)、ポリイソプロピルメタタリレート (n= 1.473)、ポリドデシルメタタリレート (n=1.474)、ポリテトラデシルメタタリレート (n=l.475)、 ポリ一 n—プロピルメタクリレー Kn=1.484)、ポリ一 3, 3, 5 トリメチルシクロへキシルメ タクリレート (η=1.484)、ポリェチルメタタリレート (η=1.485)、ポリ 2 二トロー 2—メチ ルプロピルメタタリレート (η=1.487)、ポリ 1, 1ージェチルプロピルメタタリレート (η=1. 489)、ポリメチルメタクリレー Κη=1.489)などのポリ（メタ）アクリル酸エステルが使用可 能である。これらのアクリルポリマーは必要に応じて、 2種以上共重合してもよいし、 2 種類以上をブレンドして使用することも可能である。 [0127] Typical examples of the adhesive that flows by heating or pressurization as described above include the following thermoplastic resins. For example, natural rubber (refractive index n = 1.52), polyisoprene (n = 1.521), poly 1,2 butadiene (n = l.50), polyisobutene (n = 1.505 to 1.51), polybutene (n = 1.513), poly 2 Heptilu 1, 3 Butadiene (n = l.50), Poly 2 t -Butyl 1,3 butadiene (n = l.506), poly 1,3 butadiene (n = 1.515) and other (di) ethylenes, polyoxyethylene (n = l.456), polyoxypropylene (n = l .450), polybutyl ether ( n = l .454), polybutyl hexyl ether (n = l .459), polybutyl butyl ether (n = l.456), and polybutyl acetate (n = l.467), polyesters such as polybulp mouth pionate (n = l.467), polyurethane (n = 1.5 to 1.6), ethyl cell mouth (n = 1.479), polychlorinated bule (n = 1.54 to 1.55) , Polyacrylonitrile (n = 1.52), polymethacrylonitrile ( n = l.52), polysulfone (n = l.633), polysulfide (n = 1.6), phenoxy resin (n = 1.5-1.6), polyethylatari Rate (n = 1.469), polybutyl acrylate (n = 1.466), poly (2-ethylhexyl acrylate) (n = l .463), poly (t-butyl acrylate) (N = l .464), poly 3 ethoxypropyl acrylate (n = l.465), polyoxycanorepo-noretetramethylene (n = 1.465), e. Limethyl Atallylate (n = 1.472 to 1.480), Polyisopropylmetatalylate (n = 1.473), Polydodecyl Metatalylate (n = 1.474), Polytetradecyl Metatalylate (n = l.475), Poly n-propyl methacrylate Kn = 1.484), poly-1,3,5 trimethylcyclohexyl methacrylate (η = 1.484), polyethyl methacrylate (η = 1.485), poly 2 2-tallow 2-methylpropyl methacrylate Poly (meth) acrylic acid esters such as tallylate (η = 1.487), poly 1,1-jetylpropyl methacrylate (η = 1.489), polymethylmethacrylate Κη = 1.489) can be used . Two or more kinds of these acrylic polymers may be copolymerized as needed, or two or more kinds may be blended and used.
さらにアクリル榭脂とアクリル以外との共重合榭脂としてはエポキシアタリレート (η=1. 48〜1.60)、ウレタンアタリレート (η=1.5〜1.6)、ポリエーテルアタリレート (η=1.48〜1.49) 、ポリエステルアタリレート (η=1.48〜1.54)なども使うこともできる。特に接着性の点から 、ウレタンアタリレート、エポキシアタリレート、ポリエーテルアタリレートが優れており、 エポキシアタリレートとしては、 1、 6 へキサンジオールジグリシジルエーテル、ネオ ペンチルグリコールジグリシジルエーテル、ァリルアルコールジグリシジルエーテル、 レゾルシノールジグリシジルエーテル、アジピン酸ジグリシジルエステル、フタル酸ジ グリシジルエステル、ポリエチレングリコールジグリシジルエーテル、トリメチロールプ 口パントリグリシジルエーテル、グリセリントリグリシジルエーテル、ペンタエリスリトール テトラグリシジルエーテル、ソルビトールテトラグリシジルエーテル等の（メタ）アクリル 酸付加物が挙げられる。エポキシアタリレートなどのように分子内に水酸基を有する ポリマーは接着性向上に有効である。これらの共重合榭脂は必要に応じて、 2種以 上併用することができる。これらの接着剤となるポリマーの軟ィ匕温度は、取扱い性力も 200°C以下が好適で、 150°C以下がさらに好ましい。電磁波シールド性接着フィルム の用途から、使用される環境が通常 80°C以下であるので接着剤層の軟ィ匕温度は、 加工性から 80〜120°Cが最も好ましい。一方、ポリマーの質量平均分子量 (ゲルパ 一ミエーシヨンクロマトグラフィーによる標準ポリスチレンの検量線を用いて測定したも の、以下同様）は、 500以上のものを使用することが好ましい。分子量が 500以下で は接着剤組成物の凝集力が低すぎるために被着体への密着性が低下するおそれが ある。本発明で使用する接着剤には必要に応じて、希釈剤、可塑剤、酸化防止剤、 充填剤、着色剤、紫外線吸収剤や粘着付与剤などの添加剤を配合してもよい。接着 剤の層の厚さは、 10〜80 mであることが好ましぐ導電層の厚さ以上で 20〜50 μ mとすることが特に好ましい。 In addition, copolymerized resins of acrylic and non-acrylic resins include epoxy acrylate (η = 1.48 to 1.60), urethane acrylate (η = 1.5 to 1.6), and polyether acrylate (η = 1.48 to 1.49). Polyester acrylate ( η = 1.48 to 1.54) can also be used. In particular, urethane acrylate, epoxy acrylate, and polyether acrylate are excellent in terms of adhesiveness. Examples of epoxy acrylate include 1,6 hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allylic alcohol. Diglycidyl ether, resorcinol diglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylol propane pan triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl (Meth) acrylic such as ether 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 μm, more than the thickness of the conductive layer.
また、幾何学図形を被覆する接着剤は、透明プラスチック基材との屈折率の差が 0 . 14以下とされる。また透明プラスチック基材が接着層を介して導電性材料と積層さ れている場合においては、接着層と幾何学図形を被覆する接着剤との屈折率の差 が 0. 14以下とされる。これは、透明プラスチック基材と接着剤の屈折率、または接着 剤と接着層の屈折率が異なると可視光透過率が低下するためであり、屈折率の差が 0. 14以下であると可視光透過率の低下が少なく良好となる。そのような要件を満た す接着剤の材料としては、透明プラスチック基材がポリエチレンテレフタレート (n=1.5 75；屈折率）の場合、ビスフエノール A型エポキシ榭脂ゃビスフエノール F型エポキシ 榭脂、テトラヒドロキシフエニルメタン型エポキシ榭脂、ノボラック型エポキシ榭脂、レゾ ルシン型エポキシ榭脂、ポリアルコール 'ポリダリコール型エポキシ榭脂、ポリオレフィ ン型エポキシ榭脂、脂環式やハロゲンィ匕ビスフエノールなどのエポキシ榭脂（いずれ も屈折率が 1.55〜 1.60)を使うことができる。エポキシ榭脂以外では天然ゴム (n=l .52 )、ポリイソプレン（n=1.521)、ポリ 1, 2 ブタジエン（n=l.50)、ポリイソブテン（n=l.50 5〜1.51)、ポリブテン（n=1.5125)、ポリ 2 へプチルー 1, 3 ブタジエン（n=l.50) 、ポリ 2—t—ブチルー 1, 3 ブタジエン（n=l.506)、ポリ 1, 3 ブタジエン（n=l. 515)などの（ジ）ェン類、ポリオキシエチレン（n=l.4563)、ポリオキシプロピレン（n=l.4 495)、ポリビュルェチルエーテル（n=l.454)、ポリビュルへキシルエーテル（n=l.459 1)、ポリビュルブチルエーテル（n=l.4563)などのポリエーテル類、ポリビニルァセテ ート（n=l.4665)、ポリビュルプロピオネート（n=l.4665)などのポリエステル類、ポリウ レタン（n=1.5〜1.6)、ェチルセルロース（n=1.479)、ポリ塩化ビュル（n=1.54〜1.55) 、ポリアクリロニトリル（n=1.52)、ポリメタタリ口-トリル（n=1.52)、ポリスルホン（n=1.633 )、ポリスルフイド (n=1.6)、フエノキシ榭脂（n=1.5〜1.6)などを挙げることができる。こ れらは、好適な可視光透過率を発現する。 In addition, the adhesive covering the geometric figure has a refractive index difference of 0.14 or less with respect to the transparent plastic substrate. When the transparent plastic substrate is laminated with a conductive material via an adhesive layer, 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. Adhesive materials that meet these requirements include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetraethylene when the transparent plastic substrate is polyethylene terephthalate (n = 1.5 75; refractive index). Hydroxyphenyl methane type epoxy resin, novolak type epoxy resin, resorcin type epoxy resin, polyalcohol 'polydaricol type epoxy resin, polyolefin type epoxy resin, epoxy resin such as alicyclic and halogen bisphenol Fats (both having a refractive index of 1.55 to 1.60) can be used. Other than epoxy resin, natural rubber (n = l .52), polyisoprene (n = 1.521), poly 1,2 butadiene (n = l.50), polyisobutene (n = l.50 5 to 1.51), polybutene ( n = 1.5125), poly 2 heptirool 1,3 butadiene (n = l.50), poly 2-t-butyl-1,3 butadiene (n = l.506), poly 1,3 butadiene (n = l. 515) and other (di) enes, polyoxyethylene (n = l.4563), polyoxypropylene (n = l.4 495), polybutyl ether (n = l.454), polybutylhexyl Polyethers such as ether (n = l.459 1), polybutylbutyl ether (n = l.4563), polyvinyl acetate (n = l.4665), polybulupropionate (n = l.4665) ) And other polyesters, polyuretan (n = 1.5 to 1.6), ethyl cellulose (n = 1.479), polychlorinated butyl (n = 1.54 to 1.55), polyacrylonitrile (n = 1.52), polymetathali mouth-tolyl (n = 1.52), polysulfone (n = 1.633), polysulfide (n = 1.6), phenoxy resin (n = 1.5 to 1.6), and the like. These express suitable visible light transmittance.
[0130] 一方、透明プラスチック基材がアクリル榭脂の場合、上記の榭脂以外に、ポリェチ ルアタリレート（n=1.4685)、ポリブチルアタリレート（n=1.466)、ポリ 2 ェチルへキ シルアタリレート（n=1.463)、ポリ t-ブチルアタリレート（n=1.4638)、ポリ 3 ェトキ シプロピルアタリレート（n=1.465)、ポリオキシカルボニルテトラメタタリレート（n=1.465 )、ポリメチルアタリレート（n=1.472〜1.480)、ポリイソプロピルメタタリレート（n=1.4728 )、ポリドデシルメタクリレー Hn=1.474)、ポリテトラデシルメタタリレート（n=1.4746)、 ポリ一 n—プロピルメタタリレート（n=1.484)、ポリ一 3, 3, 5 トリメチルシクロへキシル メタタリレート（n=l.484)、ポリェチルメタタリレート（n=l.485)、ポリ 2 -トロー 2—メ チルプロピルメタタリレート（n=1.4868)、ポリテトラ力ルバ-ルメタタリレート（n=1.4889 )、ポリ 1, 1ージェチルプロピルメタタリレート（n=1.4889)、ポリメチルメタクリレート（ n=l.4893)などのポリ（メタ）アクリル酸エステルが使用可能である。これらのアクリルポ リマーは必要に応じて、 2種以上共重合してもよいし、 2種類以上をブレンドして使うこ とちでさる。 [0130] On the other hand, when the transparent plastic substrate is an acrylic resin, in addition to the above-mentioned resins, a poly (ethylene acrylate) (n = 1.4685), a polybutyl acrylate (n = 1.466), a poly (2-ethyl hexyl acrylate) Rate (n = 1.463), poly t-butyl acrylate (n = 1.4638), poly (3-propyl propyl acrylate) (n = 1.465), polyoxycarbonyltetramethacrylate (n = 1.465), polymethyl acrylate ( n = 1.472 to 1.480), polyisopropylmethacrylate (n = 1.4728), polydodecylmethacrylate Hn = 1.474), polytetradecylmethacrylate (n = 1.4746), poly (n-propylmethacrylate) (n = 1.484), poly (3,3,5) trimethylcyclohexyl metatalylate (n = l.484), poly (ethyl metatalylate) (n = l.485), poly (2-tro) 2-methylpropyl metatalylate ( n = 1.4868), polytetra-force ruber meta Poly (meth) acrylic acid esters such as tallylate (n = 1.4889), poly 1,1-jetylpropyl methacrylate (n = 1.4889), polymethyl methacrylate (n = l.4893) can be used. Two or more kinds of these acrylic polymers may be copolymerized as needed, or two or more kinds may be blended and used.
[0131] さらにアクリル榭脂とアクリル以外との共重合榭脂としてはエポキシアタリレート、ウレ タンアタリレート、ポリエーテルアタリレート、ポリエステルアタリレートなども使うこともで きる。特に接着性の点から、エポキシアタリレート、ポリエーテルアタリレートが優れて おり、エポキシアタリレートとしては、 1, 6 へキサンジオールジグリシジルエーテル、 ネオペンチルグリコールジグリシジルエーテル、ァリルアルコールジグリシジルエーテ ル、レゾルシノールジグリシジルエーテル、アジピン酸ジグリシジルエステル、フタル 酸ジグリシジルエステル、ポリエチレングリコールジグリシジルエーテル、トリメチロー ルプロパントリグリシジルエーテル、グリセリントリグリシジルエーテル、ペンタエリスリト 一ルテトラグリシジルエーテル、ソルビトールテトラグリシジルエーテル等の（メタ）ァク リル酸付加物が挙げられる。エポキシアタリレートは分子内に水酸基を有するため接 着性向上に有効であり、これらの共重合榭脂は必要に応じて、 2種以上併用すること ができる。接着剤の主成分となるポリマーの質量平均分子量は、 1, 000以上のもの が使われる。分子量が 1, 000以下だと組成物の凝集力が低すぎるために被着体へ の密着性が低下する。 [0131] Further, as the copolymer resin of acrylic resin and non-acrylic resin, epoxy acrylate, urea acrylate, polyether acrylate, polyester acrylate and the like can also be used. 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. , Resorcinol diglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylo And (meth) acrylic acid adducts such as propane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, and sorbitol tetraglycidyl 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.
接着剤の硬化剤としてはトリエチレンテトラミン、キシレンジァミン、ジアミノジフエ- ルメタンなどのアミン類、無水フタル酸、無水マレイン酸、無水ドデシルコハク酸、無 水ピロメリット酸、無水ベンゾフヱノンテトラカルボン酸などの酸無水物、ジアミノジフエ ニルスルホン、トリス（ジメチルアミノメチル）フエノール、ポリアミド榭脂、ジシアンジアミ ド、ェチルメチルイミダゾールなどを使うことができる。 これらは単独で用いてもよいし 、 2種以上混合して用いてもよい。これらの架橋剤の添加量は上記ポリマー 100質量 部に対して 0. 1〜50質量部、好ましくは 1〜30質量部の範囲で選択するのがよい。 この添加量力 0. 1質量部未満であると硬化が不十分となり、 50質量部を越えると過 剰架橋となり、接着性に悪影響を与える場合がある。本発明で使用する接着剤の榭 脂組成物には必要に応じて、希釈剤、可塑剤、酸化防止剤、充填剤や粘着付与剤 などの添加剤を配合してもよい。そして、この接着剤の榭脂組成物は、透明プラスチ ック基材の表面に導電性材料で描かれた幾何学図形を設けた構成材料の基材のー 部または全面を被覆するために、塗布され、溶媒乾燥、加熱硬化工程をへたのち、 本発明に係る接着フィルムにする。上記で得られた電磁波シールド性と透明性を有 する接着フィルムは、該接着フィルムの接着剤により CRT、 PDP、液晶、 ELなどのデ イスプレイに直接貼り付け使用したり、アクリル板、ガラス板等の板やシートに貼り付け てディスプレイに使用する。また、この接着フィルムは、電磁波を発生する測定装置、 測定機器や製造装置の内部をのぞくための窓や筐体に上記と同様にして使用する。 さらに、電波塔や高圧線等により電磁波障害を受ける恐れのある建造物の窓や自動 車の窓等に設ける。そして、導電性材料で描かれた幾何学図形にはアース線を設け ることが好ましい。 [0133] 透明プラスチック基材上の透光性部は密着性向上のために意図的に凹凸を有して いたり、導電性材料の背面形状を転写したりするためにその表面で光が散乱され、 透明性が損なわれるが、その凹凸面に透明プラスチック基材と屈折率が近い樹脂が 平滑に塗布されると乱反射が最小限に押さえられ、透明性が発現するようになる。さ らに透明プラスチック基材上の導電性材料で描写された幾何学図形は、ライン幅が 非常に小さ 、ため肉眼で視認されな 、。またピッチも十分に大き 、ため見掛け上透 明性を発現すると考えられる。一方、遮蔽すべき電磁波の波長に比べて、幾何学図 形のピッチは十分に小さ 、ため、優れたシールド性を発現すると考えられる。 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. In addition, 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. In addition, 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. [0133] 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. Although 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. In addition, geometrical shapes drawn with conductive materials on transparent plastic substrates have very small line widths, so they are not visible to the naked eye. In addition, the pitch is sufficiently large, so it appears that transparency appears. On the other hand, since 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.
[0134] 特開 2003— 188576号公報に示すように、本発明の電磁波シールド膜と他の基 材とを貼り合わせるときは、透明基材フィルムとして、熱融着性の高いエチレン—酢 酸ビュル共重合榭脂、もしくはアイオノマー榭脂等の熱融着性榭脂のフィルムを単独 、または他の榭脂フィルムと積層して使用するときは、接着剤層を設けずに行なうこと も可能であるが、通常は、接着剤層を用いたドライラミネート法等によって積層を行な う。接着剤層を構成する接着剤としては、アクリル榭脂、ポリエステル榭脂、ポリウレタ ン榭脂、ポリビュルアルコール榭脂、塩化ビュル Z酢酸ビュル共重合榭脂、もしくは エチレン 酢酸ビュル共重合榭脂等の接着剤を挙げることができ、これらの他、熱硬 化性榭脂ゃ電離放射線硬化性榭脂 (紫外線硬化性榭脂、電子線硬化性榭脂等)を 用いることちでさる。  [0134] As shown in Japanese Patent Application Laid-Open No. 2003-188576, when the electromagnetic wave shielding film of the present invention and another base material are bonded together, an ethylene-acetate butyl having a high heat-fusibility is used as a transparent base film. When using a film of heat fusible resin such as copolymer resin or ionomer resin alone or laminated with other resin film, it is possible to carry out without providing an adhesive layer. However, the lamination is usually performed by a dry lamination method using an adhesive layer. Examples of 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. In addition to these, it is possible to use a thermosetting resin, such as an ionizing radiation curable resin (such as an ultraviolet curable resin, an electron beam curable resin).
なお、上記公報の電磁波遮蔽用シートとは、本発明において「電磁波シールド膜」 と記述して!/ヽる機能層を指す。  The electromagnetic wave shielding sheet of the above publication refers to a functional layer described as “electromagnetic wave shielding film” in the present invention.
[0135] 一般的には、ディスプレイの表面はガラス製であるので、粘着剤を用いて貼り合わ せるのは透明プラスチックフィルムとガラス板となり、その接着面に気泡が生じたり剥 離が生じたりすると画像が歪む、表示色がディスプレイ本来のものと異なって見える 等の問題が発生する。また、気泡および剥離の問題はいずれの場合でも粘着剤がプ ラスチックフィルムまたはガラス板より剥離することにより発生する。この現象は、プラス チックフィルム側、ガラス板側ともに発生する可能性が有り、より密着力の弱い側で剥 離が発生する。従って、高温での粘着剤とプラスチックフィルム、ガラス板との密着力 が高いことが必要となる。具体的には、透明プラスチックフィルム及びガラス板と粘着 剤層との密着力は 80°Cにお 、て lOgZcm以上であることが好まし!/、。 30gZcm以 上であることが更に好ましい。ただし、 2000gZcmを超えるような粘着剤は貼り合わ せ作業が困難と成るために好ましくない場合がある。ただし、力かる問題点が発生し ない場合は問題なく使用できる。さらに、この粘着剤の透明プラスチックフィルムと面 して 、な 、部分に不必要に他の部分に接触しな 、ように合 、紙 (セパレーター）を設 けることも可會である。 [0135] In general, 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. In any case, 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. It is preferable that the adhesive strength with the adhesive layer is at least lOgZcm at 80 ° C! /. More preferably, it is 30 gZcm or more. However, 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.
[0136] 粘着剤は透明であるものが好ましい。具体的には全光線透過率が 70%以上が好 ましぐ 80%以上が更に好ましぐ 85〜92%が最も好ましい。さらに、ヘイズが低いこ とが好ましい。具体的には、 0〜3%が好ましぐ 0〜1. 5%が更に好ましい。本発明 で用いる粘着剤は、ディスプレイ本来の表示色を変化させないために無色であること が好ましい。ただし、榭脂自体が有色であっても粘着剤の厚みが薄い場合には実質 的には無色とみなすことが可能である。また、後述のように意図的に着色を行なう場 合も同様にこの範囲ではない。  [0136] 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.
[0137] 上記の特性を有する粘着剤としては例えば、アクリル系榭脂、 a一才レフイン榭脂、 酢酸ビニル系榭脂、アクリル共重合物系榭脂、ウレタン系榭脂、エポキシ系榭脂、塩 化ビ -リデン系榭脂、塩ィ匕ビ二ル系榭脂、エチレン ビュルアセテート系榭脂、ポリ アミド系榭脂、ポリエステル系榭脂等が挙げられる。これらの内、アクリル系榭脂が好 ましい。同じ榭脂を用いる場合でも、粘着剤を重合法により合成する際に架橋剤の添 加量を下げる、粘着性付与材を加える、分子の末端基を変化させるなどの方法によ つて、粘着性を向上させることも可能である。また、同じ粘着剤を用いても、粘着剤を 貼り合わせる面、すなわち、透明プラスチックフィルムまたはガラス板の表面改質を行 なうことにより密着性を向上させることも可能である。このような表面の改質方法として は、コロナ放電処理、プラズマグロ一処理等の物理的手法、密着性を向上させるため の下地層を形成するなどの方法が挙げられる。  [0137] 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. Even when the same pressure-sensitive adhesive is used, it is possible to improve the adhesion by modifying the surface to which the pressure-sensitive adhesive is bonded, that is, the surface of the transparent plastic film or glass plate. Examples of such surface modification methods include physical methods such as corona discharge treatment and plasma glow treatment, and methods such as forming an underlayer for improving adhesion.
[0138] 透明性、無色性、ハンドリング性の観点から、粘着剤層の厚みは、 5〜50 μ m程度 であることが好ましい。粘着剤層を接着剤で形成する場合は、その厚みは上記範囲 内で薄くするとよい。具体的には 1〜20 /ζ πι程度である。ただし、上記のようにデイス プレイ自体の表示色を変化させず、透明性も上記の範囲に入っている場合には、厚 みが上記範囲を超えてもょ 、。 [0138] From the viewpoint of transparency, colorlessness, and handling properties, the thickness of the pressure-sensitive adhesive layer is preferably about 5 to 50 µm. When the pressure-sensitive adhesive layer is formed of an adhesive, the thickness is preferably reduced within the above range. Specifically, it is about 1-20 / ζ πι. However, if 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,
[0139] (2)剥離可能な保護フィルム  [0139] (2) Peelable protective film
本発明に係る光学フィルターには、剥離可能な保護フィルムを設けることができる。 保護フィルムは、光学フィルターの片側に有していても、両側に有していてもよい。 一般的に光学フィルタ一は、積層したものの表裏に、さらに、最表面の強化、反射 防止性の付与、防汚性の付与等の効果を有するシートを積層して使うものであるの で、上記の保護フィルムは、このようなさらなる積層の際には剥離する必要があり、こ のため、保護フィルムの積層は、いわゆる剥離可能に行なうことが望ましい。  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. In general, 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.
[0140] 保護フィルムは導電性金属部上に積層した際の剥離強度は 5mNZ25mm幅〜 5 NZ25mm幅であることが好ましぐより好ましくは 10mNZ25mm幅〜 100mNZ2 5mm幅である。下限未満では、剥離が容易過ぎ、取扱い中や不用意な接触により保 護フィルムが剥離する恐れがあり、好ましくなぐまた上限を超えると、剥離のために 大きな力を要する上、剥離の際に、メッシュ状の導電性金属部が透明基材フィルム（ もしくは接着剤層から)剥離する恐れがあり、やはり好ましくない。  [0140] 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.
[0141] 透明基材フィルム側に積層する保護フィルムは、エッチング条件に耐える、例えば 、 50°C程度のエッチング液、特にそのアルカリ成分によって数分間の浸漬中、侵食さ れないものであることが好ましぐあるいは、ドライエッチングの場合には 100°C程度 の温度条件に耐えるものであることが望ましい。また、感光性榭脂層を積層する際に 、積層体をディップコーティング (浸漬コーティング)するときは、コーティング液が積 層体の反対面にも付着するので、エッチング等の工程の際に、感光性榭脂が剥離し てエッチング液の中を漂うことがないよう、感光性榭脂の密着力が得られるものである ことが好ましいし、エッチング液を用いるときは、塩化鉄や塩化銅等を含むエッチング 液による汚染に耐える耐久性、もしくは、アルカリ液等のレジスト除去液による侵食も しくは汚染等に耐える耐久性を有するものであることが好ま 、。  [0141] 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. In addition, when laminating the photosensitive resin layer, when the laminate is dip coated (dip coating), 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. When using 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.
[0142] 上記の各点を満足させるために、保護フィルムを構成するフィルムとしては、ポリオ レフイン系榭脂であるポリエチレン榭脂ゃポリプロピレン榭脂、ポリエチレンテレフタレ 一ト榭脂等のポリエステル榭脂、ポリカーボネート榭脂、もしくはアクリル榭脂等の榭 脂フィルムを用いることが好ましぐまた、上記した観点により、少なくとも、保護フィル ムの、積層体に適用した際に最表面となる側の面にコロナ放電処理を施しておくか、 易接着層を積層しておくことが好ましい。 [0142] In order to satisfy each of the above points, as a film constituting the protective film, polyethylene resin, which is a polyolefin resin, polypropylene resin, polyester resin such as polyethylene terephthalate resin, It is preferable to use a resin film such as polycarbonate resin or acrylic resin, and at least from the above viewpoint, at least a protective film It is preferable to apply a corona discharge treatment to the surface which is the outermost surface when applied to a laminate, or to laminate an easy adhesion layer.
[0143] また、保護フィルムを構成する粘着剤としては、アクリル酸エステル系、ゴム系、もし くはシリコーン系のものを使用することができる。  [0143] As the pressure-sensitive adhesive constituting the protective film, acrylic acid ester-based, rubber-based, or silicone-based ones can be used.
[0144] 上記した保護フィルム用のフィルムの素材、および粘着剤の素材は、導電性金属 部側に適用する保護フィルムについても、そのまま適用できるので、両保護フィルム としては、異なるものを使用してもよいが、同じ物を、両保護フィルムとすることができ る。 [0144] 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.
[0145] (3)黒化処理  [0145] (3) Blackening treatment
本発明に係る電磁波シールド膜は、黒ィ匕処理を施したものであってもよ 、。  The electromagnetic wave shielding film according to the present invention may be blackened.
黒ィ匕処理については、例えば特開 2003— 188576号公報に開示されている。黒 化処理により形成された黒化層は、防鲭効果に加え、反射防止性を付与することが できる。黒ィ匕層は、例えば、 Co— Cu合金めつきによって形成され得るものであり、導 電性金属部上に黒ィ匕層を設けることにより、その表面の反射を防止することができる 。さらにその上に防鲭処理としてクロメート処理をしてもよい。クロメート処理は、クロム 酸もしくは重クロム酸塩を主成分とする溶液中に浸漬し、乾燥させて防鲭被膜を形成 するもので、必要に応じ、導電性金属部の片面もしくは両面に行なうことができるが、 市販のクロメート処理された銅箔等を利用してもよい。  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. Further, 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. However, a commercially available chromate-treated copper foil or the like may be used.
[0146] また、黒ィ匕層を含む構成の別の例としては、特開平 11— 266095号公報に示した 構成であってもよい。すなわち、導電性金属部上に第 1の黒ィ匕層を設け、この第 1の 黒ィ匕層上に上記の電解めつきを施した後、さらにこのめつき上に第 2の黒ィ匕層を有す る構成である。第 1の黒ィ匕層上に電解めつきを行うには、少なくとも第 1の黒ィ匕層が導 電性である必要がある。上記の導電性黒ィ匕層は、一般に、導電性金属化合物、例え ば、ニッケル (Ni)、亜鉛 (Zn)、銅 (Cu)等の化合物を使用して形成することができ、 あるいは、電着性イオン性高分子材料、例えば、電着塗装材料等を使用して形成す ることがでさる。  [0146] Further, as another example of the configuration including the black glazed layer, 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. In general, 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.
[0147] 黒ィ匕層を設ける方法は公知である（例えば、特開平 11 266095号公報の図 5参 照)。例えば、黒化材料を含有する電解液中に、導電性金属部を形成した透明支持 体を浸漬し、電気化学的なめっき法でめっきすればよい。なお、本発明において、上 記の黒化材料を含有する電解液の浴 (黒色めつき浴）は、硫酸ニッケル塩を主成分と する黒色めつき浴を使用することができ、更に、市販の黒色めつき浴も同様に使用す ることができ、具体的には、例えば、株式会社シミズ製の黒色めつき浴 (商品名、ノー ブロイ SNC、 Sn—Ni合金系）、 日本ィ匕学産業株式会社製の黒色めつき浴 (商品名、 ニツカブラック、 Sn— Ni合金系）、株式会社金属化学工業製の黒色めつき浴 (商品 名、ェボ-—クロム 85シリ—ズ、 Cr系）等を使用することができる。また、本発明にお いては、上記の黒色めつき浴としては、 Zn系、 Cu系、その他等の種々の黒色めつき 浴を使用することができる。次に、前記の導電性めつきを施し、導電性メッシュパター ンを形成した後、この上に第 2の黒ィ匕層を形成する。例えば、電界めつきの金属が C uの場合、硫化水素 (H S)液処理して、 Cuの表面を硫化銅 (CuS)として黒ィ匕し、第 [0147] A method for providing a black glazed layer is known (see, for example, Fig. 5 of JP-A-11 266095). For example, 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. In the present invention, the electrolyte bath containing the above blackening material (black tanning bath) 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. can be used. Further, in the present invention, various black tanning baths such as Zn-based, Cu-based and others can be used as the black tanning bath. Next, the conductive mesh is applied to form a conductive mesh pattern, and then a second black layer is formed thereon. For example, if the metal with an electric field is Cu, it is treated with hydrogen sulfide (HS) solution, and the surface of Cu is blackened as copper sulfide (CuS).
2  2
2の黒化層が形成される。なお、本発明において、第 2の黒ィ匕層のための黒ィ匕処理 剤としては、硫ィ匕物系化合物を用いて容易に製造でき、更にまた、市販品も多種類 の処理剤があり、例えば、商品名 'コパ—ブラック CuO、同 CuS、セレン系のコパ- ブラック No. 65等 (アイソレート化学研究所製）、商品名'ェボノール Cスペシャル (メ ルテックス株式会社製)等を使用することができる。  2 blackening layers are formed. In the present invention, as 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.
[0148] ，複合機能層 [0148], Composite functional layer
次に機能性フィルムの機能につ!、て説明する。  Next, I will explain the functions of the functional film.
ディスプレイは、照明器具等の映り込みによって表示画面が見づらくなつてしまうの で、機能性フィルム (C)は、外光反射を抑制するための反射防止 (AR:アンチリフレ クシヨン)性、または、鏡像の映り込みを防止する防眩 (AG :アンチグレア)性、または その両特性を備えた反射防止防眩 (ARAG)性の 、ずれかの機能を有して 、ること が必要である。ディスプレイ用フィルタ表面の可視光線反射率が低いと、映り込み防 止だけではなぐコントラスト等を向上させることができる。  Since the display screen becomes difficult to see due to the reflection of lighting equipment, etc., 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.
[0149] 反射防止性を有する機能性フィルムは、反射防止膜を有し、具体的には、可視域 において屈折率が 1. 5以下、好適には 1. 4以下と低い、フッ素系透明高分子榭脂 やフッ化マグネシウム、シリコン系榭脂ゃ酸ィ匕珪素の薄膜等を例えば 1Z4波長の光 学膜厚で単層形成したもの、屈折率の異なる、金属酸化物、フッ化物、ケィ化物、窒 化物、硫ィ匕物等の無機化合物またはシリコン系榭脂ゃアクリル榭脂、フッ素系榭脂等 の有機化合物の薄膜を 2層以上多層積層したものがあるが、これらに限定されるもの ではな!/、。反射防止性を有する機能性フィルム (C)の表面の可視光線反射率は 2% 以下、好ましくは 1. 3%以下、さらに好ましくは 0. 8%以下である。 [0149] The functional film having antireflection has an antireflection film. Specifically, in the visible region, the refractive index is 1.5 or less, preferably 1.4 or less, and 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.
[0150] 防眩性を有する機能性フィルムは、 0. l ^ m-lO ^ m程度の微少な凹凸の表面 状態を有する可視光線に対して透明な防眩膜を有している。具体的には、アクリル系 榭脂、シリコン系榭脂、メラミン系榭脂、ウレタン系榭脂、アルキド系榭脂、フッ素系榭 脂等の熱硬化型または光硬化型榭脂に、シリカ、有機珪素化合物、メラミン、アクリル 等の無機化合物または有機化合物の粒子を分散させインキ化したものを、基体上に 塗布、硬化させる。粒子の平均粒径は、 1〜40 /ζ πιである。または、上記の熱硬化型 または光硬化型榭脂を基体に塗布し、所望のダロス値または表面状態を有する型を 押しつけ硬化することによつても防眩性を得ることができる力 必ずしもこれら方法に 限定されるものではない。防眩性を有する機能性フィルムのヘイズは 0. 5%以上 20 %以下であり、好ましくは 1%以上 10%以下である。ヘイズが小さすぎると防眩性が 不十分であり、ヘイズが大きすぎると透過像鮮明度が低くなる傾向がある。 [0150] 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. Specifically, acrylic or silicone resin, melamine resin, urethane resin, alkyd resin, fluorinated resin, or other thermosetting or photocurable resin, silica, organic resin 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 / ζ πι. Alternatively, 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.
[0151] ディスプレイ用フィルタに耐擦傷性を付加させるために、機能性フィルムがハードコ 一ト性を有していることも好適である。ハードコート膜としてはアクリル系榭脂、シリコン 系榭脂、メラミン系榭脂、ウレタン系榭脂、アルキド系榭脂、フッ素系榭脂等の熱硬化 型または光硬化型榭脂等が挙げられるが、その種類も形成方法も特に限定されな!、 。これら膜の厚さは、 1〜50 /ζ πι程度である。ハードコート性を有する機能性フィルム の表面硬度は、 JIS (Κ— 5400)に従った鉛筆硬度が少なくとも Η、好ましくは 2Η、さ らに好ましくは 3Η以上である。ハードコート膜上に反射防止膜および Ζまたは防眩 膜を形成すると、耐擦傷性 ·反射防止性および Ζまたは防眩性を有する機能性フィ ルムが得られ好適である。  [0151] In order to add scratch resistance to the display filter, it is also preferable that the functional film has a hard coat property. Examples of 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 / ζ πι. As for the surface hardness of the functional film having hard coat properties, the pencil hardness according to JIS (Κ-5400) is at least Η, preferably 2 Η, and more preferably 3 Η or more. When an antireflection film and a wrinkle or antiglare film are formed on the hard coat film, a functional film having scratch resistance, antireflection and wrinkle or antiglare properties is obtained, which is preferable.
[0152] ディスプレイ用フィルタには、静電気帯電によりホコリが付着しやすぐまた、人体が 接触したときに放電して電気ショックを受けることがあるため、帯電防止処理が必要と される場合がある。従って、静電気防止能を付与するために、機能性フィルムが導電 性を有して ヽても良 ヽ。この場合に必要とされる導電性は面抵抗で 1011 Ω Ζ口程度 以下であれば良!ヽ。導電性を付与する方法としてはフィルムに帯電防止剤を含有さ せる方法や導電層（帯電防止層）を形成する方法が挙げられる。帯電防止剤として具 体的には、商品名ペレスタツト（三洋化成社製)、商品名エレクトロスリッパー (花王社 製)等が挙げられる。導電層としては ITOをはじめとする公知の透明導電膜や ITO超 微粒子や酸化スズ超微粒子をはじめとする導電性超微粒子を分散させた導電膜が 挙げられる。ハードコート膜や反射防止膜、防眩膜が、導電膜を有していたり導電性 微粒子を含有して 、ると好適である。 [0152] 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 Ω Good if it is below. Examples of 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. Examples of the conductive layer 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.
[0153] 機能性フィルム (C)表面が防汚性を有して!/、ると、指紋等の汚れ防止や汚れが付 いたときに簡単に取り除くことができるので好適である。防汚性を有するものとしては 、水および Zまたは油脂に対して非濡性を有するものであって、例えばフッ素化合物 やケィ素化合物が挙げられる。フッ素系防汚剤として具体的には商品名ォプツール（ ダイキン社製)等が挙げられ、ケィ素化合物としては、商品名タカタクオンタム（日本 油脂社製)等が挙げられる。反射防止膜に、これら防汚性のある層を用いると、防汚 性を有する反射防止膜が得られて好適である。  [0153] It is preferable that 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.). When these antifouling layers are used for the antireflection film, an antireflection film having antifouling properties can be obtained, which is preferable.
[0154] 機能性フィルムは、後述する色素や高分子フィルムの劣化等を防ぐ目的で紫外線 カット性を有していることが好ましい。紫外線カット性を有する機能性フィルムは、後述 する上記の高分子フィルムに紫外線吸収剤を含有させることや紫外線吸収膜を付与 する方法が挙げられる。  [0154] 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.
[0155] ディスプレイ用フィルタは、常温常湿よりも高い温度 ·湿度環境ィ匕で使用されると、フ イルムを透過した水分により後述する色素が劣化したり、貼り合せに用いる粘着材中 や貼り合せ界面に水分が凝集して曇ったり、水分による影響で粘着材中の粘着付与 剤等が相分離して析出して曇ったりすることがあるので、機能性フィルムがガスバリア 性を有していると好ましい。このような色素劣化や曇りを防ぐ為には、色素を含有する 層や粘着材層への水分の侵入を防ぐことが肝要であり、機能性フィルムの水蒸気透 過度が lOgZm2 · day以下、好ましくは 5gZm2 · day以下であることが好適である。 [0155] 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. In order to prevent such pigment deterioration and fogging, it is important to prevent moisture from entering the pigment-containing layer and the adhesive layer, and 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.
[0156] 高分子フィルム、導電メッシュ層、機能性フィルムおよび必要に応じて後述する透 明成型物は、可視光線に対して透明な任意の粘着材または接着剤を介して貼り合わ される。粘着材または接着剤として具体的にはアクリル系接着剤、シリコン系接着剤、 ウレタン系接着剤、ポリビニルブチラール接着剤（PVB)、エチレン 酢酸ビニル系 接着剤 (EVA)等、ポリビュルエーテル、飽和無定形ポリエステル、メラミン榭脂等が 挙げられ、実用上の接着強度があればシート状のものでも液状のものでもよい。粘着 材は感圧型接着剤でシート状のものが好適に使用できる。シート状粘着材貼り付け 後または接着材塗布後に各部材をラミネートすることによって貼り合わせを行う。液状 のものは塗布、貼り合わせ後に室温放置または加熱により硬化する接着剤である。 塗布方法としては、バーコート法、リバースコート法、グラビアコート法、ダイコート法、 ロールコート法等が挙げられるが、接着剤の種類、粘度、塗布量等から考慮、選定さ れる。層の厚みは、特に限定されるものではないが、 0. 5 m〜50 μ m、好ましくは 1 ix m〜30 mである。粘着材層を形成される面、貼り合わせられる面は、予め易接 着コートまたはコロナ放電処理などの易接着処理により濡れ性を向上させておくこと が好適である。本発明においては、前述の可視光線に対して透明な粘着材または接 着剤を透光性粘着材と呼ぶ。 [0156] 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. Specific examples of 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. Examples of 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 μm, 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. In the present invention, the above-mentioned adhesive or adhesive transparent to visible light is referred to as a translucent adhesive.
[0157] 本発明においては、導電性メッシュ層上に機能性フィルムを貼り合わせる際、特に 透光性粘着材層を用いる。透光性粘着材層に用いる透光性粘着材の具体例として は前記と同じだ力 その厚さが導電性メッシュ層の凹部を十分埋め込むことができる ことが肝要である。導電性メッシュ層の厚さより薄すぎると、埋め込み不十分で間隙が 出来て凹部に気泡を嚙み込み、濁りのある、透光性の不足したディスプレイ用フィル タとなってしまう。又、厚すぎると粘着材を作製するコストがアップしたり部材のハンドリ ングが悪くなる等の問題が生じる。導電性メッシュ層の厚さが d /z mの時、透光性粘 着材の厚さは（d— 2)〜（d+ 30) μ mであることが好まし!/、。  [0157] In the present invention, when the functional film is bonded onto the conductive mesh layer, a light-transmitting pressure-sensitive adhesive layer is particularly used. As a specific example of 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. When the thickness of the conductive mesh layer is d / z m, the thickness of the translucent adhesive is preferably (d-2) to (d + 30) μm! /.
[0158] ディスプレイ用フィルタの可視光線透過率は、 30〜85%が好ましい。更に好ましく は 35〜70%である。 30%未満であると輝度が下がりすぎ視認性が悪くなる。また、 ディスプレイ用フィルタの可視光線透過率が高すぎると、ディスプレイのコントラストを 改善できない。尚、本発明における可視光線透過率は、可視光線領域における透過 率の波長依存性から JIS (R- 3106)に従って計算されるものである。  [0158] 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.
[0159] また、機能性フィルムを透光性粘着材層を介して導電性メッシュ層上に貼り合せる と、凹部に気泡を嚙み込み、濁って透光性が不十分になることがある力 この場合、 例えば加圧処理すると、貼り合わせ時に部材間に入り込んだ気体を脱泡または、粘 着材に固溶させ、濁りを無くして透光性を向上させることができる。加圧処理は、上記 の構成の状態で行っても、本発明のディスプレイ用フィルタの状態で行っても良 、。 [0159] In addition, 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. in this case, For example, when pressure treatment is performed, 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.
[0160] 加圧方法としては、平板間に積層体を挟み込みプレスする方法、 -ップロール間を 加圧しながら通す方法、加圧容器内に入れて加圧する方法が挙げられるが、特に限 定はされない。加圧容器内で加圧する方法は、積層体全体に一様に圧力がかかり 加圧のムラが無ぐまた、一度に複数枚の積層体を処理できるので好適である。加圧 容器としてはオートクレープ装置を用いることが出来る。  [0160] 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.
[0161] 加圧条件としては、圧力が高い程、嚙み込んだ気泡を無くすことが出来、且つ、処 理時間を短くすることが出来るが、積層体の耐圧性、加圧方法の装置上の制限から 、 0. 2MPa〜2MPa程度、好ましくは 0. 4〜1. 3MPaである。また、加圧時間は、加 圧条件によって変わり特に限定されないが、長くなりすぎると処理時間が力かりコスト アップとなるので、適当な加圧条件にぉ 、て保持時間が 6時間以下であることが好ま しい。特に加圧容器の場合は、設定圧力に到達後、 10分〜 3時間程度保持すること が好適である。  [0161] As the pressurization conditions, the higher the pressure, the more the bubbles that are trapped can be eliminated, and the treatment time can be shortened. Therefore, 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.
[0162] また、加圧時に同時に加温すると好ましい場合がある。加温することによって、透光 性粘着材の流動性が一時的に上がり嚙み込んだ気泡を脱泡しやすくなつたり、気泡 が粘着材中に固溶しやすくなる。加温条件としてはディスプレイ用フィルタを構成す る各部材の耐熱性により、室温以上 80°C以下程度である力 特に限定を受けない。  [0162] In some cases, it is preferable to simultaneously heat at the time of pressurization. By heating, 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.
[0163] さらにまた、加圧処理、または、加圧加温処理は、ディスプレイ用フィルタを構成す る各部材間の貼り合わせ後の密着力を向上させることが出来、好適である。  [0163] Furthermore, 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.
[0164] 本発明のディスプレイ用フィルタは、高分子フィルムの導電性メッシュ層が形成され て!ヽな 、他方の主面に透光性粘着材層を設ける。透光性粘着材層に用いる透光性 粘着材の具体例は前述の通りであり、特に限定はされない。厚みも、特に限定される ものではないが、 0. 5 m〜50 μ m、好ましくは 1 μ m〜30 μ mである。透光性粘着 材層を形成される面、貼り合わせられる面は、予め易接着コートまたはコロナ放電処 理などの易接着処理により濡れ性を向上させておくことが好適である。  [0164] In the display filter of the present invention, 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 μm, preferably 1 μm to 30 μm. 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.
[0165] 透光性粘着材層上に離型フィルムが形成されて ヽても良!ヽ。すなわち、少なくとも 機能性フィルム z透光性粘着材層 z導電性メッシュ層 z高分子フィルム z透光性粘 着材層） Z離型フィルムである。離型フィルムは、粘着材層と接する高分子フィルムの 主面上にシリコーン等をコ一ティングしたものである。本発明のディスプレイ用フィル タを後述の透明成形物の主面に貼り合せる際、または、ディスプレイ表面、例えばプ ラズマディスプレイパネルの前面ガラス上に貼り合せる際には、離型フィルムを剥離し て透光性粘着材層を露出せしめた後に貼り合わせる。 [0165] 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. When the display filter of the present invention is bonded to the main surface of a transparent molded product to be described later, or when bonded to the display surface, for example, the front glass of a plasma display panel, the release film is peeled off. After the light-sensitive adhesive layer is exposed, it is bonded.
[0166] 本発明のディスプレイ用フィルタは、主として各種ディスプレイカゝら発生する電磁波 を遮断する目的で用いられる。好ましい例として、プラズマディスプレイ用フィルター が挙げられる。  [0166] 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.
[0167] 前述した様にプラズマディスプレイは強度の近赤外線を発生する為、本発明のディ スプレイ用フィルタは、実用上問題無 、レベルまで電磁波だけでなく近赤外線もカツ トする必要がある。波長領域 800〜1000nmにおける透過率を 25%以下、好ましく は 15%以下、更に好ましくは 10%以下とすることが必要である。また、プラズマデイス プレイに用いるディスプレイ用フィルタはその透過色が-ユートラルグレーまたはブル 一グレーであることが要求される。これは、プラズマディスプレイの発光特性およびコ ントラストを維持または向上させる必要があったり、標準白色より若干高めの色温度の 白色が好まれる場合がある力もである。さらにまた、カラープラズマディスプレイはそ の色再現性が不十分と言われており、その原因である蛍光体または放電ガスからの 不要発光を選択的に低減することが好ましい。特に赤色表示の発光スペクトルは、波 長 580nmから 700nm程度までにわたる数本の発光ピークを示しており、比較的強 V、短波長側の発光ピークにより赤色発光がオレンジに近 、色純度の良くな!/、ものと なってしまう問題がある。これら光学特性は、色素を用いることによって制御できる。 つまり、近赤外線カットには近赤外線吸収剤を用い、また、不要発光の低減には不 要発光を選択的に吸収する色素を用いて、所望の光学特性とすることが出来、また、 ディスプレイ用フィルタの色調も可視領域に適当な吸収のある色素を用いて好適なも のとすることができる。  [0167] As described above, 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. In addition, 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. Furthermore, it is said that 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. In particular, 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. In other words, 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.
[0168] 色素を含有させる方法としては、（1)色素を少なくとも 1種類以上、透明な榭脂に混 鍊させた高分子フィルムまたは榭脂板、（2)色素を少なくとも 1種類以上、榭脂または 榭脂モノマー z有機系溶媒の榭脂濃厚液に分散'溶解させ、キャスティング法により 作製した高分子フィルムまたは榭脂板、（3)色素を少なくとも 1種類以上を、榭脂バイ ンダ一と有機系溶媒に加え、塗料とし、高分子フィルムまたは榭脂板上にコーティン グしたもの、（4)色素を少なくとも 1種類以上を含有する透明な粘着材、のいずれか 一つ以上選択できるが、これらに限定されない。本発明でいう含有とは、基材または 塗膜等の層または粘着材の内部に含有されることは勿論、基材または層の表面に塗 布した状態を意味する。 [0168] As 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. The term “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.
[0169] 上記の色素は可視領域に所望の吸収波長を有する一般の染料または顔料、また は、近赤外線吸収剤であって、その種類は特に限定されるものではないが、例えば アントラキノン系、フタロシアニン系、メチン系、ァゾメチン系、ォキサジン系、ィモニゥ ム系、ァゾ系、スチリル系、クマリン系、ポルフィリン系、ジベンゾフラノン系、ジケトピロ ロピロール系、ローダミン系、キサンテン系、ピロメテン系、ジチオール系化合物、ジィ ミニゥム系化合物等の一般に市販もされている有機色素があげられる。その種類'濃 度は、色素の吸収波長'吸収係数、ディスプレイ用フィルタに要求される透過特性- 透過率、そして分散させる媒体または塗膜の種類'厚さから決まり、特に限定されるも のではない。 [0169] 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.
[0170] プラズマディスプレイパネルはパネル表面の温度が高ぐ環境の温度が高いときは 特にディスプレイ用フィルタの温度も上がるため、色素は、例えば 80°Cで分解等によ つて顕著に劣化しない耐熱性を有していることが好適である。また、耐熱性に加えて 色素によっては耐光性に乏しいものもある。プラズマディスプレイの発光や外光の紫 外線'可視光線による劣化が問題になる場合は、紫外線吸収剤を含む部材ゃ紫外 線を透過しな 、部材を用いることによって、色素の紫外線による劣化を低減すること、 紫外線や可視光線による顕著な劣化がない色素を用いることが肝要である。熱、光 に加えて、湿度や、これらの複合した環境においても同様である。劣化するとディス プレイ用フィルタの透過特性が変わってしま 、、色調が変化したり近赤外線カット能 が低下してしまう。さらには、媒体または塗膜中に分散させるために、適宜の溶媒へ の溶解性や分散性も重要である。また、本発明においては異なる吸収波長を有する 色素 2種類以上を一つの媒体または塗膜に含有させても良いし、色素を含有する媒 体、塗膜を 2つ以上有していても良い。 [0170] When the temperature of the environment where the temperature of the panel surface is high, the temperature of the filter for the plasma display panel rises, so the temperature of the filter for the display also rises. Therefore, 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. The same applies to humidity and these combined environments in addition to heat and light. If it deteriorates, the transmission characteristics of the display filter will change, changing the color tone or reducing the near-infrared cutting ability. Furthermore, in order to disperse in a medium or a coating film, solubility and dispersibility in an appropriate solvent are also important. In the present invention, 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.
[0171] 上記の色素を含有する方法（1)〜 (4)は、本発明においては、色素を含有する高 分子フィルム (A)、色素を含有する機能性フィルム (C)、色素を含有する透光性粘着 材 (D1)、透光性粘着材 (D2)、その他貼り合わせに用いられる色素を含有する透光 性の粘着材または接着剤の 、ずれか 1つ以上の形態をもって、本発明のディスプレ ィ用フィルタに使用できる。  [0171] In the present invention, 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.
[0172] 一般に色素は紫外線で劣化しやすい。ディスプレイ用フィルタが通常使用条件下 で受ける紫外線は、太陽光等の外光に含まれるものである。従って、色素の紫外線 による劣化を防止する為には、色素を含有する層自身および該層より外光を受ける 人側の層から選ばれる少なくとも 1層に、紫外線カット能を有する層を有していること が好適である。例えば、高分子フィルム (A)が色素を含有する場合、透光性粘着材 層および Zまたは機能性フィルムが、紫外線吸収剤を含有したり、紫外線カット能を 有する機能膜を有していれば、外光が含む紫外線から、色素を保護できる。色素を 保護するのに必要な紫外線カット能としては、波長 380nmより短い紫外線領域の透 過率が、 20%以下、好ましくは 10%以下、更に好ましくは 5%以下である。紫外線力 ット能を有する機能膜は、紫外線吸収剤を含有する塗膜であっても、紫外線を反射ま たは吸収する無機膜であっても良い。紫外線吸収剤は、ベンゾトリアゾール系やベン ゾフエノン系等、従来公知のものを使用でき、その種類'濃度は、分散または溶解さ せる媒体への分散性'溶解性、吸収波長'吸収係数、媒体の厚さ等から決まり、特に 限定されるものではない。尚、紫外線カット能を有する層またはフィルムは、可視光線 領域の吸収が少なぐ著しく可視光線透過率が低下したり黄色等の色を呈することが ないことが好ましい。色素を含有する機能性フィルムにおいては、色素を含有する層 が形成されている場合はその層よりも人側のフィルムまたは機能膜が紫外線カット能 を有すれば良ぐ高分子フィルムが色素を含有する場合はフィルムより人側に紫外線 カット能を有する機能膜や機能層を有して 、れば良 、。  [0172] In general, 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. As the ultraviolet ray cutting ability necessary to protect the dye, 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. It is preferable that 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. In 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.
[0173] 色素は、金属との接触によっても劣化する場合がある。このような色素を用いる場合 、色素は導電メッシュ層と出来るだけ接触しない様に配置することが更に好ましい。 具体的には色素含有層が機能性フィルム、高分子フィルム、透光性粘着材層である ことが好ましぐ特には透光性粘着材層であることが好ま U、。 [0173] The dye may be deteriorated by contact with a metal. When using such a pigment | dye, it is still more preferable to arrange | position so that a pigment | dye may not contact a conductive mesh layer as much as possible. Specifically, 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.
[0174] 本発明のディスプレイ用フィルタは、高分子フィルム (A)、導電性メッシュ層（B)、機 能性フィルム (C)、透光性粘着材 (D1)および透光性粘着材 (D2)が、 (C) / (D1) / (B) / (A) / (D2)の順に構成され、好ましくは導電性メッシュ層 (B)と高分子フィ ルム (A)とからなる導電性メッシュフィルムと機能性フィルムとが透光性粘着剤 (D1) で貼合され、高分子フィルム (A)の導電性メッシュ層（B)とは反対側の主面に透光性 粘着剤 (D2)が付されている。  [0174] 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.
[0175] 本発明のディスプレイ用フィルタをディスプレイに装着する際には機能性フィルム（ C)を人側に、透光性粘着剤 (D2)がディスプレイ側となるように装着する。  [0175] When the display filter of the present invention is attached to the display, the functional film (C) is attached to the person side, and the translucent adhesive (D2) is attached to the display side.
[0176] 本発明のディスプレイ用フィルタを、ディスプレイの前面に設けて使用する方法とし ては、後述の透明成形物 (E)を支持体とした前面フィルタ板として使用する方法、デ イスプレイ表面に透光性粘着材 (D2)を介して貼り合せて使用する方法がある。前者 の場合、ディスプレイ用フィルタの設置が比較的容易であり、支持体により機械的強 度が向上し、ディスプレイの保護に適している。後者の場合は、支持体が無くなること により軽量化'薄化が可能であり、また、ディスプレイ表面の反射を防止することが出 来、好適である。  [0176] As 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. There is a method of using it by attaching it through a light-sensitive adhesive (D2). In the former case, 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. In the latter case, it is possible to reduce the weight and thickness by eliminating the support, and it is preferable to prevent reflection on the display surface.
[0177] 透明成形物としては、ガラス板、透光性のプラスチック板があげられる。機械的強度 や、軽さ、割れにくさからは、プラスチック板が好ましいが、熱による変形等の少ない 熱的安定性力 ガラス板も好適に使用できる。プラスチック板の具体例を挙げると、ポ リメタクリル酸メチル (PMMA)をはじめとするアクリル榭脂、ポリカーボネート榭脂、透 明 ABS榭脂等が使用できるが、これらの榭脂に限定されるものではない。特に PM MAはその広い波長領域での高透明性と機械的強度の高さから好適に使用できる。 プラスチック板の厚みは十分な機械的強度と、たわまずに平面性を維持する剛性が 得られればよぐ特に限定されるものではないが、通常 lmn！〜 10mm程度である。ガ ラスは、機械的強度を付加するために化学強化加工または風冷強化加工を行った 半強化ガラス板または強化ガラス板が好ましい。質量を考慮すると、その厚みは 1〜 4mm程度である事が好ましいが、特に限定されない。透明成形物はフィルムを貼り 合せる前に必要な各種公知の前処理を行うことが出来るし、ディスプレイ用フィルタ 周縁部となる部分に黒色等の有色の額縁印刷を施しても良い。 [0177] 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. Considering the mass, 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.
[0178] 透明成形物を用いる場合のディスプレイ用フィルタの構成は、少なくとも機能性フィ ルム (C) Z透光性粘着材 (Dl) Z導電性メッシュ層 (B) Z高分子フィルム (A) Z透 光性粘着材 (D2) Z透明成形物 (E)である。また、透明成形物 (E)の透光性粘着材 (D2)と貼り合せられる面とは反対の主面に、機能性フィルム (C)が透光性粘着材層 を介して設けられても良い。この場合、人側に設けられる機能性フィルム (C)と同じ機 能'構成を有する必要は無ぐ例えば、反射防止能を有している場合は、支持体を有 するディスプレイ用フィルタの裏面反射を低減することができる。同じぐ透明成形物（ E)の透光性粘着材 (D2)と貼り合せられる面とは反対の主面に、反射防止膜等の機 能膜 (C2)を形成しても良い。この場合は、機能性膜 (C2)を人側にしてディスプレイ に設置することもできるが、前述の通り、紫外線カット能を有する層を色素含有層およ び色素含有層より人側の層に設けることが好ま U、。  [0178] 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). In this case, 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.
[0179] 電磁波シールドを必要とする機器には、機器のケース内部に金属層を設けたり、ケ ースに導電性材料を使用して電磁波を遮断する必要がある力 ディスプレイの如く表 示部に透明性が必要である場合には、本発明のディスプレイ用フィルタの如く透光性 の導電層を有した窓状の電磁波シールドフィルタを設置する。ここで、電磁波は導電 層において吸収されたのち電荷を誘起するため、アースをとることによって電荷を逃 がさな ヽと、再びディスプレイ用フィルタがアンテナとなって電磁波を発振し電磁波シ 一ルド能が低下する。従って、ディスプレイ用フィルタとディスプレイ本体のアース部 が電気的に接触している必要がある。そのため、前述の透光性粘着材 (D1)および 機能性フィルム (C)は、外部力 導通を取ることが出来る導通部を残して導電性メッ シュ層（B)上に形成されている必要がある。導通部の形状は特に限定しないが、ディ スプレイ用フィルタとディスプレイ本体の間に、電磁波の漏洩する隙間が存在しな!ヽ ことが肝要である。従って、導通部は、導電性メッシュ層（B)の周縁部且つ連続的に 設けられている事が好適である。すなわち、ディスプレイの表示部である中心部分を 除いて、枠状に、導通部が設けられている事が好ましい。  [0179] For devices that require electromagnetic shielding, it is necessary to provide a metal layer inside the device case or use a conductive material in the case to block electromagnetic waves. When transparency is required, a window-like electromagnetic wave shielding filter having a translucent conductive layer is installed like the display filter of the present invention. Here, since 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. When 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. Therefore, 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.
[0180] 導通部はメッシュパターン層であっても、パターユングされていない、例えば金属箔 ベタの層であっても良いが、ディスプレイ本体のアース部との電気的接触を良好とす る為には、金属箔ベタ層のようにパターユングされて ヽな 、導通部であることが好まし い。 [0180] 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.
[0181] 導通部が、例えば金属箔ベタのようにパターユングされていない場合、および Zま たは、導通部の機械的強度が十分強い場合は、導通部そのままを電極として使用で きて好適である。  [0181] If 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.
[0182] 導通部の保護のため、および Zまたは、導通部がメッシュパターン層である場合に アース部との電気的接触を良好とするために、導通部に電極を形成することが好まし い場合がある。電極形状は特に限定しないが、導通部をすベて覆うように形成されて いる事が好適である。  [0182] 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. There is a case. 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.
電極に用いる材料は、導電性、耐触性および透明導電膜との密着性等の点から、 銀、銅、ニッケル、アルミニウム、クロム、鉄、亜鉛、カーボン等の単体もしくは 2種以 上からなる合金や、合成樹脂とこれら単体または合金の混合物、もしくは、ホウケィ酸 ガラスとこれら単体または合金の混合物力もなるペーストを使用できる。ペーストの印 刷、塗工には従来公知の方法を採用できる。また市販の導電性テープも好適に使用 できる。導電性テープは両面ともに導電性を有するものであって、カーボン分散の導 電性接着剤を用いた片面接着タイプ、両面接着タイプが好適に使用できる。電極の 厚さは、これもまた特に限定されるものではないが、数/ z m〜数 mm程度である。  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.
[0183] 本発明によれば、プラズマディスプレイの輝度を著しく損なわずに、その画質を維 持または向上させることができる、光学特性に優れたディスプレイ用フィルタを得るこ とが出来る。また、プラズマディスプレイ力も発生する健康に害をなす可能性があるこ とを指摘されている電磁波を遮断する電磁波シールド能に優れ、さら〖こ、プラズマデ イスプレイ力も放射される 800〜1000nm付近の近赤外線を効率よくカットするため、 周辺電子機器のリモコン、伝送系光通信等が使用する波長に悪影響を与えず、それ らの誤動作を防ぐことができるディスプレイ用フィルタを得ることができる。さらにまた、 耐候性にも優れたディスプレイ用フィルタを低コストで提供することが出来る。  [0183] According to the present invention, it is possible to obtain a display filter having excellent optical characteristics, which can maintain or improve the image quality without significantly impairing the luminance of the plasma display. In addition, it has been pointed out that there is a possibility of harming the health of the plasma display, and it has excellent electromagnetic shielding ability to block electromagnetic waves. In order to cut efficiently, it is possible to obtain a display filter that does not adversely affect the wavelengths used by remote control of peripheral electronic devices, transmission optical communication, etc., and can prevent malfunctions thereof. Furthermore, a display filter having excellent weather resistance can be provided at low cost.
実施例  Example
[0184] 以下に実施例と比較例を挙げて本発明をさらに具体的に説明する。以下の実施例 に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない 限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例によ り限定的に解釈されるべきものではない。 [0184] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples do not depart from the spirit of the present invention. It can be changed as long as possible. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
[0185] (実施例 1)  [0185] (Example 1)
<支持体の作成 >  <Creation of support>
二軸延伸したポリエチレンテレフタレート支持体 (厚み 100 m)の両面に下記組成 の下塗層第 1層及び第 2層を塗布した。  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).
[0186] <下塗層第 1層 > [0186] <Undercoat layer 1>
コア シェル型塩化ビ-リデン共重合体（1) 15g  Core-shell type vinylidene chloride copolymer (1) 15g
2, 4 ジクロル一 6 ヒドロキシ一 s トリァジン 0. 25g  2, 4 Dichloro 1 6 Hydroxy 1 s Triazine 0.25 g
ポリスチレン微粒子（平均粒径 3 μ ) 0. 05g  Polystyrene fine particles (average particle size 3μ) 0.05g
化合物（Cpd-20) 0. 20g  Compound (Cpd-20) 0.20g
コロイダルシリカ (スノーテックス ZL :粒径 70〜： L 00 m 日産化学 (株)製）  Colloidal silica (Snowtex ZL: particle size 70 ~: L 00 m manufactured by Nissan Chemical Co., Ltd.)
0. 12g  0. 12g
水を加えて 100g  100g with water
さらに、 10質量％の1：011を加え、 pH = 6に調整した塗布液を乾燥温度 180°C2分 間で、乾燥膜厚が 0. 9 mになるように塗布した。  Further, 10% by mass of 1: 011 was added, and the coating solution adjusted to pH = 6 was applied at a drying temperature of 180 ° C. for 2 minutes so that the dry film thickness was 0.9 m.
[0187] <下塗層第 2層 > [0187] <Undercoat layer 2>
ゼラチン lg  Gelatin lg
メチノレセノレロース 0. 05g  Metino Resenorelose 0.05g
化合物（Cpd-21) 0. 02g  Compound (Cpd-21) 0.02g
C H 0(CH CH O) H 0. 03g  C H 0 (CH CH O) H 0.03 g
12 25 2 2 10  12 25 2 2 10
プロキセノレ 3. 5 X 10— 3g Proxenole 3.5 X 10— 3 g
酢酸 0. 2g  Acetic acid 0.2 g
水を加えて 100g  100g with water
この塗布液を乾燥温度 170°C2分間で、乾燥膜厚が 0. l /z mになるように塗布した  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.
[0188] [化 1] コア一ンヱル型 ィヒビ リデン共重合体 (1) [0188] [Chemical 1] Core-type hibihibin copolymer (1)
Figure imgf000066_0001
Figure imgf000066_0001
VOC Mfa 12Λ AN AA  VOC Mfa 12Λ AN AA
Core ： VDC舰 MA (80 Λ%) Shell ： VDC /AN/AA (20重量％)Core: VDC 舰 MA (80 Λ%) Shell: VDC / AN / AA (20% by weight)
^粒子サイズ： 70 n m ^ Particle size: 70 nm
化合物 （Cpd - 20) Compound (Cpd-20)
Figure imgf000066_0002
Figure imgf000066_0002
化合物 （Cpd- 21)  Compound (Cpd-21)
Figure imgf000066_0003
1.ハロゲン化銀写真感光材料試料の作成
Figure imgf000066_0003
1. Preparation of silver halide photographic material sample
<試料の作成 > <Sample preparation>
(乳剤 Aの調製） (Preparation of emulsion A)
•1液 • 1 liquid
水 750ml  750ml of water
ゼラチン 20g 塩化ナトリウム 1. 6g Gelatin 20g Sodium chloride 1.6 g
1, 3 ジメチルイミダゾリジン 2 チオン 20mg  1,3 Dimethylimidazolidine 2 Thion 20mg
ベンゼンチォスルホン酸ナトリウム lOmg  Sodium benzenethiosulfonate lOmg
クェン酸 0. 7g  Chenic acid 0.7 g
•2液 • 2 liquids
水 300ml  300ml water
硝酸銀 150g  Silver nitrate 150g
- 3m  -3m
水 300ml  300ml water
塩化ナトリウム 38g  Sodium chloride 38g
臭化カリウム 32g  Potassium bromide 32g
へキサクロ口イリジウム (III)酸カリウム (0.005% KC1 20%水溶液） 5ml  Hexaclomouth Iridium Potassium (III) (0.005% KC1 20% aqueous solution) 5ml
へキサクロ口ロジウム酸アンモ-ゥム (0.001% NaCl 20%水溶液） 7ml  Hexacloammonium rhodate ammonium (0.001% NaCl 20% aqueous solution) 7ml
3液に用いるへキサクロ口イリジウム (III)酸カリウム (0.005% KC1 20%水溶液)およびへ キサクロ口ロジウム酸アンモ-ゥム (0.001% NaC120%水溶液)は、粉末をそれぞれ KC1 20%水溶液、 NaC120%水溶液に溶解し、 40°Cで 120分間加熱して調製した。  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.
38°C、 pH4. 5に保たれた 1液に、 2液と 3液の各々 90%に相当する量を攪拌しな 力 Sら同時に 20分間にわたってカロえ、 0. 15 mの核粒子を形成した。続いて下記 4 液、 5液を 8分間にわたって加え、さらに、 2液と 3液の残りの 10%の量を 2分間にわ たって加え、 0. 18 mまで粒子を成長させた。さら〖こ、ヨウィ匕カリウム 0. 15gを加え 5 分間熟成し粒子形成を終了した。  In 1 liquid maintained at 38 ° C and pH 4.5, the amount corresponding to 90% of 2 and 3 liquids is not stirred. Formed. Subsequently, the following 4 and 5 solutions were added over 8 minutes, and the remaining 10% of the 2 and 3 solutions were added over 2 minutes to grow particles to 0.18 m. Then, 0.15 g of Sarako and Yowi Potassium was added and ripened for 5 minutes to complete the grain formation.
•4液 • 4 fluids
水 100ml  100ml water
硝酸銀 50g  Silver nitrate 50g
•5液 • 5 liquids
水 100ml  100ml water
塩化ナトリウム 13g  Sodium chloride 13g
臭化カリウム l lg 黄血塩 5mg Potassium bromide l lg Yellow blood salt 5mg
[0191] その後、常法にしたがってフロキユレーシヨン法によって水洗した。具体的には、温 度を 35°Cに下げ、下記に示すァ-オン性沈降剤 1を 3g加え、硫酸を用いてハロゲ ン化銀が沈降するまで pHを下げた。（pH3. 2±0. 2の範囲であった)次に上澄み液 を約 3リットル除去した (第一水洗)。さらに 3リットルの蒸留水を加えてから、ハロゲン 化銀が沈降するまで硫酸を加えた。再度上澄み液を 3リットル除去した (第二水洗)。 第二水洗と同じ操作をさらに 1回繰り返し (第三水洗)て水洗'脱塩行程を終了した。 水洗'脱塩後の乳剤にゼラチン 8gをカ卩え、 pH5. 6、 pAg7. 5に調整し、ベンゼンチ ォスルホン酸ナトリウム 10mg、ベンゼンチォスルフィン酸ナトリウム 3mg、チォ硫酸ナ トリウム 15mgと塩ィ匕金酸 lOmgをカ卩ぇ 55°Cにて最適感度を得るように化学増感を施 し、安定剤として 1, 3, 3a, 7—テトラァザインデン 100mg、防腐剤としてプロキセル（ 商品名、 ICI Co. , Ltd.製） lOOmgを加えた。最終的に塩化銀を 70モル％、沃化 銀を 0.08モル％含む平均粒子径 0. 18 ^ m,変動係数 9%のヨウ塩臭化銀立方体粒 子乳剤を得た。（最終的に乳剤として、 pH = 5. 7、pAg = 7. 5、電導度 = 60 /ζ 3/πι 、密度 = 1. 28 Χ 103kg/m3、粘度 = 60mPa' sとなった。 ) [0191] Thereafter, 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. After washing and desalting, 8g of gelatin was added to the emulsion, adjusted to pH 5.6, pAg 7.5, sodium benzenethiosulfonate 10mg, sodium benzenethiosulfinate 3mg, sodium thiosulfate 15mg lOmg was chemically sensitized for optimum sensitivity at 55 ° C, 1, 3, 3a, 7-tetraazaindene as a stabilizer 100mg, and proxel as a preservative (trade name, ICI Co , Ltd.) lOOmg was added. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.18 ^ m and a coefficient of variation of 9% was obtained. (Finally, as an emulsion, pH = 5.7, pAg = 7.5, conductivity = 60 / ζ 3 / πι, density = 1.28Χ10 3 kg / m 3 , viscosity = 60 mPa's )
[0192] [化 2]  [0192] [Chemical 2]
ァニオン性沈降剤—
Figure imgf000068_0001
平均分子 Jl 1 2万 Anionic precipitants—
Figure imgf000068_0001
Average molecule Jl 1 20,000
[0193] <乳剤層 > [0193] <Emulsion layer>
乳剤 Aに増感色素（SD-1) 5.7 X 10— 4モル Zモル Agを加えて分光増感を施した。さ らに KBr3.4 X 10— 4モル Zモル Ag、化合物（Cpd-3) 8.0 X 10— 4モル Zモル Agをカロえ、 よく混合した。 次いで 1,3,3a, 7-テトラァザインデン 1.2 X 10 モル/モル Ag、 ノヽイドロキノン 1.2 X 10 — 2モル Zモル Ag、クェン酸 3.0 X 10— 4モル/モル Ag、界面活性剤 (Sa-1)、（Sa- 、 (Sa - 3)を各々塗布量が 60mg/m2、 40mg/m2、 2mg/m2になるように添カ卩し、クェン酸を用い て塗布液 pHを 5.6に調整した。このようにして調製した乳剤層塗布液を上記支持体上 に Ag7. 6g/m2、ゼラチン 1. lg/m2になるように塗布した。 It was subjected to spectral sensitization by adding the sensitizing dye (SD-1) 5.7 X 10- 4 mole Z mol Ag to the emulsion A. KBr3.4 X 10- 4 mole Z mol Ag, the compound (Cpd-3) 8.0 X 10- 4 mole Z mol Ag Karoe was mixed well of al. Then 1,3,3a, 7- tetra § tetrazaindene 1.2 X 10 mole / mole Ag, Nono Idorokinon 1.2 X 10 - 2 moles Z mol Ag, Kuen acid 3.0 X 10- 4 mol / mol Ag, surfactant (Sa -1), (Sa-, (Sa-3) were added so that the coating amount would be 60 mg / m 2 , 40 mg / m 2 , 2 mg / m 2 , respectively. The emulsion layer coating solution thus prepared was coated on the above support so as to be Ag 7.6 g / m 2 and gelatin 1. lg / m 2 .
[0194] <UL層 > [0194] <UL layer>
ゼラチン 0. 23g/m2 Gelatin 0.23g / m 2
化合物 (Cpd-7) 40mg/m2 Compound (Cpd-7) 40mg / m 2
化合物 (Cpd- 14) 10mg/m2 Compound (Cpd-14) 10mg / m 2
防腐剤（プロキセル） 1. 5mg/m2 Preservative (Proxel) 1.5mg / m 2
なお、各層の塗布液は、下記構造 (Z)で表される増粘剤を加え、粘度調整した。  The coating solution for each layer was adjusted for viscosity by adding a thickener represented by the following structure (Z).
[0195] [化 3] [0195] [Chemical 3]
增粘剤 Z Thickener Z
Figure imgf000069_0001
Figure imgf000069_0001
また、本発明で使用したサンプルは下記組成のノック層および帯電防止層を形成 した。 The sample used in the present invention formed a knock layer and an antistatic layer having the following composition.
<ノ ック層 >  <Knock layer>
ゼラチン 3. 3g/m2 Gelatin 3.3 g / m 2
化合物 (Cpd- 15) 40mg/m2 化合物 (Cpd-16) 20mg/ m' 化合物 (Cpd-17) 90mgZ m' 化合物 (Cpd-18) 40mgZ m' 化合物 (Cpd-19) 26mgZ m'Compound (Cpd-15) 40mg / m 2 Compound (Cpd-16) 20mg / m 'Compound (Cpd-17) 90mgZ m' Compound (Cpd-18) 40mgZ m 'Compound (Cpd-19) 26mgZ m'
1, 3—ジビニルスルホニルー 2—プロパノール 60mg/ m' ポリメチルメタタリレート微粒子（平均粒径 6. 5 m ) 30mg/m' 流動パラフィン / 8mg, m 化合物 (Cpd-7) 120mg/m' 硝酸カルシウム 20mg/ m 防腐剤（プロキセル） 12mgZ 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
[0197] <帯電防止層 > [0197] <Antistatic layer>
ゼラチン 0. lgZ m' ドデシルベンゼンスルホン酸ナトリウム 20mg/ m Gelatin 0.lgZ m 'Sodium dodecylbenzenesulfonate 20mg / m
SnO /Sb (9Zl質量比、平均粒子径 0· 25 μ ) 200mg/m' 防腐剤（プロキセル) 0. 3mg/ m [0198] [化 4] SnO / Sb (9Zl mass ratio, average particle size 0 · 25 μ) 200mg / m 'Preservative (Proxel) 0.3mg / m [0198] [Chemical 4]
(Sa-1) (Sa-1)
H3C^CH2) CH二 CH~[CH2^:CO— CH2— CH2_S03H H 3 C ^ CH 2 ) CH 2 CH ~ [CH 2 ^: CO— CH 2 — CH 2 _S0 3 H
CH3 · Na CH 3 · Na
60mg/m  60mg / m
(Sa-2) C2H5 (Sa-2) C 2 H 5
CH2— CO - O - CH2— CH— C4H9 CH 2 — CO-O-CH 2 — CH— C 4 H 9
Na . HO3S-CH— CO-0-CH2-CH-C4H9 Na. HO3S-CH— CO-0-CH 2 -CH-C 4 H 9
フ C2H5 C 2 H 5
40mg/m  40mg / m
(Sa-3)  (Sa-3)
F3C-(-CF2 (CH2 rO-CO-CH2-CH-CO-0- CH2WCF2)-CF3 F 3 C-(-CF 2 ( CH 2 rO-CO-CH2-CH-CO-0- CH2WCF 2 ) -CF3
I I
CH2 CH 2
2mg/m2 SO3H · Na 2mg / m 2 SO3HNa
5] Five]
Figure imgf000072_0001
Figure imgf000072_0001
Qpd S Qpd S
Figure imgf000072_0002
Figure imgf000072_0002
Figure imgf000072_0003
： Z) : n - 3 3 : 1
Figure imgf000072_0003
: Z): n-3 3: 1
Figure imgf000073_0001
Figure imgf000073_0001
Cpd-18  Cpd-18
CH3(CH2)11CH=CHS03Na CH 3 (CH 2 ) 11 CH = CHS0 3 Na
Cpd-19 Cpd-19
CH3(CH2)ii-CH2-CHSQ,Na <塗布方法〉 CH3 (CH2) ii-CH 2 -CHSQ, Na <Coating method>
上記下塗層を施した支持体上に、まず乳剤面側として支持体に近 V、側より UL層、 乳剤層の順に 2層を、 35°Cに保ちながらスライドビードコーター方式により同時重層 塗布し、冷風セットゾーン（5°C)を通過させた。ここで、硬膜剤である Cpd-7は塗布直 前に UL層へ前述の量添加し、 UL層から拡散させることにより乳剤層へ含有させた。 そして、乳剤面とは反対側には、支持体に近い側より、帯電防止層、バック層の順に 、カーテンコーター方式により硬膜剤液を加えながら同時重層塗布し、冷風セットゾ ーン（5°C)を通過させた。各々のセットゾーンを通過した時点では、塗布液は充分な セット性を示した。引き続き乾燥ゾーンにて両面を同時に乾燥した。このようにして、 試料 (1— 1)を作成した。 On the support with the above subbing layer, first, close to the support as the emulsion side, V, UL layer from the side, and emulsion layer in that order in the order of two layers, while maintaining the temperature at 35 ° C, simultaneous layering by the slide bead coater method It was applied and passed through a cold air set zone (5 ° C). Here, Cpd-7 as a hardener was added to the UL layer immediately before coating, and was added to the emulsion layer by diffusing from the UL layer. Then, on the side opposite to the emulsion surface, 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). When passing through each set zone, the coating solution showed a sufficient setting property. Subsequently, both sides were simultaneously dried in the drying zone. In this way, sample (1-1) was prepared.
得られた試料（1— 1)は、塗布銀量が 7.6g/m2、乳剤層の Ag/ゼラチン質量比が 6.9 、膨潤率が 209%、 Ag/ゼラチン質量比と膨潤率の積が 13.2である乳剤層を、最上層 に有する感光材料であった。ここで乳剤層の膨潤率は以下のように求めた。すなわち 、乾燥時の試料の切片を走査型電子顕微鏡で観察することにより乾燥時の乳剤層の 膜厚 (a)を求め、 25°Cの蒸留水に 1分間浸潰した後液体窒素により凍結乾燥した試 料の切片を走査型電子顕微鏡で観察することにより膨潤時の乳剤層の膜厚 (b)を求 め、膨潤率を次式で算出した。 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. Here, 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.
膨潤率 (％) = 100 X ( (b)—（a) ) / (a)  Swell rate (%) = 100 X ((b) — (a)) / (a)
[0202] 得られた試料 1 1の表面抵抗は、三菱ケミカル製、ロレスター GP MCP-T600[0202] The surface resistance of the obtained Sample 1 1 was measured by Mitsubishi Chemical, Lorester GP MCP-T600
ZASPプローブを用いて測定した結果、 30 Ω Z口であった。 As a result of measurement using a ZASP probe, it was 30 ΩZ port.
[0203] 2.試料への露光及び処理条件 [0203] 2. Sample exposure and processing conditions
乾燥させた試料（1— 1)の乳剤層塗布膜にライン Zスペース = 10 μ m/290 μ m の現像銀像を与えうる格子状のフォトマスク（ライン Zスペース = 290 mZlO m ( ピッチ 300 μ m)の、スペースが格子状であるフォトマスク）を介して高圧水銀ランプを 光源とした平行光を用いて露光を施し、露光されたハロゲンィ匕銀フィルムを得た。 以下に示す処理工程及び処理液でランニング処理 (現像液の累積補充量が、その タンク容量の 3倍になるまで)を行った。  Lattice photomask (line Z space = 290 mZlO m (pitch 300 μm) that can give a developed silver image of line Z space = 10 μm / 290 μm to the emulsion layer coating film of the dried sample (1-1) m), a photomask having a lattice-like space) was exposed using parallel light using a high-pressure mercury lamp as a light source to obtain an exposed halogen silver film. 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.
露光されたハロゲン化銀フィルムに対し、黒白現像処理 (温度 30°C、時間 40秒）、 定着処理 (温度 30°C、時間 40秒)、硬膜処理 (温度 30°C、時間 40秒)を順次行った さらに、硬膜処理まで行われたハロゲンィ匕銀フィルムに対し、電解めつき処理を 15 回に分けて行った。最後に、防鲭処理を行い、導電膜を得た。 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 In addition, an electroplating treatment was applied to the halogenated silver film that had been subjected to the hardening process. It was divided into times. Finally, an antifouling treatment was performed to obtain a conductive film.
[0204] 各処理液の組成は以下の通りである。  [0204] The composition of each treatment solution is as follows.
〔黒白現像液 1L処方〕  [Black and white developer 1L prescription]
ハイドロキノン 20 g  Hydroquinone 20 g
亜硫酸ナトリウム 50 g  Sodium sulfite 50 g
炭酸カリウム 40 g  Potassium carbonate 40 g
エチレンジァミン'四酢酸 2 g  Ethylenediamine 'tetraacetic acid 2 g
臭化カリウム 3 g  Potassium bromide 3 g
ポジエチレング IJn—ノレ 4000 0. 5 g  Posiethylene IJn—Nore 4000 0.5 g
水酸化カリウム 4 g  Potassium hydroxide 4 g
pH 10. 3に調整  Adjust to pH 10.3
[0205] 〔定着液 1L処方〕  [0205] Fixer 1L prescription
チォ硫酸アンモニゥム液（75%) 300 ml  Ammonium thiosulfate solution (75%) 300 ml
亜硫酸アンモ-ゥム · 1水塩 25 g  Ammonium sulfite monohydrate 25 g
エチレンジミン'四酢酸 0. 5 g  Ethylenedimine 'tetraacetic acid 0.5 g
ヨウ化カリウム 2 g  Potassium iodide 2 g
pH 5. 8に調整  Adjust to pH 5.8
[0206] 〔硬膜処理 (めっき前硬膜処理)液 1L処方〕  [0206] [Hardening (hardening before plating) solution 1L prescription]
添加剤（表 1に記載） 50 g  Additives (listed in Table 1) 50 g
pH 5. 1に調整  Adjust to pH 5.1
純水を加えて 1 L  1 L with pure water
[0207] なお、添加剤は、本発明ではダルタルアルデヒドを使用して硬膜処理を行った。ま た比較例としてダルタルアルデヒドを添加せずに何も添加剤を添カ卩しなカゝったもの、 ダルタルアルデヒドを含有させずに硫酸を使用したものも行った。  [0207] In the present invention, dartal aldehyde was used as the additive for hardening. In addition, as 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.
[0208] 〔電解めつき液 1〜14 1L処方〕 [0208] [Electrolytic plating solution 1-14 1L prescription]
硫酸銅五水塩 200 g  Copper sulfate pentahydrate 200 g
硫酸 60 g  60 g sulfuric acid
Cu-Brite 20 mL (荏原ユージライト (株)製） Cu-Brite 20 mL (Hagiwara Eugelite Co., Ltd.)
純水を加えて 1 L  1 L with pure water
[0209] 〔電解めつき液 15 1L処方〕  [0209] [Electrolytic plating solution 15 1L prescription]
硫酸ニッケル 6水塩 100 g  Nickel sulfate hexahydrate 100 g
硫酸アンモ-ゥム 15 g  Ammonium sulfate 15 g
硫酸亜鉛 7水塩 25 g  Zinc sulfate heptahydrate 25 g
チォシアン酸ナトリウム 15 g  Sodium thiocyanate 15 g
pH 4. 5に調整  Adjust to pH 4.5
[0210] 〔防鲭液 1L処方〕  [0210] Antifungal solution 1L prescription
スルカップ AT— 21 20 mL  Through cup AT— 21 20 mL
(上村工業 (株)製）  (Made by Uemura Industry Co., Ltd.)
[0211] [膨潤率の測定] [0211] [Measurement of swelling rate]
得られた導電性膜の膨潤率は以下のように求めた。すなわち、乾燥時の光透過性 部の切片を走査型電子顕微鏡で観察することにより乾燥時の光透過性部層の膜厚（ a)を求め、 25°Cの蒸留水に 1分間浸漬した後液体窒素により凍結乾燥した試料の切 片を走査型電子顕微鏡で観察することにより膨潤時の光透過性部層の膜厚 (b)を求 め、膨潤率を次式で算出した。  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.
膨潤率 (％) = 100 X ( (b)—（a) ) / (a)  Swell rate (%) = 100 X ((b) — (a)) / (a)
[0212] (めっきによるタテスジムラの評価方法） [0212] (Evaluation method of vertical stripes by plating)
ランニング処理後の上記サンプルを、以下の 4段階による目視評価を行った。  The sample after the running treatment was visually evaluated according to the following four steps.
X X · · 'タテスジムラが非常に多ぐ全く許容できない。  X X · · 'There are so many vertical gyms that it is totally unacceptable.
X · · 'タテスジムラが多く許容できない。  X ·· 'Many vertical wars are not acceptable.
△ · · 'タテスジムラがある力 力ろうじて許容できる。  △ · · 'Vertical gymra is a force that is barely acceptable.
〇…タテスジムラが目視では確認できず、許容できる。  〇… Vertical streaks cannot be confirmed by visual inspection and is acceptable.
結果を表 1に示す。  The results are shown in Table 1.
[0213] (めっき品質の評価方法） [0213] (Plating quality evaluation method)
ランニング処理後の上記サンプルを、ランダムに 100視野の格子部を光顕（ X 500 )で観察し、以下 5段階による評価を行った。 5 · · · 100視野の全てでメツキが均一に付いており、許容できる。 The above sample after the running treatment was randomly observed with a light microscope (X500) for 100 fields of view, and evaluated according to the following 5 levels. 5 ················································································································.
4· · '不均一なメツキが、 100視野中 5視野未満で観察される力 力ろうじて許容で きる。  4 ·· 'Non-uniform scatter is barely tolerable with less than 5 out of 100 views.
3 · · '不均一なメツキが、 100視野中 5〜10視野で観察され、許容できない。  3 ·· 'Uneven observability is observed in 5 to 10 out of 100 views and is unacceptable.
2· · '不均一なメツキが、 100視野中 11〜50視野で観察され、許容できない。  2 ·· 'Uneven sighting is observed in 11 to 50 out of 100 views, unacceptable.
1 · · '不均一なメツキが、 100視野中 51視野以上で観察され、許容できない。  1 · · 'Unevenness is observed in 51 or more out of 100 views, which is unacceptable.
結果を表 1に示す。  The results are shown in Table 1.
[表 1]  [table 1]
Figure imgf000077_0001
Figure imgf000077_0001
[0215] (めっき進行性の評価方法） [0215] (Plating progress evaluation method)
電解めつき 1, 3, 5, 7, 9, 11, 13, 15の処理前に、実施例 1及び比較例 1および 2 の感光材料をサンプリングした。サンプリングした実施例 1及び比較例 1および 2の感 光材料を 35mm X 45mmにカットし、表面抵抗を測定した。表面抵抗は、三菱ケミカ ル製、ロレスター GP MCP— T600/ASPプローブを用いた。  Before processing the electrolytic plating 1, 3, 5, 7, 9, 11, 13, 15, the photosensitive materials of 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. For the surface resistance, Lorestar GP MCP-T600 / ASP probe manufactured by Mitsubishi Chemical was used.
[0216] 実施例 1及び比較例 1および 2の感光材料の表面抵抗の測定結果を表 2に示す。  Table 2 shows the measurement results of the surface resistance of the photosensitive materials of Example 1 and Comparative Examples 1 and 2.
[0217] [表 2] 表面抵抗 (Ω /口) [0217] [Table 2] Surface resistance (Ω / mouth)
Figure imgf000078_0001
Figure imgf000078_0001
[0218] 表 2に示した結果からわ力るように、実施例 1の感光材料では電解めつき処理後の 表面抵抗が比較例 1および 2のものよりも十分に低減されていることが確認された。 [0218] As can be seen from the results shown in Table 2, it was confirmed that the surface resistance after the electroplating treatment was sufficiently reduced in the photosensitive material of Example 1 than in Comparative Examples 1 and 2. It was done.
[0219] 表 1に示すように、硬膜剤としてダルタルアルデヒドを加えた実施例 1では、スジムラ が抑制され、めっき均一性も向上したことが分かる。  [0219] 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.
[0220] (実施例 2)  [0220] (Example 2)
前記の実施例 1のめつき前処理を次の処方に変更した以外は、実施例 1と同様に 実施した。結果、実施例 1と同様、良好な結果であった。  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.
[0221] 〔めっき前硬膜処理液 1L処方〕 [0221] [Pre-plating hardening solution 1L prescription]
酢酸 50% 15 mL  Acetic acid 50% 15 mL
硫酸ナトリウム 130 g  Sodium sulfate 130 g
無水酢酸ナトリウム 12 g  Anhydrous sodium acetate 12 g
硫酸アルミニウム 5 g  Aluminum sulfate 5 g
硫酸 0. 5 g  Sulfuric acid 0.5 g
PH 4. 0に調整 純水を加えて 1 L Adjust to PH 4.0 1 L with pure water
[0222] (実施例 3)  [0222] (Example 3)
実施例 1の試料（1— 1)に対し、硬膜剤 (Cpd— 7)の添加量とゼラチン塗布量を調 整し、試料 (3— 1)〜（3— 4)を得た。これらの試料を用いて、硬膜処理の条件を変 更した以外は、実施例 1と同様の評価を実施した。得られた結果を表 3に示す。 得られた光透過性部の乾燥膜厚は、乾燥時の光透過性部の切片を走査型電子顕 微鏡で観察することにより乾燥時の光透過性部層の膜厚 (a)を求めた。  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.
[0223] [表 3] [0223] [Table 3]
Figure imgf000079_0001
Figure imgf000079_0001
本出願は、 2005年 12月 28日出願の日本特許出願、特願 2005— 379199に基 づくものであり、その内容はここに参照として取り込まれる。 This application is based on Japanese Patent Application No. 2005-379199 filed on Dec. 28, 2005, the contents of which are incorporated herein by reference.

Claims

請求の範囲  The scope of the claims
[I] 支持体上に、導電性金属部及び光透過性部を含む導電性機能層を有し、前記光 透過性部の膨潤率が 180%以下であることを特徴とする導電性膜。  [I] A conductive film having a conductive functional layer including a conductive metal portion and a light transmissive portion on a support, wherein the light transmissive portion has a swelling ratio of 180% or less.
[2] 前記導電性膜の表面抵抗が 2. 5 Ω Zsq以下であり、かつ Z又は前記光透過性部 の透過率が 95%以上であることを特徴とする請求項 1に記載の導電性膜。  [2] The conductive film according to [1], wherein the surface resistance of the conductive film is 2.5 Ω Zsq or less, and the transmittance of Z or the light-transmitting part is 95% or more. film.
[3] 前記光透過性部の乾燥膜厚が 2. 0 μ m以下であることを特徴とする請求項 1また は 2に記載の導電性膜。 [3] The conductive film according to [1] or [2], wherein a dry film thickness of the light transmitting portion is 2.0 μm or less.
[4] 前記光透過性部が実質的に水溶性ポリマーからなることを特徴とする請求項 1〜3 の!、ずれかに記載の導電性膜。 [4] The conductive film according to any one of [1] to [3], wherein the light-transmitting portion is substantially made of a water-soluble polymer.
[5] 表面抵抗が 1〜： L 000 Ω Z口のフィルムの表面に硬膜溶液を反応させる硬膜工程 を有することを特徴とする導電性膜の製造方法。 [5] A method for producing a conductive film comprising a hardening step of reacting a hardening solution on the surface of a film having a surface resistance of 1 to: L 000 Ω Z.
[6] 前記フィルムが支持体上にハロゲンィ匕銀乳剤層を含む少なくとも 1層の親水性コロ イド層を有するハロゲン化銀写真感光材料であることを特徴とする請求項 5に記載の 導電性膜の製造方法。 6. The conductive film according to claim 5, wherein the film is a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer including a silver halide silver emulsion layer on a support. Manufacturing method.
[7] 前記硬膜溶液が、硬膜剤を含有し、該硬膜剤がゼラチンを硬膜する作用を有する 化合物であることを特徴とする請求項 5または 6に記載の導電性膜の製造方法。  [7] The conductive film according to claim 5 or 6, wherein the hardening solution contains a hardening agent, and the hardening agent has a function of hardening gelatin. Method.
[8] 前記硬膜剤が、ホルムアルデヒド、ビバリルアルデヒド、ダルタルアルデヒド、琥珀ァ ルデヒド、カリ明ばん、クロム明ばん、および硫酸アルミニウム力 選択される化合物 であることを特徴とする請求項 7に記載の導電性膜の製造方法。  8. The hardener is a compound selected from formaldehyde, bivalylaldehyde, dartalaldehyde, aldehyde, potash alum, chromium alum, and aluminum sulfate. The manufacturing method of the electroconductive film of description.
[9] 請求項 5〜8のいずれかに記載の導電性膜の製造方法によって得られたことを特 徴とする導電性膜。  [9] A conductive film obtained by the method for producing a conductive film according to any one of claims 5 to 8.
[10] 請求項 5〜8のいずれかに記載の導電性膜の製造方法によって製造されたことを 特徴とする電磁波シールド膜。  [10] An electromagnetic wave shielding film produced by the method for producing a conductive film according to any one of [5] to [8].
[II] 請求項 5〜8のいずれかに記載の導電性膜の製造方法によって製造された電磁波 シールド膜の表面抵抗が 2. 5 Ω Zsq以下であることを特徴とする電磁波シールド膜  [II] The electromagnetic wave shielding film produced by the method for producing a conductive film according to any one of claims 5 to 8, wherein the electromagnetic wave shielding film has a surface resistance of 2.5 Ω Zsq or less.
[12] 表面抵抗が 1. 5 Ω Zsq以下であることを特徴とする請求項 11に記載の電磁波シ 一ルド膜。 12. The electromagnetic shielding film according to claim 11, wherein the surface resistance is 1.5 Ω Zsq or less.
[13] 支持体上にハロゲンィ匕銀乳剤層を有するハロゲンィ匕銀フィルムを露光して現像し、 金属銀部を形成する現像工程と、 [13] A development step of exposing and developing a halogenated silver film having a halogenated silver emulsion layer on a support to form a metallic silver portion;
前記金属銀部が形成されたフィルムの表面に、硬膜剤を含有する硬膜溶液を反応 させる硬膜工程と、  A hardening step of reacting a hardening solution containing a hardening agent on the surface of the film on which the metallic silver portion is formed;
前記硬膜工程が施されたフィルムの金属銀部に対し、電解めつき処理を施す電解 めっき処理工程と、  An electroplating treatment step for subjecting the metallic silver part of the film subjected to the hardening step to an electroplating treatment;
を有する導電性膜の製造方法。  The manufacturing method of the electroconductive film which has this.
[14] 前記ハロゲン化銀乳剤層がハロゲンィ匕銀及びバインダーを含有することを特徴とす る請求項 13に記載の導電性膜の製造方法。  14. The method for producing a conductive film according to claim 13, wherein the silver halide emulsion layer contains silver halide silver and a binder.
[15] 前記ハロゲン化銀乳剤層における銀 (Ag)及びバインダー (B)の含有質量比が下 記式（1)の範囲にあることを特徴とする請求項 14に記載の導電性膜の製造方法。 [15] The conductive film production according to [14], wherein the content ratio of silver (Ag) and binder (B) in the silver halide emulsion layer is in the range of the following formula (1): Method.
AgZB = 3〜15 (1)  AgZB = 3 to 15 (1)
[16] AgZバインダー体積比が 1Z4以上の銀塩含有層を用いることを特徴とする請求 項 14または 15に記載の導電性膜の製造方法。 16. The method for producing a conductive film according to claim 14 or 15, wherein a silver salt-containing layer having an AgZ binder volume ratio of 1Z4 or more is used.
[17] 前記バインダーがゼラチンであることを特徴とする請求項 14〜16のいずれかに記載 の導電性膜の製造方法。 17. The method for producing a conductive film according to any one of claims 14 to 16, wherein the binder is gelatin.
[18] 前記硬膜剤がゼラチンを硬膜する作用を有する化合物であることを特徴とする請求 項 13〜17のいずれかに記載の導電性膜の製造方法。 18. The method for producing a conductive film according to any one of claims 13 to 17, wherein the hardener is a compound having a function of hardening gelatin.
[19] 前記硬膜剤が、ホルムアルデヒド、ビバリルアルデヒド、ダルタルアルデヒド、琥珀ァ ルデヒド、カリ明ばん、クロム明ばん、および硫酸アルミニウム力 選択される化合物 であることを特徴とする請求項 13〜18のいずれかに記載の導電性膜の製造方法。 [19] The hardener is a compound selected from formaldehyde, bivalylaldehyde, dartalaldehyde, aldehyde, potash alum, chromium alum, and aluminum sulfate. 19. A method for producing a conductive film according to any one of 18 above.
[20] 前記硬膜剤がダルタルアルデヒド又は硫酸アルミニウムであることを特徴とする請求 項 13〜19のいずれかに記載の導電性膜の製造方法。 [20] The method for producing a conductive film according to any one of [13] to [19], wherein the hardener is dartalaldehyde or aluminum sulfate.
[21] 前記硬膜溶液が硬膜剤を 0.005〜1.000mol/L含有することを特徴とする請求項 13[21] The dura solution contains 0.005 to 1.000 mol / L of a hardening agent.
〜20の 、ずれかに記載の導電性膜の製造方法。 The method for producing a conductive film according to any one of -20.
[22] 前記硬膜溶液がさらに膨潤抑制作用のある化合物を含有することを特徴とする請 求項 13〜21のいずれかに記載の導電性膜の製造方法。 [22] The method for producing a conductive film according to any one of claims 13 to 21, wherein the dura solution further contains a compound having a swelling-inhibiting action.
[23] 露光部に前記金属銀部を形成し、未露光部に光透過性部を形成することを特徴と する請求項 13〜22のいずれかに記載の導電性膜の製造方法。 [23] The metal silver portion is formed in the exposed portion, and the light transmissive portion is formed in the unexposed portion. The method for producing a conductive film according to any one of claims 13 to 22.
[24] 前記光透過性部が実質的に物理現像核を有しないことを特徴とする請求項 13〜224. The optically transparent portion substantially has no physical development nucleus.
3の 、ずれかに記載の導電性膜の製造方法。 3. The method for producing a conductive film according to any one of the above.
[25] 請求項 13〜24のいずれかに記載の製造方法により得られることを特徴とする、導 電性金属部及び光透過性部を有するプラズマディスプレイパネル用電磁波シールド 膜。 [25] An electromagnetic wave shielding film for a plasma display panel having a conductive metal portion and a light transmissive portion, which is obtained by the production method according to any one of claims 13 to 24.
[26] 請求項 11又は 12に記載の電磁波シールド膜を有することを特徴とするプラズマデ イスプレイパネル用光学フィルター。  [26] An optical filter for a plasma display panel, comprising the electromagnetic wave shielding film according to [11] or [12].
[27] 請求項 13〜24のいずれかに記載の製造方法により得られた電磁波シールド膜を 有することを特徴とするプラズマディスプレイパネル用光学フィルター。 [27] An optical filter for a plasma display panel, comprising the electromagnetic wave shielding film obtained by the production method according to any one of [13] to [24].
[28] 請求項 26又は 27に記載の光学フィルターを有することを特徴とするプラズマデイス プレイパネノレ。 [28] A plasma display panel having the optical filter according to claim 26 or 27.
[29] 請求項 13〜24の 、ずれかに記載の製造方法により得られた電磁波シールド膜を 有することを特徴とするプラズマテレビ。  [29] A plasma television comprising the electromagnetic wave shielding film obtained by the manufacturing method according to any one of [13] to [24].
PCT/JP2006/326153 2005-12-28 2006-12-27 Conductive film and method for producing same, electromagnetic shielding film and method for producing same, and plasma display panel WO2007077898A1 (en)

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JP2011131500A (en) * 2009-12-24 2011-07-07 Fujifilm Corp Photosensitive material for forming conductive film, and method for manufacturing conductive film

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