WO2007086523A1 - Silver halide photosensitive material, conductive metal film, translucent electromagnetic wave shielding film, optical filter and plasma display panel - Google Patents

Silver halide photosensitive material, conductive metal film, translucent electromagnetic wave shielding film, optical filter and plasma display panel Download PDF

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Publication number
WO2007086523A1
WO2007086523A1 PCT/JP2007/051304 JP2007051304W WO2007086523A1 WO 2007086523 A1 WO2007086523 A1 WO 2007086523A1 JP 2007051304 W JP2007051304 W JP 2007051304W WO 2007086523 A1 WO2007086523 A1 WO 2007086523A1
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WIPO (PCT)
Prior art keywords
silver
layer
film
silver halide
conductive metal
Prior art date
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PCT/JP2007/051304
Other languages
French (fr)
Japanese (ja)
Inventor
Hirotomo Sasaki
Shinichi Nakahira
Tatsuya Nomura
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Fujifilm Corporation
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Publication of WO2007086523A1 publication Critical patent/WO2007086523A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • G03C1/853—Inorganic compounds, e.g. metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • G03C1/93—Macromolecular substances therefor
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212—Electromagnetic interference shielding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/414—Translucent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/422—Luminescent, fluorescent, phosphorescent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/204—Plasma displays

Definitions

  • Silver halide photosensitive material conductive metal film, translucent electromagnetic shielding film, optical filter and plasma display panel
  • the present invention relates to a silver halide photosensitive material, a conductive metal film produced using the same, a translucent electromagnetic wave shielding film comprising the conductive metal film, an optical filter having the shield film, and plasma. It relates to a display panel.
  • the translucent electromagnetic wave shielding film in the present invention includes CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, ELP (electricular luminescence panel (EL also! /)), FED (field emission display). It is effective for shielding electromagnetic waves generated by force such as the front of displays, microwave ovens, electronic equipment, and printed circuit boards.
  • the above-mentioned countermeasure against EMI requires the ability to shield electromagnetic waves.
  • a method of making the casing a metal body or a high conductor, a method of inserting a metal plate between the circuit board and the circuit board, and a method of covering the cable with a metal foil are employed.
  • CRT, PDP, etc. it is necessary for the operator to recognize characters displayed on the screen, so transparency on the display is required. For this reason, any of the above methods is inappropriate as an electromagnetic wave shielding method in which the front surface of the display often becomes opaque.
  • a PDP generates a larger amount of electromagnetic waves than a CRT or the like, and thus a stronger electromagnetic wave shielding ability is required.
  • the electromagnetic wave shielding ability can be expressed simply by the surface resistance value.
  • the surface resistance value is about 300 ⁇ / Whereas it is required to be less than sq, translucent electromagnetic shielding material for PDP
  • the required level of transparency is about 70% or more for CRT and 8 for PDP.
  • Patent Document 1 discloses an electromagnetic shielding material such as a conductive fiber cover.
  • this shield material has a drawback that when the display screen is shielded with a thick mesh line width, the screen becomes dark and it is difficult to see the characters displayed on the display.
  • Patent Documents 5 to 8 There has been proposed a method of forming a metal thin film mesh on a transparent substrate by an etching process using a photolithography method. Since this method allows fine processing, it has the advantage that a mesh having a high aperture ratio (high transmittance) can be created and can be shielded even when strong electromagnetic waves are emitted. However, its manufacture However, it is complicated and complicated, and the production cost is high. In addition, it is known from the etching method that the intersection of the lattice pattern is thicker than the line width of the straight line. In addition, the problem of moire was pointed out and improvement was desired.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-327274
  • Patent Document 2 JP 11 170420 A
  • Patent Document 3 Japanese Patent Laid-Open No. 5-283889
  • Patent Document 4 JP-A-11-170421
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2003-46293
  • Patent Document 6 Japanese Patent Laid-Open No. 2003-23290
  • Patent Document 7 JP-A-5-16281
  • Patent Document 8 Japanese Patent Laid-Open No. 10-338848
  • Patent Document 9 Japanese Unexamined Patent Application Publication No. 2004-207001
  • Patent Document 10 Japanese Patent Application Laid-Open No. 2004-221564
  • Patent Document 10 a translucent conductive film made by using a photographic photosensitive material using silver salt is mass-produced with high transparency and low cost by being able to form a fine line pattern precisely compared to other methods. With this film, the resistance of the developed silver mesh is high, so it is difficult to perform direct electroplating, and it is difficult to apply plating to large area films. It is necessary to use both electroless plating and electrolytic plating.
  • the electrolytic plating process is performed by single wafer processing and batch processing.
  • electroplating is performed on a film with a large surface resistance of ⁇ ⁇ ⁇ ⁇ / sq or more by single-wafer processing
  • the film portion that is in contact with the plating solution has a lot of adhesion in the portion near the current-carrying side. Is done. In particular, this phenomenon occurred at the start of plating, that is, at the first power supply, and it was difficult to uniformly apply the plating even if the plating was continued thereafter.
  • the conventional mesh formation method has been powerful enough to create a mesh with only a certain area broken.
  • the pattern of the catalyst core in the electroless copper plating method is a printing method such as screen printing, so the mesh breaks in units of size such as screen or intaglio, and photolithography Then, the mesh was broken in units of exposure mask size. That is, in photolithography, there is a region without a mesh pattern.
  • the exposure method is a single-wafer photomask, the exposure to the exposed photoresist is long V, and the entire roll film cannot be exposed continuously, and exposure within the range of the photomask size is possible. It is the power that is due to the method of repeating once.
  • the shield material is placed on the optical filter material based on the created shield material mesh pattern and PDP module or front plate or glass. Manufacturing methods have been taken together. In this method, the shield material is lost, and in order to improve productivity, even if a shield-like shield material connected with the shield material is used, alignment takes time and the production speed is sufficient. I could n’t raise it.
  • near infrared cut performance is an important required characteristic for the purpose of preventing malfunction of the remote control.
  • the amount of near-infrared rays generated has increased, and so even higher near-infrared cut performance is required.
  • the electromagnetic wave shielding film is intermittent as described above. As long as the optical filter is manufactured with a large amount of loss, the film having the near-infrared cutting function also has drawbacks that are not intermittently used.
  • an antireflection function is indispensable.
  • the film or functional film having the antireflection function is also a roll-like film like the film having the near-infrared cut function, so that the electromagnetic wave shielding film has a discontinuous mesh pattern and is bonded to the antireflection film. In some cases, there is a problem that a loss portion where the antireflection film is not used is generated.
  • the means for imparting an electromagnetic wave shielding function to a plasma display panel is a PDP having a base material such as glass, plastic sheet, plastic film, etc., in which an electromagnetic wave shielding film is bonded to an image display panel using an adhesive.
  • an electromagnetic wave shielding film is attached to the optical filter.
  • Adhesives are also used when bonding films to glass or plastic.
  • adhesives used in conventional silver halide light-sensitive materials for example, those using gelatin as a raw material
  • the peel strength of the bonded surface is insufficient. It was found that there was a problem that peeling occurred over time.
  • a method of providing an easy-adhesion layer is known when a plastic support is bonded to a glass substrate. This is a method of forming a thin resin layer on a plastic support by coating or the like.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a black metal film in a conductive metal film that has excellent productivity and low cost and is manufactured through exposure and development processes.
  • An object of the present invention is to provide a silver halide silver photographic material in which defects such as color spots and fine mesh lines are suppressed, and a conductive metal film formed using the same.
  • a second object is to provide a translucent electromagnetic wave shielding film in which a continuous mesh pattern is formed in a large amount at a low cost by improving productivity with little loss of shielding material.
  • a third object is to provide an electromagnetic wave shielding film excellent in adhesiveness (peeling strength) to the glass substrate or the like of the electromagnetic wave shielding film obtained from the photosensitive material.
  • a further object of the present invention is to provide a light-sensitive material having an easy-adhesion layer in which developed silver is not substantially formed in an unexposed portion on a conductive film obtained by developing the light-sensitive material, that is, no capri is formed. And it is providing an electromagnetic wave shielding film.
  • Another object of the present invention is to provide a translucent electromagnetic wave shielding film having both high electromagnetic wave shielding properties and high near-infrared cut performance.
  • Another object of the present invention is to provide an optical filter and a plasma display having high electromagnetic shielding properties and high near infrared cut performance.
  • the present invention comprises a support
  • a silver salt emulsion layer provided on one side of the support and containing a silver salt
  • An easy-adhesion layer provided on the other surface of the support and containing a synthetic resin and conductive particles;
  • the synthetic resin is at least one selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin and a styrene butadiene rubber. It is more preferable that
  • the conductive particles include a metal oxide ZnO, TiO, SnO,
  • it is at least one of Al O, In O, MgO, BaO and MoO.
  • it contains SnO doped with ntimone.
  • the conductive particles are preferably acicular particles, and the ratio of the major axis to the minor axis is preferably in the range of 3-50. By adopting such a shape, the conductive particles are sufficiently dispersed in the easy adhesion layer.
  • the silver salt emulsion layer has a swelling ratio of 150% or more, (1-2) (1-3) the silver salt emulsion layer contains Ag and a binder, and the AgZ binder volume ratio is 1Z4 or more, (1-4) the silver salt emulsion layer Is preferably in the outermost layer. Further, when the content of the conductive particles is based on 30 parts by mass of a synthetic resin (for example, acrylic resin), the content of the conductive particles is preferably 10 to 500 parts by mass, and preferably 50 to 150 parts by mass. Part is more preferable.
  • the silver halide silver photographic material of the present invention comprises a support,
  • a silver salt emulsion layer containing a silver salt provided on one surface of the support, and an easy-adhesion layer containing a synthetic resin provided on the other surface of the support may be provided.
  • the synthetic resin is preferably provided on the outermost surface on the other surface.
  • gelatin was used as the binder for the easy adhesion layer.
  • an electrically conductive metal film was manufactured and further processed, the adhesive strength with other members was insufficient.
  • a synthetic resin particularly acrylic resin
  • a second easy-adhesion layer is provided on the other surface of the support to form a first easy-adhesion layer containing a synthetic resin and conductive particles, and further contains a synthetic resin.
  • a layer may be formed. In this case, it is possible to prevent the conductive particles from being deposited outside the easily adhesive layer.
  • the present invention also resides in a conductive metal film, an electromagnetic wave shielding film, an optical filter for a plasma display panel, or a plasma display panel, which is characterized by being manufactured using the above-described halogen-molybdenum photosensitive material.
  • the present invention provides a development process by exposing the silver salt emulsion layer of the silver halide silver photographic material to an exposure process.
  • the function and effect of the present invention will be described.
  • a conductive metal film in which defects such as black spots and mesh fine line breaks are suppressed can be obtained.
  • synthetic resin especially for silver halide photosensitive materials
  • the easy-adhesion layer is likely to be charged, and static electricity is generated during the manufacturing process.
  • fog occurs in the silver salt emulsion layer, and the fog becomes a problem of black spots on the product.
  • a large amount of energy for example, heat
  • voids which are thought to be formed when the binder burns out due to heat
  • the formation of conductive metal parts is hindered.
  • the pattern of the conductive metal part of the conductive metal film is missing, it is considered that the electromagnetic wave shielding becomes insufficient. For example, when an attempt is made to form the conductive metal portion as a mesh-like thin line, the fine line may not be formed.
  • the discontinuity of the fine mesh line is observed together with the black spot, which means that developed silver is not generated in the exposed area. Therefore, a phenomenon peculiar to ⁇ that cannot be understood from the capri phenomenon that occurs in conventional photosensitive materials for photographic use occurs simultaneously (concurrently with conventional capri).
  • the easily adhesive layer contains conductive particles, static electricity generated during the manufacturing process is not excessively charged and escapes to the outside, thereby suppressing light emission due to static electricity, It is assumed that defects such as black spots on conductive metal films and breaks in fine mesh wires can be sufficiently suppressed.
  • the present invention may be in the following forms.
  • Halogenated silver photosensitive material for obtaining a conductive metal film by exposing and developing a silver salt emulsion layer provided on one side of a support, the silver salt emulsion layer and the support
  • a silver halide light-sensitive material characterized in that an easy-adhesion layer made of a synthetic resin is provided on the outermost surface opposite to the body.
  • the easy-adhesion layer contains at least one selected from the group strength of acrylic resin, polyester resin, polyurethane resin, and styrene butadiene rubber.
  • the conductive metal oxide particles are SnO particles doped with antimony
  • the conductive metal film is formed with a mesh-like fine line force having a line width of 1 ⁇ m to 40 ⁇ m, and is continuous for 3 m or more in the longitudinal direction of the mesh-like fine line force translucent electromagnetic wave shielding film.
  • the translucent electromagnetic wave shield final described in 2-10) above.
  • An optical filter for a plasma display panel comprising the translucent electromagnetic wave shielding film according to any one of 2-10) to 13) above.
  • a plasma display panel comprising the translucent electromagnetic wave shielding film according to any one of 2-10) to 13) above.
  • a silver halide photosensitive material and a conductive metal formed using the silver halide light-sensitive material have excellent productivity and low cost without occurrence of defects such as discontinuity of capri and fine mesh wires.
  • a membrane can be provided.
  • the electromagnetic wave shielding film excellent in the adhesiveness (peeling strength) to the glass substrate etc. of the electromagnetic wave shielding film obtained from a photosensitive material can be provided.
  • FIG. 1 is a schematic diagram showing an example of an electrolytic plating bath suitably used for the electrolytic plating process of the present invention.
  • FIG. 2 is a schematic view showing an example of a conductive metal film of the present invention.
  • “mesh” in “continuous mesh pattern” or the like refers to a mesh pattern having a plurality of fine line forces or a net having a plurality of fine line forces according to an example in the art. Furthermore, “continuous” means a long film such as a roll, and means that the mesh pattern is continuous without interruption.
  • the “conductive metal film (electromagnetic wave shielding film)” is carried on a film-like transparent support, the “electromagnetic wave shielding film” is used unless there is any confusion with other components (component film) to be laminated. Or simply “film”.
  • the support for the light-sensitive material used in the present invention it is possible to use a plastic film, a plastic plate, a glass plate, or the like, which is preferably a transparent support film.
  • 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 or triacetyl cellulose (TAC) from the viewpoints of transparency, heat resistance, ease of handling and cost!
  • TAC triacetyl cellulose
  • the support is transparent. It is desirable that the sex is high.
  • 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.
  • the light-sensitive material used may be provided with a protective layer on a silver salt emulsion layer (hereinafter sometimes simply referred to as an emulsion layer) described later.
  • the “protective layer” means a layer having a binder force such as gelatin or a polymer material, and is formed on the emulsion layer in order to exhibit the effect of preventing scratches and improving mechanical properties.
  • the protective layer is thin. Its thickness is preferably less than 0.
  • the method for forming the protective layer is not particularly limited, and a known coating method can be appropriately selected.
  • the light-sensitive material used in the present invention has a silver salt emulsion layer as a photosensor on a support.
  • the emulsion layer in the present invention may contain a dye, a binder, a solvent and the like as required in addition to the silver salt.
  • the emulsion layer may contain a dye.
  • 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 17 9243.
  • compounds F1 to F34 described in the publication are preferable.
  • (IV-2) to (IV-7) described in the publication are also preferably used.
  • cyanine dyes and pyrylium dyes described in JP-A-3-138640 can be used as dyes in the form of solid fine particles that are decolored during development or fixing.
  • Aminium dyes can be used as dyes in the form of solid fine particles that are decolored during development or fixing.
  • cyanine dyes having a carboxyl group described in JP-A-9-96891, cyanine dyes not containing an acid group described in JP-A-8-245902, and JP-A-8-333519 Lake type cyanine dyes cyanine dyes described in JP-A-1-266536, horopora-type cyanine dyes described in JP-A-3-136038, pyrylium dyes described in JP-A-62-299959, JP-A-7-253639 Polymer-type cyanine dyes described in JP-A 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.
  • Silver chlorobromide, silver iodochlorobromide and silver iodobromide are also preferably used.
  • Silver chlorobromide, silver bromide, silver iodochlorobromide and silver iodobromide are more preferable, and silver chlorobromide and iodochlorobromide containing 50 mol% or more of silver chloride are most preferable.
  • Silver is 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.
  • Silver halide is a solid grain, and from the viewpoint of image quality of a patterned metallic silver portion formed after exposure and development processing, the average grain size of silver halide silver is equivalent to a sphere.
  • 0.1 to 1000 ⁇ (1 / ⁇ ⁇ ) is preferable 0.1 to 100 nm is more preferable, and 1 to 50 nm is more preferable.
  • 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, written by P. Glafkides, Chimie etPhysique Photographique (Paul Montel, 1967), G. F. Dufin. Press, 1966;), VL Zelikman et al, Making and Coating Photograb hie Emulsion (The ForcalPress, 1964).
  • a method for preparing the above-mentioned halogenated silver emulsion an acidic method, a neutral method, or the like can be used.
  • a method of reacting a soluble silver salt with a soluble halogen salt can be performed on one side. Any of a mixing method, a simultaneous mixing method, or a combination thereof 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 tetra-substituted thiourea compound, which is described in JP-A Nos. 53-82408 and 55-77737.
  • Preferred thiourea compounds include tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione.
  • 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 halogen silver halide emulsion used in the present invention may contain a metal element belonging to Group VIII or VIIB of the periodic table.
  • a metal element belonging to Group VIII or VIIB of the periodic table in particular, in order to achieve high contrast and low capri, it is preferable to contain rhodium compounds, iridium compounds, ruthenium compounds, iron compounds, osmium compounds and the like.
  • These compounds are compounds having various ligands, and examples of such ligands include pseudohalogen ligands such as cyanide ions, cyanogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions,
  • pseudohalogen ligands such as cyanide ions, cyanogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions
  • organic molecules such as amines (methylamine, ethylenediamine, etc.), heterocyclic compounds (imidazole, thiazole, 5-methylthiazole, mercaptoimidazole, etc.), urea, and thiourea can be mentioned.
  • 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, trizalatrdium (III) complex salt, K Rh Br and the like.
  • rhodium compounds are used by dissolving in water or a suitable solvent, but are generally used in order to stabilize the solution of the rhodium compound, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, odorous acid, Hydrofluoric acid, etc.) or halogenated alkali (eg ⁇
  • iridium compound examples include Hexaclo oral iridium complex salts such as K IrCl and K IrCl,
  • 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 compound examples include potassium hexanoate ( ⁇ ) and ferrous thiocyanate.
  • the ruthenium compound and the osmium compound are in the form of 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. Particularly preferred is a hexacoordination complex represented by the following formula.
  • M represents Ru or Os, and n represents 0, 1, 2, 3 or 4.
  • the counter ion has no significance, and for example, ammonium or alkali metal ions are used.
  • Preferable ligands include a halide ligand, a cyanide ligand, a cyan oxide ligand, a nitrosyl ligand, a thionitrosyl ligand, and the like. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.
  • silver halides containing Pd (II) ions and Z or Pd elements 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.
  • 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 Z or Pd metal element contained in Harogeni ⁇ is 10- 4-0 of silver halide, with respect to the number of moles of silver. 5 mol / More preferably, it is mol Ag, more preferably 0.01 to 0.3 mol Z mol Ag.
  • Examples of the Pd compound used include PdCl and Na PdCl.
  • chemical sensitization performed with a photographic emulsion can also be performed in order to further improve sensitivity as an optical sensor.
  • chemical sensitization methods sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, noble metal sensitization such as gold sensitization, reduction sensitization and the like can be used. These are used alone or in combination.
  • sulfur sensitization method and gold sensitization method sulfur sensitization method and selenium sensitization method and gold sensitization method
  • sulfur sensitization method and tellurium sensitization method sulfur sensitization method and tellurium sensitization method.
  • a combination of a sensitizing method and a gold sensitizing method is preferable.
  • the above 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.
  • the addition amount of the sulfur sensitizer, pH during chemical ripening, temperature, changes in various conditions under such size of Harogeni ⁇ particles, per mol of silver halide 10- 7 ⁇ : LO- 2 Mole is more preferred 1 0 to 10 mono.
  • the selenium sensitizer used for the selenium sensitization known selenium compounds can be used. That is, the selenium sensitization is usually performed by adding unstable and Z or non-unstable selenium compounds and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time.
  • 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. .
  • 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 the silver halide silver grains.
  • the formation rate of tellurite silver in the silver halide emulsion can be tested by the method described in JP-A-5-313284. Specifically, U.S. Pat.Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211, No. 1,121,496, No. 1,295,462, No. 1,396,696, Canadian Patent No.
  • JP-A-4 204640 4-271341, 4-333043, and 5-303157, Journal • Chemical Society ⁇ ⁇ Chemical 'Communication (J.Chem.So Chem.Com mun.) Page 635 ( 1980), 1102 (1979), 645 (1979), Journal of Chemical Society, Perkin Transaction (J. Chem. So Perkin. Trans.) 1, 21 91 (1980) ), S. Patai, The Chemistry of Organic Selenium and Tellunium Compounds, 1 ⁇ (1986), ibid. 2) (1987) can be used.
  • a compound represented by the general formula (IIKIIIXIV) in JP-A-5-313284 is preferred.
  • the amount of the selenium sensitizer and a tellurium sensitizer that can be used in the present invention, Harogeni ⁇ particles used, but the chemical ripening condition and the like and, generally Harogeni ⁇ 1 molar per 10- 8 ⁇ : L0- 2 moles, preferably 10- 7 ⁇ : L0- 3 moles is used.
  • the chemical sensitization conditions in the present invention are not particularly limited, but the pH is 5 to 8, and the pAg is 6 to 11.
  • the temperature is preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 85 ° C.
  • Examples of the noble metal sensitizer include gold, platinum, noradium, iridium and the like, and 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 Patent Publication (EP) 293917.
  • the silver halide emulsion used in the production 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 yarn compositions, crystal habits). Different types, those with different chemical sensitization conditions, and those with different sensitivities) may be used in combination.
  • a binder can be used in the emulsion layer for the purpose of uniformly dispersing silver salt grains and assisting the adhesion between the emulsion layer and the support.
  • both the water-insoluble polymer and the water-soluble polymer can be used as the binder, but it is preferable to use 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 binder contained in the emulsion layer is not particularly limited. Dispersibility and adhesion Can be appropriately determined within a range in which can be exhibited.
  • the content of the binder in the silver salt-containing layer is preferably 1Z4 to LOO (Zl) in terms of AgZ binder volume ratio, more preferably 1/3 to 10 (Zl). More preferably, it is ⁇ 2 (Z1). Most preferably, it is 1 Zl to 2 (Zl). If the silver salt-containing layer has a high silver ratio in the volume ratio of AgZ binder, the metal particles can be brought into contact with each other during physical development and Z or plating process to obtain high conductivity. U, which is easy to use and less likely to cause uneven conductivity.
  • the solvent used for forming the emulsion layer is not particularly limited, and examples thereof include water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, dimethyl sulfoxide, and the like. Examples thereof include sulfoxides, esters such as ethyl acetate, ethers, and the like, and mixed solvents thereof.
  • the content of the solvent used in the emulsion layer of the present invention is in the range of 30 to 90% by mass with respect to the total mass of silver salt and binder contained in the emulsion layer, and 50 to 80% by mass. A range is preferred.
  • the emulsion layer and other hydrophilic colloid layers of the light-sensitive material according to the present invention are preferably hardened with a hardener.
  • inorganic or organic gelatin hardeners can be used alone or in combination.
  • active bur compounds such as 1, 3, 5 triatalyloyl-hexahydro s-triazine, bis (bululsulfurylmethyl) ether, N, N'-methylenebis [j8- (bululsulfuryl) propionamide], etc.
  • H-6 CH 2 CHS0 2 (CH z ) 2 SOiCH-CH z
  • CH 2 CHS02CH 2 C0KH
  • the swelling ratio of the emulsion layer is preferably 150% or more, more preferably 170 to 500%. When the swelling ratio of the emulsion layer is 150% or more, there is an effect that the conductivity of the developed silver is improved.
  • the swelling rate was determined by observing a slice of the dried sample with a scanning electron microscope to obtain the thickness (a) of the emulsion layer at the time of drying. After immersing in 25 ° C distilled water for 1 minute, liquid nitrogen The film thickness (b) of the emulsion layer at the time of swelling was obtained by observing a section of the lyophilized sample with a scanning electron microscope, and the following formula force was also calculated.
  • the preferred amount of hardener added to the emulsion layer depends on the storage temperature and humidity of the photosensitive material after storage, the storage period, the film pH of the photosensitive material, the amount of binder contained in the photosensitive material, etc. It is not decided in general. In particular, since the hardener can diffuse over the entire layer located on the same side of the photosensitive material before reacting with the binder, the preferred addition amount of the hardener is the same side of the photosensitive material including the emulsion layer. Depends on the total binder amount on the side.
  • the preferable hardener content of the light-sensitive material is in the range of 0.2% to 15% by weight, more preferably 0.5% by weight, based on the total amount of binder on the same side of the light-sensitive material including the emulsion layer. It is in the range of ⁇ 6% by mass.
  • the hardening agent can diffuse, and therefore the hardening agent does not need to be an emulsion layer, and can be preferably added to any layer on the same side as the emulsion layer. It is also preferable to add the ingredients separately.
  • the silver salt emulsion layer is preferably the outermost layer.
  • the emulsion layer provided on the support is exposed for pattern formation, that is, the irradiated portion is patterned or the non-irradiated portion is patterned (reversed).
  • the 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.
  • a light source with a wavelength distribution may be used for exposure, or a light source with a specific wavelength may be used.
  • the light source various light emitters that emit light in the visible spectrum region are used as necessary.
  • a red light emitter, a green light emitter, and a blue light emitter are used in combination.
  • the spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used.
  • a cathode ray tube that emits white light by mixing these light emitters is often used.
  • mercury lamp g-line, mercury lamp i-line, etc. which are also preferred for ultraviolet lamps, are used.
  • the exposure in the present invention is a second harmonic light source (SHG) that combines a solid-state laser using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a semiconductor laser as an excitation light source and a nonlinear optical crystal.
  • SHG second harmonic light source
  • a scanning exposure method using monochromatic high-density light such as) can be preferably used, and a KrF excimer laser, an ArF excimer laser, an F2 laser, or the like can also be used.
  • the exposure is nonlinear with semiconductor laser, semiconductor laser or solid state laser. More preferably, a second harmonic generation light source (SHG) combined with an optical crystal is used.
  • SHG second harmonic generation light source
  • exposure is most preferably performed using a semiconductor laser.
  • the exposure energy is preferably lmj / cm 2 or less, more preferably 100 j / cm 2 or less, and even more preferably 50 j / cm 2 or less.
  • a blue semiconductor laser with a wavelength of 430 to 460 nm announced by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001
  • 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.
  • Scanning exposure with a laser beam is preferred as a method for exposing the emulsion layer in a pattern.
  • the capstan type laser scanning exposure apparatus described in Japanese Patent Application Laid-Open No. 2000-39677 is preferable.
  • the DMD described in Japanese Patent Application Laid-Open No. 2004-1244 can be used instead of the beam scanning by rotating the polygon mirror. It is also preferable to use it in a light beam scanning system.
  • 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 mask and the like.
  • the developer is not particularly limited, but PQ developer, MQ developer, MAA developer, etc. can also be used, and commercially available products such as CN-16, CR-56, CP45X Each developer such as FD-3, Papitor, KODAK prescription C-41, E-6, RA-4, D-19, D-72, or the developer included in those kits should be used. it can. You can also use lith developer.
  • the exposed portion has a metallic silver portion, preferably a butterfly.
  • a metallic silver portion in which a light-transmitting portion, which will be described later, is formed in an unexposed portion is formed in the present invention while a silver-shaped metallic silver portion is formed! Since it is formed so as to have conductivity, it is a conductive metal silver portion, and a light-transmitting electromagnetic wave shielding film is formed by this and the light-transmitting portion.
  • a dihydroxybenzene developing agent can be used as the developer.
  • dihydroxybenzene developing agents include hydroquinone, chlorohydroquinone, isopropyl hydroquinone, methyl hydroquinone, hydroquinone monosulfonic acid salt and the like.
  • auxiliary developing agents that exhibit superadditivity with the above-mentioned dihydroxybenzene-based developing agents include 1-phenol and 1-3- virazolidones and P-aminophenols.
  • the developer used in the production method of the present invention is preferably a combination of a dihydroxybenzene developing agent and 1-phenol 1-3 azolidone; or a combination of a dihydroxybenzene developing agent and p-aminophenols. It is done.
  • Examples of the developing agent used in combination with 1-phenol 3-virazolidone or a derivative thereof used as an auxiliary developing agent include 1-phenol-3-virazolidone, 1-phenyl-1,4-dimethyl. 1-pyrazolidone, 1-phenyl-4-methyl 4-hydroxymethyl-3-bisazolidone.
  • 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 / 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 / liter, more preferably 0.23 to 0.5 mol Z. Liters, the latter is less than 0.06 mol Z liters, more preferred ⁇ 0.03 Monore / Lit Nore ⁇ 0.03 Monore / Lit Nore for use in amounts!
  • both forces of the development starter and the development replenisher are set to 0. It is preferable that the pH increase is 0.5 or less when 1 mol of sodium hydroxide is added.
  • the method of imparting the above properties to the development initiator and the development replenisher is preferably a method using a buffer.
  • the buffer include carbonates, boric acid described in JP-A-62-186259, saccharides (for example, saccharose), oximes (for example, acetooxime), phenols described in JP-A-60-93433.
  • 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 buffering agent (particularly carbonate) is preferably 0.25 monolet / litnore or more, 0.25 ⁇ : L5 monole / litnore power is particularly preferred! / ⁇ .
  • the pH of the development start solution 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 content of the developer replenisher in the developer is 323 ml or less, preferably 323 to 30 ml, particularly 225 to 50 ml.
  • the development replenisher may have the same composition as the development starter, or it may have a higher concentration than the starter due to the components consumed in the development.
  • additives usually used for the developer used for developing the photosensitive 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.
  • the preservative include sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. I can get lost.
  • 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.
  • ascorbic acid derivatives may be used in small amounts in combination with sulfites as preservatives for dihydroxybenzene developing agents.
  • the ascorbic acid derivative includes ascorbic acid, its stereoisomer, erythorbic acid and its alkali metal salts (sodium and potassium salts), and the like.
  • 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, particularly preferably in the range of 0.05 to 0.10, with respect to the dihydroxybenzene-based developing agent. It is. When an ascorbic acid derivative is used as the preservative, it is preferable that 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. ; Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole or derivatives thereof, mercapto compounds, indazole compounds, benzotriazole compounds, and benzoimidazole compounds are used as anti-capricious agents. Alternatively, it may be included as a black pepper inhibitor.
  • development inhibitors such as sodium bromide and potassium bromide
  • organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and dimethylformamide.
  • Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole or derivatives thereof, mercapto compounds, indazole compounds, benzotriazole compounds, and benzoimidazole compounds are used as anti-capricious agents.
  • it may be included as
  • benzoimidazole compound examples include 5--troindazole, 5-p-trobenzoylaminoindazole, 1-methyl-5-troindazole, 6-toluindazole, 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 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 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, ashericin acid, sebacic acid, nonanedicarboxylic acid, decandi-functional norlevonic acid, undecandi-functional norlevonic acid.
  • aminopolycarboxylic acid examples include iminoniacetic acid, ditrimethyl triacetic acid, ditrimethyl tripropionic acid, ethylenediamine monohydroxyethyl triacetic acid, ethylenediamintetraacetic 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
  • organic phosphonic acid examples include hydroxyalkylidene-diphosphonic acid described in US Pat. Nos. 3214454 and 3794591, and West German Patent Publication 2227639. 181, Item 18170 ( May 1979), and the like.
  • aminophosphonic acid examples include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid and the like.
  • aminotris methylenephosphonic acid
  • ethylenediaminetetramethylenephosphonic acid examples include aminotrimethylenephosphonic acid and the like.
  • organic phosphonocanolevonic acids examples include JP-A 52-102726, 53-42730, 54-121127, 55-4024, 55-4025, 55-126241. Nos. 55-65 955, 55-65956, and the above-mentioned Research Disclosure 1 8170.
  • These chelating agents are alkali metals Can be used in the form of salt or ammonium salt.
  • JP-A-56-24347, JP-B-56-46585, JP-B-62-2849, and JP-A-4-362942 as silver stain preventing agents in the developer.
  • compounds described in JP-A-61-267759 can be used as dissolution aids.
  • 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 development processing in the present invention can include a fixing processing performed for the purpose of removing and stabilizing the silver salt in the unexposed portion.
  • a fixing process technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask and the like can be used.
  • Preferable components of the fixing solution used in the fixing step include the following.
  • Examples of the fixing agent for the fixing solution used in the present invention include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is preferred from the viewpoint of fixing speed.
  • Viewpoint power Sodium thiosulfate may be used.
  • the amount of these known fixing agents used can be appropriately changed, and is generally about 0.1 to about 2 mol Z liter. Particularly preferred is 0.2 to 1.5 mol Z liter.
  • the fixer is hard if desired.
  • Filming agent eg water-soluble aluminum compound
  • preservative eg sulfite, bisulfite
  • PH buffering agents for example, acetic acid
  • pH adjusting agents for example, ammonia, sulfuric acid
  • chelating agents for example, surfactants, wetting agents, and fixing accelerators.
  • surfactant examples include anionic surfactants such as sulfates and sulfones, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. It is done. 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 6.5, and particularly preferably 4.5 to 6.0. Further, it is possible to use a compound described in JP-A-64-4739 as the dye elution accelerator.
  • 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 temperature in the fixing step is preferably about 20 ° C to about 50 ° C, more preferably 25 to 45 ° C.
  • the fixing time is preferably 5 seconds to 1 minute, more preferably 7 seconds to 50 seconds.
  • the replenishment amount of the fixing solution is preferably 600 mlZm 2 or less relative to the processing amount of the photosensitive material. More preferably 500 mlZm 2 or less, more preferably 300 mlZm 2 or less.
  • the photosensitive material that has been subjected to development and fixing processing is preferably subjected to water washing processing and stabilization processing.
  • the amount of washing water is usually 20 liters per lm 2 of photosensitive material.
  • water-soluble surfactants and antifoaming agents are added to prevent unevenness of water bubbles, which are likely to occur when washing with a small amount of water, and to prevent transfer of the processing agent component adhering to the Z or squeeze roller to the processed film. Also good.
  • a dye adsorbent described in JP-A-63-163456 is added to a water washing tank in order to prevent contamination with dyes eluted from the photosensitive material. 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.
  • the water used in the water washing process or the stability process It is preferable to use water that has been sterilized with on-treated water, halogen, ultraviolet germicidal lamp, various oxidizing agents (such as ozone, hydrogen peroxide, and chlorate). 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.
  • the electromagnetic wave shielding film of the present invention is preferably obtained in a shape carrying a contact pattern such as a roll shape from the viewpoint of productivity and ease of production of an optical filter, it is advantageous to use a developing machine for rolls. In particular, it is preferable to use a roller conveyance type automatic developing machine.
  • roller-conveying type automatic developing machine is described in US Pat. Nos. 30,257,795, 3,545,971, etc., and is simply referred to as a roller-conveying type automatic developing machine in this specification.
  • the roller transport type automatic processor preferably has four process powers of development, fixing, washing and drying, other processes (for example, stop process) are not excluded, but these four processes are followed. Is most preferred. Further, instead of the washing step, four steps by a stable step may be used.
  • the component obtained by removing water from the composition of the developer or the fixing solution may be supplied in a solid form and dissolved in a predetermined amount of water for use as a developer or a fixing solution.
  • a form of treating agent is called a solid treating agent.
  • powder, tablet, granule, powder, lump or paste is used as the solid processing agent.
  • a preferred form of the above-mentioned treatment agent is the form or tablet described in JP-A-61-259921.
  • the method for producing the tablets is generally described in, for example, the publications of JP-A-51-61837, JP-A-54-155038, JP-A-52-88025, and British Patent No. 1,213,808. Can be manufactured by simple methods.
  • the granule treating agent is a general method described in JP-A-2-109042, JP-A-2-109043, JP-A-3-3935 and JP-A-3-39739. Can be manufactured . Further, powder processing agents are generally described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862 and German Patent 3,733,861. Can be manufactured in a conventional manner.
  • the bulk density of the solid treatment agent is preferably 0.5-6. Og / cm 3 and particularly preferably 1.0-5. Og / cm 3 in view of its solubility. ! / ⁇ .
  • At least two kinds of mutually reactive particulate materials among the materials constituting the processing agent should be reduced by a material inert to the reactive material.
  • a method may be employed in which reactive substances are placed in layers so as to be separated by one intervening separation layer, a vacuum-packable bag is used as a packaging material, and the bag is evacuated and sealed.
  • inert means that the substances do not react under normal conditions in the package when they are in physical contact with each other, or even if there is any reaction.
  • the inert material may be inert in the intended use of the two reactive materials, apart from being inert to the two mutually reactive materials.
  • an inert substance is a substance that is used simultaneously with two reactive substances.
  • hydroquinone and sodium hydroxide in a developer react when they come into direct contact with each other. Therefore, by using sodium sulfite or the like as a separation layer between hydroquinone and sodium hydroxide in vacuum packaging, Can be stored in a knockout.
  • the packaging material for these vacuum packaging materials is an inert plastic film, a bag made from a laminate of plastic material and metal foil.
  • the mass of the metallic silver contained in the exposed area after the development treatment is preferably 80% by mass or more with respect to the mass of silver contained in the exposed area before the exposure. It is even more preferable that it is at least%. If the mass of silver contained in the exposed part is 50% by mass or more with respect to the mass of V and silver contained in the exposed part before exposure, 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.
  • the means include doping of the above-described rhodium ions and iridium ions into the photosensitive halogen silver halide particles.
  • the present invention for the purpose of imparting conductivity to the metal silver portion in the conductive metal film formed by the exposure and development processing, physical development for carrying conductive metal particles on the metal silver portion and Z or It is possible to perform a clinging process.
  • the conductive metal particles are formed by combining physical development and plating. It can also be supported on a metallic silver part.
  • a metal silver part that has been subjected to physical development and Z or plating treatment is referred to as a “conductive metal part”.
  • “Physical development” in the present invention means that metal particles such as silver ions are reduced with a reducing agent on metal or metal compound nuclei to precipitate metal particles. This physical phenomenon is used in the manufacture of instant B & W films, instant slide films, printing plates, etc., and the technology can be used in the present invention.
  • the physical development may be performed simultaneously with the development processing after exposure or may be performed separately after the development processing.
  • the plating process uses electroless plating (chemical reduction plating or substitution plating), electrolysis plating, or both electroless plating and electrolytic plating. be able to.
  • the metallic silver portion after the exposure and development treatment can be further treated with an electroless plating solution.
  • an electroless plating solution a method of treating with an aqueous palladium compound solution or a method of treating with a reducing agent and / or a silver ion ligand is preferred.
  • the former is carried out by treating the metallic silver part after exposure and development with a solution containing Pd.
  • Pd may be divalent palladium ion or metal palladium. This treatment can accelerate electroless plating or physical development speed. Electroless plating with noradium is described in detail in the “Electroless plating” section of the Japan Society for the Science and Chemistry Handbook Applied Chemistry.
  • a reducing agent or a silver ion ligand it is preferable to perform treatment with a reducing agent or a silver ion ligand.
  • a reducing agent it is sufficient if the silver ion can be reduced to metallic silver, for example, thiourea dioxide, Rongalite, sodium chloride (11), sodium borohydride, sodium triacetoxyborohydride, trimethylater. Examples include minborane, triethylamine borane, pyridine borane, and borane.
  • Silver ion ligands include chlorine ions, bromine ions, halogen ions such as iodine ions, pseudohalogen ions such as thiocyanate ions, nitrogen-containing heterocyclic compounds such as pyridine and biviridine, sulfite ions, and 1 , 2, 4-triazolium-3-thiolates (eg 1, 2, 4-trimethyl-1, 2, 4-triazolium-3-thiolate)
  • a plating apparatus for suitably carrying out the above-described electroplating treatment exposes the emulsion layer and electrically feeds the sequentially fed film from a feeding reel (not shown) around which the developed film is wound.
  • the film is fed into a plating tank and the film after plating is sequentially wound around a reel for reeling (not shown).
  • Fig. 1 shows an example of an electrolytic plating bath suitably used for the electrolytic plating treatment.
  • the electrolytic plating bath 10 shown in FIG. 1 is capable of continuously plating a long film 16 (the one subjected to the above exposure and development processing).
  • the arrow indicates the transport direction of the film 16.
  • the electrolytic plating bath 10 includes a plating bath 11 for storing a plating solution 15.
  • a pair of anode plates 13 are disposed in parallel in the plating bath 11, and a pair of guide rollers 14 are disposed inside the anode plate 13 so as to be rotatable in parallel with the anode plate 13.
  • the guide roller 14 can be moved in the vertical direction, so that the processing time of the film 16 can be adjusted.
  • a pair of feed rollers (force swords) 12a and 12b for guiding the film 16 to the plating bath 11 and supplying current to the film 16 are rotatably arranged. It is.
  • a liquid draining roller 17 is rotatably disposed below the outlet-side power supply roller 12b.
  • the liquid draining roller 17 and the outlet-side power supply roller 12b are connected to each other.
  • a water spray (not shown) is installed to remove the plating solution from the film.
  • 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 feeding roller 12a on the entrance side and the film 16 are The distance between the lowermost part of the contacted surface and the plating solution surface (distance La shown in Fig. 1) is preferably 0.5 to 15 cm, more preferably l to 10 cm, and l to 7 cm. Power S is more preferable.
  • the distance between the bottom of the surface where the power supply roller 12b on the outlet side is in contact with the film 16 and the plating solution surface (distance Lb shown in FIG. 1) is preferably 0.5 to 15 cm.
  • the solution 15 is stored in the bath 11.
  • a plating solution containing 30 gZL to 300 gZL of copper sulfate pentahydrate and 30 gZL to 300 gZL of sulfuric acid can be used.
  • nickel plating nickel sulfate, nickel hydrochloride, or the like can be used.
  • additives such as surfactant, a sulfur compound, and a nitrogen compound, to a plating solution.
  • the film 16 is set in a state where it is wound on a supply reel (not shown), and the film 16 is placed so that the surface on which the film 16 is to be formed comes into contact with the feeding rollers 12a and 12b. It is wound around a conveyance roller (not shown).
  • the surface resistance of the film immediately before electroplating is 1 to: LOOO Q Zsq is preferred 5 to 500 Q Zsq is more preferred Further, the range is 10 to 100 ⁇ Zsq It is.
  • 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.
  • Film 16 is introduced into the plating bath 11 and plated Immerse in liquid 15 to form a copper finish.
  • the plating solution 15 adhering to the film 16 is wiped off and collected in the plating bath 11. This is repeated in a plurality of electrolytic baths, and finally washed with water, and then wound up on a reeling 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 tanks is not particularly limited, but 2 to 10 tanks are preferable, and 3 to 6 tanks are more preferable.
  • the applied voltage is preferably in the range of 1 to: LOOV, more preferably in the range of 2 to 60V.
  • the amount of current on the inlet side of the first tank is preferably 1 to 30 A, and more preferably 2 to LOA.
  • 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 treatment solution used for the acid cleaning can be one containing sulfuric acid or the like.
  • 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 becomes wider as the electromagnetic wave shielding material of the display is thinner. 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.
  • an electroless plating treatment may be performed before that. .
  • a known electroless plating technique can be used.
  • the electroless plating technique used in printed wiring boards can be used.
  • Chemical species contained in the electroless copper plating solution include copper sulfate and copper chloride, as a reducing agent, formalin glyoxylic acid, as a copper ligand, EDTA, triethanolamine, etc.
  • Polyethylene glycol, yellow blood salt, biviridine and the like can be mentioned as additives for improving the smoothness of wrinkles and glazing films.
  • the conductive pattern on the film is preferably continuous (not electrically interrupted). If even a part of the pattern is connected, the conductive pattern may break, and there is a risk that a non-sticky part may be formed in the first electrolytic plating tank or it may become uneven.
  • the plating rate during the plating process can be performed under moderate conditions, and further, high-speed plating of 5 ⁇ mZhr or more is possible.
  • various additives such as a ligand such as EDTA can be used to increase the stability of the plating solution.
  • FIG. 2 shows an example of the conductive metal film of the present invention.
  • a conductive metal 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 metallic silver portion can be formed, and in order to further increase the conductivity, electrolytic plating is applied.
  • a conductive metal part can be formed.
  • the unexposed portion 25 becomes a light transmissive portion (for example, one made of gelatin).
  • the support 23 of the conductive metal film in FIG. 2 is provided with the easy adhesion layer according to the present invention on the surface opposite to the conductive functional layer 22.
  • the metallic silver part after the development treatment and the conductive metal part formed by physical development and Z or staking treatment it is preferable to subject the metallic silver part after the development treatment and the conductive metal part formed by physical development and Z or staking treatment to oxidation treatment.
  • oxidation treatment for example, when a metal is slightly deposited on the light transmitting portion, the metal can be removed, and the light transmitting portion can be made almost 100% transparent.
  • the 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 emulsion layer exposure and development treatment, or after physical development or staking treatment, and further after the development treatment and after physical development or staking treatment, .
  • the metallic silver portion after the exposure and development treatment can be further treated with a solution containing Pd.
  • Pd can be divalent palladium ion or metallic palladium! /. This treatment can accelerate electroless plating or physical development speed.
  • a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid, or the like , (Regular) hexagons, (regular) octagons and other (positive) n-gons, circles, ellipses, star shapes, etc. More preferred to be.
  • the triangular shape is the most effective, but from the viewpoint of visible light transmission, if the line width is the same (positive), the larger the n number of the n-square, the higher the aperture ratio and the visible light transmission. This is advantageous because it increases the performance. From the viewpoint of creating moiré, it is also preferable to arrange these geometric patterns randomly or change the line width without periodicity.
  • the shape of the said electroconductive metal part is not specifically limited, Arbitrary shapes can be suitably determined according to the objective.
  • the line width of the mesh-like fine wire of the conductive metal part is preferably 1 ⁇ m or more and 40 ⁇ m or less, and preferably 5 ⁇ m or more and 30 ⁇ m. m or less, most preferably 10 ⁇ m or more and 25 ⁇ m or less.
  • the line spacing is preferably 50 ⁇ m or more and 500 ⁇ m or less, more preferably 200 ⁇ m or more and 400 ⁇ m or less, and most preferably 250 ⁇ m or more and 350 m or less.
  • the conductive metal part may have a part with a line width wider than 20 ⁇ m for purposes such as ground connection!
  • 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. Most preferred.
  • the aperture ratio is the percentage of the mesh without fine lines. For example, the aperture ratio of a square grid mesh with a line width of 15 ⁇ m and a pitch of 300 ⁇ m is 90%.
  • the “light transmissive part” in the present invention is a conductive metal part of the light transmissive electromagnetic wave shielding film. It means a part having transparency other than.
  • the transmittance of the light transmissive portion is 90% or more, preferably 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. Is 95% or more, more preferably 97% or more, even more preferably 98% or more, and most preferably 99% or more.
  • the mesh-like fine wire in the present invention is continuous for 3 m or more in the longitudinal direction of the translucent electromagnetic wave shielding film.
  • the longer the continuous length of the fine wire is, for example, in the case of producing an optical filter material It can be said that this is a more preferable embodiment because the loss of the above can be reduced.
  • the continuous length is too long, the roll diameter becomes large when the roll is formed, the roll mass becomes heavy, the pressure at the center of the roll becomes strong, causing problems such as adhesion and deformation, and cheapness. It is preferably 2000 m or less. It is preferably 100 m or more and 1000 m or less, more preferably 200 m or more and 800 m or less, and most preferably 300 m or more and 500 m or less.
  • the thickness of the support is preferably 200 ⁇ m or less, more preferably 20 ⁇ m or more and 180 ⁇ m or less, and most preferably 50 ⁇ m or more and 120 ⁇ m or less.
  • the pattern of intersecting straight fine lines in which the mesh is substantially parallel means a so-called lattice pattern, and refers to a case where adjacent straight lines constituting the lattice are parallel or parallel within ⁇ 2 °. .
  • the scanning method of the light beam is preferably a method of exposing with a linear light source or a rotating polygon mirror arranged in a direction substantially perpendicular to the transport direction.
  • the light beam needs to be intensity-modulated by two or more values, and the straight line is battered as a series of dots. Since the dots are continuous, the edge of the fine line of one dot is stepped, but the thickness of the fine line means the narrowest length of the constricted part.
  • the light beam As another method of scanning the light beam, it is also preferable to scan a beam whose scanning direction is inclined with respect to the carrying direction in accordance with the inclination of the grating pattern. In this case, it is preferable to arrange the two scanning light beams so as to be orthogonal to each other.
  • the light beam has a substantially single intensity on the exposed surface.
  • the mesh pattern is 3 with respect to the longitudinal direction of the translucent electromagnetic wave shielding film. It is preferable to tilt from 0 ° to 60 °. More preferably, it is 40 ° to 50 °, and most preferably 43 ° to 47 °. This is because it is generally difficult to create a mask whose mesh pattern is inclined at about 45 ° with respect to the frame, and it is difficult to create unevenness or the price is high. Rather, unevenness hardly occurs at around 45 °, so that the effect of the present invention is more remarkable for patterning by screen printing using mask contact exposure.
  • an easy-adhesion layer containing a synthetic resin and conductive particles is provided on the opposite side of the silver salt emulsion layer and the support, that is, on the other side of the support.
  • the easy-adhesion layer may be the outermost layer on the other side of the silver salt emulsion layer of the support.
  • a preferable easy-adhesion layer will be described.
  • the easy adhesion layer may be composed of a single layer containing a synthetic resin and conductive particles !, or may be composed of two or more layers as described below.
  • antistatic layer comprising water-dispersible or water-soluble synthetic resin, carpositimide compound and conductive particles (especially conductive metal oxide particles) as essential components
  • Second layer Surface layer containing water-dispersible or water-soluble synthetic resin and cross-linking agent as essential components (Some layers may be removed by laminating with other component layers, but easy adhesion. Meaning the top layer (second easy adhesion layer))
  • an antistatic layer containing a synthetic resin and conductive particles on a support and a structure in which a surface layer is provided in this order without containing conductive particles are preferable.
  • the haze of the low chargeable support obtained by providing the antistatic layer on the support is 3% or less, and the surface electric resistance of the surface layer of the resulting photosensitive material / ⁇ ⁇ ⁇ ) Conductivity is given so that it is in the range of 11 ⁇ .
  • the haze in this specification is a value measured according to JIS K-7105 using a haze meter (NDH-2000, manufactured by Nippon Denshoku) at 25 ° C and 60% RH.
  • the antistatic layer is a layer containing conductive particles (for example, conductive metal oxide particles) and generally further contains a binder.
  • conductive metal oxide particles it is preferable to use acicular particles having a major axis to minor axis ratio (major axis Z minor axis) in the range of 3 to 50. .
  • major axis Z minor axis in the range of 10 to 50 are preferred.
  • the short axis of such needle-like particles is preferably in the range of 0.001-0.:m, and more preferably in the range of 0.01 to 0.02 / z m.
  • the long axis thereof is preferably in the range of 0.1 to 5.
  • the force S is preferable, and particularly preferably in the range of 0.1 to 2.
  • Materials for the conductive metal oxide particles include ZnO, TiO2, SnO, AlO, InO.
  • metal oxides containing different atoms can be mentioned.
  • SnO metal oxide
  • ZnO, Al 0, TiO, In O, and MgO are preferred, and SnO, ZnO, In O and
  • SnO is particularly preferred, with 2 3 2 2 3 2 2 2 and TiO being preferred.
  • TiO is particularly preferred.
  • ZnO is particularly preferred, with 2 3 2 2 3 2 2 2 and TiO being preferred.
  • ZnO is particularly preferred.
  • the material of the conductive metal oxide particles is preferably a material containing a small amount of different elements with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure. Examples of the conductive metal oxide particles containing a small amount of different atoms include SnO doped with antimony.
  • the anti-axis having the short axis and long axis dimensions is used.
  • metal oxide particles such as mon-doped SnO is transparent and has good conductivity.
  • acicular metal oxide particles for example, antimony-doped Sn 2 O 3
  • a transparent antistatic layer having good conductivity can be advantageously formed.
  • the needle-like metal oxide particles have a long axis extending long in parallel with the surface of the antistatic layer, but the length of the short axis in the thickness direction of the layer. It takes up just a minute. Since such needle-like metal oxide particles are long in the long axis direction as described above, high conductivity can be obtained even in a small amount that is easy to contact with each other compared to normal spherical particles. . Therefore, the surface electrical resistance can be reduced without impairing transparency.
  • the minor axis diameter is usually smaller than or substantially the same as the thickness of the antistatic layer, and even if it protrudes slightly on the surface, the protruding portion does not protrude. Since it is weak, it is almost completely covered by the surface layer provided on the antistatic layer. Therefore, it is possible to obtain an advantage that there is almost no occurrence of powder falling which is a detachment of the protruding portion from the layer during the conveyance of the support for preparing the photosensitive material, during the conveyance of the photosensitive material for exposure and development.
  • the change in surface electrical resistance before and after the development of the photosensitive material is extremely small when the above-mentioned acicular metal oxide is used, compared to the relatively large case of spherical particles, especially after development processing. It can also be said that the transportability is significantly improved. This is presumably because in the case of spherical particles, the arrangement and state of the particles change due to swelling and shrinkage of the film due to the development process, and the number of parts in contact with each other decreases. .
  • the antistatic layer in the present invention generally contains a binder for dispersing and supporting the conductive metal oxide particles.
  • a binder material various polymers such as acrylic resin, bulle resin, polyurethane resin, and polyester resin can be used. From the viewpoint of preventing powder falling, a cured product of a polymer (preferably acrylic resin, vinyl resin, polyurethane resin or polyester resin) and a carpositimide compound is preferable. Book In the invention, from the viewpoints of maintaining a good working environment and preventing air pollution, it is preferable to use both a polymer and a carboimide compound in a water-dispersed state or an aqueous dispersion state such as an emulsion.
  • the polymer has a methylol group, a hydroxyl group, a carboxyl group, or an amino group so that a cross-linking reaction with the carpositimide compound is possible.
  • a hydroxyl group and a carboxyl group are preferred, and a carboxyl group is particularly preferred.
  • the content of the hydroxyl group or carboxyl group in the polymer is preferably from 0.0001 to L equivalent Zlkg, particularly preferably from 0.001 to L equivalent Zlkg.
  • Acrylic resins include acrylic esters such as acrylic acid and alkyl acrylate, methacrylic esters such as acrylamide, acrylonitrile, methacrylic acid, and alkyl methacrylate, methacrylamide, and meta-tolyl.
  • a homopolymer of these monomers or a copolymer obtained by polymerization of two or more of these monomers can be mentioned.
  • homopolymers of monomers of acrylic acid esters such as alkyl acrylates and methacrylic acid esters such as alkyl methacrylates, or copolymers obtained by polymerization of two or more of these monomers. Is preferred.
  • the acrylic resin has, as a main component, a monomer having any group of, for example, a methylol group, a hydroxyl group, a carboxy group, and an amino group so that a crosslinking reaction with a carpositimide compound is possible. Is a polymer obtained by partially using
  • Examples of the above-mentioned bulges include polybulu alcohol, acid-modified polyvinyl alcohol, polyphenol enore meranol, polybulu butyral, polybulu methyl ether, polyolefin, ethylene Z butadiene copolymer, polyacetate bur, chloride.
  • Mention of vinyl Z vinyl acetate copolymer, vinyl chloride Z (meth) acrylate copolymer and ethylene Z acetate butyl copolymer (preferably ethylene Z vinyl acetate Z (meth) acrylate copolymer) Can do.
  • polybulal alcohol, acid-modified polybulal alcohol, polybullymarl, polyolefin, ethylene z butadiene copolymer and ethylene Z butyl acetate copolymer (preferably ethylene Z butyl acetate Z acrylic) Acid Steal copolymers) are preferred.
  • the above-mentioned vinyl resin is capable of crosslinking reaction with a carpositimide compound so that, for example, vinyl alcohol, acid-modified polyvinyl alcohol, polybul formal, polybulutyl, polybulumethyl ether and polyacetic acid
  • a polymer having a hydroxyl group is obtained by leaving an alcohol unit in the polymer.
  • a part of a monomer having a methylol group, a hydroxyl group, a carboxyl group, or an amino group is used for crosslinking.
  • a possible polymer is used for crosslinking.
  • polyurethane resin examples include polyhydroxy compounds (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), aliphatic polyesters obtained by reacting polyhydroxy compounds with polybasic acids.
  • Mention may be made of polyurethanes derived from isocyanates.
  • the hydroxyl group remaining unreacted after the reaction between polyol and polyisocyanate can be used as a functional group capable of crosslinking reaction with a carpositimide compound.
  • polyester resin a polymer obtained by a reaction of a polyhydroxy acid compound (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane) and a polybasic acid is generally used.
  • a polyhydroxy acid compound eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane
  • the polyester resin for example, after the reaction between the polyol and the polybasic acid is completed, the unreacted hydroxyl group and carboxyl group can be used as a functional group capable of a crosslinking reaction with the calpositimide compound.
  • a third component having a functional group such as a hydroxyl group may be added.
  • acrylic resin and polyurethane resin are preferable, and acrylic resin is particularly preferable.
  • carbopositimide compound used in the present invention it is preferable to use a compound having a plurality of carbopositimide structures in the molecule.
  • Polycarposimide is usually synthesized by a condensation reaction of an organic diisocyanate.
  • organic diisodioxide used for the synthesis of compounds with multiple carposimide structures in the molecule.
  • the organic group of cyanate is not particularly limited, and either aromatic or aliphatic, or a mixture thereof can be used, but aliphatic is particularly preferable from the viewpoint of reactivity.
  • synthetic raw materials organic isocyanate, organic diisocyanate, organic triisocyanate and the like are used.
  • organic isocyanates aromatic isocyanates, aliphatic isocyanates, and mixtures thereof can be used.
  • 1,3 phenolic diisocyanate, etc. are used, and as organic monoisocyanate, isophorone isocyanate, phenyl isocyanate, cyclohexenoisocyanate, butyl isocyanate, naphthyl isocyanate, etc. are used. Is done.
  • calpositimide-based compound that can be used in the present invention is also available as a commercial product such as, for example, calpositrite V-02-L2 (trade name: manufactured by Nisshinbo Co., Ltd.).
  • the carbodiimide compound is preferably added in an amount of 1 to 200% by mass, more preferably 5 to 100% by mass, based on the binder.
  • a dispersion liquid in which the conductive metal oxide particles are dispersed as they are or in a solvent such as water (including a dispersant and a binder as necessary) is used.
  • the antistatic layer is formed by applying a coating solution for forming the antistatic layer to a surface of a plastic film such as polyester (on the side where no photosensitive layer is provided), such as a dip coating method or an air knife coating.
  • the applied plastic film such as polyester is either before sequential biaxial stretching, before simultaneous biaxial stretching, after uniaxial stretching, before re-stretching, or after biaxial stretching. Even so.
  • the layer thickness of the antistatic layer (easily adhesive layer containing conductive particles) in the present invention is preferably in the range of 0.01 to 1 111, and more preferably in the range of 0.01 to 0.2 m. Childish. If it is less than 0.01 m, it is difficult to apply the coating agent uniformly. If uneven coating occurs on the product or if it exceeds 1 ⁇ m immediately, the antistatic performance may be inferior in scratch resistance.
  • Conductive particles for example, conductive metal oxide particles
  • the amount is less than 10% by mass, sufficient antistatic properties tend not to be obtained, and if it exceeds 1000% by mass, the haze tends to be too high. On the other hand, when it exceeds 400% by mass, the peel strength after bonding with glass via an adhesive tends to be weakened.
  • the content of the conductive particles is based on 30 parts by mass of a synthetic resin (for example, acrylic resin (including solvent) or acrylic resin dispersion), the content of the conductive particles is 10 ⁇ 500 parts by weight is preferred, 50 to 150 parts by weight is more preferred.
  • the antistatic layer and the following surface layer in the present invention can be used in combination with additives such as a matting agent, a surface active agent, and a slipping agent, if necessary.
  • Matting agents include particles of oxides such as silicon oxide, aluminum oxide and magnesium oxide having a particle size of 0.001 to 10 m, and particles of polymers or copolymers such as polymethylmethalate and polystyrene. Can give.
  • Cationic surfactants amphoteric surfactants, nonionic surfactants and the like can be mentioned.
  • slip agents include natural waxes such as carnauba wax, phosphate esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof, palmitic acid, stearic acid, behenic acid and esters thereof, and silicone compounds. Can be mentioned.
  • a surface layer may be provided on the antistatic layer.
  • the surface layer mainly provides adhesion to the adhesive layer and prevents the conductive metal oxide particles from being removed from the antistatic layer.
  • various polymers such as acrylic resin, beer resin, polyurethane resin, and polyester resin can be generally used, and the polymers described as the binder in the antistatic layer are used. Is preferred. Among these, at least one selected from the group force of the reason that it is easy to adhere to the antistatic layer and the strength of acrylic resin, polyester resin, polyurethane resin, and styrene butadiene rubber is preferable.
  • the cross-linking agent used for the surface layer is preferably an epoxy compound that does not affect the photosensitive characteristics of the photosensitive material layer that is contacted when the roll is removed during the manufacturing process.
  • epoxy compound examples include 1,4 bis (2 ', 3'-epoxypropyloxy) butane, 1,3,5 triglycidyl isocyanurate, 1,3 diglycidinole-5- ( ⁇ -acetoxy-1- ⁇ -oxypropyl) isosinurate, Sorbitol polyglycidyl ethers, polyglyceryl polyglycidyl ethers, pentaerythritol polyglycidyl ethers, diglycerone polyrenoglycenosidinoatenore, 1, 3, 5 triglycidyl (2 hydroxyethyl) isocyanurate, glycerol polyglycerol Epoxy compounds such as ethers and trimethic lip-and-loop polyglycidyl ethers are preferred as specific products such as Denacol ⁇ -521 and EX- 614B (manufactured by Nagase Kasei Kogyo Co., Ltd.). Power that can be
  • the surface layer is formed by a coating method generally well known on the antistatic layer in the present invention, such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, etast. It can be formed by applying the above surface layer coating solution by a rouge coating method or the like.
  • the layer thickness of the surface layer is preferably in the range of 0.01 to 1 / ⁇ ⁇ , and more preferably in the range of 0.01 to 0.2 m. If it is less than 0.01 m, the antistatic layer has insufficient anti-detachment function for the conductive metal oxide particles, and if it exceeds 1 ⁇ m, it is difficult to apply the coating agent uniformly, so it is applied to the product. Unevenness is likely to occur.
  • the adhesive layer preferably used in the present invention will be described.
  • the translucent electromagnetic wave shielding film of the present invention is bonded via an adhesive layer when incorporated in an optical filter, a liquid crystal display panel, a plasma display panel, other image display panels, or the like.
  • the adhesive used in the present invention preferably has a refractive index of 1.40-1.70. This is related to the refractive index of the adhesive, such as a plastic film used in the present invention, to reduce the difference and 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 is also preferably an adhesive that flows by heating or pressurization, particularly heating at 200 ° C or less or application of 1 kgfZcm 2 (0.098 MPa) or more.
  • An adhesive that exhibits fluidity under pressure is preferred. Since it can flow, a translucent electromagnetic wave shielding film (electromagnetic wave shielding adhesive film) provided with an adhesive layer can be bonded to an adherend by lamination or pressure molding, particularly pressure molding. Further, it can be easily bonded to an adherend having a curved surface or a complicated shape.
  • the softening temperature of the adhesive is preferably 200 ° C or lower.
  • the softening temperature of the adhesive layer is preferably 80 ° C or higher because the environment used is usually less than 80 ° C. preferable.
  • the softening temperature is the temperature at which the viscosity is 10 12 boise (10 13 Pa • s) or less. Usually, at that temperature, flow is recognized within a time of about 1 to L0 seconds.
  • Typical examples of the adhesive that flows by heating or pressurization as described above are mainly the following thermoplastic resins.
  • the poly (meth) acrylic acid ester can be used. Two or more kinds of these acrylic polymers may be copolymerized as required, or two or more kinds may be blended and used.
  • epoxy acrylate ( ⁇ 1.
  • urethane acrylate, epoxy acrylate, and polyether acrylate are excellent from the viewpoint of adhesiveness.
  • epoxy acrylate 1,6 hexanediol diglycidyl ether, neodylate Pentyl 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, Examples include (meth) acrylic acid adducts such as pentaerythritol tetraglycidyl ether and sorbitol tetraglycidyl ether.
  • 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.
  • 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 particularly preferably 10 to 80 m, more preferably 20 to 50 m, more than the thickness of the conductive layer.
  • the adhesive provided on the easy-adhesion layer has a difference in refractive index between the support and the easy-adhesion layer of 0.14 or less. By satisfying this difference in refractive index, the visible light transmittance decreases and becomes good.
  • Methane-type epoxy resin novolak-type epoxy resin, resorcin-type epoxy resin, polyalcohol polyglycol-type epoxy resin, polyolefin-type epoxy resin, epoxy resin such as alicyclic and halogen-bisphenol (all A refractive index of 1.55 to 1.60) can be used.
  • acrylic resin is well known as one that hardly changes color over time, and is preferably used in the present invention.
  • acrylic polymers Two or more kinds of these acrylic polymers may be copolymerized as necessary, or two or more kinds may be blended and used. By blending several types of acrylic polymers with different molecular weights, it is possible to adjust the viscoelasticity of the adhesive to the desired properties.
  • epoxy acrylate, urethane acrylate, polyether acrylate, polyester acrylate and the like can also be used.
  • Epoxy acrylate and polyether acrylate are particularly excellent from the viewpoint of adhesiveness.
  • epoxy acrylate 1, 6 hexanediol diglycidyl is used.
  • Ether neopentyl glycol diglycidyl ether, aryl alcohol diglycidyl ether, resorcinol diglycidyl ether, diglycidyl adipate, diglycidyl phthalate, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin Such as triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, etc.
  • Epoxy acrylate is effective in improving adhesiveness 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. The adhesive resin composition is applied to cover part or all of the surface of the easy-adhesion layer on the support, followed by solvent drying and heat-curing steps, followed by electromagnetic wave shielding adhesion. Make a film.
  • the electromagnetic wave shielding adhesive film having the electromagnetic shielding properties and transparency obtained above can be directly attached to a display such as a CRT, PDP, liquid crystal or EL, or used on an acrylic plate, glass plate or other plate or sheet. Paste and use for display. Further, this electromagnetic wave shielding adhesive film is used in the same manner as described above for a window or a case for looking inside a measuring apparatus, measuring apparatus or manufacturing apparatus that generates electromagnetic waves. Furthermore, it is subject to electromagnetic interference by radio towers and high voltage lines. Installed in windows of buildings or automobiles where there is a fear.
  • the metal silver part is preferably provided with a ground wire.
  • the surface of the display is generally made of glass
  • bonding with the adhesive is performed by bonding the support and the glass plate, and bubbles are generated or peeled off on the bonding surface. If this happens, the image will be distorted and the display color will appear different from the original display.
  • the problem of bubbles and peeling occurs when the adhesive peels off from the support or the glass plate. This phenomenon may occur on both the support side and the glass plate side, and peeling occurs on the side with weaker adhesion. Accordingly, it is necessary that the adhesive strength between the adhesive, the support and the glass plate at a high temperature is high.
  • the adhesion between the support and the glass plate and the adhesive layer is preferably at least lOgZcm (lONZm) at 80 ° C according to the test method in conformity with IS08225! /. More preferably, it is more preferably 20 g / cm (20 N / m) or more, and particularly preferably 30 g / cm (30 N / m) or more.
  • adhesives exceeding 2000 gZcm (2 kNZm) may not be preferable because the bonding work becomes difficult. However, it can be used without problems if no significant problems occur.
  • 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 the temperature is low. Specifically, 0 to 3% is preferable, and 0 to 1.5% is more preferable.
  • the 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 is practical if the adhesive is thin. Can be considered colorless. Similarly, this is not the case when intentionally coloring as described later.
  • Examples of the adhesive having the above 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 in the case of using the same rosin, it is possible to reduce the amount of the adhesive by synthesizing the adhesive by a method such as lowering the amount of the crosslinking agent, adding a tackifier, or changing the end group of the molecule. It is also possible to improve the performance.
  • the thickness of the adhesive layer is preferably about 5 to 50 ⁇ m.
  • the thickness is preferably reduced within the above range. Specifically, it is about 1-20 / ⁇ ⁇ . However, if the display color of the display itself is not changed as described above and the transparency is within the above range, the thickness may exceed the above range.
  • the thickness of the support in the translucent electromagnetic shielding film of the present invention is preferably 200 ⁇ m or less, more preferably 20 to 180 m, and most preferably 50 to 120 m. Within this range, a desired visible light transmittance can be obtained, and handling is easy.
  • the thickness of the metallic silver portion provided on the support before physical development and Z or staking treatment may be appropriately determined according to the coating thickness of the emulsion layer coating applied on the support. it can.
  • 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 preferred to be m That's right.
  • a metal silver part is pattern shape.
  • the metallic silver part may be a single layer or a multilayer structure of two or more layers. When the metallic silver part has a pattern and has a multilayer structure of two or more layers, different color sensitivities can be imparted so as to be sensitive to different wavelengths. As a result, when the exposure wavelength is changed for exposure, different patterns can be formed in each layer.
  • the translucent electromagnetic wave shielding film including the patterned metal silver portion having the multilayer structure formed as described above can be used as a high-density printed wiring board.
  • the thickness of the conductive metal portion is preferably as the electromagnetic wave shielding material of the display, since the viewing angle of the display is wider as it is thinner.
  • 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 metallic silver portion having a desired thickness is formed by controlling the coating thickness of the emulsion layer described above, and further, the thickness of the layer having conductive metal particle force can be freely controlled by physical development and Z or tacking treatment. Since it can be controlled, even a translucent electromagnetic shielding film having a thickness of less than 5 ⁇ m, preferably less than 3 ⁇ m can be easily formed.
  • the present invention supports a pattern containing 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 adhesion strength between the translucent electromagnetic wave shielding film of the present invention and the glass substrate is preferably as follows.
  • the peel strength is preferably 20 N / m or more. Further, it is preferable that the peel strength after a lapse of 72 hours at a temperature of 60 ° C. and a relative humidity of 90% is a peel strength of 20 N / m or more.
  • the light-transmitting electromagnetic wave shielding film of the present invention preferably exposes a photosensitive material having an emulsion layer containing a photosensitive halogenated silver salt on a support and applies a development treatment to exposed and unexposed areas. Each is obtained by forming a metallic silver portion and a light transmitting portion. Further, if necessary, the metallic silver portion may be subjected to physical development and Z or staking treatment to carry a conductive metal on the metallic silver portion.
  • the method for forming a translucent electromagnetic wave shielding film of the present invention includes the following three forms depending on the photosensitive material and the form of development processing.
  • a photosensitive silver halide silver / white photosensitive material that does not contain physical development nuclei and an image-receiving sheet that has a non-photosensitive layer containing physical development nuclei are overlaid and diffusion transfer developed to make the metallic silver portion non-photosensitive.
  • the mode (I) is an integrated black-and-white development type, in which metallic silver is formed on the photosensitive material.
  • the resulting developed silver is chemically developed silver or heat developed silver, and is highly active in the subsequent staking or physical development process in that it is a filament with a high specific surface.
  • the silver halide grains close to the physical development nucleus are dissolved and deposited on the development nucleus, whereby metallic silver is formed on the photosensitive material.
  • This is also an integrated black-and-white development type. Since the developing action is precipitation on physical development nuclei, it is highly active, but developed silver has a small specific surface and is spherical.
  • the silver halide silver particles are dissolved and diffused in the unexposed area, and are deposited on the development nuclei on the image receiving sheet to form metallic silver on the image receiving sheet.
  • This is a so-called separate type, in which the image-receiving sheet is used with the photosensitive material force peeled off.
  • the mode of deviation can also be selected as negative development between negative development processing and reversal development processing (in the case of the diffusion transfer method, negative development processing can be performed by using an auto positive photosensitive material as the photosensitive material. Possible).
  • the chemical development, thermal development, and dissolution physical development referred to here have the meanings commonly used in the art, and are general textbooks of photographic chemistry such as “Photochemistry” written by Shinichi Kikuchi (Kyoritsu Publishing Co., 1955). Published in CEK Mees, “The Theory of Photographic Proces ses, 4th edition” (Mcmillan, 1977). This case is liquid processing, but for other applications, the thermal development method is also applied as the development method.
  • Japanese Patent Application Laid-Open Nos. 2004-184693, 2004-334077, 2005-010752, Japanese Patent Application Nos. 2004-244080, 2004-085655, and the like can be used.
  • the translucent electromagnetic wave shielding film of the present invention can be provided with a peelable protective film.
  • the protective film need not be provided on both sides of the translucent electromagnetic wave shielding film, and can be provided only on the metallic silver portion or the conductive metallic portion, or only on the opposite side. When the protective film is provided on the metallic silver portion or the conductive metallic portion, it is desirable that the protective film be peelable.
  • the peel strength of the protective film is preferably 5mNZ25mm width to 5NZ25mm width under the above test conditions, more preferably 10mNZ25mm width to 100mNZ25mm width. If it is less than the lower limit, peeling is too easy 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 metallic silver part or the conductive metallic part may be peeled off from the support, which is also not preferable.
  • polyethylene resin which is polyolefin resin, polypropylene resin, polyester resin such as polyethylene terephthalate resin, resin resin film such as polycarbonate resin, acrylic resin, etc. It is preferable to use, and the surface to which the protective film is bonded is preferably subjected to corona discharge treatment.
  • an acrylic ester-based, rubber-based, or silicone-based adhesive can be used as the adhesive constituting the protective film.
  • the roll-shaped translucent electromagnetic shielding film of the present invention and the optical film incorporating it are In addition, it may have been subjected to black wrinkle processing.
  • the black wrinkle process is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-188576.
  • the blackened layer formed even by the blackening treatment can impart antireflection properties in addition to the antifungal effect.
  • the black layer can be formed by, for example, Co—Cu alloy plating, and can prevent reflection of the surface of the metal foil.
  • a chromate treatment may be performed thereon as a fouling treatment.
  • the chromate treatment is performed by immersing in a solution containing chromic acid or dichromate as a main component and drying to form an anti-fouling coating, which can be performed on one or both sides of the metal foil as required. Force Commercially available chromate-treated copper foil or the like may be used.
  • a metal foil that has been blackened in advance can be used, it may be blackened in an appropriate later step. Formation of the black wrinkle layer is accomplished by forming a photosensitive resin layer that can be a resist layer using a black colored composition, and leaving the resist layer without removal after etching is completed. Alternatively, a plating method that gives a black film may be used.
  • the configuration shown in Japanese Patent Laid-Open No. 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.
  • the electrolyte bath containing the blackening material may be a black tanning bath containing nickel sulfate as a main component.
  • black plating baths can also be used in the same way. Specifically, for example, a black plating bath manufactured by Shimizu Co., Ltd. (trade name, Novroy SNC, Sn—Ni alloy system), Nippon Chemical Industry Co., Ltd. Black bathing bath (trade name, Nitsuka Black, Sn—Ni alloy) manufactured by Co., Ltd., Black bathing bath (trade name, Evo--Chromium 85 series-85 series, manufactured by Metal Chemical Co., Ltd.) Cr type) can be used.
  • the black tanning bath includes Zn, Cu, Various black tanning baths such as others can be used.
  • 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
  • treat the surface of Cu with hydrogen sulfide (HS) solution treatment.
  • HS hydrogen sulfide
  • the second black layer is formed.
  • the metal as the above-mentioned good conductive substance can be used as the most advantageous material. Therefore, when forming the above-mentioned metal electrodeposition layer, general-purpose metal electrolytes can be used, so there are many kinds of inexpensive metal electrolytes, and the choice according to the purpose is free. There is an advantage that can be done. In general, Cu is frequently used as an inexpensive and highly conductive metal, and in the present invention, it is useful to use Cu in accordance with the purpose. Of course, other metals are similarly used. It can be used for Next, in the present invention, the mesh-like conductive pattern 4 does not need to be composed of only a single metal layer.
  • the mesh-like conductive pattern 4 made of Cu in the above example is used. Since it is relatively soft and easily scratched, the protective layer can be a two-layer metal electrodeposition layer using a general-purpose hard metal such as Ni or Cr.
  • the blackening agent for the second blackening layer it can be easily manufactured using a sulfide-based compound, and there are many types of treating agents on the market. 'Copper black CuO, CuS, selenium-based Copa Black No. 65, etc. (made by Isolate Chemical Laboratories), trade name' Ebonol C Special (made by Meltex Co., Ltd.), etc. can be used. Functional layers other than electromagnetic shielding of optical electromagnetic shielding film]
  • a functional layer having functionality may be separately provided as necessary.
  • This functional layer can have various specifications for each application.
  • an antireflection layer with an antireflection function that adjusts the refractive index and film thickness a non-glare layer or an antiglare layer (both have a glare prevention function), and absorbs near infrared rays.
  • Near-infrared absorbing layer made of a compound or metal that absorbs visible light in a specific wavelength range, a layer that adjusts the color tone to absorb visible light, an antifouling layer that easily removes dirt such as fingerprints, and scratch-resistant
  • a hard coat layer a layer having an impact absorbing function, a layer having a function of preventing glass scattering when glass is broken, and the like can be provided.
  • These functional layers are metal It may be provided on the opposite side of the silver part or conductive metal part and the support, or on the same side.
  • a material provided with these functional layers is called an optical filter (or simply a filter).
  • each functional layer When using a translucent electromagnetic shielding film for a display (especially a plasma display), it is preferable to attach each functional layer by attaching a functional layer (functional film) described below.
  • the functional film can be directly or indirectly attached to the translucent electromagnetic shielding film via an adhesive or the like.
  • the functional film can be formed by providing a functional layer having antireflection properties and antiglare properties on a suitable transparent substrate. (Anti-reflective 'Anti-glare)
  • the translucent electromagnetic wave shielding film has anti-reflection (AR: anti-reflection) properties to suppress external light reflection, anti-glare properties (AG: anti-glare) properties to prevent reflection of mirror images, or both. It is preferable to provide any anti-glare and anti-glare (ARAG) function provided.
  • AR anti-reflection
  • AG anti-glare
  • the visible light reflectance is preferably 2% or less, more preferably 1.3% or less. More preferably, it is 0.8% or less.
  • the antireflection layer for example, a thin film made of a fluorine-based transparent polymer resin, magnesium fluoride, a silicon-based resin, silicon oxide, or the like, for example, with an optical film thickness of 1Z4 wavelength, Two or more layers of thin films of inorganic compounds such as metal oxides, fluorides, halides, nitrides and sulfides, or organic compounds such as silicon-based resins, acrylic resins, and fluorine-based resins with different rates Can be formed.
  • thermosetting or photocuring type such as acrylic resin, silicon resin, melamine resin, urethane resin, alkyd resin, fluorine resin, etc. It can be formed by coating and curing a resin obtained by dispersing particles of inorganic compound or organic compound such as silica, organic silicon compound, melamine, acrylic, etc. on the resin.
  • the average particle size of the particles is preferably about 1 to 40 m.
  • the antiglare layer can also be formed by applying the thermosetting or photocurable resin as described above and then pressing and curing a mold having a desired dalos value or surface state. Monkey.
  • the haze generated during light transmission of the translucent electromagnetic shielding film is preferably 0.5% or more and 20% or less, more 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 layer include thermosetting type or photosetting type resin such as acrylic resin, silicone resin, melamine resin, urethane resin, alkyd resin, and fluorine resin.
  • the type and formation method are not particularly limited.
  • the thickness of the hard coat layer is preferably about 1 to 50 / ⁇ ⁇ .
  • the surface hardness of the translucent electromagnetic shielding film with hard coat properties is JIS ( ⁇ -54
  • the pencil hardness according to (00) is preferably at least H, more preferably 2H, even more preferably 3H or more.
  • the transmissive electromagnetic wave shielding film has antistatic properties.
  • a film having high conductivity can be used.
  • the conductivity is about 10 11 ⁇ Zsq or less in terms of surface resistance
  • a highly conductive film can be formed by providing an antistatic layer on a transparent substrate.
  • the antistatic agent used in the antistatic layer include the trade name Perester. (Sanyo Kasei Co., Ltd.) and trade name Electro Slipper (Kao Co., Ltd.).
  • the antistatic layer may be formed of a known transparent conductive film such as ITO, or a conductive film in which conductive ultrafine particles such as ITO ultrafine particles and tin oxide ultrafine particles are dispersed.
  • the above hard coat layer, antireflection layer, antiglare layer and the like may be provided with antistatic properties by containing conductive fine particles.
  • the light-transmitting electromagnetic wave shielding film has antifouling property, it is preferable because it can be easily removed when it is prevented from being smudged or smudged.
  • a functional film having antifouling properties can be obtained, for example, by applying a compound having antifouling properties on a transparent substrate.
  • a compound having antifouling property for example, a fluorine compound or a key compound may be used as long as the compound has non-wetting property with respect to water and Z or oil.
  • Specific examples of the fluorine compound include trade name OPTOOL (manufactured by Daikin) and the like, and examples of the key compound include trade name Takata Quantum (manufactured by NOF Corporation).
  • the functional film having ultraviolet cut-off property can be formed by a method of containing an ultraviolet absorber in the support itself or by providing an ultraviolet absorbing layer on the support.
  • 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.
  • a functional film having an ultraviolet cutting property can be obtained by forming a layer containing an ultraviolet absorber or an inorganic compound that reflects or absorbs ultraviolet rays on a transparent substrate.
  • Conventionally known UV absorbers such as benzotriazoles and benzophenones can be used, and their type 'concentration is dispersibility in the medium to be dispersed or dissolved' solubility, absorption wavelength-absorption coefficient, medium It is determined by the thickness of the material and is not particularly limited.
  • the functional film having ultraviolet cut-off property preferably has little absorption in the visible light region and does not significantly reduce the visible light transmittance or exhibit a color such as yellow. Moreover, when the layer containing the pigment
  • the translucent electromagnetic wave shielding film has a gas barrier property because it may be clouded or the adhesive may be phase-separated and deposited due to the influence of moisture.
  • the water vapor permeability of the functional film is preferably lOgZm 2 ⁇ day or less, preferably Is preferably 5 gZm 2 ⁇ day or less.
  • a plasma display Since a plasma display generates intense near-infrared rays, it is preferable to provide a near-infrared cut-off property, particularly when a light-transmitting electromagnetic wave shielding film is used for a plasma display.
  • a film having a transmittance of 25% or less in a wavelength region of 800 to 1 OOOnm is preferably less than 15%, more preferably less than 10%. is there.
  • the transmitted color is-neutral gray or blue gray. This is to maintain or improve the light emission characteristics and contrast of the plasma display, and is also a force that may prefer a white color temperature slightly higher than the standard white color.
  • color plasma displays are said to have insufficient color reproducibility.
  • the emission spectrum of red display shows several emission peaks ranging from about 580 nm to about 700 nm.
  • red emission becomes poor in color purity close to orange due to a strong emission peak on the short wavelength side. Therefore, it is preferable that the functional film has a function of selectively reducing unnecessary light emission of the phosphor or discharge gas force that is the cause thereof.
  • These optical properties can be controlled by using a dye.
  • a dye for near-infrared cut
  • a dye having an appropriate absorption can be used.
  • the dye may be a general dye or pigment having a desired absorption wavelength in the visible region, or a compound known as a near infrared absorber, and the type thereof is not particularly limited.
  • a compound known as a near infrared absorber for example, anthraquinone, phthalocyanine, methine, azomethine, oxazine, imonium, azo, styryl, coumarin, porphyrin, dibenzofuranone, diketopyrrolopyrrole, rhodamine, xanthene
  • organic dyes that are generally commercially available, such as pyromethene-based compounds, dithiol-based compounds, and diiminium-based compounds.
  • the dye has a heat resistance that does not deteriorate at about 80 ° C, for example. It is preferable to speak.
  • some dyes have poor light resistance. If such dyes cause problems with the light emission of plasma displays and the deterioration of UV light and visible light from outside light, functional films as described above. It is preferable to prevent the dye from being deteriorated by ultraviolet rays or visible rays by adding an ultraviolet absorber to the layer or providing a layer that does not transmit ultraviolet rays.
  • the transmission characteristics of the optical filter change, and the color tone may change or the near-infrared cutting ability may decrease.
  • the dye in order to dissolve or disperse in a resin composition for forming a support or a coating composition for forming a coating layer, is preferably highly soluble and dispersible in a solvent. .
  • the concentration of the dye is appropriately set based on the absorption wavelength of the dye, the absorption coefficient, the transmission characteristics required for the light-transmitting electromagnetic wave shielding film, the transmittance, and the type of the medium or coating film to be dispersed. can do.
  • the functional film When the functional film contains a pigment, it may be contained inside the support, A layer containing a dye may be coated on the surface of the support. Further, two or more kinds of dyes having different absorption wavelengths may be mixed and contained in one layer, or two or more layers containing dyes may be provided.
  • the functional film containing the dye has a layer containing the light transmitting electromagnetic wave shield. It is more preferable that the metal silver part or the conductive metal part on the metal film be disposed so as not to contact.
  • the translucent electromagnetic shielding film with the functional film attached is attached to the display, it is usually attached so that the functional film is on the outside and the adhesive layer is on the display side.
  • the functional film is on the outside and the adhesive layer is on the display side.
  • the conducting part is preferably provided around the metallic silver part or the conductive metal part along the peripheral edge of the translucent electromagnetic shielding film.
  • the conductive portion may be formed of a mesh pattern, or may be patterned! /,
  • the conductive portion may be formed of a mesh pattern, or may be patterned! /,
  • the metal foil is not patterned like a solid metal foil.
  • the conductive portion may be a mesh pattern layer or not patterned, for example, a solid layer of metal foil. However, in order to improve the electrical contact with the ground portion of the display main body. For this, it is preferable that the conductive portion be patterned like a metal foil solid layer.
  • the conductive part When the conductive part is not patterned, such as a solid metal foil, and when the mechanical strength of Z or the conductive part is sufficiently strong, the conductive part itself can be used as an electrode. It is.
  • an electrode on the conductive portion for protecting the conductive portion and for good electrical contact with the ground portion when Z or the conductive portion 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.
  • an optical filter having excellent optical characteristics that can maintain or improve the image quality without significantly impairing the luminance of the plasma display.
  • it has excellent electromagnetic shielding ability to block electromagnetic waves that have been pointed out to be harmful to the health of the plasma display, and near infrared rays near 800 to 1000 nm are also emitted from the plasma display. Therefore, it is possible to obtain an optical filter that does not adversely affect the wavelengths used by the remote control of peripheral electronic devices, transmission optical communication, etc., and can prevent malfunctions thereof.
  • an optical filter having excellent weather resistance can be provided at a low cost.
  • Hexaclo oral rhodate ammonium (0.001% NaCl 20% aqueous solution) 7ml Potassium hexaloiridium (III) (0.005% KC1 20% aqueous solution) and hexachloro oral rhodate ammonium 0.001% NaC120% aqueous solution) was prepared by dissolving the powder in KC1 20% aqueous solution and NaC120% aqueous solution, respectively, and heating at 40 ° C. for 120 minutes.
  • the substrate 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.
  • Emulsion A to sensitizing dye (sd-2) 5.7 X 10- 4 mole of Z moles Ag in example mosquitoes ⁇ subjected to spectral sensitization. Further to KBr3.4 X 10- 4 mole Z mol Ag, the compound (Cpd- 3) 8.0 X 10- 4 mole Z mol Ag Karoe, and mixed well.
  • G / m 2 gelatin 1. It was applied so as to be 1 lg / m 2 .
  • the silver / binder (volume ratio) was about 1/1.
  • the molten PET resin is discharged from a die part onto a chill roll that is electrostatically applied to obtain a non-crystalline base.
  • the obtained amorphous base was stretched 3.3 times in the direction of travel of the base and then stretched 3.8 times in the width direction to produce a support having a thickness of 96 m in the form of a roll.
  • Easy adhesion layer Back layer (easy adhesion layer located on the opposite side of the silver salt emulsion layer and the support)> A coating solution having the following composition on the support under the following coating conditions, Coating and drying were performed to form a back layer (easy adhesion layer) 1.
  • Polyacrylic resin Jiurimer ET-410: Nippon Pure Chemical Co., Ltd., solid content 30%
  • Needle-shaped tin oxide particles F-10D: Ishihara Sangyo Co., Ltd., solid content 20%
  • 131.1 parts by mass Carposiimide compound Carposiimide compound (Carpolite V-02-L2: Nisshinbo, solid content 40%)
  • Surfactant Sandet BL: Sanyo Chemical Industries, solid content 44.6%)
  • Surfactant surfactant HN-100 Sanyo Chemical Industrial 100% solids
  • Silica fine particle dispersion (Seahoster KE-W30: Nippon Shokubai 0.3 m solid content 20%) 5.0 parts by mass
  • a surface layer coating solution having the following composition was applied on the antistatic layer at a coating amount of 5.05 ccZm 2 on the antistatic layer while maintaining the conveyance speed of 105 mZ. Subsequently, a back layer having a two-layer structure was obtained by drying at 160 ° C. for 1 minute in an air flotation drying zone.
  • Polyacrylic resin Julimer ET-410: Nippon Pure Chemical Co., Ltd., 30% solid content
  • Epoxy compound Denacol EX-521: Nagase Chemical Industries, 100% solid content
  • Surfactant (Sandet BL: Sanyo Chemical Industries, solids 44.6%) 0.5 parts by mass
  • composition of the coating solution was changed from that of the easy-adhesion layer 1 as follows to form the following easy-adhesion layer.
  • the easy-adhesion layer 2 was formed by adjusting the coating solution without adding acicular structure tin oxide particles (FS-10D: manufactured by Ishihara Sangyo Co., Ltd., solid content 20%) to the easy-adhesion layer 1.
  • F-10D acicular structure tin oxide particles
  • Polystyrene fine particles (average particle size 2 ⁇ m)
  • Acetic acid (specially pure glacial acetic acid: manufactured by Daicel Chemical Industries, solid content 99%) 0.42 parts by mass
  • An undercoat layer coating solution having the following composition was simultaneously applied to the surface of the support opposite to the surface on which the back layer was formed, to form an undercoat layer for an emulsion layer.
  • the surface of the support was subjected to corona discharge treatment under a condition of 467 jZm 2 to obtain a coating solution for the first subbing layer having the following composition. It applied by the bar coat method.
  • the coating amount was 5.05 ccZm 2 and the first undercoat layer was obtained by drying at 180 ° C. for 1 minute in the air flotation drying zone, the same as the back layer antistatic layer drying zone.
  • Polystyrene fine particles (average particle size 2 ⁇ )
  • the emulsion layer side is close to the support, and two layers, the UL layer and the emulsion layer from the side, in that order, are applied simultaneously by the slide bead coater method while maintaining at 35 ° C. And passed through a cold air set zone (5 ° C).
  • the hardener Cpd-7 is applied to 3 ⁇ 4HU.
  • the above-mentioned amount was added to the UL layer and diffused from the UL layer to be contained in the emulsion layer. Then, it was passed through 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.
  • the obtained various samples had a coating silver amount of 7.6 g / m 2 and an emulsion layer Ag / gelatin mass ratio of 6.
  • An emulsion layer with a swelling ratio of 209% and a product of Ag / gelatin mass ratio and swelling ratio of 13.2 is the top layer. It was a photosensitive material having.
  • the swelling ratio of the emulsion layer was determined as follows. Specifically, the thickness (a) of the emulsion layer at the time of drying is obtained by observing a section of the sample at the time of drying with a scanning electron microscope, immersed in distilled water at 25 ° C for 1 minute, and then freeze-dried with liquid nitrogen. The film thickness (b) of the emulsion layer at the time of swelling was determined by observing a slice of the sample with a scanning electron microscope, and the swelling ratio was calculated by the following equation.
  • the exposure amount was adjusted to be optimal for each sample.
  • the exposed sample was subsequently subjected to development processing to produce a metallic silver portion, and subsequently subjected to a plating treatment to produce a conductive film in which the conductive metallic portion was composed of developed silver and copper.
  • composition of each treatment liquid is as follows.
  • Electrolytic copper plating solution composition (same replenisher composition)
  • the oxidation-reduction potential of the black-and-white developer was 340 mVvs SCE, expressed as the bath potential obtained by immersing the rotating platinum electrode in the developer.
  • each sample was subjected to the exposure and processing described above, and a conductive metal film composed of a transparent metal transmission part and a conductive metal part substantially free of metal was formed.
  • the conductive metal part had a mesh pattern corresponding to the exposure pattern, and the line Z space width was 15 ⁇ m / 285 ⁇ m in all samples. In all samples, the aperture ratio of the light transmission part was about 90%.
  • the surface resistivity was JIS7194 measured using the Mitsubishi Chemical Corporation low resistivity meter outlet GPZASP probe. It had sufficient conductivity as an electromagnetic shielding film for PDP.
  • This black spot is mesh It has the characteristic that it is accompanied by the interruption of the fine line of the pattern.
  • capri which is well known in negative-type halogen silver photographic light-sensitive materials, refers to a phenomenon in which developed silver is produced in unexposed areas.
  • the discontinuity of the fine mesh line seen in the black spot of the present application means that developed silver is not generated in the exposed area, and is a phenomenon peculiar to this system that cannot be understood by the conventional Capri phenomenon.
  • the evaluation criteria were as follows.
  • Level A 0 to 3 black spots.
  • Level B Number of black spots 4 to: L 0.
  • Level C More than 10 black spots.
  • a sheet-like adhesive was affixed to the easy adhesion layer side of each sample, and was affixed to a glass substrate. 180 ° peel strength was measured according to the above measurement method. In addition, after storing for 72 hours at 60% humidity and 90% humidity, the 180 ° peel strength was also measured.
  • Table 1 shows the evaluation results.
  • X indicates that the attached film partially peeled off the glass and floated, resulting in defects.
  • ⁇ indicates that the attached film is lighter than “X” from the glass, but partly peeled off and floated to cause a defect. ⁇ indicates that this problem was not observed.
  • a metal conductive film was produced in the same manner as in Sample Nol. Except that the conductive metal oxide was changed as shown in Table 2 in Sample Nol. Table 2 shows the results obtained. Various evaluation criteria and units are the same as in Table 1.
  • the amount of antimony-doped tin oxide added in Sample 1 was 222% by mass.
  • a conductive film can be produced by pattern exposure and development using a halogen silver photographic material, and can be used as a translucent conductive film for PDP. ing.
  • the easy adhesion layer using gelatin which has been widely used in conventional halogen silver photographic materials, has a problem in terms of peel strength after wet heat aging (Sample 4).
  • the one with acrylic resin in the top layer of the easy-adhesion layer (Sample 2) has excellent peel strength.
  • the silver halide light-sensitive materials conventionally used in the industry are light-sensitive materials having a protective layer on the emulsion layer where the silver halide emulsion layer is not the uppermost layer.
  • a black spot with mesh breakage was also observed by providing a protective layer made of gelatin on the emulsion layer.
  • the defect was strong. From the above, it can be seen that the defect is a problem peculiar to the present system capable of forming a conductive metal film.
  • a protective layer is provided on the outermost layer on the emulsion layer side of the photosensitive material prepared in Example 1, a conductive low-conductivity portion of 10 ⁇ / port or more can be readily obtained, and a conductive metal film or an electromagnetic shielding film can be obtained immediately. It was a good force for the purpose.
  • a photosensitive material having a silver / binder volume ratio of 1/4 or less in the silver halide silver emulsion layer can produce a conductive metal film or an electromagnetic shielding film immediately after forming a portion with low conductivity of 10 ⁇ / mouth or more. It was not preferable for the purpose.
  • an acrylic translucent adhesive with a thickness of 25 m is formed on the inner translucent electromagnetic shielding film excluding the outer edge of 20 mm.
  • the glass plate was bonded together.
  • the acrylic light-transmitting pressure-sensitive adhesive layer contained a toning dye (PS-Red-G, PS-Violet-RC, manufactured by Mitsui Chemicals) that adjusts the transmission characteristics of the optical filter.
  • an antireflection film having a near-infrared cutting ability (trade name “Realak 77 2UV” manufactured by NOF Corporation) was bonded to the opposite main surface of the glass plate via an adhesive material to produce an optical filter.
  • the obtained optical filter has a black metal mesh, and when this is used in a plasma display panel, the display image does not take on a metallic color, and is also problematic in practice! In addition, it has near-infrared cutting ability and excellent visibility due to the antireflection layer. It was. Further, by adding a pigment, a toning function can be imparted, and it can be suitably used as an optical filter such as a plasma display.

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Abstract

A silver halide photosensitive material that in the production of conductive metal film, avoids defects, such as fogging and break of mesh fine lines; and a conductive metal film produced therewith. There is provided a silver halide photosensitive material characterized by having a support, a silver halide emulsion layer superimposed on one major surface of the support and containing a silver salt, and an easy bonding layer superimposed on the other major surface of the support and containing a synthetic resin and conductive particles. Further, there are provided, produced with the use of the silver halide photosensitive material, a conductive metal film and translucent electromagnetic wave shielding film, and, having the shield film, an optical filter and plasma display panel.

Description

ハロゲン化銀感光材料、導電性金属膜、透光性電磁波シールドフィルム 、光学フィルターおよびプラズマディスプレイパネル  Silver halide photosensitive material, conductive metal film, translucent electromagnetic shielding film, optical filter and plasma display panel
技術分野  Technical field
[0001] 本発明は、ハロゲン化銀感光材料、これを用いて製造された導電性金属膜、該導 電性金属膜からなる透光性電磁波シールドフィルム、該シールドフィルムを有する光 学フィルターおよびプラズマディスプレイパネルに関するものである。本発明における 透光性電磁波シールドフィルムは、 CRT (陰極線管）、 PDP (プラズマディスプレイパ ネル）、液晶、 ELP (エレクト口ルミネッセンスパネル（ELとも!/、う。））、 FED (フィール ドエミッションディスプレイ）などのディスプレイの前面、電子レンジ、電子機器、プリン ト配線板など力 発生する電磁波を遮蔽するのに有効である。  [0001] The present invention relates to a silver halide photosensitive material, a conductive metal film produced using the same, a translucent electromagnetic wave shielding film comprising the conductive metal film, an optical filter having the shield film, and plasma. It relates to a display panel. The translucent electromagnetic wave shielding film in the present invention includes CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, ELP (electricular luminescence panel (EL also! /)), FED (field emission display). It is effective for shielding electromagnetic waves generated by force such as the front of displays, microwave ovens, electronic equipment, and printed circuit 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!、、電磁波障害 (Electr 0- 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、電子電気機器では、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 (Electr 0- Magnetic Interference: EMI) has been rapidly increasing with the increasing use of various electric facilities and electronic application facilities. 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, electronic and electrical equipment is required to keep the intensity of electromagnetic wave emission within the standards or regulations.
[0003] 上記 EMIの対策には電磁波をシールドする必要がある力 それには金属の電磁波 を貫通させない性質を利用すればよいことは自明である。例えば、筐体を金属体又 は高導電体にする方法や、回路基板と回路基板との間に金属板を挿入する方法、ケ 一ブルを金属箔で覆う方法などが採用されている。しかし、 CRT, PDPなどではオペ レーターが画面に表示される文字等を認識する必要があるため、ディスプレイにおけ る透明性が要求される。このため、前記の方法では、いずれもディスプレイ前面が不 透明になることが多ぐ電磁波のシールド法としては不適切なものであった。  [0003] It is self-evident that the above-mentioned countermeasure against EMI requires the ability to shield electromagnetic waves. For example, a method of making the casing a metal body or a high conductor, a method of inserting a metal plate between the circuit board and the circuit board, and a method of covering the cable with a metal foil are employed. However, in CRT, PDP, etc., it is necessary for the operator to recognize characters displayed on the screen, so transparency on the display is required. For this reason, any of the above methods is inappropriate as an electromagnetic wave shielding method in which the front surface of the display often becomes opaque.
[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いる。電磁波シールド能は、簡便には表面抵抗値で表す ことができ、 CRT用の透光性電磁波シールド材料では、表面抵抗値は凡そ 300 Ω / sq以下であることが要求されるのに対し、 PDP用の透光性電磁波シールド材料では[0004] In particular, a PDP generates a larger amount of electromagnetic waves than a CRT or the like, and thus a stronger electromagnetic wave shielding ability is required. The electromagnetic wave shielding ability can be expressed simply by the surface resistance value. In the case of a light-transmitting electromagnetic wave shielding material for CRT, the surface resistance value is about 300 Ω / Whereas it is required to be less than sq, translucent electromagnetic shielding material for PDP
、 2. 5 Q Zsq以下が要求され、 PDPを用いた民生用プラズマテレビにおいては、 1.2.5 Q Zsq or less is required, and for consumer plasma televisions using PDP, 1.
5 Ω /sq以下とする必要性が高ぐより望ましくは 0. l Q Zsq以下という極めて高い 導電性が要求されている。 The necessity of being 5 Ω / sq or less is high, and it is desirable to have extremely high conductivity of 0. l Q Zsq or less.
また、透明性に関する要求レベルは、 CRT用として凡そ 70%以上、 PDP用として 8 The required level of transparency is about 70% or more for CRT and 8 for PDP.
0%以上が要求されており、更により高い透明性が望まれている。 0% or more is required, and higher transparency is desired.
[0005] 上記の問題を解決するために、以下に示されるように、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種々の材料'方法がこれまで 提案されている。 [0005] In order to solve the above problems, as described below, various materials' methods have been proposed so far that make use of a metal mesh having an opening to achieve both electromagnetic shielding properties and transparency. ing.
[0006] (1)導電性繊維 [0006] (1) Conductive fiber
例えば、特許文献 1には、導電性繊維カゝらなる電磁波シールド材が開示されている For example, Patent Document 1 discloses an electromagnetic shielding material such as a conductive fiber cover.
。し力し、このシールド材はメッシュ線幅が太くディスプレイ画面をシールドすると、画 面が暗くなり、ディスプレイに表示された文字が見えにくいという欠点があった。 . However, this shield material has a drawback that when the display screen is shielded with a thick mesh line width, the screen becomes dark and it is difficult to see the characters displayed on the display.
[0007] (2)無電解めつき加工メッシュ  [0007] (2) Electroless meshed mesh
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、次 、で無電解めつきを 行う方法が提案されている（例えば、特許文献 2、特許文献 3など)。しかし、印刷され る触媒の線幅は 60 m程度と太ぐ比較的小さな線幅、緻密なパターンが要求され るディスプレイの用途としては不適切であった。  There has been proposed a method in which an electroless plating catalyst is printed as a grid pattern by a printing method, and then electroless plating is performed in the following manner (for example, Patent Document 2 and Patent Document 3). However, the printed catalyst has a line width of about 60 m, which is inappropriate for displays that require a thick, relatively small line width and a fine pattern.
さらに、無電解めつき触媒を含有するフォトレジストを塗布して露光と現像を行うこと により無電解めつき触媒のパターンを形成した後、無電解めつきする方法が提案され ている（例えば、特許文献 4)。しかし、導電膜の可視光透過率は 72%であり、透明性 が不十分であった。更には、露光後に大部分を除去する無電解めつき触媒として極 めて高価なパラジウムを用いる必要があるため、製造コストの面でも問題があった。  Furthermore, a method of applying electroless plating after forming a pattern of an electroless plating catalyst by applying a photoresist containing an electroless plating catalyst and performing exposure and development has been proposed (for example, patents). Reference 4). However, the visible light transmittance of the conductive film was 72%, and the transparency was insufficient. Furthermore, since it is necessary to use extremely expensive palladium as an electroless plating catalyst that removes most after exposure, there is also a problem in terms of production cost.
[0008] (3)フォトリソグラフィ一法により形成されたメッシュ [0008] (3) Mesh formed by a photolithography method
フォトリソグラフィ一法を利用したエッチング加工により、透明基体上に金属薄膜のメ ッシュを形成する方法が提案されている（例えば、特許文献 5〜8など)。この方法で は、微細加工が可能であるため、高開口率 (高透過率)のメッシュを作成することがで き、強力な電磁波が放出されても遮蔽できるという利点を有する。しかし、その製造ェ 程は煩雑かつ複雑で、生産コストが高価になるという問題点があった。また、エツチン グ法によるところから、格子模様の交点部が直線部分の線幅より太い問題があること が知られている。また、モアレの問題も指摘され、改善が要望されていた。 There has been proposed a method of forming a metal thin film mesh on a transparent substrate by an etching process using a photolithography method (for example, Patent Documents 5 to 8). Since this method allows fine processing, it has the advantage that a mesh having a high aperture ratio (high transmittance) can be created and can be shielded even when strong electromagnetic waves are emitted. However, its manufacture However, it is complicated and complicated, and the production cost is high. In addition, it is known from the etching method that the intersection of the lattice pattern is thicker than the line width of the straight line. In addition, the problem of moire was pointed out and improvement was desired.
[0009] (4)ハロゲン化銀を現像する方法により形成されたメッシュ  [0009] (4) Mesh formed by a method of developing silver halide
ハロゲン化銀を現像して得られる導電性金属銀で導電性メッシュを形成する方法、 あるいは該導電性メッシュにさらに金属銅をめつきしてメッシュを形成する方法が提案 されている（例えば、特許文献 9、 10)。  A method of forming a conductive mesh with conductive metal silver obtained by developing silver halide, or a method of forming a mesh by further attaching metal copper to the conductive mesh has been proposed (for example, patents). Reference 9, 10).
特許文献 1：特開平 5— 327274号公報  Patent Document 1: Japanese Patent Laid-Open No. 5-327274
特許文献 2：特開平 11 170420号公報  Patent Document 2: JP 11 170420 A
特許文献 3：特開平 5 - 283889号公報  Patent Document 3: Japanese Patent Laid-Open No. 5-283889
特許文献 4：特開平 11— 170421号公報  Patent Document 4: JP-A-11-170421
特許文献 5 :特開 2003— 46293号公報  Patent Document 5: Japanese Unexamined Patent Publication No. 2003-46293
特許文献 6：特開 2003 - 23290号公報  Patent Document 6: Japanese Patent Laid-Open No. 2003-23290
特許文献 7 :特開平 5— 16281号公報  Patent Document 7: JP-A-5-16281
特許文献 8：特開平 10— 338848号公報  Patent Document 8: Japanese Patent Laid-Open No. 10-338848
特許文献 9：特開 2004— 207001号公報  Patent Document 9: Japanese Unexamined Patent Application Publication No. 2004-207001
特許文献 10：特開 2004 - 221564号公報  Patent Document 10: Japanese Patent Application Laid-Open No. 2004-221564
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0010] 背景技術の項に前記した特許文献は、それぞれの目的に対しては改善がなされた 技術の開示ではある力 その一方次のような課題が残されている。 [0010] The patent document described in the section of the background art is a disclosure of the technology that has been improved for each purpose. On the other hand, the following problems remain.
(無電解めつきによる低生産性）  (Low productivity due to electroless plating)
また、特許文献 10では、銀塩を用いた写真感光材料を利用して作る透光性導電膜 は他の方式に比べて、細線パターンを精密に形成できることによる高い透明性、安 価に大量生産が可能などのような優れた点がある力 このフィルムでは現像銀メッシ ュの抵抗が高いために、直接電解めつきを行うことが困難で、めっき処理を大面積フ イルムに対して行う際には無電解めつきと電解めつきを併用する必要がある。  Also, in Patent Document 10, a translucent conductive film made by using a photographic photosensitive material using silver salt is mass-produced with high transparency and low cost by being able to form a fine line pattern precisely compared to other methods. With this film, the resistance of the developed silver mesh is high, so it is difficult to perform direct electroplating, and it is difficult to apply plating to large area films. It is necessary to use both electroless plating and electrolytic plating.
特許文献 10のように、無電解めつきと電解めつきを併用すると、生産性が悪ぐめつ きコストが高 、等の問題があり改善が望まれて 、た。 As in Patent Document 10, when electroless and electrolytic plating are used together, productivity is poor. There were problems such as high cost, and improvement was desired.
また、上記特許文献 1では、電解めつき処理を枚葉処理でかつバッチ処理により行 つている。表面抵抗が Ι Ω /sq以上と大きいフィルムに対して枚葉処理により電解め つきを行うと、めっき液と接触しているフィルム部分のうち、電流を流した側に近い部 分で多くめつきされる。特に、めっき開始時、即ち最初の給電時にこの現象がおき、 その後めつきを続けてもめっきを均一に付けることが困難であった。  In Patent Document 1, the electrolytic plating process is performed by single wafer processing and batch processing. When electroplating is performed on a film with a large surface resistance of 大 き い Ω / sq or more by single-wafer processing, the film portion that is in contact with the plating solution has a lot of adhesion in the portion near the current-carrying side. Is done. In particular, this phenomenon occurred at the start of plating, that is, at the first power supply, and it was difficult to uniformly apply the plating even if the plating was continued thereafter.
[0011] (不連続なメッシュパターンによる低生産性）  [0011] (Low productivity due to discontinuous mesh pattern)
また、従来のメッシュの形成方法は上述した繊維方式を除き、ある一定の面積しか 断線のな 、メッシュを作成することができな力つた。これはメッシュのパターンを形成 する場合に無電解銅めつき方式ではめつきの触媒核のパターユングがスクリーン印 刷の如き印刷方式であるためスクリーンまたは凹版などのサイズ単位でメッシュが途 切れ、フォトリソグラフィーでは露光マスクサイズ単位にメッシュが途切れてしまって ヽ た。つまりフォトリソグラフィーでは、メッシュパターンのない領域が存在していた。その 理由は、露光方式が枚葉のフォトマスクである為に露光フォトレジストへの露光を長 V、ロールフィルム全体に渡って連続で露光することができず、フォトマスクの大きさの 範囲の露光を 1回 1回繰り返す方法によるものだ力 である。  In addition, the conventional mesh formation method, except for the fiber method described above, has been powerful enough to create a mesh with only a certain area broken. This is because, in the case of forming a mesh pattern, the pattern of the catalyst core in the electroless copper plating method is a printing method such as screen printing, so the mesh breaks in units of size such as screen or intaglio, and photolithography Then, the mesh was broken in units of exposure mask size. That is, in photolithography, there is a region without a mesh pattern. The reason is that, since the exposure method is a single-wafer photomask, the exposure to the exposed photoresist is long V, and the entire roll film cannot be exposed continuously, and exposure within the range of the photomask size is possible. It is the power that is due to the method of repeating once.
[0012] このため、例えば、 PDP用途の場合では、作成したシールド材料のメッシュのパター ンと PDPのモジュールな 、しは前面板ある 、はガラス等を基体とした光学フィルター 材料にシールド材料を位置あわせする製造方法がとられてきた。この方法ではシー ルド材料にロスが出るうえ、生産性を向上するために、シールド材料が連結された口 ール状のシールド材料を使おうとしても、位置合せに時間がかかり、生産速度を十分 に上げることができな力つた。  [0012] For this reason, for example, in the case of PDP applications, the shield material is placed on the optical filter material based on the created shield material mesh pattern and PDP module or front plate or glass. Manufacturing methods have been taken together. In this method, the shield material is lost, and in order to improve productivity, even if a shield-like shield material connected with the shield material is used, alignment takes time and the production speed is sufficient. I could n’t raise it.
[0013] 更には、上記のような電磁波シールド膜では、リモコンの誤作動等を防止する目的 で近赤外線カット性能が重要な要求特性とされている。特に、最近では、 PDPの輝 度の向上に伴って、近赤外線の発生量も多くなつていることから、より一層高度な近 赤外線カット性能が必要とされて ヽる。  Furthermore, in the electromagnetic wave shielding film as described above, near infrared cut performance is an important required characteristic for the purpose of preventing malfunction of the remote control. In particular, with the recent increase in PDP brightness, the amount of near-infrared rays generated has increased, and so even higher near-infrared cut performance is required.
この近赤外カット機能を付与することは、該機能層を電磁波シールド膜と貼り合わ せるなどして得られると考えられる力 電磁波シールドフィルムが上記の様に断続的 なものであって多量のロスを生じながら光学フィルターが製造される限り、近赤外カツ ト機能を有するフィルムもまた、断続的にし力利用されな 、欠点を抱えて 、る。 Giving this near-infrared cut function is a force that is considered to be obtained by laminating the functional layer with an electromagnetic wave shielding film, etc. The electromagnetic wave shielding film is intermittent as described above. As long as the optical filter is manufactured with a large amount of loss, the film having the near-infrared cutting function also has drawbacks that are not intermittently used.
カロえて、 PDP用途において、上記の電磁波シールド能、近赤外線カット能に加え、 反射防止機能が不可欠である。この反射防止機能を有するフィルムまたは機能膜も 、近赤外線カット機能を有するフィルムと同様、ロール状のフィルムであるため、電磁 波シールドフィルムが不連続なメッシュパターンであると反射防止フィルムと貼り合せ た場合に、反射防止フィルムの使用されないロス部分が生じる問題があった。  For PDP applications, in addition to the electromagnetic wave shielding ability and near infrared ray cutting ability described above, an antireflection function is indispensable. The film or functional film having the antireflection function is also a roll-like film like the film having the near-infrared cut function, so that the electromagnetic wave shielding film has a discontinuous mesh pattern and is bonded to the antireflection film. In some cases, there is a problem that a loss portion where the antireflection film is not used is generated.
[0014] (密着強度の問題）  [0014] (Adhesion strength problem)
前述のように、プラズマディスプレイパネルに電磁波シールド機能を付与する手段 は、電磁波シールドフィルムを画像表示パネルに接着剤を利用して貼り合わせる、ガ ラスやプラスチックシート、プラスチックフィルムなどの基材を有する PDP用光学フィル ターに電磁波シールドフィルムを貼り合わせる、などの方法が採られる。フィルムをガ ラスやプラスチックに貼り合わせる場合にも、接着剤が利用される。しかし、従来の銀 塩感光材料に使用される接着剤（例えば、原料にゼラチンを利用するもの）では、支 持体を接着剤でガラスに貼り合せた場合、貼り合せ面の剥離強度が不足し、経時で 剥れが生じる問題があることが判明した。  As described above, the means for imparting an electromagnetic wave shielding function to a plasma display panel is a PDP having a base material such as glass, plastic sheet, plastic film, etc., in which an electromagnetic wave shielding film is bonded to an image display panel using an adhesive. For example, an electromagnetic wave shielding film is attached to the optical filter. Adhesives are also used when bonding films to glass or plastic. However, with adhesives used in conventional silver halide light-sensitive materials (for example, those using gelatin as a raw material), when the support is bonded to glass with an adhesive, the peel strength of the bonded surface is insufficient. It was found that there was a problem that peeling occurred over time.
[0015] (感光材料のカプリ等の問題）  [0015] (Problems such as photosensitive material capri)
一般に、プラスチック支持体をガラス基材に貼り合せる場合、易接着層を設ける方 法が知られている。これは、プラスチック支持体上に、薄い榭脂層を塗布などにより形 成する方法である。  In general, a method of providing an easy-adhesion layer is known when a plastic support is bonded to a glass substrate. This is a method of forming a thin resin layer on a plastic support by coating or the like.
しかしながら、感光性ハロゲン化銀乳剤を塗設した感光材料に易接着層を設けた 場合、感光材料を現像すると、未露光部でも現像が起こることがゎカゝつた。なお、未 露光部での現像銀の発生は、黒色のスポット '斑点状の欠陥を引き起こすという問題 がある。  However, when an easy-adhesion layer is provided on a photosensitive material coated with a photosensitive silver halide emulsion, it has been found that when the photosensitive material is developed, development occurs even in an unexposed area. Incidentally, the development of developed silver in the unexposed area has a problem of causing a black spot 'spotted defect.
[0016] 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、優れた生産性 、低コスト性を有し、露光及び現像工程を経て製造される導電性金属膜において黒 色スポットやメッシュ細線の途切れなどの欠陥が抑制された、ハロゲンィ匕銀感光材料 およびこれを用いて形成された導電性金属膜を提供することにある。 また第 2の目的は、シールド材料のロスが少なく生産性を向上させ、安価に大量に 、連続メッシュパターンを形成した透光性電磁波シールド膜を提供することにある。 また、第 3の目的は、感光材料から得られる電磁波シールドフィルムのガラス基材な どへの接着性 (剥離強度）に優れた電磁波シールドフィルムを提供することである。 本発明のさらなる目的は、感光材料を現像して得られる導電性膜上の未露光部に 現像銀が実質的に形成しない、即ちカプリを生じることのない、易接着層を有する感 光材料、及び、電磁波シールドフィルムを提供することである。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide a black metal film in a conductive metal film that has excellent productivity and low cost and is manufactured through exposure and development processes. An object of the present invention is to provide a silver halide silver photographic material in which defects such as color spots and fine mesh lines are suppressed, and a conductive metal film formed using the same. A second object is to provide a translucent electromagnetic wave shielding film in which a continuous mesh pattern is formed in a large amount at a low cost by improving productivity with little loss of shielding material. A third object is to provide an electromagnetic wave shielding film excellent in adhesiveness (peeling strength) to the glass substrate or the like of the electromagnetic wave shielding film obtained from the photosensitive material. A further object of the present invention is to provide a light-sensitive material having an easy-adhesion layer in which developed silver is not substantially formed in an unexposed portion on a conductive film obtained by developing the light-sensitive material, that is, no capri is formed. And it is providing an electromagnetic wave shielding film.
さらに本発明の別目的は、高い電磁波シールド性と高い近赤外線カット性能が両 立した透光性電磁波シールドフィルムを提供することである。  Furthermore, another object of the present invention is to provide a translucent electromagnetic wave shielding film having both high electromagnetic wave shielding properties and high near-infrared cut performance.
また、本発明のさらなる目的は、高い電磁波シールド性と高い近赤外線カット性能 を有する光学フィルターおよびプラズマディスプレイを提供することである。  Another object of the present invention is to provide an optical filter and a plasma display having high electromagnetic shielding properties and high near infrared cut performance.
課題を解決するための手段 Means for solving the problem
上記課題は、以下の発明により解決された。  The above problems have been solved by the following invention.
すなわち、本発明は、支持体と、 That is, the present invention comprises a support,
前記支持体の一方の面上に設けられ、銀塩を含有する銀塩乳剤層と、  A silver salt emulsion layer provided on one side of the support and containing a silver salt;
前記支持体の他方面上に設けられ、合成樹脂及び導電性粒子を含有する易接着 層と、  An easy-adhesion layer provided on the other surface of the support and containing a synthetic resin and conductive particles;
を有することを特徴とするハロゲンィ匕銀感光材料。 A halogenated silver photographic material characterized by comprising:
上記ハロゲン化銀感光材料においては、前記合成樹脂が、アクリル榭脂、ポリエス テル榭脂、ポリウレタン榭脂およびスチレンブタジエンゴム力もなる群力も選択される 少なくとも 1種であることが好ましぐアクリル榭脂であることがより好ましい。  In the above-mentioned silver halide photosensitive material, it is preferable that the synthetic resin is at least one selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin and a styrene butadiene rubber. It is more preferable that
また、前記導電性粒子が、金属酸化物を含むことが好ましぐ ZnO、 TiO、 SnO、  In addition, it is preferable that the conductive particles include a metal oxide ZnO, TiO, SnO,
2 2 twenty two
Al O、 In O、 MgO、 BaO及び MoOの少なくとも 1種であることがより好ましぐァMore preferably, it is at least one of Al O, In O, MgO, BaO and MoO.
2 3 2 3 3 2 3 2 3 3
ンチモンがドープされた SnOを含むことがさらに好ましい。 More preferably, it contains SnO doped with ntimone.
2  2
前記導電性粒子が針状粒子であり、その短軸に対する長軸の比が 3〜50の範囲 にあることが好ましい。このような形状にすることで、導電性粒子が易接着層で十分に 分散する。  The conductive particles are preferably acicular particles, and the ratio of the major axis to the minor axis is preferably in the range of 3-50. By adopting such a shape, the conductive particles are sufficiently dispersed in the easy adhesion layer.
また、（1— 1)前記銀塩乳剤層の膨潤率が 150%以上であること、（1— 2)前記支 持体が透明支持フィルムであること、（1— 3)前記銀塩乳剤層は、 Ag及びバインダー を含有し、 AgZバインダー体積比が 1Z4以上であること、（1—4)前記銀塩乳剤層 が最外層にあること、の態様をさらに満たすことが好ましい。また、導電性粒子の含有 量を合成樹脂 (例えば、アクリル榭脂) 30質量部を基準とした場合には、導電性粒子 の含有量は、 10〜500質量部が好ましぐ 50〜150質量部がさらに好ましい。 また、本発明のハロゲンィヒ銀感光材料は、支持体と、 (1-1) The silver salt emulsion layer has a swelling ratio of 150% or more, (1-2) (1-3) the silver salt emulsion layer contains Ag and a binder, and the AgZ binder volume ratio is 1Z4 or more, (1-4) the silver salt emulsion layer Is preferably in the outermost layer. Further, when the content of the conductive particles is based on 30 parts by mass of a synthetic resin (for example, acrylic resin), the content of the conductive particles is preferably 10 to 500 parts by mass, and preferably 50 to 150 parts by mass. Part is more preferable. The silver halide silver photographic material of the present invention comprises a support,
前記支持体の一方の面上に設けられ、銀塩を含有する銀塩乳剤層と、 前記支持体の他方面上に設けられ、合成樹脂を含有する易接着層と、 を有する形態としてもよい。なお、この形態の場合には、合成樹脂は他方面上の最表 面に設けられていることが好ましい。写真用途の感光材料では、易接着層のバインダ 一としてゼラチンが使用されていた。しかし、ゼラチンを使用した場合には、導電性金 属膜を製造し、さらに加工しょうとすると、他の部材との接着強度が不十分であった。 これに対して、ゼラチンに代えて合成樹脂 (特に、アクリル榭脂）を使用した場合には 、十分な接着強度が得られた。なお、本発明においては、前記支持体の他方面上に 設けられ、合成樹脂及び導電性粒子を含有する第一の易接着層を形成し、さらに合 成榭脂を含有する第二の易接着層を形成してもよい。この場合には、導電粒子が易 接着層の外部に析出することを防止することができる。  A silver salt emulsion layer containing a silver salt provided on one surface of the support, and an easy-adhesion layer containing a synthetic resin provided on the other surface of the support may be provided. . In the case of this embodiment, the synthetic resin is preferably provided on the outermost surface on the other surface. In photographic materials for photographic use, gelatin was used as the binder for the easy adhesion layer. However, when gelatin was used, when an electrically conductive metal film was manufactured and further processed, the adhesive strength with other members was insufficient. On the other hand, when a synthetic resin (particularly acrylic resin) was used instead of gelatin, sufficient adhesive strength was obtained. In the present invention, a second easy-adhesion layer is provided on the other surface of the support to form a first easy-adhesion layer containing a synthetic resin and conductive particles, and further contains a synthetic resin. A layer may be formed. In this case, it is possible to prevent the conductive particles from being deposited outside the easily adhesive layer.
さらに、本発明は、前記ハロゲンィ匕銀感光材料を用いて製造されたことを特徴とす る導電性金属膜、電磁波シールドフィルム、プラズマディスプレイパネル用光学フィ ルター、又は、プラズマディスプレイパネルにもある。  Furthermore, the present invention also resides in a conductive metal film, an electromagnetic wave shielding film, an optical filter for a plasma display panel, or a plasma display panel, which is characterized by being manufactured using the above-described halogen-molybdenum photosensitive material.
またさらに、本発明は、前記ハロゲンィ匕銀感光材料の前記銀塩乳剤層に対し、露 光して現像処理を施し、現像処理工程と、  Furthermore, the present invention provides a development process by exposing the silver salt emulsion layer of the silver halide silver photographic material to an exposure process.
更に物理現像処理及び Zまたはめつき処理を施して導電性金属部を形成し、導電 性金属膜を得る導電性金属部形成工程と、  Further, a conductive metal part forming step of forming a conductive metal part by performing physical development processing and Z or staking treatment to obtain a conductive metal film,
を有することを特徴とする導電性金属膜の製造方法にもある。 There is also a method for producing a conductive metal film characterized by comprising:
以下、本発明の作用効果を説明する。本発明のハロゲンィ匕銀感光材料を用いるこ とで、黒色スポットやメッシュ細線の途切れなどの欠陥が抑制された導電性金属膜が 得られる。導電性金属膜を製造する際に、ハロゲン化銀感光材料に合成樹脂 (特に 、アクリル榭脂)を含有する易接着層が設けられている場合には、かかる易接着層が 帯電し易くなり、製造工程中において静電気が発生すると考えられる。かかる静電気 によって発光が起きると、銀塩乳剤層にかぶりが発生し、そのかぶり部分が製品の黒 色スポットの問題となる。また上記発光の際には多量のエネルギー（例えば、熱）が発 生し、銀塩乳剤層の発光ポイントに対応する部分で空隙 (バインダーが熱により焼失 することで形成すると考えられる）が発生し、導電性金属部 (メッシュなどの細線)の形 成が阻害される。ここで、導電性金属膜の導電性金属部のパターンに抜けが生じると 、電磁波遮蔽が不十分になると考えられる。例えば、導電性金属部をメッシュ状の細 線として形成しょうとした場合には、その細線が形成されない虞がある。より具体的に は、金属導電膜では、黒色スポットと併せて、メッシュ細線の途切れが観察され、これ は、露光部に現像銀が生じていないことを意味している。従って、従来の写真用途の 感光材料で生じるカプリ現象では理解できな ヽ特有の現象が、（従来のカプリと同時 に)併発している。しかしながら、本発明では、易接着層に導電性粒子が含有されて いることで、製造工程中で発生する静電気が過剰に帯電せず、外部に逃げることで、 静電気に起因する発光が抑制され、導電性金属膜の黒色スポットやメッシュ細線の 途切れなどの欠陥が十分に抑制できると推察される。 Hereinafter, the function and effect of the present invention will be described. By using the silver halide silver photographic material of the present invention, a conductive metal film in which defects such as black spots and mesh fine line breaks are suppressed can be obtained. When manufacturing conductive metal films, synthetic resin (especially for silver halide photosensitive materials) In the case where an easy-adhesion layer containing (acrylic resin) is provided, the easy-adhesion layer is likely to be charged, and static electricity is generated during the manufacturing process. When light is emitted due to such static electricity, fog occurs in the silver salt emulsion layer, and the fog becomes a problem of black spots on the product. In addition, a large amount of energy (for example, heat) is generated during the light emission described above, and voids (which are thought to be formed when the binder burns out due to heat) are generated in the portion corresponding to the light emission point of the silver salt emulsion layer. In addition, the formation of conductive metal parts (fine wires such as mesh) is hindered. Here, when the pattern of the conductive metal part of the conductive metal film is missing, it is considered that the electromagnetic wave shielding becomes insufficient. For example, when an attempt is made to form the conductive metal portion as a mesh-like thin line, the fine line may not be formed. More specifically, in the metal conductive film, the discontinuity of the fine mesh line is observed together with the black spot, which means that developed silver is not generated in the exposed area. Therefore, a phenomenon peculiar to ヽ that cannot be understood from the capri phenomenon that occurs in conventional photosensitive materials for photographic use occurs simultaneously (concurrently with conventional capri). However, in the present invention, since the easily adhesive layer contains conductive particles, static electricity generated during the manufacturing process is not excessively charged and escapes to the outside, thereby suppressing light emission due to static electricity, It is assumed that defects such as black spots on conductive metal films and breaks in fine mesh wires can be sufficiently suppressed.
また、本発明は、以下の形態としてもよい。  Moreover, the present invention may be in the following forms.
2— 1)支持体の一方の側に設けられた銀塩乳剤層に露光と現像処理を施すことに より導電性金属膜を得るハロゲンィ匕銀感光材料であって、前記銀塩乳剤層と支持体 をはさんで反対側の最表面に合成樹脂からなる易接着層を設けたことを特徴とする ハロゲン化銀感光材料。  2-1) Halogenated silver photosensitive material for obtaining a conductive metal film by exposing and developing a silver salt emulsion layer provided on one side of a support, the silver salt emulsion layer and the support A silver halide light-sensitive material characterized in that an easy-adhesion layer made of a synthetic resin is provided on the outermost surface opposite to the body.
2— 2)前記易接着層が、アクリル榭脂、ポリエステル榭脂、ポリウレタン榭脂および スチレンブタジエンゴム力 なる群力 選択された少なくとも 1種を含有することを特 徴とする上記 2— 1)に記載のハロゲンィ匕銀感光材料。  2-2) The above-mentioned 2-1) characterized in that the easy-adhesion layer contains at least one selected from the group strength of acrylic resin, polyester resin, polyurethane resin, and styrene butadiene rubber. The halogenated silver photographic material described.
2— 3)前記易接着層が、アクリル榭脂からなることを特徴とする上記 2— 2)に記載 のハロゲンィ匕銀感光材料。  2-3) The silver halide silver photographic material according to the above 2-2), wherein the easy-adhesion layer is made of acrylic resin.
2-4)前記易接着層が、導電性金属酸化物粒子を含有することを特徴とする上記 2- 1)〜3)のいずれかに記載のハロゲン化銀感光材料。 2— 5)前記導電性金属酸ィ匕物粒子が針状粒子であり、その短軸に対する長軸の 比が 3〜50の範囲にあることを特徴とする上記 2—4)に記載のハロゲンィ匕銀感光材 料。 2-4) The silver halide photosensitive material as described in any one of 2-1) to 3) above, wherein the easy-adhesion layer contains conductive metal oxide particles. 2-5) The halogen oxide according to the above 2-4), wherein the conductive metal oxide particles are acicular particles, and the ratio of the major axis to the minor axis is in the range of 3 to 50. A silver-sensitive material.
2— 6)前記導電性金属酸化物粒子が、アンチモンがドープされた SnO粒子である  2-6) The conductive metal oxide particles are SnO particles doped with antimony
2 ことを特徴とする上記 2—4)または 5)に記載のハロゲンィ匕銀感光材料。  2) A halogenated silver photographic material as described in 2-4) or 5) above.
2— 7)前記銀塩乳剤層の膨潤率が 150%以上であることを特徴とする上記 2—1) 2-7) The above 2-1) characterized in that the silver salt emulsion layer has a swelling ratio of 150% or more.
〜6)の!、ずれかに記載のハロゲン化銀感光材料。 ~ 6) !, The silver halide light-sensitive material described in any one of the above.
2-8)上記 2— 1)〜7)のいずれかに記載のハロゲンィ匕銀感光材料を用いて形成 されたことを特徴とする導電性金属膜。  2-8) A conductive metal film formed using the halogenated silver photographic material according to any one of 2-1) to 7) above.
2— 9)前記銀塩乳剤層を露光して現像処理を施した後、更に物理現像処理及び 2-9) After the silver salt emulsion layer is exposed and developed, further physical development and
Zまたはめつき処理を施して形成されたことを特徴とする上記 2— 8)に記載の導電性 金属膜。 The conductive metal film as described in 2-8) above, wherein the conductive metal film is formed by applying Z or a mating treatment.
2— 10)上記 2— 9)に記載の導電性金属膜がプラスチックフィルム支持体に担持さ れていることを特徴とする透光性電磁波シールドフィルム。  2-10) A translucent electromagnetic wave shielding film, wherein the conductive metal film described in 2-9) is supported on a plastic film support.
2- 11)前記導電性金属膜が線幅 1 μ mから 40 μ mのメッシュ状の細線力 形成さ れ、かつ前記メッシュ状の細線力 透光性電磁波シールドフィルムの長手方向に 3m 以上連続していることを特徴とする上記 2— 10)に記載の透光性電磁波シールドフィ ノレム。  2- 11) The conductive metal film is formed with a mesh-like fine line force having a line width of 1 μm to 40 μm, and is continuous for 3 m or more in the longitudinal direction of the mesh-like fine line force translucent electromagnetic wave shielding film. The translucent electromagnetic wave shield final described in 2-10) above.
2- 14)上記 2— 10)〜13)のいずれかに記載の透光性電磁波シールドフィルムを 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。  2-14) An optical filter for a plasma display panel, comprising the translucent electromagnetic wave shielding film according to any one of 2-10) to 13) above.
2- 15)上記 2— 10)〜 13)のいずれかに記載の透光性電磁波シールドフィルム 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。  2- 15) A plasma display panel comprising the translucent electromagnetic wave shielding film according to any one of 2-10) to 13) above.
発明の効果 The invention's effect
本発明によれば、優れた生産性、低コスト性を有し、カプリやメッシュ細線の途切れ などの欠陥が発生しな ヽ、ハロゲン化銀感光材料およびこれを用いて形成された導 電性金属膜を提供することができる。  According to the present invention, a silver halide photosensitive material and a conductive metal formed using the silver halide light-sensitive material have excellent productivity and low cost without occurrence of defects such as discontinuity of capri and fine mesh wires. A membrane can be provided.
また本発明によれば、シールド材料のロスが少なく生産性を向上させ、安価に大量 に、連続メッシュパターンを形成した透光性電磁波シールド膜を提供することができ る。 Further, according to the present invention, it is possible to provide a translucent electromagnetic wave shielding film in which a continuous mesh pattern is formed in a large amount at a low cost by improving productivity with little loss of shielding material. The
また、感光材料から得られる電磁波シールドフィルムのガラス基材などへの接着性 ( 剥離強度）に優れた電磁波シールドフィルムを提供することができる。  Moreover, the electromagnetic wave shielding film excellent in the adhesiveness (peeling strength) to the glass substrate etc. of the electromagnetic wave shielding film obtained from a photosensitive material can be provided.
さらにまた、感光材料を現像して得られる導電性膜上の未露光部に現像銀が実質 的に形成しない、即ちカプリを生じることのない、易接着層を有する感光材料、及び、 電磁波シールドフィルムを提供することができる。  Furthermore, a photosensitive material having an easy-adhesion layer in which developed silver is not substantially formed in an unexposed portion on a conductive film obtained by developing the photosensitive material, that is, no capri is formed, and an electromagnetic wave shielding film Can be provided.
カロえて、高 ヽ電磁波シールド性と高 、近赤外線カット性能が両立した透光性電磁 波シールド膜を提供することができ、高 ヽ電磁波シールド性と高 ヽ近赤外線カット性 能を有する光学フィルターおよびプラズマディスプレイを提供することができる。  It is possible to provide a translucent electromagnetic wave shielding film having both high electromagnetic shielding properties and high near infrared cut performance, and an optical filter having high electromagnetic shielding properties and high near infrared cut performance and A plasma display can be provided.
図面の簡単な説明  Brief Description of Drawings
[0019] [図 1]本発明の電解めつき処理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。  FIG. 1 is a schematic diagram showing an example of an electrolytic plating bath suitably used for the electrolytic plating process of the present invention.
[図 2]本発明の導電性金属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 metal film of the present invention.
符号の説明  Explanation of symbols
[0020] 10 電解めつき槽 [0020] 10 Electrolytic bath
11 めっき浴  11 Plating bath
12a, 12b 給電ローラ  12a, 12b Feed roller
13 アノード板  13 Anode plate
14 ガイドローラー  14 Guide roller
15 めっき液  15 Plating solution
16 フィルム  16 films
17 液切ローラー  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 27 電解めつき処理部 26 Electrolytic plating section 27 Electrolytic plating section
28 ノ、ロゲンィ匕銀乳剤層  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
[0021] 以下に、本発明をさらに詳細に説明する。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。 [0021] Hereinafter, the present invention will be described in more detail. In the present specification, “to” is used as a meaning including numerical values described before and after as a lower limit value and an upper limit value.
また、本明細書で、「連続メッシュパターン」等における「メッシュ」とは、当業界の用 例にしたがって複数の細線力 なる網目パターンまたは複数の細線力 なる網を指 す。さらに「連続」の意味は、ロール状などの長尺フィルムを指し、かつ、メッシュパタ ーンが途切れずに連続して 、ることを意味する。  Further, in this specification, “mesh” in “continuous mesh pattern” or the like refers to a mesh pattern having a plurality of fine line forces or a net having a plurality of fine line forces according to an example in the art. Furthermore, “continuous” means a long film such as a roll, and means that the mesh pattern is continuous without interruption.
また、「導電性金属膜 (電磁波シールド膜)」はフィルム状の透明支持体に担持され ているので、積層される他の構成要素 (構成フィルム）との混乱がない限り「電磁波シ 一ルドフィルム」又は単に「フィルム」と呼ぶこともある。  In addition, since the “conductive metal film (electromagnetic wave shielding film)” is carried on a film-like transparent support, the “electromagnetic wave shielding film” is used unless there is any confusion with other components (component film) to be laminated. Or simply “film”.
[0022] (1)感光材料 [0022] (1) Photosensitive material
(1 1)支持体  (1 1) Support
本発明に用いられる感光材料の支持体としては、透明支持フィルムを用いることが 好ましぐ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 for the light-sensitive material used in the present invention, it is possible to use a plastic film, a plastic plate, a glass plate, or the like, which is preferably a transparent support film.
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又はトリァセチルセルロース（ TAC)であることが好まし!/ヽ。  In the present invention, the plastic film is preferably a polyethylene terephthalate film or triacetyl cellulose (TAC) from the viewpoints of transparency, heat resistance, ease of handling and cost!
[0023] ディスプレイ用の電磁波シールド膜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。 [0023] Since the electromagnetic shielding film for a display requires transparency, the support is transparent. It is desirable that the sex is high. 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.
[0024] (1 2)保護層 [0024] (1 2) Protective layer
用いられる感光材料は、後述する銀塩乳剤層（以下、単に乳剤層ということもある） 上に保護層を設けていてもよい。本発明において「保護層」とは、ゼラチンや高分子 材料などのバインダー力 なる層を意味し、擦り傷防止や力学特性を改良する効果 を発現するために乳剤層上に形成される。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. 以下が好 ましい。上記保護層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 ることがでさる。  The light-sensitive material used may be provided with a protective layer on a silver salt emulsion layer (hereinafter sometimes simply referred to as an emulsion layer) described later. In the present invention, the “protective layer” means a layer having a binder force such as gelatin or a polymer material, and is formed on the emulsion layer in order to exhibit the effect of preventing scratches and improving mechanical properties. Although it is preferable not to provide the protective layer when performing the fitting process, it is preferable that the protective layer is thin. Its thickness is preferably less than 0. The method for forming the protective layer is not particularly limited, and a known coating method can be appropriately selected.
[0025] (1 3)乳剤層 [0025] (1 3) Emulsion layer
本発明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乳剤層を有 する。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 present invention has a silver salt emulsion layer as a photosensor on a support. The emulsion layer in the present invention may contain a dye, a binder, a solvent and the like as required in addition to the silver salt.
<染料 >  <Dye>
乳剤層には染料が含まれていてもよい。該染料は、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 17 9243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。 [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 に脱色する固体微粒子分散状の染料として、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ニ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い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 5913 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。 The emulsion layer may contain a dye. 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 17 9243. Specifically, compounds F1 to F34 described in the publication are preferable. Further, (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. (IV-2) to (IV-7) described in the publication are also preferably used. [0026] In addition, as dyes that can be used in the present invention, cyanine dyes and pyrylium dyes described in JP-A-3-138640 can be used as dyes in the form of solid fine particles that are decolored during development or fixing. And Aminium dyes. Further, as dyes that do not decolorize during processing, cyanine dyes having a carboxyl group described in JP-A-9-96891, cyanine dyes not containing an acid group described in JP-A-8-245902, and JP-A-8-333519 Lake type cyanine dyes, cyanine dyes described in JP-A-1-266536, horopora-type cyanine dyes described in JP-A-3-136038, pyrylium dyes described in JP-A-62-299959, JP-A-7-253639 Polymer-type cyanine dyes described in JP-A No. 2-282244, solid fine particle dispersions of oxonol dyes described in JP-A-2-282244, light-scattering particles described in JP-A-63-131135, Yb3 described in JP-A-9 5913 + Compounds and ITO powders described in JP-A-7-113072 and the like.
[0027] また、上記染料としては、水溶性染料を含有することもできる。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] Further, 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。塩臭化銀、沃塩臭化銀、沃臭化銀もまた好ましく用 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. Silver chlorobromide, silver iodochlorobromide and silver iodobromide are also preferably used. Silver chlorobromide, silver bromide, silver iodochlorobromide and silver iodobromide are more preferable, and silver chlorobromide and iodochlorobromide containing 50 mol% or more of silver chloride are most preferable. Silver is 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、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の 金属銀部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] Silver halide is a solid grain, and from the viewpoint of image quality of a patterned metallic silver portion formed after exposure and development processing, the average grain size of silver halide silver is equivalent to a sphere. 0.1 to 1000 ηπι (1 / ζ πι) is preferable 0.1 to 100 nm is more preferable, and 1 to 50 nm is more preferable.
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 Montel 社刊、 1967年）、 G . F. Dufin 著 Photographic Emulsion Chemistry (The Forcal Press 刊、 1966年；)、 V. L. Zelikman et al著 Making and Coating Photograp hie Emulsion (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, written by P. Glafkides, Chimie etPhysique Photographique (Paul Montel, 1967), G. F. Dufin. Press, 1966;), VL Zelikman et al, Making and Coating Photograb hie Emulsion (The ForcalPress, 1964).
[0036] すなわち、上記ハロゲンィ匕銀乳剤の調製方法としては、酸性法、中性法等の!/、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。  [0036] That is, as a method for preparing the above-mentioned halogenated silver emulsion, an acidic method, a neutral method, or the like can be used. Alternatively, a method of reacting a soluble silver salt with a soluble halogen salt can be performed on one side. Any of a mixing method, a simultaneous mixing method, or a combination thereof 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号などの各公報に記載され ている。好ましいチォ尿素化合物として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などが挙げられる。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 モノレあたり 10— 5〜： L0— 2モノレが好まし!/、。 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 tetra-substituted thiourea compound, which is described in JP-A Nos. 53-82408 and 55-77737. Preferred thiourea compounds include tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. Type and particle size of interest of Harogeni匕銀amount of the solvent used compounds, different forces Harogeni匕銀per Monore 10- 5 ~ by halogen composition:! L0- 2 Monore is preferably /,.
[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号公報、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 、て速く 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, Japanese Patent Publication Nos. 48-36890 and 52-16364, silver nitrate and 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 fast 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、周期律表の VIII族、 VIIB族に属する金 属元素を含有してもよい。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 ゥム化合物、イリジウム化合物、ルテニウム化合物、鉄化合物、オスミウム化合物など 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の擬ハロゲンリガンド、アンモニアのほか 、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、チアゾ 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 halogen silver halide emulsion used in the present invention may contain a metal element belonging to Group VIII or VIIB of the periodic table. In particular, in order to achieve high contrast and low capri, it is preferable to contain rhodium compounds, iridium compounds, ruthenium compounds, iron compounds, osmium compounds and the like. These compounds are compounds having various ligands, and examples of such ligands include pseudohalogen ligands such as cyanide ions, cyanogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions, In addition to ammonia, organic molecules such as amines (methylamine, ethylenediamine, etc.), heterocyclic compounds (imidazole, thiazole, 5-methylthiazole, mercaptoimidazole, etc.), urea, and thiourea can be mentioned.
また、高感度化のためには K [Fe (CN) ) ^>K [Ru (CN)〕 K〔Cr  In addition, K [Fe (CN)) ^> K [Ru (CN)] K [Cr
4 6 4 6、 3  4 6 4 6, 3
(CN)〕のごとき六シァノ化金属錯体のドープが有利に行われる。  Doping of a metal hexasyanide complex such as (CN)] is advantageously performed.
6  6
[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、トリザラトロジウム（III)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, trizalatrdium (III) complex salt, K Rh Br and the like.
3 2 9  3 2 9
これらのロジウム化合物は、水或いは適当な溶媒に溶解して用いられるが、ロジゥ ム化合物の溶液を安定ィ匕させるために一般によく行われる方法、すなわち、ハロゲン 化水素水溶液 (例えば塩酸、臭酸、フッ酸等）、或いはハロゲンィ匕アルカリ（例えば κ These rhodium compounds are used by dissolving in water or a suitable solvent, but are generally used in order to stabilize the solution of the rhodium compound, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, odorous acid, Hydrofluoric acid, etc.) or halogenated alkali (eg κ
Cl、 NaCl、 KBr、 NaBr等）を添加する方法を用いることができる。水溶性ロジウムを 用いる代わりにハロゲンィ匕銀調製時に、あら力じめロジウムをドープしてある別のハロ ゲンィ匕銀粒子を添加して溶解させることも可能である。 [0041] 上記イリジウム化合物としては、 K IrCl、 K IrCl等のへキサクロ口イリジウム錯塩、 Cl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add other halogen silver particles doped with rhodium and dissolve it at the time of preparing the silver halide silver. [0041] Examples of the iridium compound include Hexaclo oral iridium complex salts such as K IrCl and K IrCl,
2 6 3 6  2 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 compound include potassium hexanoate (π) and ferrous thiocyanate.
[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 溶性錯塩の形で添加され、特に好ましいものとして、以下の式で示される六配位錯 体が挙げられる。  [0042] The ruthenium compound and the osmium compound are in the form of 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. Particularly preferred is a hexacoordination complex represented by the following formula.
〔ML〕— n [ML] — n
6  6
(ここで、 Mは Ru、または Osを表し、 nは 0、 1、 2、 3または 4を表す。 )  (Here, M represents Ru or Os, and n represents 0, 1, 2, 3 or 4.)
この場合、対イオンは重要性を持たず、例えば、アンモ-ゥム若しくはアルカリ金属 イオンが用いられる。また好ましい配位子としてはハロゲン化物配位子、シアン化物 配位子、シアン酸化物配位子、ニトロシル配位子、チォニトロシル配位子等が挙げら れる。以下に本発明に用いられる具体的錯体の例を示すが、本発明はこれに限定さ れるものではない。  In this case, the counter ion has no significance, and for example, ammonium or alkali metal ions are used. Preferable ligands include a halide ligand, a cyanide ligand, a cyan oxide ligand, a nitrosyl ligand, a thionitrosyl ligand, and the like. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.
[0043] 〔RuCl〕— 3、 [RuCl (Η Ο) Υ [RuCl (NO) ]"2, [RuBr (NS)〕— 2、 [Ru (CO) CI ] [0043] [RuCl] — 3 , [RuCl (Η Ο) Υ [RuCl (NO)] ” 2 , [RuBr (NS)] — 2 , [Ru (CO) CI]
6 4 2 2 5 5 3 3 6 4 2 2 5 5 3 3
—2、〔Ru (CO) Cl〕— 2、〔Ru (CO) Br〕— 2、〔OsCl〕— 3、 [OsCl (NO) ]"2, [Os (NO) (C - 2, [Ru (CO) Cl] - 2, [Ru (CO) Br] - 2, [OsCl] - 3, [OsCl (NO) ] "2, [Os (NO) (C
5 5 6 5  5 5 6 5
N) Y 〔Os (NS) Br〕— 2、 [Os (CN)〕— 4、〔Os (0) (CN)〕— 4。 N) Y [Os (NS) Br] - 2, [Os (CN)] - 4, [Os (0) (CN)] - 4.
5 5 6 2 5  5 5 6 2 5
[0044] これらの化合物の添加量はハロゲン化銀 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 Zモル Agであることがさらに好ましい。 It L0- is 3 mol Z mole Ag: [0044] These addition amount of the compound preferably be a silver halide per mole of 10-omega to 10-2 mol Z mol Ag tool 10 9 - Further preferred.
[0045] その他、本発明では、 Pd (II)イオンおよび Zまたは Pd元素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。 [0045] In addition, in the present invention, silver halides containing Pd (II) ions and Z or Pd elements 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. Mean to have a layer Taste.
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. .
[0046] 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 Zまたは Pd金属元素の 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/モル Agであるこ と力 子ましく、 0. 01-0. 3モル Zモル Agであることがさらに好ましい。 [0046] Contact with the present invention, Te, content of Pd ions and Z or Pd metal element contained in Harogeni匕銀is 10- 4-0 of silver halide, with respect to the number of moles of silver. 5 mol / More preferably, it is mol Ag, more preferably 0.01 to 0.3 mol Z mol Ag.
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
[0047] 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 ルル増感等のカルコゲン増感、金増感などの貴金属増感、及び還元増感等を用い 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 also be performed in order to further improve sensitivity as an optical sensor. As chemical sensitization methods, sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, noble metal sensitization such as gold sensitization, reduction sensitization and the like can be used. These are used alone or in combination. When a combination of the above chemical sensitization methods is used, for example, sulfur sensitization method and gold sensitization method, sulfur sensitization method and selenium sensitization method and gold sensitization method, sulfur sensitization method and tellurium sensitization method. A combination of a sensitizing method and a gold sensitizing method is preferable.
[0048] 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〜 10 モノレである。 [0048] The above 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 Mole is more preferred 1 0 to 10 mono.
[0049] 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。すなわち、上記セレン増感は、通常、不安定型および Zまたは非不安 定型セレンィ匕合物を添加して 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。上記不安定型セレンィ匕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。特に特開平 4— 324855号公報中の一般式 (VIII)および (IX)で示される化合物を用いることが好ま 、。  [0049] As the selenium sensitizer used for the selenium sensitization, known selenium compounds can be used. That is, the selenium sensitization is usually performed by adding unstable and Z or non-unstable selenium compounds and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. 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. . In particular, it is preferable to use compounds represented by the general formulas (VIII) and (IX) in JP-A-4-324855.
[0050] 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。ハロゲン 化銀乳剤中のテルルイ匕銀生成速度については特開平 5— 313284号公報に記載の 方法で試験することができる。具体的には、米国特許 US第 1, 623, 499号明細書、 同第 3, 320, 069号明細書、同第 3, 772, 031号明細書、英国特許第 235, 211 号明細書、同第 1, 121, 496号明細書、同第 1, 295, 462号明細書、同第 1, 396 , 696号明細書、カナダ特許第 800, 958号明細書、特開平 4 204640号公報、 同 4— 271341号公報、同 4— 333043号公報、同 5— 303157号公報、ジャーナル •ォブ ·ケミカル ·ソサイァティ^ ~ ·ケミカル 'コミュニケーション（J.Chem.So Chem.Com mun.) 635頁（1980)、同 1102頁（1979)、同 645頁（1979)、ジャーナル ·ォブ ·ケミ カル.ソサイァティ一.パーキン.トランザクション (J.Chem.So Perkin.Trans.) 1卷， 21 91頁（1980)、 S.パタイ（S. Patai)編、ザ'ケミストリ一'ォブ 'オーガニック'セレニゥ ム'アンド'テルリウム 'カンパウンズ（The Chemistry of Organic Selenium and Telluniu m Compounds)、 1卷（1986)、同 2卷（1987)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 (IIKIIIXIV)で示される化合物が好まし い。 [0050] 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 the silver halide silver grains. The formation rate of tellurite silver in the silver halide emulsion can be tested by the method described in JP-A-5-313284. Specifically, U.S. Pat.Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211, No. 1,121,496, No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,958, JP-A-4 204640, 4-271341, 4-333043, and 5-303157, Journal • Chemical Society ^ ~ Chemical 'Communication (J.Chem.So Chem.Com mun.) Page 635 ( 1980), 1102 (1979), 645 (1979), Journal of Chemical Society, Perkin Transaction (J. Chem. So Perkin. Trans.) 1, 21 91 (1980) ), S. Patai, The Chemistry of Organic Selenium and Tellunium Compounds, 1 卷 (1986), ibid. 2) (1987) can be used. In particular, a compound represented by the general formula (IIKIIIXIV) in JP-A-5-313284 is preferred.
[0051] 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。 [0051] 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 chemical sensitization conditions in the present invention are not particularly limited, but the pH is 5 to 8, and the pAg is 6 to 11. The temperature is preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 85 ° C.
[0052] 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。 [0052] Examples of the noble metal sensitizer include gold, platinum, noradium, iridium and the like, and 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.
[0053] 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号明細書に示される 方法により、チォスルホン酸化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 均粒子サイズの異なるもの、ハロゲン糸且成の異なるもの、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 、ほど高感度な乳剤を塗布することが好ま U、。  [0053] 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 Patent Publication (EP) 293917. The silver halide emulsion used in the production 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 yarn compositions, crystal habits). Different types, those with different chemical sensitization conditions, and those with different sensitivities) may be used in combination. In particular, in order to obtain a high contrast, it is preferable to apply an emulsion having a high sensitivity close to the support as described in JP-A-6-324426.
[0054] <バインダー >  [0054] <Binder>
乳剤層には、銀塩粒子を均一に分散させ、かつ乳剤層と支持体との密着を補助す る目的でバインダーを用いることができる。本発明におい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いずれもバインダーとして用いることがで きるが、水溶性ポリマーを用いることが好ましい。  A binder can be used in the emulsion layer for the purpose of uniformly dispersing silver salt grains and assisting the adhesion between the emulsion layer and the support. In the present invention, both the water-insoluble polymer and the water-soluble polymer can be used as the binder, but it is preferable to use 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.
[0055] 乳剤層中に含有されるバインダーの含有量は、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。なお、銀塩含有層中のバインダーの 含有量は、 AgZバインダー体積比で 1Z4〜： LOO (Zl)であることが好ましぐ 1/3 〜10 (Zl)であることがより好ましぐ 1Z2〜2(Z1)であることがさらに好ましい。 1 Zl〜2 (Zl)であることが最も好ましい。銀塩含有層中にバインダーを AgZバイン ダー体積比で高 ヽ銀比率を有すれば、物理現像及び Z又はメツキ処理工程にぉ ヽ て金属粒子同士が互いに接触しやすぐ高い導電性を得ることが容易である、また、 導電性にムラを生じにくい点で好ま U、。 [0055] The content of the binder contained in the emulsion layer is not particularly limited. Dispersibility and adhesion Can be appropriately determined within a range in which can be exhibited. The content of the binder in the silver salt-containing layer is preferably 1Z4 to LOO (Zl) in terms of AgZ binder volume ratio, more preferably 1/3 to 10 (Zl). More preferably, it is ˜2 (Z1). Most preferably, it is 1 Zl to 2 (Zl). If the silver salt-containing layer has a high silver ratio in the volume ratio of AgZ binder, the metal particles can be brought into contact with each other during physical development and Z or plating process to obtain high conductivity. U, which is easy to use and less likely to cause uneven conductivity.
[0056] <溶媒 > [0056] <Solvent>
上記乳剤層の形成に用いられる溶媒は、特に限定されるものではないが、例えば、 水、有機溶媒 (例えば、メタノール等アルコール類、アセトンなどケトン類、ホルムアミ ドなどのアミド類、ジメチルスルホキシドなどのスルホキシド類、酢酸ェチルなどのエス テル類、エーテル類等）、およびこれらの混合溶媒を挙げることができる。  The solvent used for forming the emulsion layer is not particularly limited, and examples thereof include water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, dimethyl sulfoxide, and the like. Examples thereof include sulfoxides, esters such as ethyl acetate, ethers, and the like, and mixed solvents thereof.
本発明の乳剤層に用いられる溶媒の含有量は、前記乳剤層に含まれる銀塩、バイ ンダ一等の合計の質量に対して 30〜90質量％の範囲であり、 50〜80質量％の範 囲であることが好ましい。  The content of the solvent used in the emulsion layer of the present invention is in the range of 30 to 90% by mass with respect to the total mass of silver salt and binder contained in the emulsion layer, and 50 to 80% by mass. A range is preferred.
[0057] <硬膜剤> [0057] <Hardener>
本発明に係る感光材料の乳剤層およびその他の親水性コロイド層は、硬膜剤によ つて硬膜されることが好まし 、。  The emulsion layer and other hydrophilic colloid layers of the light-sensitive material according to the present invention are preferably hardened with a hardener.
硬膜剤としては、無機又は有機のゼラチン硬化剤を単独又は組合せて用いること ができる。例えば活性ビュル化合物（1, 3, 5 トリアタリロイル—へキサヒドロ s ト リアジン、ビス（ビュルスルホ -ルメチル）エーテル、 N, N' —メチレンビス一〔 j8— ( ビュルスルホ -ル）プロピオンアミド〕など）活性ハロゲン化合物（2, 4 ジクロル 6 —ヒドロキシ一 s トリァジンなど）、ムコハロゲン酸類（ムコクロル酸など）、 N—力ルバ モイルピリジ -ゥム塩類、ハロアミジ-ゥム塩類（1一（1 クロロー 1 ピリジノメチレン )ピロリジ-ゥム一 2—ナフタレンスルホナートなど）を単独または組合せて用いること 力 sでさる。な力でち、特開日召 53— 41220号、同 53— 57257号、同 59— 162546号 、同 60— 80846号などの各公報に記載の活性ビ-ルイ匕合物および米国特許 3, 32 5, 287号明細書に記載の活性ハロゲンィ匕合物が好ましい。以下にゼラチン硬化剤 の代表的な化合物例を示す。 As the hardener, inorganic or organic gelatin hardeners can be used alone or in combination. For example, active bur compounds such as 1, 3, 5 triatalyloyl-hexahydro s-triazine, bis (bululsulfurylmethyl) ether, N, N'-methylenebis [j8- (bululsulfuryl) propionamide], etc. Compound (2, 4 dichloro 6 -hydroxy monostriazine, etc.), mucohalogen acids (mucochloric acid, etc.), N-strength rubamoyl pyridi-um salt, haloamidi-um salt (1 (1 chloro-1 pyridinomethylene) pyrrolidine - such © beam one 2-naphthalenesulfonate) to leave alone or in combination used that force s. Active belieu compounds and U.S. patents described in JP-A-53-41220, 53-57257, 59-162546, 60-80846, etc. The active halogen compounds described in 32,287 are preferred. Gelatin hardener below Examples of typical compounds are shown below.
[0058] [化 1]  [0058] [Chemical 1]
H一 1
Figure imgf000024_0001
H 1 1
Figure imgf000024_0001
H - 2 H-2
HGCtd _NHCK20H NHCHzOH HGCtd _NHCK 2 0H NHCHzOH
H 一 3 H one 3
CI
Figure imgf000024_0002
CI
Figure imgf000024_0002
H— 4H—4
sNa
Figure imgf000024_0003
sNa
Figure imgf000024_0003
[0059] [化 2] [0059] [Chemical 2]
H - 5 CH2-CHS0ZCH2S02CH = CH2 H-5 CH 2 -CHS0 Z CH 2 S0 2 CH = CH2
H - 6 CH2 = CHS02(CHz)2SOiCH-CHz H-6 CH 2 = CHS0 2 (CH z ) 2 SOiCH-CH z
H一 7 CH2 = CHS02(CHi)4SOiCH = CHz H 1 7 CH 2 = CHS0 2 (CHi) 4 SO i CH = CH z
H一 8
Figure imgf000025_0001
CH2 H 1 8
Figure imgf000025_0001
CH2
H - 9 CH2=CHS02(CH2)2O(CH2)2S02CH = CH2 H-9 CH 2 = CHS0 2 (CH 2 ) 2 O (CH 2 ) 2 S0 2 CH = CH 2
H H
0  0
H - 1 0  H-1 0
CHz = CHS02CH2CHCH2S02CH = CH; CH z = CHS0 2 CH 2 CHCH 2 S0 2 CH = CH ;
H - 1 1 2-CHS0zCH2C0NH H-1 1 2 -CHS0 z CH 2 C0NH
Ί  Ί
CH2-CHS02CHZCOHH CH 2 -CHS0 2 CH Z COHH
H - 1 2 CHSOzCHzCONH H-1 2 CHSOzCHzCONH
(CHZ) (CH Z )
CH2=CHS02CH2C0KH CH 2 = CHS02CH 2 C0KH
H - 1 3
Figure imgf000026_0001
H-1 3
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000026_0002
H - 1 5 、 ®N
Figure imgf000026_0003
H-15, ®N
Figure imgf000026_0003
H - 1 6 CH2 = CH— S02 \ H-1 6 CH 2 = CH— S0 2 \
CH - (CH 2h-^ ^SOa a CH-(CH 2 h- ^ ^ SOa a
CH 2 = CH -S0¾ / 乳剤層の硬膜剤の添加量等を調製することにより、乳剤層の膨潤率を任意にコント ロールすることができる。乳剤層の膨潤率は、 150%以上が好ましぐさらに好ましく は 170〜500%である。乳剤層の膨潤率が 150%以上であることにより、現像銀の導 電性が向上するという効果を奏する。 By preparing CH 2 = CH -S0 amount of hardener of ¾ / emulsion layer or the like, can be arbitrarily control the swelling rate of the emulsion layer. The swelling ratio of the emulsion layer is preferably 150% or more, more preferably 170 to 500%. When the swelling ratio of the emulsion layer is 150% or more, there is an effect that the conductivity of the developed silver is improved.
膨潤率は、乾燥時のサンプル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 凍結乾燥したサンプル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、次式力も算出した値である。  The swelling rate was determined by observing a slice of the dried sample with a scanning electron microscope to obtain the thickness (a) of the emulsion layer at the time of drying. After immersing in 25 ° C distilled water for 1 minute, liquid nitrogen The film thickness (b) of the emulsion layer at the time of swelling was obtained by observing a section of the lyophilized sample with a scanning electron microscope, and the following formula force was also calculated.
膨潤率 (％) = 100 X ( (b)—（a) ) / (a)  Swell rate (%) = 100 X ((b) — (a)) / (a)
乳剤層へ添加する硬膜剤量の好ま 、範囲は、硬膜剤添加後の感光材料の保存 温湿度、保存期間、感光材料の膜 pHおよび感光材料に含まれるバインダー量等に よって異なるため、一概には決まらない。特に硬膜剤はバインダーと反応する前に感 光材料の同一面側に位置する全層にわたつて拡散し得るため、硬膜剤の好ま ヽ添 加量は乳剤層を含む感光材料の同一面側の全バインダー量に依存する。本発明の 感光材料の、好ましい硬膜剤の含有量は、乳剤層を含む感光材料の同一面側の総 バインダー量に対して 0. 2質量％〜15質量％の範囲であり、より好ましくは 0.5質量 %〜6質量％の範囲である。 The preferred amount of hardener added to the emulsion layer depends on the storage temperature and humidity of the photosensitive material after storage, the storage period, the film pH of the photosensitive material, the amount of binder contained in the photosensitive material, etc. It is not decided in general. In particular, since the hardener can diffuse over the entire layer located on the same side of the photosensitive material before reacting with the binder, the preferred addition amount of the hardener is the same side of the photosensitive material including the emulsion layer. Depends on the total binder amount on the side. Of the present invention The preferable hardener content of the light-sensitive material is in the range of 0.2% to 15% by weight, more preferably 0.5% by weight, based on the total amount of binder on the same side of the light-sensitive material including the emulsion layer. It is in the range of ˜6% by mass.
また前述のように硬膜剤は拡散し得るため、硬膜剤の添加位置は乳剤層である必 要は無ぐ乳剤層と同一面側のいずれの層にも好ましく添加でき、また複数の層に分 割して添加することも好ま 、。  Further, as described above, the hardening agent can diffuse, and therefore the hardening agent does not need to be an emulsion layer, and can be preferably added to any layer on the same side as the emulsion layer. It is also preferable to add the ingredients separately.
本発明のハロゲンィ匕銀感光材料にぉ ヽて、前記銀塩乳剤層は最外層にあることが 好ましい。  In the silver halide silver photographic material of the present invention, the silver salt emulsion layer is preferably the outermost layer.
[0062] (2)露光'現像処理 [0062] (2) Exposure 'development processing
(2— 1)露光  (2-1) Exposure
本発明では、支持体上に設けられた乳剤層にパターン形成用、すなわち照射部が パターン状または非照射部がパターン状 (反転)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ょ 、。  In the present invention, the emulsion layer provided on the support is exposed for pattern formation, that is, the irradiated portion is patterned or the non-irradiated portion is patterned (reversed). The 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. In addition, a light source with a wavelength distribution may be used for exposure, or a light source with a specific wavelength may be used.
[0063] 上記光源としては、必要に応じて可視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。  [0063] As the light source, various light emitters that emit light in the visible spectrum region are used as necessary. For example, one or more of a red light emitter, a green light emitter, and a blue light emitter are used in combination. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used. In addition, mercury lamp g-line, mercury lamp i-line, etc., which are also preferred for ultraviolet lamps, are used.
[0064] 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好まし 、。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 体レーザー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 一、 F2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、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より好ましい 。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最も好まし 、。 [0064] In the present invention, exposure is preferably performed using various laser beams. For example, the exposure in the present invention is a second harmonic light source (SHG) that combines a solid-state laser using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a semiconductor laser as an excitation light source and a nonlinear optical crystal. A scanning exposure method using monochromatic high-density light such as) can be preferably used, and a KrF excimer laser, an ArF excimer laser, an F2 laser, or the like can also be used. In order to make the system compact and inexpensive, the exposure is nonlinear with semiconductor laser, semiconductor laser or solid state laser. More preferably, a second harmonic generation light source (SHG) combined with an optical crystal is used. In order to design a device that is particularly compact, inexpensive, long-lived and highly stable, exposure is most preferably performed using a semiconductor laser.
露光のエネルギーとしては、ハロゲンィ匕銀を用いる場合には、照射エネルギー量は lmj/cm2以下が好ましぐ 100 j/cm2以下がより好ましぐ 50 j/cm2以下がさ らに好ましい。 In the case of using halogen silver, the exposure energy is preferably lmj / cm 2 or less, more preferably 100 j / cm 2 or less, and even more preferably 50 j / cm 2 or less. .
[0065] 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  [0065] Specifically, as a laser light source, a blue semiconductor laser with a wavelength of 430 to 460 nm (announced 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.
[0066] 乳剤層をパターン状に露光する方法は、レーザービームによる走査露光が好まし V、。特に特開 2000-39677号公報記載のキヤプスタン方式のレーザー走査露光装置 が好ましく、さらには該キヤブスタン方式にぉ 、てポリゴンミラーの回転によるビーム 走査の代わりに特開 2004-1244号公報記載の DMDを光ビーム走査系に用いることも 好ましい。  [0066] Scanning exposure with a laser beam is preferred as a method for exposing the emulsion layer in a pattern. In particular, the capstan type laser scanning exposure apparatus described in Japanese Patent Application Laid-Open No. 2000-39677 is preferable. In addition, the DMD described in Japanese Patent Application Laid-Open No. 2004-1244 can be used instead of the beam scanning by rotating the polygon mirror. It is also preferable to use it in a light beam scanning system.
[0067] (2— 2)現像処理  [0067] (2-2) Development processing
本発明では、乳剤層を露光した後、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マスク等に 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。現像液については特に限 定はしないが、 PQ現像液、 MQ現像液、 MAA現像液等を用いることもでき、市販品 では、例えば、富士フィルム社処方の CN— 16、 CR— 56、 CP45X、 FD— 3、パピト ール、 KODAK社処方の C—41、 E— 6、 RA—4、 D—19、 D— 72などの各現像液 、またはそれらのキットに含まれる現像液を用いることができる。また、リス現像液を用 いることちでさる。  In the present invention, after the emulsion layer is exposed, further development processing is 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 mask and the like. The developer is not particularly limited, but PQ developer, MQ developer, MAA developer, etc. can also be used, and commercially available products such as CN-16, CR-56, CP45X Each developer such as FD-3, Papitor, KODAK prescription C-41, E-6, RA-4, D-19, D-72, or the developer included in those kits should be used. it can. You can also use lith developer.
リス現像液としては、 KODAK社処方の D85などを用いることができる。本発明で は、上記の露光および現像処理を行うことにより露光部に金属銀部、好ましくはバタ ーン状金属銀部が形成されると共に、未露光部に後述する光透過性部が形成される 金属銀部は本発明にお！ヽては導電性を具備するように形成されるので導電性金属 銀部であり、これと光透過性部とによって透光性電磁波シールド膜が形成される。 As the squirrel developer, D85 prescribed by KODAK can be used. In the present invention, by performing the above exposure and development processing, the exposed portion has a metallic silver portion, preferably a butterfly. A metallic silver portion in which a light-transmitting portion, which will be described later, is formed in an unexposed portion is formed in the present invention while a silver-shaped metallic silver portion is formed! Since it is formed so as to have conductivity, it is a conductive metal silver portion, and a light-transmitting electromagnetic wave shielding film is formed by this and the light-transmitting portion.
[0068] 本発明にお 、ては、上記現像液として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。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、クロロハイドロキ 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、ハイドロキノンモノスルホン酸 塩などが挙げられる力 特にノ、イドロキノンが好ましい。上記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 ビラゾリドン 類や P アミノフヱノール類が挙げられる。本発明の製造方法において用いる現像液 としては、ジヒドロキシベンゼン系現像主薬と 1 フエ-ル一 3 ビラゾリドン類との組 合せ；またはジヒドロキシベンゼン系現像主薬と p -ァミノフエノール類との組合せが 好ましく用いられる。  [0068] In the present invention, a dihydroxybenzene developing agent can be used as the developer. Examples of dihydroxybenzene developing agents include hydroquinone, chlorohydroquinone, isopropyl hydroquinone, methyl hydroquinone, hydroquinone monosulfonic acid salt and the like. Examples of auxiliary developing agents that exhibit superadditivity with the above-mentioned dihydroxybenzene-based developing agents include 1-phenol and 1-3- virazolidones and P-aminophenols. The developer used in the production method of the present invention is preferably a combination of a dihydroxybenzene developing agent and 1-phenol 1-3 azolidone; or a combination of a dihydroxybenzene developing agent and p-aminophenols. It is done.
[0069] 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 組み合わせられる現像主薬としては、具体的に、 1—フエ-ル— 3—ビラゾリドン、 1— フエニル一 4, 4 ジメチル一 3 ピラゾリドン、 1—フエニル一 4—メチル 4 ヒドロキ シメチル一 3—ビラゾリドンなどがある。  [0069] Examples of the developing agent used in combination with 1-phenol 3-virazolidone or a derivative thereof used as an auxiliary developing agent include 1-phenol-3-virazolidone, 1-phenyl-1,4-dimethyl. 1-pyrazolidone, 1-phenyl-4-methyl 4-hydroxymethyl-3-bisazolidone.
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。ジヒドロキシベンゼン系現像主薬は、通常 0. 05〜0. 8モル/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―フエニル 3 ビラゾリドン類若しくは -アミノフ ェ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/リットル、さらに 好ましくは 0. 23〜0. 5モル Zリットル、後者を 0. 06モル Zリットル以下、さらに好ま しく ίま 0. 03モノレ/リットノレ〜 0. 003モノレ/リットノレの量で用! /、るの力好まし!/ヽ。  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. The dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / 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. In the case of using a combination of dihydroxybenzenes and 1-phenyl 3 bisazolidones or -aminophenols, the former is 0.23 to 0.6 mol / liter, more preferably 0.23 to 0.5 mol Z. Liters, the latter is less than 0.06 mol Z liters, more preferred ί 0.03 Monore / Lit Nore ~ 0.03 Monore / Lit Nore for use in amounts!
[0070] 本発明においては、現像開始液および現像補充液の双方力 「該液 1リットルに 0. 1モルの水酸ィ匕ナトリウムをカ卩えたときの pH上昇が 0. 5以下」である性質を有すること が好まし ヽ。使用する現像開始液な ヽし現像補充液がこの性質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いし現像補充液の 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モル添カ卩し、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性質を有すると判定す 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 、。 In the present invention, both forces of the development starter and the development replenisher are set to 0. It is preferable that the pH increase is 0.5 or less when 1 mol of sodium hydroxide is added. To confirm that the development replenisher to be used and the development replenisher have this property, adjust the pH of the development starter or developer replenisher to be tested to 10.5, and then add 1 liter of this solution. Add 0.1 mol of sodium hydroxide to the solution, measure the pH value of the liquid at this time, and determine that it has the properties specified above if the increase in pH value is 0.5 or less. In the production method of the present invention, it is particularly preferable to use a development starting solution and a development replenisher that have an increase in pH value of 0.4 or less when the above test is performed.
[0071] 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 した方法によることが好ましい。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 一ス）、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。  [0071] The method of imparting the above properties to the development initiator and the development replenisher is preferably a method using a buffer. Examples of the buffer include carbonates, boric acid described in JP-A-62-186259, saccharides (for example, saccharose), oximes (for example, 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 buffering agent (particularly carbonate) is preferably 0.25 monolet / litnore or more, 0.25 ~: L5 monole / litnore power is particularly preferred! / ヽ.
[0072] 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。  [0072] In the present invention, it is particularly preferable that the pH of the development start solution 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.
[0073] 本発明にお 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 液の含有量は 323ミリリットル以下、好ましくは 323〜30ミリリットル、特に 225〜50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し、現像 で消費される成分にっ 、て開始液よりも高 、濃度を有して 、てもよ 、。  In the present invention, when processing 1 square meter of the photosensitive material, the content of the developer replenisher in the developer is 323 ml or less, preferably 323 to 30 ml, particularly 225 to 50 ml. . The development replenisher may have the same composition as the development starter, or it may have a higher concentration than the starter due to the components consumed in the development.
[0074] 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 余りに多量添加すると現像液中の 銀汚れの原因になるので、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/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、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 (ナトリウム、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 、。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、モノ kb匕で 0. 03〜0. 12の範囲力好ましく、特に好ましく ίま 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 、ことが好まし 、。 [0074] Additives usually used for the developer used for developing the photosensitive 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. Examples of the preservative include sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. I can get lost. 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 added too much, it causes silver stains in the developer, so the upper limit is 1. 2 mol Z liter is desirable. Particularly preferred is 0.35 to 0.7 mol / 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 includes ascorbic acid, its stereoisomer, erythorbic acid and its alkali metal salts (sodium and potassium salts), and the like. As the above 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, particularly preferably in the range of 0.05 to 0.10, with respect to the dihydroxybenzene-based developing agent. It is. When an ascorbic acid derivative is used as the preservative, it is preferable that the developer does not contain a boron compound.
[0075] 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 -トロベ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 -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—〔 (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 ゥム、 5 アミノー 1, 3, 4 チアジアゾールー 2 チオール、メチルベンゾトリァゾー 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。  [0075] 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. ; Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole or derivatives thereof, mercapto compounds, indazole compounds, benzotriazole compounds, and benzoimidazole compounds are used as anti-capricious agents. Alternatively, it may be included as a black pepper inhibitor. Specific examples of the benzoimidazole compound include 5--troindazole, 5-p-trobenzoylaminoindazole, 1-methyl-5-troindazole, 6-toluindazole, 3-methyl-5--. Troindazole, 5 --- Trobenzimidazole, 2-Isopropyl-5-Trobenzimidazole, 5-Trobenstriazole, 4-[(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. The content of these benzoimidazole compounds is usually from 0.01 to LOmmol, more preferably from 0.1 to 2mmol per liter of developer.
[0076] 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。 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。 Further, various 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. 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、ァシエライン酸、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, ashericin acid, sebacic acid, nonanedicarboxylic acid, decandi-functional norlevonic acid, undecandi-functional norlevonic acid. , Maleic acid, itaconic acid, malic acid, citrate, tartaric acid and the like, but are not limited thereto.
[0077] 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。 [0077] Examples of the aminopolycarboxylic acid include iminoniacetic acid, ditrimethyl triacetic acid, ditrimethyl tripropionic acid, ethylenediamine monohydroxyethyl triacetic acid, ethylenediamintetraacetic 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.
[0078] 有機ホスホン酸としては、米国特許 US第 3214454号、同 3794591号の各明細 書、および西独特許公開 2227639号公報等に記載のヒドロキシアルキリデン—ジホ スホン酸やリサーチ 'ディスクロージャー（Research Disclosure)第 181卷、 Item 18170 (1979年 5月号)等に記載の化合物が挙げられる。  [0078] Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid described in US Pat. Nos. 3214454 and 3794591, and West German Patent Publication 2227639. 181, Item 18170 (May 1979), and the like.
上記アミノホスホン酸としては、アミノトリス (メチレンホスホン酸）、エチレンジアミンテ トラメチレンホスホン酸、アミノトリメチレンホスホン酸等が挙げられる力 その他上記リ サーチ ·ディスクロージャー 18170号、特開昭 57— 208554号、同 54— 61125号、 同 55— 29883号の各公報および同 56 - 97347号公報等に記載の化合物を挙げる ことができる。  Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid and the like. In addition, the above-mentioned Research Disclosure No. 18170, JP-A-57-208554, The compounds described in 54-61125, 55-29883, 56-97347 and the like can be mentioned.
[0079] 有機ホスホノカノレボン酸としては、特開日召 52— 102726号、同 53— 42730号、同 5 4— 121127号、同 55— 4024号、同 55— 4025号、同 55— 126241号、同 55— 65 955号、同 55— 65956号等の各公報、および前述のリサーチ 'ディスクロージャー 1 8170号等に記載の化合物を挙げることができる。これらのキレート剤はアルカリ金属 塩やアンモニゥム塩の形で使用してもよ 、。 [0079] Examples of organic phosphonocanolevonic acids include JP-A 52-102726, 53-42730, 54-121127, 55-4024, 55-4025, 55-126241. Nos. 55-65 955, 55-65956, and the above-mentioned Research Disclosure 1 8170. These chelating agents are alkali metals Can be used in the form of salt or ammonium salt.
[0080] 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 [0080] As is preferably developer per liter添Ka卩量these chelating agents, 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.
[0081] さらに、現像液中に銀汚れ防止剤として、特開昭 56— 24347号、特公昭 56— 465 85号、特公昭 62— 2849号、特開平 4— 362942号の各公報記載の化合物を用い ることができる。また、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。  [0081] Further, compounds described in JP-A-56-24347, JP-B-56-46585, JP-B-62-2849, and JP-A-4-362942 as silver stain preventing agents in the developer. Can be used. Further, compounds described in JP-A-61-267759 can be used as dissolution aids. 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.
[0082] 現像液の搬送コスト、包装材料コスト、省スペース等の目的から、現像液を濃縮化し 、使用時に希釈して用いるように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。  [0082] For the purpose of transporting the developer, packaging material costs, space saving, and the like, an embodiment in which the developer is concentrated and diluted before use is also preferable. In order to concentrate the developer, it is effective to salt the salt component contained in the developer.
[0083] 本発明における現像処理は、未露光部分の銀塩を除去して安定化させる目的で行 われる定着処理を含むことができる。本発明における定着処理は、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マスク等に用いられる定 着処理の技術を用いることができる。  The development processing in the present invention can include a fixing processing performed for the purpose of removing and stabilizing the silver salt in the unexposed portion. For the fixing process in the present invention, a fixing process technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask and the like can be used.
[0084] 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。  [0084] 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、チォ硫酸アンモニゥム、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、タイ口 ン、エチレンジァミン四酢酸、ジエチレントリアミン五酢酸、二トリ口三酢酸これらの塩 等を含むことが好ましい。近年の環境保護の観点からは、ホウ酸は含まれない方が 好ましい。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、近年の環境保護の観点力 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ウム化合物）、保恒剤 (例えば、亜硫酸塩、重亜硫酸塩）That is, sodium thiosulfate, ammonium thiosulfate, and if necessary, tartaric acid, citrate, darconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, darcoheptanoic acid, Thai diamine, ethylenediamine tetraacetic acid, diethylenetriaminepentaacetic acid, nitrite It is preferable to contain a salt of acetic acid. From the viewpoint of environmental protection in recent years, it is preferable not to contain boric acid. Examples of the fixing agent for the fixing solution used in the present invention include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is preferred from the viewpoint of fixing speed. Viewpoint power Sodium thiosulfate may be used. The amount of these known fixing agents used can be appropriately changed, and is generally about 0.1 to about 2 mol Z liter. Particularly preferred is 0.2 to 1.5 mol Z liter. The fixer is hard if desired. Filming agent (eg water-soluble aluminum compound), preservative (eg sulfite, bisulfite)
、 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。 PH buffering agents (for example, acetic acid), pH adjusting agents (for example, ammonia, sulfuric acid), chelating agents, surfactants, wetting agents, and fixing accelerators.
[0085] 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。 [0085] Examples of the surfactant include anionic surfactants such as sulfates and sulfones, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. It is done. 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. 0〜6. 5力好ましく、特に好ましくは 4. 5〜6. 0の範囲で ある。また、上記色素溶出促進剤として、特開昭 64— 4739号公報記載の化合物を 用いることちでさる。  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 6.5, and particularly preferably 4.5 to 6.0. Further, it is possible to use a compound described in JP-A-64-4739 as the dye elution accelerator.
[0086] 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。  [0086] 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.
[0087] 上記定着工程における定着温度は、約 20°C〜約 50°Cが好ましぐさらに好ましく は 25〜45°Cである。また、定着時間は 5秒〜 1分が好ましぐさらに好ましくは 7秒〜 50秒である。定着液の補充量は、感光材料の処理量に対して 600mlZm2以下が好 ましぐ 500mlZm2以下がさらに好ましぐ 300mlZm2以下が特に好ましい。 [0087] The fixing temperature in the fixing step is preferably about 20 ° C to about 50 ° C, more preferably 25 to 45 ° C. The fixing time is preferably 5 seconds to 1 minute, more preferably 7 seconds to 50 seconds. The replenishment amount of the fixing solution is preferably 600 mlZm 2 or less relative to the processing amount of the photosensitive material. More preferably 500 mlZm 2 or less, more preferably 300 mlZm 2 or less.
[0088] 現像、定着処理を施した感光材料は、水洗処理や安定化処理を施されるのが好ま しい。上記水洗処理または安定化処理においては、水洗水量は通常感光材料 lm2 当り、 20リ [0088] The photosensitive material that has been subjected to development and fixing processing is preferably subjected to water washing processing and stabilization processing. In the above washing treatment or stabilization treatment, the amount of washing water is usually 20 liters per lm 2 of photosensitive material.
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、自現機設置の配管を不 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公害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〖こ、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から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 、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加してもよい。  It can be carried out with a replenishment volume of less than 3 liters (including zero, ie, rinsing with water). For this reason, not only water-saving treatment can be performed, but also the piping for installing the automatic machine can be dispensed with. As a method for reducing the replenishment amount of flush water, a multi-stage counter-current system (for example, 2 stages, 3 stages, 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. Further, various oxidizer additions and filter filtrations may be combined in order to reduce the pollution load that becomes a problem when washing with a small amount of water. Furthermore, in the above method, an overflow liquid from the washing bath or the stable bath 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, a part or all of them can be used for a processing solution having a fixing function, which is a previous processing step. In addition, water-soluble surfactants and antifoaming agents are added to prevent unevenness of water bubbles, which are likely to occur when washing with a small amount of water, and to prevent transfer of the processing agent component adhering to the Z or squeeze roller to the processed film. Also good.
[0089] 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。 [0089] In addition, in the water washing treatment or the stable water treatment, a dye adsorbent described in JP-A-63-163456 is added to a water washing tank in order to prevent contamination with dyes eluted from the photosensitive material. 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. In addition to tap water, the water used in the water washing process or the stability process It is preferable to use water that has been sterilized with on-treated water, halogen, ultraviolet germicidal lamp, various oxidizing agents (such as ozone, hydrogen peroxide, and chlorate). 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.
[0090] 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管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。  [0090] For storage of processing solutions such as a developer and a fixing solution used in the present invention, it is preferable to store them in a packaging material with 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.
本発明の電磁波シールド膜はロール状などの連絡パターンを担持した形状で得ら れることが生産性や光学フィルター作製の容易さの点で好ま 、ので、ロール用現像 機を用いることが有利であり、とくにローラー搬送型自動現像機を用いることが好まし い。  Since the electromagnetic wave shielding film of the present invention is preferably obtained in a shape carrying a contact pattern such as a roll shape from the viewpoint of productivity and ease of production of an optical filter, it is advantageous to use a developing machine for rolls. In particular, it is preferable to use a roller conveyance type automatic developing machine.
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おり、本明細書においては単にローラー搬 送型自動現像機として言及する。また、ローラー搬送型自動現像機は現像、定着、 水洗および乾燥の四工程力 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 程の代わりに安定工程による四工程でも構わない。  The roller-conveying type automatic developing machine is described in US Pat. Nos. 30,257,795, 3,545,971, etc., and is simply referred to as a roller-conveying type automatic developing machine in this specification. Also, in the present invention where the roller transport type automatic processor preferably has four process powers of development, fixing, washing and drying, other processes (for example, stop process) are not excluded, but these four processes are followed. Is most preferred. Further, instead of the washing step, four steps by a stable step may be used.
[0091] 上記各工程においては、現像液や定着液の組成から水を除いた成分を固形にして 供給し、使用に当たって所定量の水で溶解して現像液や定着液として使用してもよ い。このような形態の処理剤は固形処理剤と呼ばれる。固形処理剤は、粉末、錠剤、 顆粒、粉末、塊状またはペースト状のものが用いられる。上記処理剤の、好ましい形 態は、特開昭 61— 259921号公報記載の形態或いは錠剤である。該錠剤の製造方 法は、例えば特開昭 51— 61837号、同 54— 155038号、同 52— 88025号の各公 報、英国特許 1, 213, 808号明細書等に記載される一般的な方法で製造できる。さ らに顆粒の処理剤は、 f列えば特開平 2— 109042号、同 2— 109043号、同 3— 397 35号各公報および同 3— 39739号公報等に記載される一般的な方法で製造できる 。また、粉末の処理剤は、例えば特開昭 54— 133332号公報、英国特許 725, 892 号、同 729, 862号各明細書およびドイツ特許 3, 733, 861号明細書等に記載され る一般的な方法で製造できる。 [0091] In each of the above steps, the component obtained by removing water from the composition of the developer or the fixing solution may be supplied in a solid form and dissolved in a predetermined amount of water for use as a developer or a fixing solution. Yes. Such a form of treating agent is called a solid treating agent. As the solid processing agent, powder, tablet, granule, powder, lump or paste is used. A preferred form of the above-mentioned treatment agent is the form or tablet described in JP-A-61-259921. The method for producing the tablets is generally described in, for example, the publications of JP-A-51-61837, JP-A-54-155038, JP-A-52-88025, and British Patent No. 1,213,808. Can be manufactured by simple methods. Further, the granule treating agent is a general method described in JP-A-2-109042, JP-A-2-109043, JP-A-3-3935 and JP-A-3-39739. Can be manufactured . Further, powder processing agents are generally described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862 and German Patent 3,733,861. Can be manufactured in a conventional manner.
[0092] 上記固形処理剤の嵩密度は、その溶解性の観点と、 0. 5〜6. Og/cm3のものが 好ましく、特に 1. 0〜5. Og/cm3のもの力好まし!/ヽ。 [0092] The bulk density of the solid treatment agent is preferably 0.5-6. Og / cm 3 and particularly preferably 1.0-5. Og / cm 3 in view of its solubility. ! / ヽ.
[0093] 上記固形処理剤を調製するに当たっては、処理剤を構成する物質の中の、少なく とも 2種の相互に反応性の粒状物質を、反応性物質に対して不活性な物質による少 なくとも一つの介在分離層によって分離された層になるように層状に反応性物質を置 き、真空包装可能な袋を包材とし、袋内から排気しシールする方法を採用してもよい 。ここにおいて、「不活性」とは、物質が互いに物理的に接触されたときにパッケージ 内の通常の状態下で反応しな 、こと若しくは何らかの反応があっても著しくな 、ことを 意味する。不活性物質は、二つの相互に反応性の物質に対して不活性であることは 別にして、二つの反応性の物質が意図される使用において不活発であればよい。さ らに不活性物質は二つの反応性物質と同時に用いられる物質である。例えば、現像 液においてハイドロキノンと水酸ィ匕ナトリウムは直接接触すると反応してしまうので、真 空包装においてハイドロキノンと水酸ィ匕ナトリウムの間に分別層として亜硫酸ナトリウ ム等を使うことで、長期間ノ ッケージ中に保存できる。また、ハイド口キノン等をブリケ ットイ匕して水酸ィ匕ナトリウムとの接触面積を減らす事により保存性が向上し混合して用 V、ることもできる。これらの真空包装材料の包材として用いられるのは不活性なプラス チックフィルム、プラスチック物質と金属箔のラミネートから作られたバッグである。  [0093] In preparing the above-mentioned solid processing agent, at least two kinds of mutually reactive particulate materials among the materials constituting the processing agent should be reduced by a material inert to the reactive material. Alternatively, a method may be employed in which reactive substances are placed in layers so as to be separated by one intervening separation layer, a vacuum-packable bag is used as a packaging material, and the bag is evacuated and sealed. As used herein, “inert” means that the substances do not react under normal conditions in the package when they are in physical contact with each other, or even if there is any reaction. The inert material may be inert in the intended use of the two reactive materials, apart from being inert to the two mutually reactive materials. Furthermore, an inert substance is a substance that is used simultaneously with two reactive substances. For example, hydroquinone and sodium hydroxide in a developer react when they come into direct contact with each other. Therefore, by using sodium sulfite or the like as a separation layer between hydroquinone and sodium hydroxide in vacuum packaging, Can be stored in a knockout. In addition, by reducing the contact area with sodium hydroxide by briquetting a quinone or the like from the mouth, it is possible to improve the preservability and mix it. The packaging material for these vacuum packaging materials is an inert plastic film, a bag made from a laminate of plastic material and metal foil.
[0094] 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 、。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 V、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 好ましい。  [0094] The mass of the metallic silver contained in the exposed area after the development treatment is preferably 80% by mass or more with respect to the mass of silver contained in the exposed area before the exposure. It is even more preferable that it is at least%. If the mass of silver contained in the exposed part is 50% by mass or more with respect to the mass of V and silver contained in the exposed part before exposure, high conductivity can be obtained.
[0095] 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感光性ハロゲンィ匕 銀粒子へのドープが挙げられる。 [0095] 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. Set the gradation to 4.0 or higher Examples of the means include doping of the above-described rhodium ions and iridium ions into the photosensitive halogen silver halide particles.
[0096] (2— 3)物理現像およびめつき処理  [0096] (2-3) Physical development and tacking
本発明では、前記露光および現像処理により形成された導電性金属膜における金 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 ための物理現像および Zまたはめつき処理を行うことができる。本発明では物理現像 またはめつき処理のいずれか一方のみで導電性金属粒子を金属性銀部に担持させ ることが可能である力 さらに物理現像とめっき処理とを組み合わせて導電性金属粒 子を金属銀部に担持させることもできる。尚、金属銀部に物理現像および Zまたはめ つき処理を施したものを「導電性金属部」と称する。  In the present invention, for the purpose of imparting conductivity to the metal silver portion in the conductive metal film formed by the exposure and development processing, physical development for carrying conductive metal particles on the metal silver portion and Z or It is possible to perform a clinging process. In the present invention, the power capable of supporting the conductive metal particles on the metallic silver portion by only one of the physical development and the staking process. Further, the conductive metal particles are formed by combining physical development and plating. It can also be supported on a metallic silver part. A metal silver part that has been subjected to physical development and Z or plating treatment is referred to as a “conductive metal part”.
本発明における「物理現像」とは、金属や金属化合物の核上に、銀イオンなどの金 属イオンを還元剤で還元して金属粒子を析出させることをいう。この物理現象は、ィ ンスタント B&Wフィルム、インスタントスライドフィルムや、印刷版製造等に利用され ており、本発明ではその技術を用いることができる。  “Physical development” in the present invention means that metal particles such as silver ions are reduced with a reducing agent on metal or metal compound nuclei to precipitate metal particles. This physical phenomenon is used in the manufacture of instant B & W films, instant slide films, printing plates, etc., and the technology can be used in the present invention.
また、物理現像は、露光後の現像処理と同時に行っても、現像処理後に別途行つ てもよい。  The physical development may be performed simultaneously with the development processing after exposure or may be performed separately after the development processing.
[0097] 本発明にお!/、て、めっき処理は、無電解めつき（ィ匕学還元めつきや置換めつき）、電 解めつき、または無電解めつきと電解めつきの両方を用いることができる。  [0097] In the present invention, the plating process uses electroless plating (chemical reduction plating or substitution plating), electrolysis plating, or both electroless plating and electrolytic plating. be able to.
<無電解めつき >  <Electroless plating>
本発明では、露光および現像処理後の金属銀部を、さらに無電解めつき用溶液で 処理することもできる。無電解めつきには、パラジウム化合物水溶液で処理する方法 、還元剤又は銀イオン配位子あるいはその両方で処理する方法が好ま 、。  In the present invention, the metallic silver portion after the exposure and development treatment can be further treated with an electroless plating solution. For electroless plating, a method of treating with an aqueous palladium compound solution or a method of treating with a reducing agent and / or a silver ion ligand is preferred.
前者については、露光および現像処理後の金属銀部を、 Pdを含有する溶液で処 理することによって行われる。 Pdは、 2価のパラジウムイオンであっても金属パラジゥ ムであってもよい。この処理により無電解めつきまたは物理現像速度を促進させること ができる。ノラジウムによる無電解めつきは、日本科学会編、化学便覧応用化学編の 「無電解めつき」の章に詳記されている。  The former is carried out by treating the metallic silver part after exposure and development with a solution containing Pd. Pd may be divalent palladium ion or metal palladium. This treatment can accelerate electroless plating or physical development speed. Electroless plating with noradium is described in detail in the “Electroless plating” section of the Japan Society for the Science and Chemistry Handbook Applied Chemistry.
[0098] 本発明で好ましく用いられる還元剤又は銀イオン配位子による処理にっ 、て説明 する。 [0098] The treatment with the reducing agent or silver ion ligand preferably used in the present invention will be described. To do.
本発明にお ヽては、還元剤又は銀イオン配位子による処理を行うことが好ま Uヽ。 還元剤としては、銀イオンを金属銀に還元可能であればよぐ例えば、二酸化チォ 尿素、ロンガリット、塩ィ匕錫（11)、水素化ホウ素ナトリウム、ソジゥムトリァセトキシボロハ イドライド、トリメチルァミンボラン、トリェチルァミンボラン、ピリジンボラン、ボランなど が挙げられる。  In the present invention, it is preferable to perform treatment with a reducing agent or a silver ion ligand. As the reducing agent, it is sufficient if the silver ion can be reduced to metallic silver, for example, thiourea dioxide, Rongalite, sodium chloride (11), sodium borohydride, sodium triacetoxyborohydride, trimethylater. Examples include minborane, triethylamine borane, pyridine borane, and borane.
銀イオン配位子としては、塩素イオン、臭素イオン、沃素イオン等のハロゲンイオン 、チオシァネートイオンなどの擬ハロゲンイオン、ピリジン、ビビリジン等の含窒素へテ 口環化合物、亜硫酸イオン、また、 1, 2, 4—トリアゾリゥム— 3—チォラート類 (例えば 、 1, 2, 4-トリメチル -1, 2, 4-トリアゾリゥム- 3-チォラート）などのメソィ  Silver ion ligands include chlorine ions, bromine ions, halogen ions such as iodine ions, pseudohalogen ions such as thiocyanate ions, nitrogen-containing heterocyclic compounds such as pyridine and biviridine, sulfite ions, and 1 , 2, 4-triazolium-3-thiolates (eg 1, 2, 4-trimethyl-1, 2, 4-triazolium-3-thiolate)
オン化合物、 3, 6-ジチアオクタン- 1, 8-ジオールなどのチォエーテル化合物 など が挙げられる。  ON compounds, and thioether compounds such as 3,6-dithiaoctane-1,8-diol.
[0099] く電解めつき〉  [0099] Electrolytic plating>
以下に電解めつき処理方法の好ましい態様について図面を参照して具体的に説 明する。上記の電解めつき処理を好適に実施するためのめっき装置は、乳剤層を露 光し、現像処理した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気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いる。  Hereinafter, preferred embodiments of the electrolytic plating process will be specifically described with reference to the drawings. A plating apparatus for suitably carrying out the above-described electroplating treatment exposes the emulsion layer and electrically feeds the sequentially fed film from a feeding reel (not shown) around which the developed film is wound. The film is fed into a plating tank and the film after plating is sequentially wound around a reel for reeling (not shown).
[0100] 図 1に上記電解めつ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に示す電解めつき槽 10は、長尺のフィルム 16 (上記の露光、現像処理を施した もの）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。電解めつき槽 10は、めっき液 15を貯留するめつき浴 11を備えて いる。めっき浴 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。  [0100] Fig. 1 shows an example of an electrolytic plating bath suitably used for the electrolytic plating treatment. The electrolytic plating bath 10 shown in FIG. 1 is capable of continuously plating a long film 16 (the one subjected to the above exposure and development processing). The arrow indicates the transport direction of the film 16. The electrolytic plating bath 10 includes a plating bath 11 for storing a plating solution 15. A pair of anode plates 13 are disposed in parallel in the plating bath 11, and a pair of guide rollers 14 are disposed inside the anode plate 13 so as to be rotatable in parallel with the anode plate 13. The guide roller 14 can be moved in the vertical direction, so that the processing time of the film 16 can be adjusted.
[0101] めっき浴 11の上方には、フィルム 16をめつき浴 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、めっき浴 11の上方には、出口側の給電ローラ 12bの下方に液切り口 ーラ 17が回動可能に配設されており、この液切りローラ 17と出口側の給電ローラ 12 bとの間には、フィルムからめっき液を除去するための水洗用スプレー（図示せず）が 設置されている。 [0101] Above the plating bath 11, a pair of feed rollers (force swords) 12a and 12b for guiding the film 16 to the plating bath 11 and supplying current to the film 16 are rotatably arranged. It is. In addition, above the plating bath 11, a liquid draining roller 17 is rotatably disposed below the outlet-side power supply roller 12b. The liquid draining roller 17 and the outlet-side power supply roller 12b are connected to each other. In the meantime, a water spray (not shown) is installed to remove the plating solution from the film.
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.
[0102] 上記の電解めつき槽 10において、例えば、電解めつき槽のサイズが 10 X 10 X 10c m〜 100 X 200 X 300cmである場合は、入り口側の給電ローラ 12aとフィル ム 16とが接している面の最下部とめっき液面との距離（図 1に示す距離 La)は、 0. 5 〜 15cmとすることが好ましぐ l〜10cmとすることがより好ましぐ l〜7cmとすること 力 Sさらに好ましい。また、出口側の給電ローラ 12bとフィルム 16とが接している面の最 下部とめっき液面との距離（図 1に示す距離 Lb)は、 0. 5〜15cmとすることが好まし い。  [0102] In the electrolytic bath 10 described above, for example, when the size of the electrolytic bath is 10 X 10 X 10cm to 100 X 200 X 300cm, the feeding roller 12a on the entrance side and the film 16 are The distance between the lowermost part of the contacted surface and the plating solution surface (distance La shown in Fig. 1) is preferably 0.5 to 15 cm, more preferably l to 10 cm, and l to 7 cm. Power S is more preferable. The distance between the bottom of the surface where the power supply roller 12b on the outlet side is in contact with the film 16 and the plating solution surface (distance Lb shown in FIG. 1) is preferably 0.5 to 15 cm.
[0103] 次に、上記電解めつき槽 10を備えためっき装置を使用して、フィルムのメッシュ状 銀細線パターンに銅めつき層を形成させて導電性を強化する方法を説明する。 まずめつき浴 11にめつき液 15を貯留する。めっき液としては、銅めつきの場合は、 硫酸銅 5水塩を 30gZL〜300gZL、硫酸を 30gZL〜300gZLを含むものを用い ることができる。なお、ニッケルめっきの場合は、硫酸ニッケル、塩酸ニッケル等、鉄 銀めつきの場合は、シアンィ匕銀等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よい。  [0103] Next, a method for enhancing conductivity by forming a copper plating layer on a mesh-like silver fine wire pattern of a film using the plating apparatus provided with the electrolytic plating tank 10 will be described. First, the solution 15 is stored in the bath 11. In the case of copper plating, a plating solution containing 30 gZL to 300 gZL of copper sulfate pentahydrate and 30 gZL to 300 gZL of sulfuric acid can be used. In the case of nickel plating, nickel sulfate, nickel hydrochloride, or the like can be used. Moreover, you may add additives, such as surfactant, a sulfur compound, and a nitrogen compound, to a plating solution.
[0104] 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。なお、電解めつき直前のフィルムの表面抵抗 は、 1〜： LOOO Q Zsqであることが好ましぐ 5〜500 Q Zsqであることがより好ましぐ さらに好まし 、範囲は 10〜100 Ω Zsqである。  [0104] The film 16 is set in a state where it is wound on a supply reel (not shown), and the film 16 is placed so that the surface on which the film 16 is to be formed comes into contact with the feeding rollers 12a and 12b. It is wound around a conveyance roller (not shown). In addition, the surface resistance of the film immediately before electroplating is 1 to: LOOO Q Zsq is preferred 5 to 500 Q Zsq is more preferred Further, the range is 10 to 100 Ω Zsq It is.
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をめつき浴 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を拭い取り、めっき浴 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. Film 16 is introduced into the plating bath 11 and plated Immerse in liquid 15 to form a copper finish. When passing between the liquid draining rollers 17, the plating solution 15 adhering to the film 16 is wiped off and collected in the plating bath 11. This is repeated in a plurality of electrolytic baths, and finally washed with water, and then wound up on a reeling 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.
[0105] 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。  [0105] The number of electrolytic plating tanks is not particularly limited, but 2 to 10 tanks are preferable, and 3 to 6 tanks are more preferable.
印加電圧は、 1〜： LOOVの範囲であることが好ましぐ 2〜60Vの範囲であることがよ り好ましい。電解めつき槽が複数設置されている場合は、電解めつき槽の印加電圧を 段階的に下げることが好ましい。また、第 1槽目の入り口側の電流量としては、 1〜30 Aが好ましく、 2〜： LOAがより好ましい。  The applied voltage is preferably in the range of 1 to: LOOV, more preferably in the range of 2 to 60V. When multiple electrolytic baths are installed, it is preferable to step down the applied voltage of the electrolytic bath. In addition, the amount of current on the inlet side of the first tank is preferably 1 to 30 A, and more preferably 2 to LOA.
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).
[0106] なお、上記電解めつき槽においてめっき処理を行う前に、水洗および酸洗浄を行う ことが好ましい。酸洗浄の際に用いる処理液には、硫酸等が含まれるものを用いるこ とがでさる。 [0106] It is preferable to perform water washing and acid washing before the plating treatment in the electrolytic bath. The treatment solution used for the acid cleaning can be one containing sulfuric acid or the like.
[0107] 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。  [0107] 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 becomes wider as the electromagnetic wave shielding material of the display is thinner. 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.
[0108] また、本発明のめっき処理においては、上記のめっき処理を行う直前のフィルムの 表面抵抗が l〜1000 Q Zsqのフィルムであれば、その前に無電解めつき処理を行 つてもよい。 無電解めつきを行う場合は、公知の無電解めつき技術を用いることがで き、例えば、プリント配線板などで用いられている無電解めつき技術を用いることがで き、無電解めつきは無電解銅めつきであることが好まし 、。 無電解銅めつき液に含まれる化学種としては、硫酸銅や塩化銅、還元剤として、ホ ルマリンゃグリオキシル酸、銅の配位子として、 EDTA,トリエタノールアミン等、その 他、浴の安定ィ匕やめつき皮膜の平滑性向上の為の添加剤としてポリエチレングリコー ル、黄血塩、ビビリジン等が挙げられる。 [0108] Further, in the plating treatment of the present invention, if the film has a surface resistance of l to 1000 Q Zsq immediately before the above plating treatment, an electroless plating treatment may be performed before that. . When performing electroless plating, a known electroless plating technique can be used. For example, the electroless plating technique used in printed wiring boards can be used. Is preferably electroless copper plating. Chemical species contained in the electroless copper plating solution include copper sulfate and copper chloride, as a reducing agent, formalin glyoxylic acid, as a copper ligand, EDTA, triethanolamine, etc. Polyethylene glycol, yellow blood salt, biviridine and the like can be mentioned as additives for improving the smoothness of wrinkles and glazing films.
[0109] また、フィルム上の導電性パターンは連続している（電気的に途切れていない）こと が好ましい。一部でも繋がっていればよぐ導電性パターンが途切れると第 1槽目の 電解めつき槽でめつきがつかない部分ができたり、ムラになったりするおそれがある。  [0109] Further, the conductive pattern on the film is preferably continuous (not electrically interrupted). If even a part of the pattern is connected, the conductive pattern may break, and there is a risk that a non-sticky part may be formed in the first electrolytic plating tank or it may become uneven.
[0110] めっき処理時のめっき速度は、緩やかな条件で行うことができ、さらに 5 μ 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 力もは、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。  [0110] The plating rate during the plating process can be performed under moderate conditions, and further, high-speed plating of 5 μmZhr or more is possible. In the plating process, various additives such as a ligand such as EDTA can be used to increase the stability of the plating solution.
[0111] 図 2に本発明の導電性金属膜の一例を示す。図 2に示す導電性金属膜 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、本発明のハロゲン化銀感光材料の露光部 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。なお、図 2には明示していないが、図 2の導電性金属膜の支持体 23で は、導電性機能層 22の反対側の面に本発明に係る易接着層が設けられている。  FIG. 2 shows an example of the conductive metal film of the present invention. A conductive metal 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, by performing exposure 'development processing on the exposed portion 24 of the silver halide photosensitive material of the present invention, a metallic silver portion can be formed, and in order to further increase the conductivity, electrolytic plating is applied. A conductive metal part can be formed. As an example, there is a mode in which Cu is electroplated in the electrolytic plating treatment section 26 and Ni is electrolytically plated in the electrolytic plating treatment section 27. The unexposed portion 25 becomes a light transmissive portion (for example, one made of gelatin). Although not clearly shown in FIG. 2, the support 23 of the conductive metal film in FIG. 2 is provided with the easy adhesion layer according to the present invention on the surface opposite to the conductive functional layer 22.
[0112] (2— 4)酸化処理  [0112] (2-4) Oxidation treatment
本発明では、現像処理後の金属銀部、並びに、物理現像および Zまたはめつき処 理によって形成された導電性金属部には、酸化処理を施すことが好ましい。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, it is preferable to subject the metallic silver part after the development treatment and the conductive metal part formed by physical development and Z or staking treatment to oxidation treatment. By performing the oxidation treatment, for example, when a metal is slightly deposited on the light transmitting portion, the metal can be removed, and the light transmitting portion can be made 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。上述の通り、酸化処理は、乳剤層の露光および現像処理後、 或いは物理現像またはめつき処理後に行うことができ、さらに現像処理後と物理現像 またはめつき処理後のそれぞれで行ってもょ 、。 [0113] 本発明では、さらに露光およ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または物理現像速度を促進させることができる。 Examples of the oxidation treatment include known methods using various oxidizing agents such as Fe (III) ion treatment. As described above, the oxidation treatment can be carried out after the emulsion layer exposure and development treatment, or after physical development or staking treatment, and further after the development treatment and after physical development or staking treatment, . [0113] In the present invention, the metallic silver portion after the exposure and development treatment can be further treated with a solution containing Pd. Pd can be divalent palladium ion or metallic palladium! /. This treatment can accelerate electroless plating or physical development speed.
[0114] (3)導電性金属部  [0114] (3) Conductive metal part
本発明において、導電性金属部は、透光性電磁波シールド膜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からは同一のライン幅なら（ 正) n角形の n数が大き 、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。モアレを生じに《する観点ではこれらの幾何学模様をランダムに配置したり、 ライン幅を周期性なしに変化させることも好まし 、。  In the present invention, when the conductive metal portion is used as a light-transmitting electromagnetic wave shielding film, a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid, or the like , (Regular) hexagons, (regular) octagons and other (positive) n-gons, circles, ellipses, star shapes, etc. More preferred to be. From the viewpoint of EMI shielding properties, the triangular shape is the most effective, but from the viewpoint of visible light transmission, if the line width is the same (positive), the larger the n number of the n-square, the higher the aperture ratio and the visible light transmission. This is advantageous because it increases the performance. From the viewpoint of creating moiré, it is also preferable to arrange these geometric patterns randomly or change the line width without periodicity.
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。  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.
[0115] 透光性電磁波シールド膜の用途において、上記導電性金属部のメッシュ状の細線 の線幅は 1 μ m以上 40 μ m以下であることが好ましぐ好ましくは 5 μ m以上 30 μ m以下 、最も好ましくは 10 μ m以上 25 μ m以下である。線間隔は 50 μ m以上 500 μ m以下で あることが好ましぐ更に好ましくは 200 μ m以上 400 μ m以下、最も好ましくは 250 μ m 以上 350 m以下である。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 μ mより広 、部分を有して 、てもよ!/、。  [0115] In the use of the light-transmitting electromagnetic wave shielding film, the line width of the mesh-like fine wire of the conductive metal part is preferably 1 μm or more and 40 μm or less, and preferably 5 μm or more and 30 μm. m or less, most preferably 10 μm or more and 25 μm or less. The line spacing is preferably 50 μm or more and 500 μm or less, more preferably 200 μm or more and 400 μm or less, and most preferably 250 μm or more and 350 m or less. In addition, the conductive metal part may have a part with a line width wider than 20 μm for purposes such as ground connection!
[0116] 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 15 μ m、ピッチ 300 μ mの正方形の格子状メッシュの開口率は、 90%である  [0116] 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. Most preferred. The aperture ratio is the percentage of the mesh without fine lines. For example, the aperture ratio of a square grid mesh with a line width of 15 μm and a pitch of 300 μm is 90%.
[0117] (4)光透過性部 [0117] (4) Light transmissive part
本発明における「光透過性部」とは、透光性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 is a conductive metal part of the light transmissive electromagnetic wave shielding film. It means a part having transparency other than. As described above, the transmittance of the light transmissive portion is 90% or more, preferably 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. Is 95% or more, more preferably 97% or more, even more preferably 98% or more, and most preferably 99% or more.
[0118] 本発明におけるメッシュ状の細線は透光性電磁波シールド膜の長手方向に 3m以 上連続していることが好ましぐ該細線の連続長が多いほど、例えば光学フィルター 材料を生産する場合の損失が低減できるためより好ましい態様であるといえる。一方 、連続長が長すぎるとロール状にした場合にロール径が大きくなる、ロールの質量が 重くなる、ロールの中心部の圧力が強くなり接着や変形などの問題を生じ安くなる等 の理由で 2000m以下であることが好ましい。好ましくは 100m以上 1000m以下であり、 更に好ましくは 200m以上 800m以下であり、最も好ましくは 300m以上 500m以下であ る。  [0118] It is preferable that the mesh-like fine wire in the present invention is continuous for 3 m or more in the longitudinal direction of the translucent electromagnetic wave shielding film. The longer the continuous length of the fine wire is, for example, in the case of producing an optical filter material It can be said that this is a more preferable embodiment because the loss of the above can be reduced. On the other hand, if the continuous length is too long, the roll diameter becomes large when the roll is formed, the roll mass becomes heavy, the pressure at the center of the roll becomes strong, causing problems such as adhesion and deformation, and cheapness. It is preferably 2000 m or less. It is preferably 100 m or more and 1000 m or less, more preferably 200 m or more and 800 m or less, and most preferably 300 m or more and 500 m or less.
同様の理由により支持体の厚みは 200 μ m以下が好ましぐ更に好ましくは 20 μ m以 上 180 μ m以下、最も好ましくは 50 μ m以上 120 μ m以下である。  For the same reason, the thickness of the support is preferably 200 μm or less, more preferably 20 μm or more and 180 μm or less, and most preferably 50 μm or more and 120 μm or less.
[0119] 本発明においてメッシュが実質的に平行である直線状細線の交差するパターンと は、いわゆる格子模様を意味し、格子を構成する隣り合う直線が平行または平行 ±2 ° 以内の場合をいう。 [0119] In the present invention, the pattern of intersecting straight fine lines in which the mesh is substantially parallel means a so-called lattice pattern, and refers to a case where adjacent straight lines constituting the lattice are parallel or parallel within ± 2 °. .
[0120] 該光ビームの走査方法としては、搬送方向に対して実質的に垂直な方向に配列し たライン状の光源または回転ポリゴンミラーによって露光する方法が好ましい。この場 合、光ビームは 2値以上の強度変調を行う必要があり、直線はドットの連続としてバタ 一ユングされる。ドットの連続であるため一ドットの細線の縁は階段状になるが、細線 の太さはくびれた部分の一番狭い長さを意味する。  [0120] The scanning method of the light beam is preferably a method of exposing with a linear light source or a rotating polygon mirror arranged in a direction substantially perpendicular to the transport direction. In this case, the light beam needs to be intensity-modulated by two or more values, and the straight line is battered as a series of dots. Since the dots are continuous, the edge of the fine line of one dot is stepped, but the thickness of the fine line means the narrowest length of the constricted part.
[0121] 該光ビームの走査方法のもう一つの方式として、格子パターンの傾きに合わせて搬 送方向に対して走査方向を傾力せたビームを走査することも好ましい。この場合、 2 つの走査光ビームを直交するように配列することが好ましく。光ビームは露光面状で は実質的に 1値の強度をとる。  [0121] As another method of scanning the light beam, it is also preferable to scan a beam whose scanning direction is inclined with respect to the carrying direction in accordance with the inclination of the grating pattern. In this case, it is preferable to arrange the two scanning light beams so as to be orthogonal to each other. The light beam has a substantially single intensity on the exposed surface.
[0122] 本発明にお 、てメッシュパターンは透光性電磁波シールド膜の長手方向に対して 3 0° から 60° 傾力せることが好ましい。より好ましくは 40° から 50° であり、最も好まし くは 43° から 47° である。これはメッシュパターンが枠に対して 45° 程度の傾きとなる マスクの作成が一般的に難しく、ムラが出やす 、或いは価格が高 、などの問題を生 じゃすいのに対して、本方式はむしろ 45° 付近にてムラが出にくいため、本発明の 効果がマスク密着露光方式のフォトリソグラフィーゃスクリーン印刷によるパターニン グ対してより顕著な効果がある。 [0122] In the present invention, the mesh pattern is 3 with respect to the longitudinal direction of the translucent electromagnetic wave shielding film. It is preferable to tilt from 0 ° to 60 °. More preferably, it is 40 ° to 50 °, and most preferably 43 ° to 47 °. This is because it is generally difficult to create a mask whose mesh pattern is inclined at about 45 ° with respect to the frame, and it is difficult to create unevenness or the price is high. Rather, unevenness hardly occurs at around 45 °, so that the effect of the present invention is more remarkable for patterning by screen printing using mask contact exposure.
[0123] [易接着層] [0123] [Easily adhesive layer]
本発明では銀塩乳剤層と支持体をはさんで反対側の面、すなわち、支持体の銀塩 乳剤層とは他方面上に合成樹脂および導電性粒子を含有する易接着層を設ける。 なお、易接着層は、支持体の銀塩乳剤層とは他方面上の最表面層としてもよい。以 下、好ましい易接着層について説明する。易接着層は合成樹脂と導電性粒子を含 有させて一層で構成されて!、てもよ 、が、下記のような二層以上で構成してもよ 、。  In the present invention, an easy-adhesion layer containing a synthetic resin and conductive particles is provided on the opposite side of the silver salt emulsion layer and the support, that is, on the other side of the support. The easy-adhesion layer may be the outermost layer on the other side of the silver salt emulsion layer of the support. Hereinafter, a preferable easy-adhesion layer will be described. The easy adhesion layer may be composed of a single layer containing a synthetic resin and conductive particles !, or may be composed of two or more layers as described below.
[0124] (組成） [0124] (Composition)
一層目：水分散性あるいは水溶性合成樹脂、カルポジイミド化合物および導電性 粒子 (特に、導電性金属酸化物粒子)を必須成分とした帯電防止層 (第一の易接着 層）  First layer: antistatic layer (first easy-adhesion layer) comprising water-dispersible or water-soluble synthetic resin, carpositimide compound and conductive particles (especially conductive metal oxide particles) as essential components
二層目：水分散性あるいは水溶性合成樹脂、および架橋剤を必須成分とした表面 層（他の部材の構成層と積層することによって表面層ではなくなることがある場合もあ るが、易接着層の最上層という意味 (第二の易接着層)）  Second layer: Surface layer containing water-dispersible or water-soluble synthetic resin and cross-linking agent as essential components (Some layers may be removed by laminating with other component layers, but easy adhesion. Meaning the top layer (second easy adhesion layer))
易接着層としては、支持体上に合成樹脂および導電性粒子を含有する帯電防止 層と導電性粒子を含有しな 、表面層がこの順で設けられる構成のものが好ま 、。 本発明の帯電防止層においては、支持体上に帯電防止層を設けて得られる低帯電 性支持体のヘイズが 3%以下にあり、そして得られる感材の表面層の表面電気抵抗 カ^ ^/〜丄 ^)11 Ωの範囲にあるように、導電性が付与されている。帯電防止層 を付与することで、プラスチック支持体をノヽンドリングする製造プロセスにお 、て発生 する静電気起因のゴミ付き故障の発生、および感光材料のスタチック放電カプリの発 生を抑制することができる。易接着層を帯電防止層と表面層の 2層で形成した場合に は、帯電防止層の導電粒子が易接着層の外部に析出することを防止することができ る。 As the easy-adhesion layer, an antistatic layer containing a synthetic resin and conductive particles on a support and a structure in which a surface layer is provided in this order without containing conductive particles are preferable. In the antistatic layer of the present invention, the haze of the low chargeable support obtained by providing the antistatic layer on the support is 3% or less, and the surface electric resistance of the surface layer of the resulting photosensitive material / ~ 丄 ^) Conductivity is given so that it is in the range of 11 Ω. By providing the antistatic layer, it is possible to suppress the occurrence of dust-related failure due to static electricity and the occurrence of static discharge capri of the photosensitive material in the manufacturing process of bonding the plastic support. When the easy-adhesion layer is formed of two layers, an antistatic layer and a surface layer, it is possible to prevent the conductive particles of the antistatic layer from depositing outside the easy-adhesion layer. The
なお本明細書でいうヘイズは、 25°C, 60%RHの測定条件において、ヘイズメータ 一（NDH— 2000、日本電色製）を用い、 JIS K— 7105に従って測定した値である  The haze in this specification is a value measured according to JIS K-7105 using a haze meter (NDH-2000, manufactured by Nippon Denshoku) at 25 ° C and 60% RH.
[0125] 上記帯電防止層は、導電性粒子 (例えば、導電性金属酸化物粒子)を含む層であ り、一般に更に結合剤を含んでいる。上記導電性金属酸ィ匕物粒子としては、針状粒 子であり、その短軸に対する長軸の比 (長軸 Z短軸）が 3〜50の範囲にあるものを使 用することが好ましい。特に長軸 Z短軸が 10〜50の範囲のものが好ましい。このよう な針状粒子の短軸は、 0. 001-0.： mの範囲にあることが好ましぐ特に 0. 01〜 0. 02 /z mの範囲にあることが好ましい。またその長軸は、 0. 1〜5. の範囲に あること力 S好ましく、特に 0. 1〜2. の範囲にあることが好ましい。 [0125] The antistatic layer is a layer containing conductive particles (for example, conductive metal oxide particles) and generally further contains a binder. As the conductive metal oxide particles, it is preferable to use acicular particles having a major axis to minor axis ratio (major axis Z minor axis) in the range of 3 to 50. . In particular, those having a major axis Z minor axis in the range of 10 to 50 are preferred. The short axis of such needle-like particles is preferably in the range of 0.001-0.:m, and more preferably in the range of 0.01 to 0.02 / z m. Further, the long axis thereof is preferably in the range of 0.1 to 5. The force S is preferable, and particularly preferably in the range of 0.1 to 2.
[0126] 上記導電性金属酸化物粒子の材料としては、 ZnO、 TiO 、 SnO 、 Al O、 In O  [0126] Materials for the conductive metal oxide particles include ZnO, TiO2, SnO, AlO, InO.
2 2 2 3 2 2 2 2 3 2
、 MgO、 BaO及び MoO 及びこれらの複合酸化物、そしてこれらの金属酸化物にMgO, BaO and MoO and their complex oxides, and their metal oxides
3 3 3 3
更に異種原子を含む金属酸ィ匕物を挙げることができる。金属酸ィ匕物としては、 SnO  Furthermore, metal oxides containing different atoms can be mentioned. For metal oxides, SnO
2 2
、ZnO、Al 0、TiO 、 In O、及び MgOが好ましぐさらに SnO 、 ZnO、 In O 及 ZnO, Al 0, TiO, In O, and MgO are preferred, and SnO, ZnO, In O and
2 3 2 2 3 2 2 2 び TiOが好ましぐ SnOが特に好ましい。異種原子を少量含む例としては、 ZnOに SnO is particularly preferred, with 2 3 2 2 3 2 2 2 and TiO being preferred. As an example containing a small amount of different atoms, ZnO
2 2 twenty two
対して A1あるいは In、 TiOに対して Nbあるいは Ta、 In O に対して Sn、及び SnO  In contrast, A1 or In, Nb or Ta for TiO, Sn for In O, and SnO
2 2 3 2 に対して Sb、 Nbあるいはハロゲン元素などの異種元素を 0. 01〜30モル0 /0 (好まし くは 0. 1〜10モル0 /0)ドープしたものを挙げることができる。異種元素の添加量が、 0 . 01モル％未満の場合は酸化物または複合酸化物に充分な導電性を付与すること ができず、 30モル％を超えると粒子の黒ィ匕度が増し、帯電防止層が黒ずむため感光 材料 (以下感材ともいう）用としては適さない。従って、本発明では導電性金属酸ィ匕 物粒子の材料としては、金属酸ィ匕物または複合金属酸ィ匕物に対し異種元素を少量 含むものが好ましい。また結晶構造中に酸素欠陥を含むものも好ましい。上記異種 原子を少量含む導電性金属酸ィ匕物粒子としては、アンチモンがドープされた SnO 2 2 3 Sb to two, different kinds of elements such as Nb or a halogen element from 0.01 to 30 mole 0/0 (rather preferably 1 to 10 mol 0/0 0.) can be mentioned those doped . When the amount of the different element added is less than 0.01 mol%, sufficient conductivity cannot be imparted to the oxide or composite oxide, and when it exceeds 30 mol%, the blackness of the particles increases. Since the antistatic layer darkens, it is not suitable for photosensitive materials (hereinafter also referred to as photosensitive materials). Therefore, in the present invention, the material of the conductive metal oxide particles is preferably a material containing a small amount of different elements with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure. Examples of the conductive metal oxide particles containing a small amount of different atoms include SnO doped with antimony.
2 粒子が好ましぐ特にアンチモンが 0. 2〜2. 0モル％ドープされた  2 Particles preferred, especially antimony doped 0.2-2.0 mol%
SnO 粒子が好ましい。従って、本発明では前記短軸、長軸の寸法を有するアンチ SnO particles are preferred. Therefore, in the present invention, the anti-axis having the short axis and long axis dimensions is used.
2 2
モンドープ SnO等の金属酸ィ匕物粒子を使用することが、透明で、良好な導電性を有 する帯 Using metal oxide particles such as mon-doped SnO is transparent and has good conductivity. Obi
電防止層を形成するのに有利である。これにより、ヘイズが 3%以下にある低帯電性 支持体を有し、表面層の表面電気抵抗が 8 X 106〜6 Χ 108 Ωの範囲にある感材を容 勿に It is advantageous for forming an antistatic layer. This makes it easy to use a light-sensitive material that has a low-chargeable support with a haze of 3% or less and whose surface layer has a surface electrical resistance in the range of 8 X 10 6 to 6 Χ 10 8 Ω.
得ることができる。  Obtainable.
[0127] 前記短軸、長軸の寸法を有する針状の金属酸化物粒子 (例、アンチモンドープ Sn O )を使用することにより、透明で、良好な導電性を有する帯電防止層を有利に形 [0127] By using acicular metal oxide particles (for example, antimony-doped Sn 2 O 3) having the short axis and long axis dimensions, a transparent antistatic layer having good conductivity can be advantageously formed.
2 2
成できる理由については、次のように考えられる。上記針状の金属酸化物粒子は、帯 電防止層内では、長軸方向が帯電防止層の表面に平行に、長く伸びているが、層の 厚さ方向には短軸の径の長さ分だけ占めて 、るに過ぎな、、。このような針状の金属 酸ィ匕物粒子は、上記のように長軸方向に長いため、通常の球状の粒子に比べて、互 いに接触し易ぐ少ない量でも高い導電性が得られる。従って、透明性を損なうことな ぐ表面電気抵抗を低下させることができる。また、上記針状の金属酸化物粒子では 、短軸の径は、通常、帯電防止層の厚さより小さいか、ほぼ同じであり、表面に突出 することは少なぐ仮に突出してもその突出部分はわず力なため、帯電防止層上に設 けられる表面層によりほぼ完全に覆われることになる。従って、感材作成用の支持体 の搬送中、露光、現像のための感材搬送中に、層より突出部分の脱離である粉落ち の発生がほとんどないとの優位性も得られる。さらに、感材の現像処理前後の表面電 気抵抗の変化が、球状の粒子の場合比較的大きいのに比べて、上記針状の金属酸 化物を用 、た場合は極めて小さく、特に現像処理後の搬送性が格段に向上して 、る ということもできる。これは、球状の粒子の場合には、現像処理による膜の膨潤、収縮 により、針状の粒子の場合よりその配列状態が変化し、互いに接触する部分が減少 するためではな 、かと推測される。  The reasons for this can be considered as follows. In the antistatic layer, the needle-like metal oxide particles have a long axis extending long in parallel with the surface of the antistatic layer, but the length of the short axis in the thickness direction of the layer. It takes up just a minute. Since such needle-like metal oxide particles are long in the long axis direction as described above, high conductivity can be obtained even in a small amount that is easy to contact with each other compared to normal spherical particles. . Therefore, the surface electrical resistance can be reduced without impairing transparency. Further, in the above-mentioned acicular metal oxide particles, the minor axis diameter is usually smaller than or substantially the same as the thickness of the antistatic layer, and even if it protrudes slightly on the surface, the protruding portion does not protrude. Since it is weak, it is almost completely covered by the surface layer provided on the antistatic layer. Therefore, it is possible to obtain an advantage that there is almost no occurrence of powder falling which is a detachment of the protruding portion from the layer during the conveyance of the support for preparing the photosensitive material, during the conveyance of the photosensitive material for exposure and development. Furthermore, the change in surface electrical resistance before and after the development of the photosensitive material is extremely small when the above-mentioned acicular metal oxide is used, compared to the relatively large case of spherical particles, especially after development processing. It can also be said that the transportability is significantly improved. This is presumably because in the case of spherical particles, the arrangement and state of the particles change due to swelling and shrinkage of the film due to the development process, and the number of parts in contact with each other decreases. .
[0128] 本発明における帯電防止層は、導電性金属酸化物粒子を分散、支持する結合剤 を、一般に含んでいる。結合剤の材料としては、アクリル榭脂、ビュル榭脂、ポリウレ タン榭脂、ポリエステル榭脂等の種々のポリマーを使用することができる。粉落ちを防 止する観点から、ポリマー (好ましくは、アクリル榭脂、ビニル榭脂、ポリウレタン榭脂 又はポリエステル榭脂）とカルポジイミド化合物との硬化物であることが好ましい。本 発明では、良好な作業環境の維持、及び大気汚染防止の観点から、ポリマーもカル ポジイミドィ匕合物も、水溶性のものを使用する力、あるいはェマルジヨン等の水分散 状態で使用することが好ましい。また、ポリマーは、カルポジイミド化合物との架橋反 応が可能なように、メチロール基、水酸基、カルボキシル基及びアミノ基のいずれか の基を有する。水酸基及びカルボキシル基が好ましぐ特にカルボキシル基が好まし い。ポリマー中の水酸基又はカルボキシル基の含有量は、 0. 0001〜： L当量 Zlkg が好ましぐ特に 0. 001〜： L当量 Zlkgが好ましい。 [0128] The antistatic layer in the present invention generally contains a binder for dispersing and supporting the conductive metal oxide particles. As the binder material, various polymers such as acrylic resin, bulle resin, polyurethane resin, and polyester resin can be used. From the viewpoint of preventing powder falling, a cured product of a polymer (preferably acrylic resin, vinyl resin, polyurethane resin or polyester resin) and a carpositimide compound is preferable. Book In the invention, from the viewpoints of maintaining a good working environment and preventing air pollution, it is preferable to use both a polymer and a carboimide compound in a water-dispersed state or an aqueous dispersion state such as an emulsion. In addition, the polymer has a methylol group, a hydroxyl group, a carboxyl group, or an amino group so that a cross-linking reaction with the carpositimide compound is possible. A hydroxyl group and a carboxyl group are preferred, and a carboxyl group is particularly preferred. The content of the hydroxyl group or carboxyl group in the polymer is preferably from 0.0001 to L equivalent Zlkg, particularly preferably from 0.001 to L equivalent Zlkg.
[0129] アクリル榭脂としては、アクリル酸、アクリル酸アルキル等のアクリル酸エステル類、 アクリルアミド、アクリロニトリル、メタクリル酸、メタクリル酸アルキル等のメタクリル酸ェ ステル類、メタクリルアミド及びメタタリ口-トリルの 、ずれかのモノマーの単独重合体 又はこれらのモノマー 2種以上の重合により得られる共重合体を挙げることができる。 これらの中では、アクリル酸アルキル等のアクリル酸エステル類、及びメタクリル酸ァ ルキル等のメタクリル酸エステル類のいずれかのモノマーの単独重合体又はこれらの モノマー 2種以上の重合により得られる共重合体が好ましい。例えば、炭素原子数 1 〜6のアルキル基を有するアクリル酸エステル類及びメタクリル酸エステル類のいず れかのモノマーの単独重合体又はこれらのモノマー 2種以上の重合により得られる共 重合体を挙げることができる。上記アクリル榭脂は、上記組成を主成分とし、カルポジ イミドィ匕合物との架橋反応が可能なように、例えば、メチロール基、水酸基、カルボキ シル基及びアミノ基の 、ずれかの基を有するモノマーを一部使用して得られるポリマ 一である。 [0129] Acrylic resins include acrylic esters such as acrylic acid and alkyl acrylate, methacrylic esters such as acrylamide, acrylonitrile, methacrylic acid, and alkyl methacrylate, methacrylamide, and meta-tolyl. A homopolymer of these monomers or a copolymer obtained by polymerization of two or more of these monomers can be mentioned. Among these, homopolymers of monomers of acrylic acid esters such as alkyl acrylates and methacrylic acid esters such as alkyl methacrylates, or copolymers obtained by polymerization of two or more of these monomers. Is preferred. For example, homopolymers of monomers of acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 6 carbon atoms, or copolymers obtained by polymerization of two or more of these monomers are listed. be able to. The acrylic resin has, as a main component, a monomer having any group of, for example, a methylol group, a hydroxyl group, a carboxy group, and an amino group so that a crosslinking reaction with a carpositimide compound is possible. Is a polymer obtained by partially using
[0130] 上記ビュル榭脂としては、ポリビュルアルコール、酸変性ポリビニルアルコール、ポ リビエノレホノレマーノレ、ポリビュルブチラール、ポリビュルメチルエーテル、ポリオレフィ ン、エチレン Zブタジエン共重合体、ポリ酢酸ビュル、塩化ビニル Z酢酸ビニル共重 合体、塩化ビニル Z (メタ）アクリル酸エステル共重合体及びエチレン Z酢酸ビュル 系共重合体 (好ましくはエチレン Z酢酸ビニル Z (メタ)アクリル酸エステル共重合体） を挙げることができる。これらの中で、ポリビュルアルコール、酸変性ポリビュルアルコ ール、ポリビュルホリマール、ポリオレフイン、エチレン zブタジエン共重合体及びェ チレン Z酢酸ビュル系共重合体 (好ましくは、エチレン Z酢酸ビュル Zアクリル酸ェ ステル共重合体）が好ましい。上記ビニル榭脂は、カルポジイミド化合物との架橋反 応が可能なように、ポリビュルアルコール、酸変性ポリビニルアルコール、ポリビュル ホルマール、ポリビュルプチラール、ポリビュルメチルエーテル及びポリ酢酸ビュルで は、例えば、ビニルアルコール単位をポリマー中に残すことにより水酸基を有するポリ マーとし、他のポリマーについては、例えば、メチロール基、水酸基、カルボキシル基 及びアミノ基のいずれかの基を有するモノマーを一部使用することにより架橋可能な ポリマーとする。 [0130] Examples of the above-mentioned bulges include polybulu alcohol, acid-modified polyvinyl alcohol, polyphenol enore meranol, polybulu butyral, polybulu methyl ether, polyolefin, ethylene Z butadiene copolymer, polyacetate bur, chloride. Mention of vinyl Z vinyl acetate copolymer, vinyl chloride Z (meth) acrylate copolymer and ethylene Z acetate butyl copolymer (preferably ethylene Z vinyl acetate Z (meth) acrylate copolymer) Can do. Among these, polybulal alcohol, acid-modified polybulal alcohol, polybullymarl, polyolefin, ethylene z butadiene copolymer and ethylene Z butyl acetate copolymer (preferably ethylene Z butyl acetate Z acrylic) Acid Steal copolymers) are preferred. The above-mentioned vinyl resin is capable of crosslinking reaction with a carpositimide compound so that, for example, vinyl alcohol, acid-modified polyvinyl alcohol, polybul formal, polybulutyl, polybulumethyl ether and polyacetic acid A polymer having a hydroxyl group is obtained by leaving an alcohol unit in the polymer. For other polymers, for example, a part of a monomer having a methylol group, a hydroxyl group, a carboxyl group, or an amino group is used for crosslinking. A possible polymer.
[0131] 上記ポリウレタン榭脂としては、ポリヒドロキシィ匕合物（例、エチレングリコール、プロ ピレンダリコール、グリセリン、トリメチロールプロパン）、ポリヒドロキシ化合物と多塩基 酸との反応により得られる脂肪族ポリエステル系ポリオール、ポリエーテルポリオール (例、ポリ（ォキシプロピレンエーテル）ポリオール、ポリ（ォキシエチレン プロピレン エーテル）ポリオール）、ポリカーボネート系ポリオール、及びポリエチレンテレフタレ ートポリオールの!/、ずれか一種、あるいはこれらの混合物とポリイソシァネートから誘 導されるポリウレタンを挙げることができる。上記ポリウレタン榭脂では、例えば、ポリ オールとポリイソシァネートとの反応後、未反応として残った水酸基をカルポジイミド 化合物との架橋反応が可能な官能基として利用することができる。  [0131] Examples of the polyurethane resin include polyhydroxy compounds (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), aliphatic polyesters obtained by reacting polyhydroxy compounds with polybasic acids. Polyols, polyether polyols (eg, poly (oxypropylene ether) polyols, poly (oxyethylene propylene ether) polyols), polycarbonate polyols, and polyethylene terephthalate polyols! Mention may be made of polyurethanes derived from isocyanates. In the polyurethane resin, for example, the hydroxyl group remaining unreacted after the reaction between polyol and polyisocyanate can be used as a functional group capable of crosslinking reaction with a carpositimide compound.
[0132] 上記ポリエステル榭脂としては、一般にポリヒドロキシィ匕合物（例、エチレングリコー ル、プロピレングリコール、グリセリン、トリメチロールプロパン）と多塩基酸との反応に より得られるポリマーが使用される。上記ポリエステル榭脂では、例えば、ポリオール と多塩基酸との反応終了後、未反応として残った水酸基、カルボキシル基をカルポジ イミドィ匕合物との架橋反応が可能な官能基として利用することができる。勿論、水酸 基等の官能基を有する第三成分を添加してもよ 、。  [0132] As the polyester resin, a polymer obtained by a reaction of a polyhydroxy acid compound (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane) and a polybasic acid is generally used. In the polyester resin, for example, after the reaction between the polyol and the polybasic acid is completed, the unreacted hydroxyl group and carboxyl group can be used as a functional group capable of a crosslinking reaction with the calpositimide compound. Of course, a third component having a functional group such as a hydroxyl group may be added.
[0133] 上記ポリマーの中で、アクリル榭脂及びポリウレタン榭脂が好ましぐ特にアクリル榭 脂が好ましい。  [0133] Among the above polymers, acrylic resin and polyurethane resin are preferable, and acrylic resin is particularly preferable.
[0134] 本発明で使用されるカルポジイミドィ匕合物としては、分子内にカルポジイミド構造を 複数有する化合物を使用することが好まし ヽ。  [0134] As the carbopositimide compound used in the present invention, it is preferable to use a compound having a plurality of carbopositimide structures in the molecule.
ポリカルポジイミドは、通常、有機ジイソシァネートの縮合反応により合成される。こ こで分子内にカルポジイミド構造を複数有する化合物の合成に用いられる有機ジイソ シァネートの有機基は特に限定されず、芳香族系、脂肪族系のいずれか、あるいは それらの混合系も使用可能であるが、反応性の観点から脂肪族系が特に好ましい。 合成原料としては、有機イソシァネート、有機ジイソシァネート、有機トリイソシァネ ート等が使用される。 Polycarposimide is usually synthesized by a condensation reaction of an organic diisocyanate. Here, organic diisodioxide used for the synthesis of compounds with multiple carposimide structures in the molecule. The organic group of cyanate is not particularly limited, and either aromatic or aliphatic, or a mixture thereof can be used, but aliphatic is particularly preferable from the viewpoint of reactivity. As synthetic raw materials, organic isocyanate, organic diisocyanate, organic triisocyanate and the like are used.
有機イソシァネートの例としては、芳香族イソシァネート、脂肪族イソシァネート、及 び、それらの混合物が使用可能である。  As examples of organic isocyanates, aromatic isocyanates, aliphatic isocyanates, and mixtures thereof can be used.
具体的には、 4, 4'ージフエ-ルメタンジイソシァネート、 4, 4ージフエ-ルジメ チルメタンジイソシァネート、 1, 4 フエ二レンジイソシァネート、 2, 4 トリレンジイソ シァネート、 2, 6 トリレンジイソシァネート、へキサメチレンジイソシァネート、シクロ へキサンジイソシァネート、キシリレンジイソシァネート、 2, 2, 4 トリメチルへキサメ チレンジイソシァネート、 4, 4'ージシクロへキシノレメタンジイソシァ  Specifically, 4,4'-dimethanemethane diisocyanate, 4,4-diphenylmethanemethane diisocyanate, 1,4 phenolic diisocyanate, 2,4 tolylene diisocyanate, 2, 6 Tolylene diisocyanate, Hexamethylene diisocyanate, Cyclohexane diisocyanate, Xylylene diisocyanate, 2, 2, 4 Trimethylhexamethylene diisocyanate, 4, 4'-Dicyclohexylinole Methane diisocyanate
ネート、 1, 3 フエ-レンジイソシァネート等が用いられ、また、有機モノイソシァネー トとしては、イソホロンイソシァネート、フエ二ルイソシァネート、シクロへキシノレイソシァ ネート、ブチルイソシァネート、ナフチルイソシァネート等が使用される。 1,3 phenolic diisocyanate, etc. are used, and as organic monoisocyanate, isophorone isocyanate, phenyl isocyanate, cyclohexenoisocyanate, butyl isocyanate, naphthyl isocyanate, etc. are used. Is done.
また、本発明に用いうるカルポジイミド系化合物は、例えば、カルポジライト V— 02 — L2 (商品名：日清紡社製)などの市販品としても入手可能である。  In addition, the calpositimide-based compound that can be used in the present invention is also available as a commercial product such as, for example, calpositrite V-02-L2 (trade name: manufactured by Nisshinbo Co., Ltd.).
カルボジイミド系化合物はバインダーに対して 1〜200質量％、より好ましくは 5〜 100 質量％の範囲で添加することが好ま 、。  The carbodiimide compound is preferably added in an amount of 1 to 200% by mass, more preferably 5 to 100% by mass, based on the binder.
本発明における帯電防止層を形成するには、まず、例えば前記導電性金属酸化物 粒子をそのままあるいは水等の溶媒 (必要に応じて分散剤、結合剤を含む）に分散さ せた分散液を、上記結合剤（例、ポリマー、カルポジイミドィ匕合物及び適当な添加剤） を含む水分散液あるいは水溶液に、添加、混合 (必要に応じて分散）して帯電防止 層形成用塗布液を調製する。上記帯電防止層は、上記帯電防止層形成用塗布液を ポリエステル等のプラスチックフィルムの表面 (感光層が設けられな 、側）に一般によ く知られた塗布方法、例えばディップコート法、エアーナイフコート法、カーテンコート 法、ワイヤーバーコート法、グラビアコート法、エタストルージョンコート法などにより塗 布することができる。塗布されるポリエステル等のプラスチックフィルムは、逐次二軸 延伸前、同時二軸延伸前、一軸延伸後で再延伸前、あるいは二軸延伸後のいずれ であってもよ 、。帯電防止層形成用塗布液を塗布するプラスチック支持体の表面は、 あら力じめ紫外線照射処理、コロナ放電処理、グロ一放電処理などの表面処理を施 しておくことが好ましい。 In order to form the antistatic layer in the present invention, first, for example, a dispersion liquid in which the conductive metal oxide particles are dispersed as they are or in a solvent such as water (including a dispersant and a binder as necessary) is used. Addition and mixing (dispersing if necessary) to an aqueous dispersion or aqueous solution containing the above binder (eg, polymer, carpositimide compound and appropriate additive) to prepare a coating solution for forming an antistatic layer . The antistatic layer is formed by applying a coating solution for forming the antistatic layer to a surface of a plastic film such as polyester (on the side where no photosensitive layer is provided), such as a dip coating method or an air knife coating. It can be applied by a method such as a coating method, a curtain coating method, a wire bar coating method, a gravure coating method or an etha trusion coating method. The applied plastic film such as polyester is either before sequential biaxial stretching, before simultaneous biaxial stretching, after uniaxial stretching, before re-stretching, or after biaxial stretching. Even so. The surface of the plastic support on which the coating solution for forming the antistatic layer is preferably subjected to surface treatment such as ultraviolet irradiation treatment, corona discharge treatment, and glow discharge treatment.
[0136] 本発明における帯電防止層（導電性粒子を含有する易接着層）の層厚は、 0. 01 〜1 111の範囲力 子ましく、さらに 0. 01〜0. 2 mの範囲力 子ましい。 0. 01 m未 満では塗布剤を均一に塗布しにくいため製品に塗布むらが生じやすぐ 1 μ mを超え る場合は、帯電防止性能ゃ耐傷性が劣る場合がある。導電性粒子 (例えば、導電性 金属酸化物粒子）は、帯電防止層中に、結合剤（例、上記ポリマー及びカルポジイミ ド化合物の合計）に対して 10〜： L000質量％の範囲で含まれていることが好ましぐ 更に 100〜500質量％の範囲が好ましぐ特に、 150〜400質量％の範囲が好ましい  [0136] The layer thickness of the antistatic layer (easily adhesive layer containing conductive particles) in the present invention is preferably in the range of 0.01 to 1 111, and more preferably in the range of 0.01 to 0.2 m. Childish. If it is less than 0.01 m, it is difficult to apply the coating agent uniformly. If uneven coating occurs on the product or if it exceeds 1 μm immediately, the antistatic performance may be inferior in scratch resistance. Conductive particles (for example, conductive metal oxide particles) are included in the antistatic layer in the range of 10 to L000 mass% with respect to the binder (eg, the sum of the polymer and the calpositimide compound). More preferably, the range of 100 to 500% by mass is particularly preferable, and the range of 150 to 400% by mass is preferable.
10質量％未満の場合は、充分な帯電防止性が得られない傾向があり、 1000質量 %を超えた場合はヘイズが高くなり過ぎる傾向がある。また、 400質量％を超えた場 合は、接着剤を介してガラスと貼り合わせた後の剥離強度が弱まる傾向がある。 また導電性粒子の含有量を合成樹脂 (例えば、アクリル榭脂 (溶媒を含む)又はァク リル樹脂の分散物） 30質量部を基準とした場合には、導電性粒子の含有量は、 10〜 500質量部が好ましく、 50〜 150質量部がさらに好まし 、。 If the amount is less than 10% by mass, sufficient antistatic properties tend not to be obtained, and if it exceeds 1000% by mass, the haze tends to be too high. On the other hand, when it exceeds 400% by mass, the peel strength after bonding with glass via an adhesive tends to be weakened. In addition, when the content of the conductive particles is based on 30 parts by mass of a synthetic resin (for example, acrylic resin (including solvent) or acrylic resin dispersion), the content of the conductive particles is 10 ~ 500 parts by weight is preferred, 50 to 150 parts by weight is more preferred.
[0137] 本発明における帯電防止層および下記の表面層には必要に応じて、マット剤、界 面活性剤、滑り剤などの添加剤を併用して使用することができる。マット剤としては、 0 . 001〜 10 mの粒径をもつ酸化珪素、酸化アルミニウム、酸化マグネシウムなどの 酸化物の粒子や、ポリメチルメタタリレート、ポリスチレン等の重合体あるいは共重合 体等の粒子をあげることができる。界面活性剤としては公知のァ-オン系界面活性剤[0137] The antistatic layer and the following surface layer in the present invention can be used in combination with additives such as a matting agent, a surface active agent, and a slipping agent, if necessary. Matting agents include particles of oxides such as silicon oxide, aluminum oxide and magnesium oxide having a particle size of 0.001 to 10 m, and particles of polymers or copolymers such as polymethylmethalate and polystyrene. Can give. Known surfactant surfactants as surfactants
、カチオン系界面活性剤、両性系界面活性剤、非イオン系界面活性剤等があげるこ とができる。滑り剤としては、カルナバワックス等の天然ワックス、炭素数 8〜22の高級 アルコールのリン酸エステルもしくはそのアミノ塩；パルミチン酸、ステアリン酸、ベへ ン酸およびそのエステル類;及びシリコーン系化合物等を挙げることができる。 Cationic surfactants, amphoteric surfactants, nonionic surfactants and the like can be mentioned. Examples of slip agents include natural waxes such as carnauba wax, phosphate esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof, palmitic acid, stearic acid, behenic acid and esters thereof, and silicone compounds. Can be mentioned.
[0138] 本発明においては、帯電防止層の上に表面層が設けられ得る。表面層は、主とし て接着剤層との接着性付与、及び帯電防止層の導電性金属酸化物粒子の脱離防 止機能を補助するために設けられる。表面層の材料には、一般にアクリル榭脂、ビ- ル榭脂、ポリウレタン榭脂、ポリエステル榭脂等の種々のポリマーを使用することがで き、上記帯電防止層中の結合剤として記載したポリマーが好ましい。中でも好ましく は、帯電防止層と接着し易いという理由力もアクリル榭脂、ポリエステル榭脂、ポリウレ タン榭脂およびスチレンブタジエンゴム力もなる群力 選択された少なくとも 1種であ る。 [0138] In the present invention, a surface layer may be provided on the antistatic layer. The surface layer mainly provides adhesion to the adhesive layer and prevents the conductive metal oxide particles from being removed from the antistatic layer. Provided to assist the stop function. As the material for the surface layer, various polymers such as acrylic resin, beer resin, polyurethane resin, and polyester resin can be generally used, and the polymers described as the binder in the antistatic layer are used. Is preferred. Among these, at least one selected from the group force of the reason that it is easy to adhere to the antistatic layer and the strength of acrylic resin, polyester resin, polyurethane resin, and styrene butadiene rubber is preferable.
表面層に用いられる架橋剤は、製造プロセス中のロール卷取り形態時にコンタクト する感光材料層の感光特性に影響を与えな 、エポキシィ匕合物が好ま 、。  The cross-linking agent used for the surface layer is preferably an epoxy compound that does not affect the photosensitive characteristics of the photosensitive material layer that is contacted when the roll is removed during the manufacturing process.
エポキシ化合物としては、 1, 4 ビス（2' , 3 '—エポキシプロピルォキシ）ブタン、 1 , 3, 5 トリグリシジルイソシァヌレート、 1, 3 ジクリシジノレ一 5— ( γ ァセトキシ一 β ォキシプロピル)イソシヌレート、ソルビトールポリグリシジルエーテル類、ポリグリ セロールポリグリシジルエーテル類、ペンタエリスリトールポリグリシジルエーテル類、 ジグリセ口一ノレポリグノレシジノレエーテノレ、 1, 3, 5 トリグリシジル（2 ヒドロキシェチ ル)イソシァヌレート、グリセロールポリグリセロールエーテル類およびトリメチ口—ルプ 口パンポリグリシジルエーテル類等のエポキシィ匕合物が好ましぐその具体的な巿販 品としては、例えばデナコール ΕΧ— 521や EX— 614B (ナガセ化成工業 (株)製)な どを挙げることができる力 これらに限定されるものではない。  Examples of the epoxy compound include 1,4 bis (2 ', 3'-epoxypropyloxy) butane, 1,3,5 triglycidyl isocyanurate, 1,3 diglycidinole-5- (γ-acetoxy-1-β-oxypropyl) isosinurate, Sorbitol polyglycidyl ethers, polyglyceryl polyglycidyl ethers, pentaerythritol polyglycidyl ethers, diglycerone polyrenoglycenosidinoatenore, 1, 3, 5 triglycidyl (2 hydroxyethyl) isocyanurate, glycerol polyglycerol Epoxy compounds such as ethers and trimethic lip-and-loop polyglycidyl ethers are preferred as specific products such as Denacol ΕΧ-521 and EX- 614B (manufactured by Nagase Kasei Kogyo Co., Ltd.). Power that can be raised, etc. It is not a thing.
また、感光特性に影響を与えない添加量の範囲では、他の架橋性化合物との併用 も可能であり、例えば C.E.K.Meersおよび T.H.James著「The Theory of the Photogra phic ProcessJ第 3版（1966年）、米国特許第 3316095号、同 3232764号、同 328 8775^-,同„ 3号、同 3635718号、同 3232763号、同 2732316号、同 25 86168号、同 3103437号、同 3017280号、同 2983611号、同 2725294号、同 2 725295号、同 3100704号、同 3091537号、同 3321313号、同 3543292号及び 同 3125449号、並び【こ英国特許 994869号及び同 1167207号の各明糸田書等【こ記 載されて!ヽる硬化剤などがあげられる。  In addition, it can be used in combination with other crosslinkable compounds within a range that does not affect the photosensitivity. For example, “The Theory of the Photographic ProcessJ 3rd Edition” (1966) by CEKMeers and THJames. U.S. Patent Nos. 3316095, 3232764, 328 8775 ^-, „3, 3635718, 3232763, 2732316, 25 86168, 3103437, 3017280, 2983611 2725294, 2725295, 3100704, 3091537, 3321313, 3543292, and 3125449, alongside each of these books, such as British Patents 994869 and 1167207, etc. Examples of hardeners are listed.
代表的な例としては、二個以上 (好ましくは三個以上）のメチロール基およびアルコ キシメチル基の少なくとも一方を含有するメラミンィ匕合物またはそれらの縮重合体で あるメラミン榭脂あるいはメラミン 'ユリア榭脂、さらにはムコクロル酸、ムコブロム酸、ム コフエノキシクロル酸、ムコフエノキシプロム酸、ホルムアルデヒド、グリオキザール、モ ノメチルギリォキザール、 2, 3 ジヒドロキシ 1, 4 ジォキサン、 2, 3 ジヒドロキシ 5—メチルー 1, 4 ジォキサンサクシンアルデヒド、 2, 5 ジメトキシテトラヒドロフラ ン及びダルタルアルデヒド等のアルデヒド系化合物およびその誘導体；ジビニルスル ホン一 N, N' エチレンビス（ビニノレスノレホニノレァセトアミド）、 1, 3 ビス（ビニノレス ルホ-ル）一 2 プロパノール、メチレンビスマレイミド、 5 ァセチルー 1, 3 ジアタリ ロイル一へキサヒドロ一 s トリァジン、 1, 3, 5 トリアタリロイル一へサヒドロ一 s トリ ァジン及び 1, 3, 5 トリビュルスルホ -ル—へキサヒドロ s トリァジンなどの活性 ビュル系化合物； 2, 4 ジクロロ 6 ヒドロキシ— s トリァジンナトリウム塩、 2, 4— ジクロロ一 6— (4—スルホア-リノ）一 s トリァジンナトリウム塩、 2, 4 ジクロロ一 6— (2—スルホェチルァミノ）—s トリァジン及び N, N，—ビス（2—クロロェチルカルバ ミル）ピぺラジン等の活性ハロゲン系化合物；ビス（2, 3 エポキシプロピル)メチルプ 口ピルアンモ-ゥム ·ρ トルエンスルホン酸塩、 2, 4, 6 トリエチレン— s トリアジン 、 1, 6 へキサメチレン一 Ν, Ν，一ビスエチレン尿素およびビス一 β—エチレンイミ ノエチルチオエーテル等のエチレンイミン系化合物； 1 , 2—ジ (メタンスルホンォキシ )ェタン、 1, 4ージ（メタンスルホンォキシ）ブタン及び 1, 5 ジ（メタンスルホンォキシ )ペンタン等のメタンスルホン酸エステル系化合物；ジシクロへキシルカルボジイミド及 び 1 ジシクロへキシル 3— (3 トリメチルァミノプロピル)カルボジイミド塩酸塩等 のカルボジイミド化合物； 2, 5 ジメチルイソォキサゾール等のイソォキサゾール系化 合物；クロム明ばん及び酢酸クロム等の無機系化合物； Ν—カルボエトキシ— 2—イソ プロポキシ 1, 2 ジヒドロキノリン及び Ν— (1—モルホリノカルボキシ） 4—メチル ピリジゥムクロリド等の脱水縮合型ペプチド試薬; Ν, Ν，—アジボイルジォキシジサク シンイミド及び Ν, Ν，ーテレフタロイルジォキシジサクシンイミド等の活性エステル系 化合物：トルエン—2, 4 ジイソシァネート及び 1, 6 へキサメチレンジイソシァネー ト等のイソシァネート類;及びポリアミド ポリアミンーェピクロルヒドリン反応物等のェ ピクロルヒドリン系化合物を挙げることができる力 これに限定されるものではない。 上記表面層の形成には、まず、例えば水等の溶媒 (必要に応じて分散剤、結合剤 を含む）に上記ポリマー、エポキシ化合物、及び適当な添加剤を添加、混合 (必要に 応じて分散)して表面層塗布液を調製する。 As a typical example, a melamine compound containing at least one of two or more (preferably three or more) methylol groups and an alkoxymethyl group, or a condensation polymer thereof, melamine fat or melamine 'urea'. Fat, and also mucochloric acid, mucobromic acid, mu Cofenoxycyclouric acid, mucophenoxypromic acid, formaldehyde, glyoxal, monomethylglyoxal, 2,3 dihydroxy 1,4 dioxane, 2,3 dihydroxy 5-methyl-1,4 dioxane succinaldehyde, Aldehyde compounds such as 2,5 dimethoxytetrahydrofuran and dartalaldehyde and their derivatives; divinyl sulfone N, N 'ethylene bis (vininores norephonino acetoamide), 1, 3 bis (vinino resulfol) 1-propanol, methylenebismaleimide, 5-acetyl-1,3-diataliroyl-hexahydro-s-triazine, 1,3,5 tri-tallyloyl-to-sahydro-s-triazine and 1,3,5-tribylsulfol Active bur compounds such as oxahydro s triazine; 2, 4 dichloro 6 hydroxy-s tria Gin sodium salt, 2, 4-dichloro-6- (4-sulfo-lino) monostriazine sodium salt, 2,4 dichloro-6- (2-sulfoethylamino) -s triazine and N, N, —Active halogen compounds such as bis (2-chloroethylcarbamyl) piperazine; bis (2,3 epoxypropyl) methylpyramine · ρ toluenesulfonate, 2, 4, 6 triethylene— s Triazines, 1, 6 Hexamethylene mono-, tri-, ethylene-imine compounds such as bis-ethylene urea and bis-β-ethyleneiminoethyl thioether; 1, 2-di (methanesulfonoxy) ethane, 1, 4- Methanesulfonic acid ester compounds such as di (methanesulfonoxy) butane and 1,5 di (methanesulfonoxy) pentane; dicyclohexylcarbodiimide and 1 dicyclohexyl 3- (3 Carbodiimide compounds such as trimethylaminopropyl) carbodiimide hydrochloride; 2, 5 isoxazole compounds such as dimethylisoxazole; inorganic compounds such as chromium alum and chromium acetate; Ν-carboethoxy-2-isopropoxy 1, 2 Dihydroquinoline and Ν— (1-morpholinocarboxy) 4-methylpyridium chloride and other dehydration-condensed peptide reagents; —, Ν, — adiboyldioxydisuccinimide and Ν, Ν, terephthaloyldi Active ester compounds such as oxydisuccinimide: Isocyanates such as toluene-2,4 diisocyanate and 1,6 hexamethylenediisocyanate; and epichlorohydrin such as polyamide polyamine-epoxyhydrin reactant Power that can mention a compound based on the present invention is not limited to this. For the formation of the surface layer, first, the polymer, epoxy compound, and appropriate additive are added and mixed in a solvent such as water (including a dispersant and a binder as necessary). Disperse accordingly) to prepare a surface layer coating solution.
[0141] 上記表面層は、本発明における帯電防止層上に一般によく知られた塗布方法、例 えばディップコート法、エアーナイフコート法、カーテンコート法、ワイヤーバーコート 法、グラビアコート法、エタストルージョンコート法などにより上記表面層塗布液を塗布 することにより形成することができる。上記表面層の層厚は、 0. 01〜1 /ζ πιの範囲が 好ましぐさらに 0. 01-0. 2 mの範囲が好ましい。 0. 01 m未満では帯電防止 層の導電性金属酸ィ匕物粒子の脱離防止機能が不十分で、 1 μ mを超える場合は、 塗布剤を均一に塗布しにく ヽため製品に塗布むらが生じやす ヽ。  [0141] The surface layer is formed by a coating method generally well known on the antistatic layer in the present invention, such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, etast. It can be formed by applying the above surface layer coating solution by a rouge coating method or the like. The layer thickness of the surface layer is preferably in the range of 0.01 to 1 / ζ πι, and more preferably in the range of 0.01 to 0.2 m. If it is less than 0.01 m, the antistatic layer has insufficient anti-detachment function for the conductive metal oxide particles, and if it exceeds 1 μm, it is difficult to apply the coating agent uniformly, so it is applied to the product. Unevenness is likely to occur.
[0142] [接着剤層]  [0142] [Adhesive layer]
本発明に好ましく用いられる接着剤層につ ヽて説明する。  The adhesive layer preferably used in the present invention will be described.
本発明の透光性電磁波シールド膜は、光学フィルターや、液晶表示板、プラズマ ディスプレイパネル、その他の画像表示パネルなどに組み込まれる際には、接着剤 層を介して接合される。  The translucent electromagnetic wave shielding film of the present invention is bonded via an adhesive layer when incorporated in an optical filter, a liquid crystal display panel, a plasma display panel, other image display panels, or the like.
[0143] 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支持体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。  [0143] The adhesive used in the present invention preferably has a refractive index of 1.40-1.70. This is related to the refractive index of the adhesive, such as a plastic film used in the present invention, to reduce the difference and prevent the visible light transmittance from being lowered. 40-1.70 is good with little decrease in visible light transmittance.
[0144] 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 (0. 098MPa)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 ヽ。流動できるので接着剤層 を設けた透光性電磁波シールド膜 (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貼りあわせることができる。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、接着剤の軟化温 度が 200°C以下であると好ましい。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未満であるので接着剤層の軟ィ匕温度は、 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（1013Pa •s)以下になる温度のことで、通常その温度では 1〜： L0秒程度の時間のうちに流動 が認められる。 [0145] 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)、ポリビニノレ 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 エーテル (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 プロピオネート (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 セルロース (n=l .479)、ポリ塩化ビュル (n=l .54〜 1.55)、ポリアタリ口-トリル (n=l .52) 、ポリメタタリ口-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=l.469)、ポリブチルアタリレ ート (n=1.466)、ポリー2—ェチルへキシルァクリレート =1.463)、ポリ—tーブチルァク リレート (n=1.464)、ポリ 3 エトキシプロピルアタリレート (n=1.465)、ポリオキシカノレボ 二ルテトラメチレン (n=l.465)、ポリメチルアタリレート (n=1.472〜1.480)、ポリ [0144] The adhesive used in the present invention is also preferably an adhesive that flows by heating or pressurization, particularly heating at 200 ° C or less or application of 1 kgfZcm 2 (0.098 MPa) or more. An adhesive that exhibits fluidity under pressure is preferred. Since it can flow, a translucent electromagnetic wave shielding film (electromagnetic wave shielding adhesive film) provided with an adhesive layer can be bonded to an adherend by lamination or pressure molding, particularly pressure molding. Further, it can be easily bonded to an adherend having a curved surface or a complicated shape. 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 softening temperature of the adhesive layer is preferably 80 ° C or higher because the environment used is usually less than 80 ° C. preferable. The softening temperature is the temperature at which the viscosity is 10 12 boise (10 13 Pa • s) or less. Usually, at that temperature, flow is recognized within a time of about 1 to L0 seconds. [0145] Typical examples of the adhesive that flows by heating or pressurization as described above are mainly 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 (Di) -enes such as heptirool 1,3 butadiene (n = l.50), poly 2-tert-butyl-1,3 butadiene (n = l.506), poly 1,3 butadiene (n = 1.515), Polyoxyethylene (n = l.456), Polyoxypropylene (n = l.450), Polyvinylinol ether ( n = l .454), Polybutylhexyl ether (n = l .459), Polybutylbutyl ether (n = l.456) and other polyethers, polybutylacetate (n = l.467), polyesters such as polybulu propionate (n = l.467), polyurethane (n = 1.5-1.6), ethyl cellulose ( n = l.479), polychlorinated bur (n = l .54 to 1.55), polyatari mouth-tolyl (n = l .52), polymetatalit mouth-tolyl (n = l.52), polysulfone (n = l.6) 33), polysulfide (n = 1.6), phenoxy resin (n = 1.5-1.6), polyethyl acrylate (n = l.469), polybutyl acrylate (n = 1.466), poly 2- Ethyl hexyl acrylate = 1.463), poly-tert-butyl acrylate (n = 1.464), poly 3 ethoxypropyl acrylate (n = 1.465), polyoxycanol tetramethylene (n = l.465), poly Methyl acrylate (n = 1.472 to 1.480), poly
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=l.474)、ポリテトラデ シルメタタリレート (n=1.475)、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タリレート (η=1.484)、ポリェチルメタ  Isopropyl methacrylate (n = 1.473), polydodecyl methacrylate (n = 1.474), polytetradecyl methacrylate (n = 1.475), poly (n-propyl methacrylate) Kn = 1.484), poly 1,3 3,5-Trimethylcyclohexylmetatalylate (η = 1.484), Polyethylmeta
タリレート (η=1.485)、ポリー2 -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。  Talylate (η = 1.485), poly-2-troh 2 methylpropyl methacrylate (η = 1.487), poly-1,1-jetylpropyl methacrylate (η = 1.489), polymethylmethacrylate (Κη = 1.489), etc. The poly (meth) acrylic acid ester can be used. Two or more kinds of these acrylic polymers may be copolymerized as required, or two or more kinds may be blended and used.
[0146] 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.  [0146] Further, as a copolymer resin of acrylic resin and other than acrylic resin, epoxy acrylate (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 mとすることが特に好ま 、。 48 to 1.60), urethane acrylate (η = 1.5 to 1.6), polyether acrylate (η = 1.48 to 1.49), polyester acrylate ( η = 1.48 to 1.54), and the like can also be used. In particular, urethane acrylate, epoxy acrylate, and polyether acrylate are excellent from the viewpoint of adhesiveness. As epoxy acrylate, 1,6 hexanediol diglycidyl ether, neodylate Pentyl 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, Examples include (meth) acrylic acid adducts such as pentaerythritol tetraglycidyl ether and sorbitol tetraglycidyl ether. 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 particularly preferably 10 to 80 m, more preferably 20 to 50 m, more than the thickness of the conductive layer.
また、易接着層上に設けられる接着剤は、支持体および前記易接着層との屈折率 の差が 0. 14以下とされる。この屈折率の差を満たすことにより、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、支持体がポリ エチレンテレフタレート（n=1.575；屈折率）の場合、ビスフエノール A型エポキシ榭脂 やビスフエノール 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'ポリグリコー ル型エポキシ榭脂、ポリオレフイン型エポキシ榭脂、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=1.52)、ポリイソプレン (n=1.521)、ポリ 1, 2 ブタジエン（ n=1.50)、ポリイソブテン（n=1.505〜1.51)、ポリブテン（n=1.5125)、ポリ 2 へプチ ルー 1, 3 ブタジエン（n=1.50)、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=1.515)などの（ジ）ェン類、ポリオキシエチレン（n=l.45 63)、ポリオキシプロピレン（n=1.4495)、ポリビュルェチルエーテル（n=1.454)、ポリビ -ルへキシルエーテル（n=1.4591)、ポリビュルブチルエーテル（n=1.4563)などのポ リエ一テル類、ポリビュルアセテート（n=l.4665)、ポリビュルプロピオネート（n=l.466Further, the adhesive provided on the easy-adhesion layer has a difference in refractive index between the support and the easy-adhesion layer of 0.14 or less. By satisfying this difference in refractive index, the visible light transmittance decreases and becomes good. Adhesive materials that satisfy these requirements include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and tetrahydroxyphenyl when the support is polyethylene terephthalate (n = 1.575; refractive index). Methane-type epoxy resin, novolak-type epoxy resin, resorcin-type epoxy resin, polyalcohol polyglycol-type epoxy resin, polyolefin-type epoxy resin, epoxy resin such as alicyclic and halogen-bisphenol (all A refractive index of 1.55 to 1.60) can be used. Except for epoxy resin, natural rubber (n = 1.52), polyisoprene (n = 1.521), poly 1,2 butadiene (n = 1.50), polyisobutene (n = 1.505 to 1.51), polybutene (n = 1.5125), poly 2 Heptip (Di) enes such as lu 1,3 butadiene (n = 1.50), poly 2-t-butyl-1,3 butadiene (n = l.506), poly 1,3 butadiene (n = 1.515), polyoxy Ethylene (n = l.45 63), polyoxypropylene (n = 1.4495), polybutyl ether (n = 1.454), polyvinyl hexyl ether (n = 1.4591), polybutyl butyl ether (n = 1.4563) Polyurate acetates such as polybutyrate ( n = l.4665), polybulupropionate ( n = l.466)
5)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〜l.Polyesters such as 5), polyurethane (n = 1.5 to 1.6), ethyl cellulose (n = 1.479), polychlorinated butyl (n = 1.54 to 1.55), polyacrylonitrile (n = 1.52), polymetatalie mouth-tolyl (n = 1.52), polysulfone (n = 1.633), polysulfide (n = 1.6), phenoxy resin (n = 1.5-l.
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。 6). These express suitable visible light transmittance.
[0148] また、経時で変色し難いものとしてアクリル榭脂がよく知られており、本発明に好まし く用いられる。例としては、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=l.4638)、ポリ 3 エトキシプロピルアタリレート（n=l.465)、ポリオキシカル ボ -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)、ポリドデシルメタタリレート（n=1.474)、ポリテトラ デシルメタクリレート（11=1.4746)、ポリー11ープロピルメタクリレート（11=1.484)、ポリー3 , 3, 5 トリメチルシクロへキシルメタタリレート（n=1.484)、ポリェチルメタタリレート（n =1.485)、ポリ一 2 -トロ一 2—メチルプロピルメタタリレート（n=l.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=l .4889)、ポリメチルメタタリレート（n=1.4893)などのポリ（メタ）アクリル酸エステル、また 、アクリル酸、メタクリル酸が使用可能である。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もできる。分子量 の異なる複数種類のアクリルポリマーをブレンドすることにより、接着剤の粘弾性を所 望の性質に調整することが可能である。 [0148] In addition, acrylic resin is well known as one that hardly changes color over time, and is preferably used in the present invention. Examples include polyethyl acrylate (n = 1.4685), polybutyl acrylate (n = 1.466), poly butyl hexyl acrylate (n = 1.463), poly tert-butyl acrylate (n = l.4638) , Poly 3 ethoxypropyl acrylate (n = l.465), polyoxycarboxyl tetramethacrylate ( n = 1.465), polymethyl acrylate (n = 1.472 to 1.480), polyisopropyl methacrylate (n = 1.4728) ), Polydodecyl methacrylate (n = 1.474), polytetradecyl methacrylate (11 = 1.4746), poly-11-propyl methacrylate (11 = 1.484), poly-3,3,5 trimethylcyclohexyl methacrylate (n = 1.484) ), Poly (ethyl methacrylate) (n = 1.485), poly (2-tro-l-methyl-2-methylpropyl methacrylate) ( n = l.4868), poly (tetra-tetra) rubber-metal methacrylate ( n = 1.4889), poly (1) , 1-Jetylpropylmetata Rate (n = l .4889), poly (meth) acrylic acid esters such as polymethyl methacrylate Tari rate (n = 1.4893), also acrylic acid, methacrylic acid can be used. Two or more kinds of these acrylic polymers may be copolymerized as necessary, or two or more kinds may be blended and used. By blending several types of acrylic polymers with different molecular weights, it is possible to adjust the viscoelasticity of the adhesive to the desired properties.
[0149] さらにアクリル榭脂とアクリルィ匕合物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[0149] Further, as a copolymer resin other than an acrylic resin and an acrylic compound, epoxy acrylate, urethane acrylate, polyether acrylate, polyester acrylate and the like can also be used. Epoxy acrylate and polyether acrylate are particularly excellent from the viewpoint of adhesiveness. As epoxy acrylate, 1, 6 hexanediol diglycidyl is used. Ether, neopentyl glycol diglycidyl ether, aryl alcohol diglycidyl ether, resorcinol diglycidyl ether, diglycidyl adipate, diglycidyl phthalate, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin Such as triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, etc.
(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。 (Meth) acrylic acid adduct is mentioned. Epoxy acrylate is effective in improving adhesiveness 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、支持体上の易 接着層の表面の一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、電磁波シールド性接着フィルムにする。上記で得られた電磁波シ ルド性と透明性を有する電磁波シールド性接着フィルムは、 CRT, PDP、液晶、 E Lなどのディ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、この電磁波シールド性接着フィルムは、 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、金属銀部にはアース線を 設けることが好ましい。 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. The adhesive resin composition is applied to cover part or all of the surface of the easy-adhesion layer on the support, followed by solvent drying and heat-curing steps, followed by electromagnetic wave shielding adhesion. Make a film. The electromagnetic wave shielding adhesive film having the electromagnetic shielding properties and transparency obtained above can be directly attached to a display such as a CRT, PDP, liquid crystal or EL, or used on an acrylic plate, glass plate or other plate or sheet. Paste and use for display. Further, this electromagnetic wave shielding adhesive film is used in the same manner as described above for a window or a case for looking inside a measuring apparatus, measuring apparatus or manufacturing apparatus that generates electromagnetic waves. Furthermore, it is subject to electromagnetic interference by radio towers and high voltage lines. Installed in windows of buildings or automobiles where there is a fear. The metal silver part is preferably provided with a ground wire.
[0151] 支持体が凸凹を有していて、光を散乱するためにヘイズを有する場合でも、その凹 凸面に支持体と屈折率が近い樹脂が平滑に塗布または、榭脂シートが貼合わされる 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。また本発明における メッシュ状の細線は、ライン幅が非常に小さいため肉眼で視認されない。またピッチも 十分に大きい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、ピッチは十分に小さいため、優れたシールド性を発現すると考え られる。  [0151] Even when the support has unevenness and has haze to scatter light, a resin having a refractive index close to that of the support is smoothly applied to the uneven surface, or a resin sheet is laminated. As a result, diffuse reflection is minimized and transparency is developed. Further, the fine mesh line in the present invention is not visually recognized by the naked eye because the line width is very small. In addition, the pitch is sufficiently large so that it appears to be transparent. On the other hand, since the pitch is sufficiently small compared to the wavelength of the electromagnetic wave to be shielded, it is considered that excellent shielding properties are exhibited.
[0152] 一般的には、ディスプレイの表面はガラス製であるので、接着剤を用いて貼り合わ せるのは支持体とガラス板との貼り合わせであり、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んだり、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接着剤が 支持体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、支持体側、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 、高温での接着剤と支持体、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、支持体及びガラス板と接着剤層との密着力は 80°Cにおいて IS08225準拠の試 験方法にぉ 、て lOgZcm ( lONZm)以上であることが好まし!/、。 20g/cm (20N / )以上であることが更に好ましぐ 30g/cm (30N/m)以上であることがとくに好 ましい。ただし、 2000gZcm (2kNZm)を超えるような接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、この接着剤の支持体と面していない部分に不必要に 他の部分に接触しな 、ように合 、紙 (セパレーター）を設けることも可能である。  [0152] Since the surface of the display is generally made of glass, bonding with the adhesive is performed by bonding the support and the glass plate, and bubbles are generated or peeled off on the bonding surface. If this happens, the image will be distorted and the display color will appear different from the original display. In any case, the problem of bubbles and peeling occurs when the adhesive peels off from the support or the glass plate. This phenomenon may occur on both the support side and the glass plate side, and peeling occurs on the side with weaker adhesion. Accordingly, it is necessary that the adhesive strength between the adhesive, the support and the glass plate at a high temperature is high. Specifically, the adhesion between the support and the glass plate and the adhesive layer is preferably at least lOgZcm (lONZm) at 80 ° C according to the test method in conformity with IS08225! /. More preferably, it is more preferably 20 g / cm (20 N / m) or more, and particularly preferably 30 g / cm (30 N / m) or more. However, adhesives exceeding 2000 gZcm (2 kNZm) may not be preferable because the bonding work becomes difficult. However, it can be used without problems if no significant problems occur. Furthermore, it is also possible to provide a paper (separator) so that the portion not facing the support of the adhesive does not unnecessarily contact other portions.
[0153] 接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、霞度が低いこと 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 用いる接着剤は、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接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。 [0153] 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 the temperature is low. Specifically, 0 to 3% is preferable, and 0 to 1.5% is more preferable. The 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 is practical if the adhesive is thin. Can be considered colorless. Similarly, this is not the case when intentionally coloring as described later.
[0154] 上記の特性を有する接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、接着剤を重合法により合成する際に架橋剤の添 加量を下げること、粘着性付与材を加えること、分子の末端基を変化させることなどの 方法によって、粘着性を向上させることも可能である。また、同じ接着剤を用いても、 接着剤を貼り合わせる面、すなわち、支持体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。  [0154] Examples of the adhesive having the above 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 in the case of using the same rosin, it is possible to reduce the amount of the adhesive by synthesizing the adhesive by a method such as lowering the amount of the crosslinking agent, adding a tackifier, or changing the end group of the molecule. It is also possible to improve the performance. Even when the same adhesive is used, it is possible to improve the adhesion by modifying the surface to which the adhesive is bonded, that is, the surface of the support or the 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.
[0155] 透明性、無色性、ハンドリング性の観点から、接着剤層の厚みは、 5〜50 μ m程度 であることが好ましい。接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 、。  [0155] From the viewpoint of transparency, colorlessness, and handling properties, the thickness of the adhesive layer is preferably about 5 to 50 µm. When the 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 as described above and the transparency is within the above range, the thickness may exceed the above range.
[0156] [透光性電磁波シールド膜]  [0156] [Translucent electromagnetic wave shielding film]
次に、本発明の透光性電磁波シールド膜について説明する。  Next, the translucent electromagnetic wave shielding film of the present invention will be described.
本発明の透光性電磁波シールド膜における支持体の厚みは 200 μ m以下が好ま しく、更に好ましく ίま 20 m以上 180 m以下、最も好ましく ίま 50 m以上 120 m 以下である。この範囲であれば所望の可視光の透過率が得られ、かつ取り扱いも容 易である。  The thickness of the support in the translucent electromagnetic shielding film of the present invention is preferably 200 μm or less, more preferably 20 to 180 m, and most preferably 50 to 120 m. Within this range, a desired visible light transmittance can be obtained, and handling is easy.
[0157] 物理現像及び Z又はめつ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乳剤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しい。金属銀部は 1層でもよぐ 2 層以上の重層構成であってもよい。金属銀部がパターン状であり、かつ 2層以上の重 層構成である場合、異なる波長に感光できるように、異なる感色性を付与することが できる。これにより、露光波長を変えて露光すると、各層において異なるパターンを形 成することができる。このようにして形成された多層構造のパターン状金属銀部を含 む透光性電磁波シールド膜は、高密度なプリント配線板として利用することができる。 [0157] The thickness of the metallic silver portion provided on the support before physical development and Z or staking treatment may be appropriately determined according to the coating thickness of the emulsion layer coating applied on the support. it can. 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 preferred to be m That's right. Moreover, it is preferable that a metal silver part is pattern shape. The metallic silver part may be a single layer or a multilayer structure of two or more layers. When the metallic silver part has a pattern and has a multilayer structure of two or more layers, different color sensitivities can be imparted so as to be sensitive to different wavelengths. As a result, when the exposure wavelength is changed for exposure, different patterns can be formed in each layer. The translucent electromagnetic wave shielding film including the patterned metal silver portion having the multilayer structure formed as described above can be used as a high-density printed wiring board.
[0158] 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。 [0158] The thickness of the conductive metal portion is preferably as the electromagnetic wave shielding material of the display, since the viewing angle of the display is wider as it is thinner. 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、上述した乳剤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、さらに物理現像及び Z又はめつき処理により導電性金属粒子 力 なる層の厚みを自在にコントロールできるため、 5 μ m未満、好ましくは 3 μ m未 満の厚みを有する透光性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 metallic silver portion having a desired thickness is formed by controlling the coating thickness of the emulsion layer described above, and further, the thickness of the layer having conductive metal particle force can be freely controlled by physical development and Z or tacking treatment. Since it can be controlled, even a translucent electromagnetic shielding film having a thickness of less than 5 μm, preferably less than 3 μm can be easily formed.
[0159] 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。  [0159] In the conventional method using etching, most of the metal thin film needs to be removed by etching and discarded. However, the present invention supports a pattern containing 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.
[0160] (剥離強度）  [0160] (Peel strength)
本発明の透光性電磁波シールドフィルムとガラス基板との密着強度は、以下のよう なものであることが好まし 、。  The adhesion strength between the translucent electromagnetic wave shielding film of the present invention and the glass substrate is preferably as follows.
フィルム試料をガラスに貼り付け、引っ張り速度 lOOmm/minで接合方向に対して — 180° 方向に引っ張って剥離強度を測定した場合に、 20N/m以上の剥離強度で あることが好ましい。更には、 60°Cの温度で相対湿度 90%のもとで 72時間経時した 後の上記剥離強度で、 20N/m以上の剥離強度であることが好ま 、。  When a peel strength is measured by sticking a film sample on glass and pulling in a direction of 180 ° to the joining direction at a pulling speed of lOOmm / min, the peel strength is preferably 20 N / m or more. Further, it is preferable that the peel strength after a lapse of 72 hours at a temperature of 60 ° C. and a relative humidity of 90% is a peel strength of 20 N / m or more.
[0161] [透光性電磁波シールド膜の作製方法] 本発明の透光性電磁波シールド膜は、好ましくは支持体上に感光性ハロゲンィ匕銀 塩を含有する乳剤層を有する感光材料を露光し、現像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て得られる。さ らに必要に応じて前記金属銀部に物理現像および Zまたはめつき処理を施すことに よって前記金属銀部に導電性金属を担持させてもよい。 [0161] [Method for producing translucent electromagnetic shielding film] The light-transmitting electromagnetic wave shielding film of the present invention preferably exposes a photosensitive material having an emulsion layer containing a photosensitive halogenated silver salt on a support and applies a development treatment to exposed and unexposed areas. Each is obtained by forming a metallic silver portion and a light transmitting portion. Further, if necessary, the metallic silver portion may be subjected to physical development and Z or staking treatment to carry a conductive metal on the metallic silver portion.
本発明の透光性電磁波シールド膜の形成方法は、感光材料と現像処理の形態に よって、次の 3通りの形態が含まれる。  The method for forming a translucent electromagnetic wave shielding film of the present invention includes the following three forms depending on the photosensitive material and the form of development processing.
(I)物理現像核を含まな ヽ感光性ハロゲンィ匕銀黒白感光材料を化学現像又は熱現 像して金属銀部を該感光材料上に形成させる方法  (I) A method of forming a metallic silver portion on a photosensitive material by chemically developing or thermally developing a photosensitive halogen-silver-black / white photosensitive material that does not contain physical development nuclei.
(II)物理現像核をハロゲン化銀乳剤層中に含む感光性ハロゲンィ匕銀黒白感光材料 を溶解物理現像して金属銀部を該感光材料上に形成させる方法  (II) A method in which a photosensitive silver halide silver-white photosensitive material containing physical development nuclei in a silver halide emulsion layer is dissolved and physically developed to form a metallic silver portion on the photosensitive material.
(III)物理現像核を含まな ヽ感光性ハロゲンィ匕銀黒白感光材料と、物理現像核を含 む非感光性層を有する受像シートを重ね合わせて拡散転写現像して金属銀部を非 感光性受像シート上に形成させる方法  (III) A photosensitive silver halide silver / white photosensitive material that does not contain physical development nuclei and an image-receiving sheet that has a non-photosensitive layer containing physical development nuclei are overlaid and diffusion transfer developed to make the metallic silver portion non-photosensitive. Method of forming on image receiving sheet
上記 (I)の態様は、一体型黒白現像タイプであり、感光材料上に金属銀が形成され る。得られる現像銀は化学現像銀又は熱現像銀であり、高比表面のフィラメントであ る点で後続するめつき又は物理現像過程で活性が高い。  The mode (I) is an integrated black-and-white development type, in which metallic silver is formed on the photosensitive material. The resulting developed silver is chemically developed silver or heat developed silver, and is highly active in the subsequent staking or physical development process in that it is a filament with a high specific surface.
上記 (Π)の態様は、露光部では、物理現像核近縁のハロゲンィ匕銀粒子が溶解され て現像核上に沈積することによって感光材料上に金属銀が形成される。これも一体 型黒白現像タイプである。現像作用が、物理現像核上への析出であるので高活性で あるが、現像銀は比表面は小さ 、球形である。  In the above aspect (ii), in the exposed portion, the silver halide grains close to the physical development nucleus are dissolved and deposited on the development nucleus, whereby metallic silver is formed on the photosensitive material. This is also an integrated black-and-white development type. Since the developing action is precipitation on physical development nuclei, it is highly active, but developed silver has a small specific surface and is spherical.
上記 (ΠΙ)の態様は、未露光部にぉ 、てハロゲンィ匕銀粒子が溶解されて拡散して受 像シート上の現像核上に沈積することによって受像シート上に金属銀が形成される。 いわゆるセパレートタイプであって、受像シートを感光材料力も剥離して用いる態様 である。  In the aspect (ii), the silver halide silver particles are dissolved and diffused in the unexposed area, and are deposited on the development nuclei on the image receiving sheet to form metallic silver on the image receiving sheet. This is a so-called separate type, in which the image-receiving sheet is used with the photosensitive material force peeled off.
V、ずれの態様もネガ型現像処理および反転現像処理の ヽずれの現像を選択する こともできる (拡散転写方式の場合は、感光材料としてオートポジ型感光材料を用い ることによってネガ型現像処理が可能となる)。 ここでいう化学現像、熱現像、及び溶解物理現像は、当業界で通常用いられている 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 Proces ses,第 4版」（Mcmillan社、 1977刊行）に解説されている。本件は液処理であるが、そ の他の出願については現像方式として、熱現像方式も適用される。例えば、特開 20 04— 184693号、同 2004— 334077号、同 2005— 010752号、特願 2004— 244 080号、同 2004— 085655号などの各公報力 用できる。 V, the mode of deviation can also be selected as negative development between negative development processing and reversal development processing (in the case of the diffusion transfer method, negative development processing can be performed by using an auto positive photosensitive material as the photosensitive material. Possible). The chemical development, thermal development, and dissolution physical development referred to here have the meanings commonly used in the art, and are general textbooks of photographic chemistry such as “Photochemistry” written by Shinichi Kikuchi (Kyoritsu Publishing Co., 1955). Published in CEK Mees, “The Theory of Photographic Proces ses, 4th edition” (Mcmillan, 1977). This case is liquid processing, but for other applications, the thermal development method is also applied as the development method. For example, Japanese Patent Application Laid-Open Nos. 2004-184693, 2004-334077, 2005-010752, Japanese Patent Application Nos. 2004-244080, 2004-085655, and the like can be used.
[0162] 剥離可能な保護フィルム [0162] Peelable protective film
本発明の透光性電磁波シールド膜は、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、透光性電磁波シールド膜の両面に設ける必要はなぐ金属銀部 あるいは導電性金属部上のみ、あるいはその逆側のみに設けることもできる。保護フ イルムは、金属銀部あるいは導電性金属部上に設けた場合は、いわゆる剥離可能で あることが望ましい。  The translucent electromagnetic wave shielding film of the present invention can be provided with a peelable protective film. The protective film need not be provided on both sides of the translucent electromagnetic wave shielding film, and can be provided only on the metallic silver portion or the conductive metallic portion, or only on the opposite side. When the protective film is provided on the metallic silver portion or the conductive metallic portion, it is desirable that the protective film be peelable.
[0163] 保護フィルムの剥離強度は前記の試験条件で 5mNZ25mm幅〜 5NZ25mm幅 であることが好ましぐより好ましくは 10mNZ25mm幅〜 100mNZ25mm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、金属銀部あるいは導電性金属部が支持体から剥離する恐れ があり、やはり好ましくない。  [0163] The peel strength of the protective film is preferably 5mNZ25mm width to 5NZ25mm width under the above test conditions, more preferably 10mNZ25mm width to 100mNZ25mm width. If it is less than the lower limit, peeling is too easy 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 metallic silver part or the conductive metallic part may be peeled off from the support, which is also not preferable.
[0164] 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ー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く 、また、保護フィルムの接着される面にはコロナ放電処理を施しておくことが好ましい  [0164] As a film constituting the protective film, polyethylene resin, which is polyolefin resin, polypropylene resin, polyester resin such as polyethylene terephthalate resin, resin resin film such as polycarbonate resin, acrylic resin, etc. It is preferable to use, and the surface to which the protective film is bonded is preferably subjected to corona discharge treatment.
[0165] また、保護フィルムを構成する接着剤としては、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。 [0165] As the adhesive constituting the protective film, an acrylic ester-based, rubber-based, or silicone-based adhesive can be used.
[0166] [黒化層] [0166] [Blackening layer]
本発明のロール状透光性電磁波シールド膜や、それを組み込んだ光学フィルムは 、黒ィ匕処理を施したものであってもよい。 The roll-shaped translucent electromagnetic shielding film of the present invention and the optical film incorporating it are In addition, it may have been subjected to black wrinkle processing.
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えた黒化層は、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、金 属箔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、金属箔の片面 もしくは両面に行なうことができる力 市販のクロメート処理された銅箔等を利用しても よい。なお、予め黒ィ匕処理された金属箔を用いることもできるが、後の適宜な工程に おいて、黒化処理してもよい。黒ィ匕層の形成は、レジスト層となり得る感光性榭脂層 を、黒色に着色した組成物を用いて形成し、エッチングが終了した後に、レジスト層を 除去せずに残留させることによつても形成できるし、黒色系の被膜を与えるめっき法 によってもよい。  The black wrinkle process is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-188576. The blackened layer formed even by the blackening treatment can impart antireflection properties in addition to the antifungal effect. The black layer can be formed by, for example, Co—Cu alloy plating, and can prevent reflection of the surface of the metal foil. Further, a chromate treatment may be performed thereon as a fouling treatment. The chromate treatment is performed by immersing in a solution containing chromic acid or dichromate as a main component and drying to form an anti-fouling coating, which can be performed on one or both sides of the metal foil as required. Force Commercially available chromate-treated copper foil or the like may be used. Although a metal foil that has been blackened in advance can be used, it may be blackened in an appropriate later step. Formation of the black wrinkle layer is accomplished by forming a photosensitive resin layer that can be a resist layer using a black colored composition, and leaving the resist layer without removal after etching is completed. Alternatively, a plating method that gives a black film may be used.
[0167] 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。  [0167] Further, as another example of the configuration including the black glazed layer, the configuration shown in Japanese Patent Laid-Open No. 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.
[0168] 本発明にお ヽて、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 めっき浴 (商品名、ノ―ブロイ SNC、 Sn— Ni合金系）、日本化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— 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 Cuの場合、硫化水素（H S)液処理して、 Cuの表面を硫 [0168] In the present invention, the electrolyte bath containing the blackening material (black tanning bath) may be a black tanning bath containing nickel sulfate as a main component. Commercially available black plating baths can also be used in the same way. Specifically, for example, a black plating bath manufactured by Shimizu Co., Ltd. (trade name, Novroy SNC, Sn—Ni alloy system), Nippon Chemical Industry Co., Ltd. Black bathing bath (trade name, Nitsuka Black, Sn—Ni alloy) manufactured by Co., Ltd., Black bathing bath (trade name, Evo--Chromium 85 series-85 series, manufactured by Metal Chemical Co., Ltd.) Cr type) can be used. In the present invention, the black tanning bath includes Zn, Cu, Various black tanning baths such as others can be used. 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, treat the surface of Cu with hydrogen sulfide (HS) solution treatment.
2  2
ィ匕銅 (CuS)として黒ィ匕し、第 2の黒ィ匕層が形成される。メッシュ状の導電性バタ—ン を構成する材料としては、前述の良導電性物質としての金属が最も有利な材料として 使用することがでる。而して、上記の金属電着層を形成する場合には、汎用金属の 電解液を使用することができるので、多種類の、安価な金属電解液が存在し、目的 に適った選択を自由に行うことができるという利点がある。一般に、安価な良導電性 金属としては、 Cuが多用されており、本発明においても、 Cuを使用することが、その 目的にも合致して有用なものであり、勿論、その他の金属も同様に用いることができ るものである。次にまた、本発明において、メッシュ状の導電性パターン 4は、単一金 属層のみで構成する必要はなぐ例えば、図示しないが、上記の例の Cuからなるメッ シュ状の導電性バタ一ンは、比較的に柔らかく傷がつき易いので、その保護層として 、 Niや Cr等の汎用の硬質金属を用いて 2層からなる金属電着層とすることもできる。 なお、第 2の黒ィ匕層のための黒ィ匕処理剤としては、硫化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 'コパーブラッ ク CuO、同 CuS、セレン系のコパ一ブラック No. 65等（アイソレ一ト化学研究所製）、 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 [透光性電磁波シールド膜の電磁波シールド以外の機能層] As a result, the second black layer is formed. As a material constituting the mesh-like conductive pattern, the metal as the above-mentioned good conductive substance can be used as the most advantageous material. Therefore, when forming the above-mentioned metal electrodeposition layer, general-purpose metal electrolytes can be used, so there are many kinds of inexpensive metal electrolytes, and the choice according to the purpose is free. There is an advantage that can be done. In general, Cu is frequently used as an inexpensive and highly conductive metal, and in the present invention, it is useful to use Cu in accordance with the purpose. Of course, other metals are similarly used. It can be used for Next, in the present invention, the mesh-like conductive pattern 4 does not need to be composed of only a single metal layer. For example, although not shown, the mesh-like conductive pattern 4 made of Cu in the above example is used. Since it is relatively soft and easily scratched, the protective layer can be a two-layer metal electrodeposition layer using a general-purpose hard metal such as Ni or Cr. In addition, as the blackening agent for the second blackening layer, it can be easily manufactured using a sulfide-based compound, and there are many types of treating agents on the market. 'Copper black CuO, CuS, selenium-based Copa Black No. 65, etc. (made by Isolate Chemical Laboratories), trade name' Ebonol C Special (made by Meltex Co., Ltd.), etc. can be used. Functional layers other than electromagnetic shielding of optical electromagnetic shielding film]
本発明では、必要に応じて、別途、機能性を有する機能層を設けていてもよい。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、金属 銀部あるいは導電性金属部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。 In the present invention, a functional layer having functionality may be separately provided as necessary. This functional layer can have various specifications for each application. For example, as an electromagnetic shielding material for displays, an antireflection layer with an antireflection function that adjusts the refractive index and film thickness, a non-glare layer or an antiglare layer (both have a glare prevention function), and absorbs near infrared rays. Near-infrared absorbing layer made of a compound or metal that absorbs visible light in a specific wavelength range, a layer that adjusts the color tone to absorb visible light, an antifouling layer that easily removes dirt such as fingerprints, and scratch-resistant A hard coat layer, a layer having an impact absorbing function, a layer having a function of preventing glass scattering when glass is broken, and the like can be provided. These functional layers are metal It may be provided on the opposite side of the silver part or conductive metal part and the support, or on the same side.
これらの機能層を設けた材料を光学フィルター（または単にフィルター）と呼ぶ。  A material provided with these functional layers is called an optical filter (or simply a filter).
[0170] く機能性フィルム〉  [0170] Special Functional Film>
透光性電磁波シールド膜をディスプレイ (特にプラズマディスプレイ）に用いる場合 には、以下に説明する機能層 (機能性フィルム)を貼付することにより、各機能性を付 与することが好ま Uヽ。機能性フィルムは接着剤等を介して透光性電磁波シールド膜 に直接または間接的に貼付することができる。機能性フィルムは、適当な透明基材上 に反射防止性 ·防眩性を有する機能層を設けることにより形成することができる。 (反射防止性'防眩性）  When using a translucent electromagnetic shielding film for a display (especially a plasma display), it is preferable to attach each functional layer by attaching a functional layer (functional film) described below. The functional film can be directly or indirectly attached to the translucent electromagnetic shielding film via an adhesive or the like. The functional film can be formed by providing a functional layer having antireflection properties and antiglare properties on a suitable transparent substrate. (Anti-reflective 'Anti-glare)
透光性電磁波シールド膜には、外光反射を抑制するための反射防止 (AR:アンチ リフレクション)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 、ずれかの機能性を付与 することが好ましい。  The translucent electromagnetic wave shielding film has anti-reflection (AR: anti-reflection) properties to suppress external light reflection, anti-glare properties (AG: anti-glare) properties to prevent reflection of mirror images, or both. It is preferable to provide any anti-glare and anti-glare (ARAG) function provided.
これらの性能により、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 うのを防止できる。また、膜表面の可視光線反射率が低くすることにより、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。反射防止性 ·防眩性を有す る機能性フィルムを透光性電磁波シールド膜に貼付した場合の可視光線反射率は、 2%以下であることが好ましぐより好ましくは 1. 3%以下、さらに好ましくは 0. 8%以 下である。  With these performances, it is possible to prevent the display screen from becoming difficult to see due to the reflection of lighting equipment. In addition, by reducing the visible light reflectance on the film surface, it is possible to improve contrast and the like that can be achieved only by preventing reflection. Anti-glare property ・ When a functional film having anti-glare properties is applied to a translucent electromagnetic wave shielding film, the visible light reflectance is preferably 2% or less, more preferably 1.3% or less. More preferably, it is 0.8% or less.
[0171] 反射防止層としては、例えば、フッ素系透明高分子榭脂ゃフッ化マグネシウム、シリ コン系榭脂ゃ酸化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、硫化物等の無機化合 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等で形成することができる。  [0171] As the antireflection layer, for example, a thin film made of a fluorine-based transparent polymer resin, magnesium fluoride, a silicon-based resin, silicon oxide, or the like, for example, with an optical film thickness of 1Z4 wavelength, Two or more layers of thin films of inorganic compounds such as metal oxides, fluorides, halides, nitrides and sulfides, or organic compounds such as silicon-based resins, acrylic resins, and fluorine-based resins with different rates Can be formed.
[0172] 防眩性層としては、 0. 1 π！〜 10 m程度の微少な凹凸の表面状態を有する層 力 形成することができる。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塗布、硬化することにより形成することが可能 である。粒子の平均粒径は、 1〜40 m程度が好ましい。 [0172] As the antiglare layer, 0.1 π! It is possible to form a laminar force having a surface state with minute irregularities of about 10 m. Specifically, thermosetting or photocuring type such as acrylic resin, silicon resin, melamine resin, urethane resin, alkyd resin, fluorine resin, etc. It can be formed by coating and curing a resin obtained by dispersing particles of inorganic compound or organic compound such as silica, organic silicon compound, melamine, acrylic, etc. on the resin. The average particle size of the particles is preferably about 1 to 40 m.
また、防眩性層としては、上記の熱硬化型または光硬化型榭脂を塗布した後、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形成するこ とがでさる。  The antiglare layer can also be formed by applying the thermosetting or photocurable resin as described above and then pressing and curing a mold having a desired dalos value or surface state. Monkey.
防眩性層を設けた場合の透光性電磁波シールド膜の光透過の際に生じるヘイズは 0. 5%以上 20%以下であることが好ましぐより好ましくは 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。  When the antiglare layer is provided, the haze generated during light transmission of the translucent electromagnetic shielding film is preferably 0.5% or more and 20% or less, more 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.
[0173] (ハードコート性） [0173] (Hard coat)
透光性電磁波シールド膜に耐擦傷性を付加するために、機能性フィルムがハード コート性を有していることも好適である。ハードコート層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 い。ハードコート層の厚さは、 1〜50 /ζ πι程度であることが好ましい。ハードコート層 上に上記の反射防止層および Ζまたは防眩層を形成すると、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。  In order to add scratch resistance to the translucent electromagnetic wave shielding film, it is also preferable that the functional film has a hard coat property. Examples of the hard coat layer include thermosetting type or photosetting type resin such as acrylic resin, silicone resin, melamine resin, urethane resin, alkyd resin, and fluorine resin. However, the type and formation method are not particularly limited. The thickness of the hard coat layer is preferably about 1 to 50 / ζ πι. When the above-mentioned antireflection layer and wrinkle or antiglare layer are formed on the hard coat layer, a functional film having scratch resistance / antireflection and wrinkle or antiglare property is preferably obtained.
ハードコート性が付与された透光性電磁波シールド膜の表面硬度は、 JIS (κ— 54The surface hardness of the translucent electromagnetic shielding film with hard coat properties is JIS (κ-54
00)に従った鉛筆硬度が少なくとも Hであることが好ましぐより好ましくは 2H、さらに 好ましくは 3H以上である。 The pencil hardness according to (00) is preferably at least H, more preferably 2H, even more preferably 3H or more.
[0174] (帯電防止性） [0174] (Antistatic property)
静電気帯電によるホコリの付着や、人体との接触による静電気放電を防止するため 、透過性電磁波シールド膜には、帯電防止性が付与されることが好ましい。  In order to prevent dust adhesion due to electrostatic charging and electrostatic discharge due to contact with the human body, it is preferable that the transmissive electromagnetic wave shielding film has antistatic properties.
帯電防止性を有する機能性フィルムとしては、導電性の高 、フィルムを用いることが でき、例えば導電性が面抵抗で 1011 Ω Zsq程度以下であればょ 、。 As the functional film having antistatic properties, a film having high conductivity can be used. For example, if the conductivity is about 10 11 ΩZsq or less in terms of surface resistance,
導電性の高いフィルムは、透明基材上に帯電防止層を設けることにより形成するこ とができる。帯電防止層に用いる帯電防止剤としては、具体的には、商品名ペレスタ ット (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。他に、 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で帯電防止層を形成してもよい。上述 のハードコート層、反射防止層、防眩層等に、導電性微粒子を含有させる等して帯 電防止性を付与してもよい。 A highly conductive film can be formed by providing an antistatic layer on a transparent substrate. Specific examples of the antistatic agent used in the antistatic layer include the trade name Perester. (Sanyo Kasei Co., Ltd.) and trade name Electro Slipper (Kao Co., Ltd.). In addition, the antistatic layer may be formed of a known transparent conductive film such as ITO, or a conductive film in which conductive ultrafine particles such as ITO ultrafine particles and tin oxide ultrafine particles are dispersed. The above hard coat layer, antireflection layer, antiglare layer and the like may be provided with antistatic properties by containing conductive fine particles.
[0175] (防汚性）  [0175] (Anti-fouling property)
透光性電磁波シールド膜が防汚性を有して 、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。  If the light-transmitting electromagnetic wave shielding film has antifouling property, it is preferable because it can be easily removed when it is prevented from being smudged or smudged.
防汚性を有する機能性フィルムは、例えば透明基材上に防汚性を有する化合物を 付与することにより得られる。防汚性を有する化合物としては、水および Zまたは油 脂に対して非濡性を有する化合物であればよぐ例えばフッ素化合物やケィ素化合 物が挙げられる。フッ素化合物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。  A functional film having antifouling properties can be obtained, for example, by applying a compound having antifouling properties on a transparent substrate. As the compound having antifouling property, for example, a fluorine compound or a key compound may be used as long as the compound has non-wetting property with respect to water and Z or oil. Specific examples of the fluorine compound include trade name OPTOOL (manufactured by Daikin) and the like, and examples of the key compound include trade name Takata Quantum (manufactured by NOF Corporation).
[0176] (紫外線カット性）  [0176] (UV-cutting property)
透光性電磁波シールド膜には、後述する色素や支持体の劣化等を防ぐ目的で紫 外線カット性を付与することが好ま U、。紫外線カット性を有する機能性フィルムは、 支持体自体に紫外線吸収剤を含有させる方法や支持体上に紫外線吸収層を設ける こと〖こより形成することができる。  It is preferable to give the translucent electromagnetic wave shielding film an ultraviolet ray-cutting property for the purpose of preventing deterioration of the dye and the support described later. The functional film having ultraviolet cut-off property can be formed by a method of containing an ultraviolet absorber in the support itself or by providing an ultraviolet absorbing layer on the support.
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。 紫外線カット性を有する機能性フィルムは、紫外線吸収剤や紫外線を反射または吸 収する無機化合物を含有する層を透明基材上に形成することにより得られる。紫外 線吸収剤は、ベンゾトリアゾール系やべンゾフエノン系等、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。  As the ultraviolet ray cutting ability necessary for protecting 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. A functional film having an ultraviolet cutting property can be obtained by forming a layer containing an ultraviolet absorber or an inorganic compound that reflects or absorbs ultraviolet rays on a transparent substrate. Conventionally known UV absorbers such as benzotriazoles and benzophenones can be used, and their type 'concentration is dispersibility in the medium to be dispersed or dissolved' solubility, absorption wavelength-absorption coefficient, medium It is determined by the thickness of the material and is not particularly limited.
[0177] なお、紫外線カット性を有する機能性フィルムは、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。 また、機能性フィルムに後述する色素を含有する層が形成されている場合は、その 層よりも外側に紫外線カット性を有する層が存在することが望ましい。 [0177] It should be noted that the functional film having ultraviolet cut-off property preferably has little absorption in the visible light region and does not significantly reduce the visible light transmittance or exhibit a color such as yellow. Moreover, when the layer containing the pigment | dye mentioned later is formed in the functional film, it is desirable that the layer which has ultraviolet-cutting property exists outside the layer.
[0178] (ガスバリア性）  [0178] (Gas barrier property)
透光性電磁波シールド膜を常温常湿よりも高い温度，湿度環境化で使用すると、水 分により後述する色素が劣化したり、貼り合せに用いる接着剤中や貼合界面に水分 が凝集して曇ったり、水分による影響で接着剤が相分離して析出して曇ったりするこ とがあるので、透光性電磁波シールド膜はガスバリア性を有して ヽることが好ま 、。 このような色素劣化や曇りを防ぐためには、色素を含有する層や接着剤層への水 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。 If a translucent electromagnetic shielding film is used in a temperature and humidity environment higher than normal temperature and humidity, the dye described later deteriorates due to moisture, or moisture aggregates in the adhesive used for bonding and the bonding interface. It is preferable that the translucent electromagnetic wave shielding film has a gas barrier property because it may be clouded or the adhesive may be phase-separated and deposited due to the influence of moisture. In order to prevent such deterioration and fogging of the pigment, it is important to prevent the penetration of water into the pigment-containing layer and the adhesive layer, and the water vapor permeability of the functional film is preferably lOgZm 2 · day or less, preferably Is preferably 5 gZm 2 · day or less.
[0179] (その他の光学特性） [0179] (Other optical properties)
プラズマディスプレイは強度の近赤外線を発生するため、透光性電磁波シールド膜 を特にプラズマディスプレイに用いる場合は、近赤外線カット性を付与することが好ま しい。  Since a plasma display generates intense near-infrared rays, it is preferable to provide a near-infrared cut-off property, particularly when a light-transmitting electromagnetic wave shielding film is used for a plasma display.
近赤外線カット性を有する機能性フィルムとしては、波長領域 800〜 1 OOOnmにお ける透過率を 25%以下であるものが好ましぐより好ましくは 15%以下、さらに好まし くは 10%以下である。  As a functional film having near-infrared cutting properties, a film having a transmittance of 25% or less in a wavelength region of 800 to 1 OOOnm is preferably less than 15%, more preferably less than 10%. is there.
[0180] また、透光性電磁波シールド膜をプラズマディスプレイに用いる場合、その透過色 が-ユートラルグレーまたはブルーグレーであることが好ましい。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ためであり、また、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。  [0180] Further, when the translucent electromagnetic wave shielding film is used for a plasma display, it is preferable that the transmitted color is-neutral gray or blue gray. This is to maintain or improve the light emission characteristics and contrast of the plasma display, and is also a force that may prefer a white color temperature slightly higher than the standard white color.
[0181] さらに、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、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、比較的強い短波長側の発光ピークにより赤色発光がオレン ジに近い色純度の良くないものとなってしまう問題がある。そこで、機能性フィルムは その原因である蛍光体または放電ガス力 の不要発光を選択的に低減させる機能を 有することが好ましい。  [0181] Furthermore, color plasma displays are said to have insufficient color reproducibility. In particular, the emission spectrum of red display shows several emission peaks ranging from about 580 nm to about 700 nm. There is a problem that red emission becomes poor in color purity close to orange due to a strong emission peak on the short wavelength side. Therefore, it is preferable that the functional film has a function of selectively reducing unnecessary light emission of the phosphor or discharge gas force that is the cause thereof.
[0182] 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でき、また、光学フィルターの色調も可 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。 [0182] These optical properties can be controlled by using a dye. In other words, for near-infrared cut Uses near-infrared absorbers, and a dye that selectively absorbs unnecessary light emission to reduce unnecessary light emission can achieve the desired optical characteristics, and the color tone of the optical filter is also visible. And a dye having an appropriate absorption can be used.
[0183] 色素としては、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や、近 赤外線吸収剤として知られている化合物を用いることができ、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、ジイミ-ゥム系化合物等の一般に市販もされている有機 色素が挙げられる。  [0183] The dye may be a general dye or pigment having a desired absorption wavelength in the visible region, or a compound known as a near infrared absorber, and the type thereof is not particularly limited. For example, anthraquinone, phthalocyanine, methine, azomethine, oxazine, imonium, azo, styryl, coumarin, porphyrin, dibenzofuranone, diketopyrrolopyrrole, rhodamine, xanthene, Examples thereof include organic dyes that are generally commercially available, such as pyromethene-based compounds, dithiol-based compounds, and diiminium-based compounds.
[0184] プラズマディスプレイはパネル表面の温度が高ぐ環境の温度が高いときは透光性 電磁波シールド膜の温度も上がるため、色素は、例えば 80°C程度で劣化しない耐熱 '性を有して ヽることが好適である。  [0184] When the temperature of the environment where the temperature of the panel surface is high is high, the temperature of the translucent electromagnetic wave shielding film also rises. Therefore, the dye has a heat resistance that does not deteriorate at about 80 ° C, for example. It is preferable to speak.
また、色素によっては耐光性に乏しいものもある力 このような色素を用いることでプ 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、前述のように機能性フィルムに紫外線吸収剤を含有させたり、紫外線を透過しな い層を設けることによって、紫外線や可視光線による色素の劣化を防止することが好 ましい。  In addition, some dyes have poor light resistance. If such dyes cause problems with the light emission of plasma displays and the deterioration of UV light and visible light from outside light, functional films as described above. It is preferable to prevent the dye from being deteriorated by ultraviolet rays or visible rays by adding an ultraviolet absorber to the layer or providing a layer that does not transmit ultraviolet rays.
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 光学フィルター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 低下する場合がある。  The same applies to humidity and a combined environment in addition to heat and light. When it deteriorates, the transmission characteristics of the optical filter change, and the color tone may change or the near-infrared cutting ability may decrease.
また、支持体を形成するための榭脂組成物や、塗布層を形成するための塗布組成 物中に溶解又は分散させるために、色素は溶媒への溶解性や分散性も高 、ことが 好ましい。  Further, in order to dissolve or disperse in a resin composition for forming a support or a coating composition for forming a coating layer, the dye is preferably highly soluble and dispersible in a solvent. .
[0185] また、色素の濃度は、色素の吸収波長'吸収係数、透光性電磁波シールド膜に要 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'厚さから適宜 設定することができる。  [0185] The concentration of the dye is appropriately set based on the absorption wavelength of the dye, the absorption coefficient, the transmission characteristics required for the light-transmitting electromagnetic wave shielding film, the transmittance, and the type of the medium or coating film to be dispersed. can do.
機能性フィルムに色素を含有させる場合、支持体の内部に含有していてもよいし、 支持体表面に色素を含有する層をコーティングしてもよい。また、異なる吸収波長を 有する色素 2種類以上を混合して一つの層中に含有させてもよ ヽし、色素を含有す る層を 2層以上有して 、てもよ 、。 When the functional film contains a pigment, it may be contained inside the support, A layer containing a dye may be coated on the surface of the support. Further, two or more kinds of dyes having different absorption wavelengths may be mixed and contained in one layer, or two or more layers containing dyes may be provided.
[0186] また、色素は金属との接触によっても劣化する場合があるため、このような色素を用 いる場合、色素を含有する機能性フィルムは、色素を含有する層が透光性電磁波シ 一ルド膜上の金属銀部或いは導電性金属部と接触しな 、ように配置することが更に 好ましい。 [0186] In addition, since the dye may be deteriorated by contact with a metal, when such a dye is used, the functional film containing the dye has a layer containing the light transmitting electromagnetic wave shield. It is more preferable that the metal silver part or the conductive metal part on the metal film be disposed so as not to contact.
[0187] 機能性フィルムを貼付した透光性電磁波シールド膜をディスプレイに装着する際に は、通常、機能性フィルムが外側、接着剤層がディスプレイ側となるように装着する。 ここで、透光性電磁波シールド膜の電磁波シールド能が低下させないために、金属 銀部或いは導電性金属部にアースをとることが望ましい。このため、透光性電磁波シ 一ルド膜上にアースをとるための導通部を形成し、この導通部がディスプレイ本体の アース部に電気的に接触するようにすることが望ましい。導通部は、透光性電磁波シ 一ルド膜の周縁部に沿って金属銀部或 、は導電性金属部の周りに設けられて 、るこ とが好適である。  [0187] When the translucent electromagnetic shielding film with the functional film attached is attached to the display, it is usually attached so that the functional film is on the outside and the adhesive layer is on the display side. Here, in order not to reduce the electromagnetic wave shielding ability of the translucent electromagnetic wave shielding film, it is desirable to ground the metallic silver part or the conductive metallic part. For this reason, it is desirable to form a conductive portion for grounding on the translucent electromagnetic wave shielding film so that the conductive portion is in electrical contact with the ground portion of the display body. The conducting part is preferably provided around the metallic silver part or the conductive metal part along the peripheral edge of the translucent electromagnetic shielding film.
導通部はメッシュパターンにより形成されて 、てもよ 、し、パターユングされて!/、な い、例えば金属箔ベタにより形成されていてもよいが、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、金属箔ベタのようにパターユングされていないこ とが好ましい。  The conductive portion may be formed of a mesh pattern, or may be patterned! /, For example, may be formed of a solid metal foil, but may be in electrical contact with the ground portion of the display body. In order to improve the quality, it is preferable that the metal foil is not patterned like a solid metal foil.
[0188] 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よ 、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。  [0188] The conductive portion may be a mesh pattern layer or not patterned, for example, a solid layer of metal foil. However, in order to improve the electrical contact with the ground portion of the display main body. For this, it is preferable that the conductive portion be patterned like a metal foil solid layer.
[0189] 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。  [0189] When the conductive part is not patterned, such as a solid metal foil, and when the mechanical strength of Z or the conductive part is sufficiently strong, the conductive part itself can be used as an electrode. It is.
[0190] 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。 [0190] It is preferable to form an electrode on the conductive portion for protecting the conductive portion and for good electrical contact with the ground portion when Z or the conductive portion 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.
[0191] 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、光学特性に優れた光学フィルターを得ることが出 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、さらに、プラズマディスプ レイカも放射される 800〜1000nm付近の近赤外線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光学フィルターを得ることができる。さらにまた、耐候性に も優れた光学フィルターを低コストで提供することが出来る。 [0191] According to the present invention, it is possible to obtain an optical filter having excellent optical characteristics that can maintain or improve the image quality without significantly impairing the luminance of the plasma display. In addition, it has excellent electromagnetic shielding ability to block electromagnetic waves that have been pointed out to be harmful to the health of the plasma display, and near infrared rays near 800 to 1000 nm are also emitted from the plasma display. Therefore, it is possible to obtain an optical filter that does not adversely affect the wavelengths used by the remote control of peripheral electronic devices, transmission optical communication, etc., and can prevent malfunctions thereof. Furthermore, an optical filter having excellent weather resistance can be provided at a low cost.
実施例  Example
[0192] 以下に実施例を挙げて本発明の特徴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。  [0192] The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
[0193] (乳剤 Aの調整）  [0193] (Emulsion A adjustment)
•1液：  • 1 solution:
水 750ml  750ml of water
ゼラチン 20g  Gelatin 20g
塩化ナトリウム 1. 6g 1, 3 ジメチルイミダゾリジン 2 チオン 20mg Sodium chloride 1.6 g 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 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 K C1 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 rhodate ammonium (0.001% NaCl 20% aqueous solution) 7ml Potassium hexaloiridium (III) (0.005% KC1 20% aqueous solution) and hexachloro oral rhodate ammonium 0.001% NaC120% aqueous solution) was prepared by dissolving the powder in KC1 20% aqueous solution and NaC120% aqueous solution, respectively, and heating at 40 ° C. for 120 minutes.
[0194] 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。 [0194] In 1 liquid maintained at 38 ° C and pH 4.5, the amount corresponding to 90% of 2 and 3 liquids was not stirred. Nuclear particles were 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.
[0195] ·4液 [0195] · 4 liquids
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  Potassium bromide l lg
黄血塩 5mg [0196] 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 l,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 X 103kg/m3、粘度 = 60mPa' sとなった。 )。 Yellow blood salt 5mg [0196] Thereafter, the substrate 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 is chemically sensitized for optimum sensitivity at 55 ° C, l, 3,3a, 7-tetraazaindene is 100 mg as a stabilizer and proxel is used as a preservative (trade name, ICI Co , Ltd.) lOOmg was added. Finally, a silver iodochlorobromide cubic emulsion containing 70 mol% silver chloride and 0.08 mol% silver iodide with 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 = 1.28 × 10 3 kg / m 3 , and viscosity = 60 mPa ′s.
[0197] [化 4] ァニオン性沈降剤— 1
Figure imgf000074_0001
平均分子 * 1 2万 [0197] [Chemical 4] Anionic precipitants — 1
Figure imgf000074_0001
Average numerator * 1 20,000
[0198] 下記に示すポリエチレンテレフタレートフィルム支持体上に、 UL層 Z乳剤層の構 成となるように塗布してサンプルを作製した。以下に各層の調製方法、塗布量および 塗布方法を示す。 [0198] On the polyethylene terephthalate film support shown below, a sample was prepared by coating so as to form the UL layer Z emulsion layer. The preparation method, coating amount and coating method for each layer are shown below.
<乳剤層 >  <Emulsion layer>
乳剤 Aに増感色素（sd-2) 5.7 X 10— 4モル Zモル Agをカ卩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、 良く混合した。 Emulsion A to sensitizing dye (sd-2) 5.7 X 10- 4 mole of Z moles Ag in example mosquitoes卩subjected to spectral sensitization. Further to KBr3.4 X 10- 4 mole Z mol Ag, the compound (Cpd- 3) 8.0 X 10- 4 mole Z mol Ag Karoe, and mixed well.
次いで 1,3,3a, 7-テトラァザインデン 1.2 X 10— 4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- 2)、 (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支持体上に A g7. 6 Then 1,3,3a, 7- tetra § tetrazaindene 1.2 X 10- 4 mol / mol Ag, Nono Idorokinon 1.2 X 10 2 moles Z mol Ag, Kuen acid 3.0 X 10- 4 mol / mol Ag, surfactants ( Sa-1), (Sa-2), (Sa -3) was added so that the coating amounts were 60 mg / m 2 , 40 mg / m 2 , and 2 mg / m 2 , respectively, and the coating solution pH was adjusted to 5.6 using citrate. The emulsion layer coating solution prepared in this way was placed on a support with Ag 7.6
g/m2、ゼラチン 1. lg/m2になるように塗布した。なお、銀/バインダー（体積比）は、 約 1/1であった。 G / m 2 , gelatin 1. It was applied so as to be 1 lg / m 2 . The silver / binder (volume ratio) was about 1/1.
[0199] <UL層 >  [0199] <UL layer>
ゼラチン 0. 23g/m'  Gelatin 0.23g / m '
化合物 (Cpd-7) 40mgZ m  Compound (Cpd-7) 40mgZ m
化合物 (Cpd-YF) 7mg/ m  Compound (Cpd-YF) 7mg / m
防腐剤（プロキセル) 1. 5mg/ m  Preservative (Proxel) 1.5mg / m
[0200] 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 [0201] [化 5] 増粘剤 z  [0200] The viscosity of the coating solution for each layer was adjusted by adding a thickener represented by the following structure (Z). [0201] [Chemical formula 5] Thickener z
Figure imgf000075_0001
Figure imgf000075_0001
[0202] <支持体>  [0202] <Support>
三酸ィ匕アンチモンを主触媒として重縮合した固有粘度 0. 66のポリエチレンテレフ タレート榭脂を含水率 50ppm以下に乾燥させ、ヒーター温度が 280〜300°C設定の 押し出し機内で溶融させた。  Polyethylene terephthalate resin having an inherent viscosity of 0.66, polycondensed using antimony trioxide and antimony as the main catalyst, was dried to a moisture content of 50 ppm or less and melted in an extruder set at a heater temperature of 280 to 300 ° C.
溶融させた PET榭脂をダイ部より静電印加されたチルロール上に吐出させ、非結 晶ベースを得る。得られた非結晶ベースをベース進行方向に 3. 3倍に延伸後、巾方 向に 3. 8倍に延伸し、厚さ 96 mの支持体をロール形態で製造した。  The molten PET resin is discharged from a die part onto a chill roll that is electrostatically applied to obtain a non-crystalline base. The obtained amorphous base was stretched 3.3 times in the direction of travel of the base and then stretched 3.8 times in the width direction to produce a support having a thickness of 96 m in the form of a roll.
[0203] く易接着層:バック層 (銀塩乳剤層と支持体をはさんで逆側に位置する易接着層） > 支持体上に下記組成の塗布液を下記塗布条件にて、逐次、塗工、乾燥し、バック 層 (易接着層） 1を形成した。  [0203] Easy adhesion layer: Back layer (easy adhesion layer located on the opposite side of the silver salt emulsion layer and the support)> A coating solution having the following composition on the support under the following coating conditions, Coating and drying were performed to form a back layer (easy adhesion layer) 1.
[0204] 二軸延伸した上記ポリエチレンテレフタレート支持体を、搬送速度 105mZ分条件 で搬送した状態で、概支持体表面を印加工ネルギー 727jZm2条件でコロナ放電処 理を行ったのち、下記組成力もなる帯電防止層用塗布液を塗布量、 7. lccZm2で バーコート法により塗布した。続いてエアー浮上乾燥ゾーンで 180°C1分乾燥するこ とで帯電防止層を得た。 [0204] The above-mentioned biaxially stretched polyethylene terephthalate support was transported at 105mZ. After carrying out corona discharge treatment on the surface of the general support under the condition of printing energy 727jZm 2 under the condition of transported in step 1 , the coating amount for the antistatic layer with the following compositional strength is applied. 7. Bar coating method with lccZm 2 Applied. Subsequently, an antistatic layer was obtained by drying at 180 ° C. for 1 minute in an air flotation drying zone.
[0205] (1層目塗布液 （帯電防止層用）） [0205] (First-layer coating solution (for antistatic layer))
蒸留水 781.7質量部  Distilled water 781.7 parts by mass
ポリアクリル榭脂（ジユリマー ET- 410：日本純薬製、固形分 30%) 30.9質量部 針状構造酸化スズ粒子 (FS-10D :石原産業製、固形分 20%) 131.1質量部 カルポジイミドィ匕合物 (カルポジライト V-02-L2 :日清紡製、固形分 40%) 6.4質量部 界面活性剤 (サンデット BL:三洋化成工業製 固形分 44.6%) 1.4質量部 界面活性剤けロアクティー HN-100 :三洋化成工業製 固形分 100%) 0.7質量 部  Polyacrylic resin (Jiurimer ET-410: Nippon Pure Chemical Co., Ltd., solid content 30%) 30.9 parts by mass Needle-shaped tin oxide particles (FS-10D: Ishihara Sangyo Co., Ltd., solid content 20%) 131.1 parts by mass Carposiimide compound (Carpolite V-02-L2: Nisshinbo, solid content 40%) 6.4 parts by mass Surfactant (Sandet BL: Sanyo Chemical Industries, solid content 44.6%) 1.4 parts by mass Surfactant surfactant HN-100: Sanyo Chemical Industrial 100% solids) 0.7 parts by mass
シリカ微粒子分散液 (シーホスター KE- W30 :日本触媒製 0.3 m固形分 20%) 5.0質 量部  Silica fine particle dispersion (Seahoster KE-W30: Nippon Shokubai 0.3 m solid content 20%) 5.0 parts by mass
[0206] 搬送速度 105mZ分を保ったまま、上記帯電防止層上に、引き続き、下記組成から なる表面層用塗布液をバーコート法により塗布量 5. 05ccZm2で塗布した。続いて エアー浮上乾燥ゾーンで 160°C1分乾燥することで 2層構成のバック層を得た。 [0206] A surface layer coating solution having the following composition was applied on the antistatic layer at a coating amount of 5.05 ccZm 2 on the antistatic layer while maintaining the conveyance speed of 105 mZ. Subsequently, a back layer having a two-layer structure was obtained by drying at 160 ° C. for 1 minute in an air flotation drying zone.
[0207] (2層目塗布液 （表面層用））  [0207] (Second layer coating solution (for surface layer))
蒸留水 941.0質量部  941.0 parts by mass of distilled water
ポリアクリル榭脂（ジユリマー ET- 410：日本純薬製、固形分 30%) 57.3質量部 エポキシィ匕合物 (デナコール EX-521：ナガセ化成工業製、固形分 100%) 1.2質量部 界面活性剤 (サンデット BL:三洋化成工業製 固形分 44.6%) 0.5質量部 Polyacrylic resin (Julimer ET-410: Nippon Pure Chemical Co., Ltd., 30% solid content) 57.3 parts by weight Epoxy compound (Denacol EX-521: Nagase Chemical Industries, 100% solid content) 1.2 parts by mass Surfactant ( (Sandet BL: Sanyo Chemical Industries, solids 44.6%) 0.5 parts by mass
[0208] また、塗布液組成を、上記易接着層 1のものから下記のように変更し、下記易接着 層を形成した。 [0208] Further, the composition of the coating solution was changed from that of the easy-adhesion layer 1 as follows to form the following easy-adhesion layer.
[0209] 易接着層 2  [0209] Easy adhesion layer 2
易接着層 1に対し、針状構造酸化スズ粒子 (FS-10D :石原産業製、固形分 20%)を含 有させることなぐ塗布液を調整し、易接着層 2を形成した。  The easy-adhesion layer 2 was formed by adjusting the coating solution without adding acicular structure tin oxide particles (FS-10D: manufactured by Ishihara Sangyo Co., Ltd., solid content 20%) to the easy-adhesion layer 1.
[0210] 易接着層 4 上記の 1層目塗布液と、 2層目塗布液とを下記組成に変更して易接着層 4を形成し た。（1層目塗布液） [0210] Easy adhesion layer 4 The easy-adhesion layer 4 was formed by changing the first-layer coating liquid and the second-layer coating liquid to the following composition. (1st layer coating solution)
蒸留水 578.7質量部  Distilled water 578.7 parts by mass
スチレン ブタジエン共重合体ラテックス  Styrene Butadiene copolymer latex
(Nipol Latex LX407C4C :日本ゼオン製 固形分 43%) 192.2質量部 スチレン ブタジエン共重合体ラテックス  (Nipol Latex LX407C4C: Nippon Zeon solid content 43%) 192.2 parts by mass Styrene Butadiene copolymer latex
(Nipol Latex LX407C4E:日本ゼオン製 固形分 43%) 54.4質量部 ポリアクリルラテックス  (Nipol Latex LX407C4E: ZEON solid content 43%) 54.4 parts by weight Polyacrylic latex
(ダイセル化学工業製 固形分 20%) 2.7質量部  (Daicel Chemical Industries solid content 20%) 2.7 parts by mass
2,4—ジクロロ一 6 ヒドロキシ一 s トリァジンナトリウム塩 25.0質量部  2,4-dichloro-6-hydroxy-1-striazine sodium salt 25.0 parts by mass
ポリスチレン微粒子（平均粒径 2 μ m)  Polystyrene fine particles (average particle size 2 μm)
(Nipol UFN1008 :日本ゼオン製 固形分 10%) 0.5質量部 界面活性剤 (三協化学製 Cpd-23) 0.5質量部  (Nipol UFN1008: ZEON solid content 10%) 0.5 parts by mass Surfactant (Sankyo Chemical Cpd-23) 0.5 parts by mass
[0211] (2層目塗布液）  [0211] (2nd layer coating solution)
蒸留水 988.4質量部  988.4 parts by mass of distilled water
ゼラチン (アルカリ処理） 10.0質量部  Gelatin (alkali treatment) 10.0 parts by mass
酢酸 (特 純良氷酢酸:ダイセル化学工業製、固形分 99%) 0.42質量部  Acetic acid (specially pure glacial acetic acid: manufactured by Daicel Chemical Industries, solid content 99%) 0.42 parts by mass
化合物（Cpd-21) 0.23質量部  Compound (Cpd-21) 0.23 parts by mass
プロキセル (Cpd-22 固形分 3.5%) 1.0質量部  Proxel (Cpd-22 solid content 3.5%) 1.0 part by mass
[0212] <乳剤層用 下塗層 >  [0212] <Emulsion layer primer layer>
上記支持体のバック層を形成する面とは反対面に、下記組成の下塗層塗布液を、 バック層塗工時に同時塗工することで、乳剤層用の下塗層とした。  An undercoat layer coating solution having the following composition was simultaneously applied to the surface of the support opposite to the surface on which the back layer was formed, to form an undercoat layer for an emulsion layer.
[0213] 即ち、搬送速度 105mZ分条件で支持体を搬送した状態で、該支持体の表面を 4 67jZm2条件でコロナ放電処理を行い、下記組成からなる下塗層 1層目用塗布液を バーコート法により塗布した。塗布量は、 5.05ccZm2とし、バック層帯電防止層乾燥 ゾーンと同じ、エアー浮上乾燥ゾーンで 180°C1分乾燥することで下塗層 1層目を得 た。 [0213] That is, in the state where the support was transported at a transport speed of 105 mZ, the surface of the support was subjected to corona discharge treatment under a condition of 467 jZm 2 to obtain a coating solution for the first subbing layer having the following composition. It applied by the bar coat method. The coating amount was 5.05 ccZm 2 and the first undercoat layer was obtained by drying at 180 ° C. for 1 minute in the air flotation drying zone, the same as the back layer antistatic layer drying zone.
[0214] <下塗層 1層目 > 蒸留水 823.0質量部 [0214] <Undercoat layer 1st layer> Distilled water 823.0 parts by mass
スチレン ブタジエン共重合体ラテックス  Styrene Butadiene copolymer latex
(Nipol Latex LX407C5 :日本ゼオン製 固形分 40%) 151.5質量部 (Nipol Latex LX407C5: Nippon Zeon solid content 40%) 151.5 parts by mass
2,4—ジクロロ一 6 ヒドロキシ一 s トリァジンナトリウム塩 2,4-dichloro-6-hydroxy-1-s-triazine sodium salt
25.0質量部  25.0 parts by mass
ポリスチレン微粒子（平均粒径 2 μ )  Polystyrene fine particles (average particle size 2μ)
(Nipol UFN 1008 :日本ゼオン製 固形分 10%) 0.5質量部  (Nipol UFN 1008: ZEON solid content 10%) 0.5 parts by mass
[0215] 搬送速度 105mZ分を保ったまま、上記下塗層 1層目上に、引き続き、下記組成か らなる下塗層第 2層用塗布液をバーコート法により塗布した。塗布量は、 8.7cc/m2 とし、エアー浮上乾燥ゾーンで 160°C1分乾燥することで 2層構成の下塗層を得た。 [0215] With the conveying speed maintained at 105 mZ, a coating solution for the second undercoat layer having the following composition was applied onto the first undercoat layer by the bar coating method. The coating amount was 8.7 cc / m 2, and a two-layer undercoat layer was obtained by drying at 160 ° C. for 1 minute in an air flotation drying zone.
[0216] <下塗層第 2層 > ccl[0216] <Undercoat layer 2> ccl
2 H  2 H
蒸留水 9825.4質量部  9825.4 parts by weight of distilled water
c  c
4  Four
ゼラチン (アルカリ処理） 14.8 H質量部  Gelatin (alkali treatment) 14.8 parts by mass
メチルセルロース (TC-5：信越化学工業製） 0.46質量部  Methylcellulose (TC-5: Shin-Etsu Chemical Co., Ltd.) 0.46 parts by mass
化合物（Cpd-21) 0.33質量部  Compound (Cpd-21) 0.33 parts by mass
プロキセル (Cpd-22 固形分 3.5%) 2.0質量部  Proxel (Cpd-22 solid content 3.5%) 2.0 parts by mass
[化 6]  [Chemical 6]
(Sa-1 )
Figure imgf000078_0001
(Sa-1)
Figure imgf000078_0001
(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
I  I
Na · HC S— CH——CO— O - CH2 Na · HC S— CH——CO— O — CH 2
40m g/m 40 mg / m
(Sa-3)  (Sa-3)
:3C-^CF2)-fCH2)-0-CO-CH2-CH-CO-0-(CH2)- CF2)-CF3 : 3C- ^ CF 2 ) -fCH 2 ) -0-CO-CH 2 -CH-CO-0- (CH 2 )-CF 2 ) -CF3
CH2 CH 2
2mg/m S03H ■ Na 2mg / m S0 3 H ■ Na
Figure imgf000079_0001
Figure imgf000079_0001
置〕1902 1902
3 : =  3: =
¾d 3¾d 3
18027
Figure imgf000080_0001
18027
Figure imgf000080_0001
(SD-2) 1 :2モル比の混合物  (SD-2) 1: 2 molar ratio mixture
Figure imgf000080_0002
Figure imgf000080_0002
化合物 ( Cpd- 21 ) H■ HCl
Figure imgf000081_0001
Compound (Cpd-21) H
Figure imgf000081_0001
化合物 ( Cpd-22 ) Compound (Cpd-22)
Figure imgf000081_0002
Figure imgf000081_0002
化合物 ( Cpd- 23 )  Compound (Cpd-23)
CH— COO-C6H1 3 CH— COO-C 6 H 1 3
Na033— CH— COO-C6H13 Na0 3 3— CH— COO-C 6 H 13
[0221] <塗布方法 > [0221] <Application method>
上記下塗層を施した支持体上に、まず乳剤層面側として支持体に近 、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 ¾HUに  On the support with the above subbing layer, the emulsion layer side is close to the support, and two layers, the UL layer and the emulsion layer from the side, in that order, are applied simultaneously by the slide bead coater method while maintaining at 35 ° C. And passed through a cold air set zone (5 ° C). Here, the hardener Cpd-7 is applied to ¾HU.
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、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。  The above-mentioned amount was added to the UL layer and diffused from the UL layer to be contained in the emulsion layer. Then, it was passed through 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.
[0222] 得られた各種サンプルは、塗布銀量が 7.6g/m2、乳剤層の Ag/ゼラチン質量比が 6. [0222] The obtained various samples had a coating silver amount of 7.6 g / m 2 and an emulsion layer Ag / gelatin mass ratio of 6.
9、  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 、乾燥時のサンプル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分間浸漬した後液体窒素により凍結乾燥し たサンプル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。 An emulsion layer with a swelling ratio of 209% and a product of Ag / gelatin mass ratio and swelling ratio of 13.2 is the top layer. It was a photosensitive material having. Here, the swelling ratio of the emulsion layer was determined as follows. Specifically, the thickness (a) of the emulsion layer at the time of drying is obtained by observing a section of the sample at the time of drying with a scanning electron microscope, immersed in distilled water at 25 ° C for 1 minute, and then freeze-dried with liquid nitrogen. The film thickness (b) of the emulsion layer at the time of swelling was determined by observing a slice of the sample 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)
[0223] (露光'現像処理） [0223] (Exposure 'development process)
乾燥させた各サンプルの乳剤層上に青色半導体レーザーを搭載したイメージセ ッター（ESCHER— GRAD社製 Cobalt8、レーザー波長 410nm)を用いて、線幅 1 5 m、ピッチ 300 μ mのメッシュパターン状の露光を与えた。  Using an image setter (ESCHER—GRAD Cobalt8, laser wavelength: 410 nm) equipped with a blue semiconductor laser on the emulsion layer of each dried sample, a mesh pattern with a line width of 15 m and a pitch of 300 μm was used. Exposure was given.
このとき露光量は各試料に合わせて最適となるよう調節した。  At this time, the exposure amount was adjusted to be optimal for each sample.
露光後の試料に対し、続いて現像処理を施し、金属銀部を作成し、引き続き、メッ キ処理を施すことにより、導電性金属部が現像銀及び銅からなる導電性膜を作成し た。  The exposed sample was subsequently subjected to development processing to produce a metallic silver portion, and subsequently subjected to a plating treatment to produce a conductive film in which the conductive metallic portion was composed of developed silver and copper.
[0224] ·現像処理  [0224] · Development processing
腿工程 温 度 時 間  Thigh process temperature time
黒白現像 20°C 60秒  Black and white development 20 ° C 60 seconds
定着 35°C 40秒  Fixing 35 ° C 40 seconds
リンス 1* 35°C 60秒  Rinse 1 * 35 ° C 60 seconds
リンス 2* 35°C 60秒  Rinse 2 * 35 ° C 60 seconds
乾 燥 50°C 60秒  Drying 50 ° C 60 seconds
[0225] · 'メツキ処理  [0225] · 'Handling process
酸洗浄 35°C 30秒  Acid cleaning 35 ° C 30 seconds
電解めつき 1 35°C 30秒 電圧 70V  Electrolytic plating 1 35 ° C 30 seconds Voltage 70V
電解めつき 2 35°C 30秒 電圧 20V  Electrolytic plating 2 35 ° C 30 seconds Voltage 20V
電解めつき 3 35°C 30秒 電圧 10V  Electrolytic plating 3 35 ° C 30 seconds Voltage 10V
電解めつき 4 35°C 30秒 電圧 5V  Electrolytic plating 4 35 ° C 30 seconds Voltage 5V
リンス 3* 35°C 10秒 リンス 4* 35°C 10秒 Rinse 3 * 35 ° C 10 seconds Rinse 4 * 35 ° C 10 seconds
防鲭液 35°C 30秒  Antifungal liquid 35 ° C 30 seconds
リンス 5* 25°C 60秒  Rinse 5 * 25 ° C 60 seconds
リンス 6* 25°C 60秒  Rinse 6 * 25 ° C 60 seconds
乾 燥 50°C 60秒  Drying 50 ° C 60 seconds
* ス は、リンス 2力ら 1、リンス 4力ら 3、リンス 6力ら 5への 2タンク向 方式とした。  * The two-tank system was used for rinse 2 force 1 and rinse 4 force 3 and rinse 6 force 5 and so on.
各処理液の組成は以下の通りである。  The composition of each treatment liquid 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
ポジエチレングリコーノレ 2000 1  Positive ethylene glycol nore 2000 1
水酸化カリウム 4 g  Potassium hydroxide 4 g
PH 10. 3に調整  Adjust to PH 10.3
〔定着液 1L処方〕  (Fixing solution 1L prescription)
ATS 1. 2 モル  ATS 1.2 mol
沃化アンモニゥム 5 g  Ammonium iodide 5 g
亜硫酸アンモニゥム · 1水塩 25 g  Ammonium sulfiteMonohydrate 25 g
酢酸 5 g  Acetic acid 5 g
アンモニア水（27%) 1  Ammonia water (27%) 1
PH 6. 2に調整  Adjust to PH 6.2
〔酸洗浄液 1L処方〕  [Acid cleaning solution 1L formulation]
硫酸 190 g  190 g of sulfuric acid
塩酸 (35%) 0. 06 mし  Hydrochloric acid (35%) 0.06 m
力バーグリーム PCM 5 mし (ローム.アンド.ハース電子材料 (株)製） Power Bergream PCM 5 m (Rohm and Haas Electronic Materials Co., Ltd.)
純水を加えて 1 L  1 L with pure water
[0229] 〔電解めつき液 1L処方〕  [0229] [Electrolytic plating solution 1L prescription]
•電解銅めつき液組成 (補充液も同組成）  • Electrolytic copper plating solution composition (same replenisher composition)
硫酸銅五水塩 75 g  Copper sulfate pentahydrate 75 g
硫酸 190 g  190 g of sulfuric acid
塩酸（35%) 0. 06 mL  Hydrochloric acid (35%) 0.06 mL
力バーグリーム PCM 5 mL  Power Bergream PCM 5 mL
(ローム.アンド.ハース電子材料 (株)製）  (Rohm and Haas Electronic Materials Co., Ltd.)
純水を加えて 1 L  1 L with pure water
[0230] 防鲭液として、ベンゾトリアゾールの 0. 01モル ZLの水溶液を用いた。  [0230] A 0.01 mol ZL aqueous solution of benzotriazole was used as an antifungal solution.
[0231] 〔リンス液 1L処方（リンス 1〜6は共通）〕 [0231] [Rinse 1L prescription (Rinse 1-6 are common)]
脱イオン水（導電率 5 SZcm以下） 1000 mL  Deionized water (conductivity 5 SZcm or less) 1000 mL
pH 6. 5に調製  Adjust to pH 6.5
[0232] なお、黒白現像液の酸化還元電位は、回転白金電極を現像液中に浸漬して求め た浸浴電位で表示すると— 340mVvsSCEであった。  [0232] The oxidation-reduction potential of the black-and-white developer was 340 mVvs SCE, expressed as the bath potential obtained by immersing the rotating platinum electrode in the developer.
[0233] 各サンプルに上記の露光、処理を行!、、導電性金属部および金属が実質的に存 在しな!ヽ光透過部からなる導電性金属膜が形成された。ここで導電性金属部は露光 パターンに応じたメッシュ状パターンを呈しており、ライン Zスペース幅はいずれの試 料においても 15 μ m/285 μ mであった。またいずれの試料においても、光透過部 の開口率は約 90%であった。また、表面抵抗率を、三菱化学 (株)低抵抗率計口レス ター GPZASPプローブを用いて、 JIS7194〖こ従 ヽ測定した処、表面抵抗率は!、ず れも 0.5 Ω /sq以下であり、 PDPの電磁波シールドフィルムとして十分な導電性を有し ていた。 [0233] Each sample was subjected to the exposure and processing described above, and a conductive metal film composed of a transparent metal transmission part and a conductive metal part substantially free of metal was formed. Here, the conductive metal part had a mesh pattern corresponding to the exposure pattern, and the line Z space width was 15 μm / 285 μm in all samples. In all samples, the aperture ratio of the light transmission part was about 90%. In addition, the surface resistivity was JIS7194 measured using the Mitsubishi Chemical Corporation low resistivity meter outlet GPZASP probe. It had sufficient conductivity as an electromagnetic shielding film for PDP.
[0234] (評価） [0234] (Evaluation)
(評価 1：黒色スポットの評価）  (Evaluation 1: Black spot evaluation)
各サンプルを未露光のまま現像処理を行 ヽ、目視により各試料上を観察して黒色 でスポット状の欠陥が形成されている力否かを評価した。この黒色スポットは、メッシュ 状パターンの細線の途切れを伴なつて 、る特徴を持って 、た。 Each sample was developed without being exposed, and each sample was visually observed to evaluate whether or not the black spot-like defects were formed. This black spot is mesh It has the characteristic that it is accompanied by the interruption of the fine line of the pattern.
従来、ネガ型ハロゲンィ匕銀写真感光材料においてよく知られているカプリは、未露 光部に現像銀が生じる現象を指す。しかし、本願の黒色スポットに見られるメッシュ細 線の途切れは、露光部に現像銀が生じていないことを意味しており、従来のカプリ現 象では理解できない、本系に特有の現象である。  Conventionally, capri, which is well known in negative-type halogen silver photographic light-sensitive materials, refers to a phenomenon in which developed silver is produced in unexposed areas. However, the discontinuity of the fine mesh line seen in the black spot of the present application means that developed silver is not generated in the exposed area, and is a phenomenon peculiar to this system that cannot be understood by the conventional Capri phenomenon.
なお、評価基準は以下の通りとした。  The evaluation criteria were as follows.
<メッシュ細線の途切れを伴なつた黒色スポットの発生頻度の評価基準 (現像後の 試料 lm2を観察） > <Evaluation criteria for frequency of black spots with discontinuity of fine mesh wire (observation of sample lm 2 after development)>
レベル A：黒色スポット数 0〜 3個。  Level A: 0 to 3 black spots.
レベル B：黒色スポット数 4個〜： L 0個。  Level B: Number of black spots 4 to: L 0.
レベル C：黒色スポット数 10個超。  Level C: More than 10 black spots.
得られた評価結果を表 1に示す。  The obtained evaluation results are shown in Table 1.
[0235] (評価 2 :剥離強度の評価） [0235] (Evaluation 2: Evaluation of peel strength)
各試料の易接着層側にシート状接着剤を貼付し、ガラス基板に貼合した。 上記の測定方法に従い 180° 剥離強度を測定した。また、 60°C湿度 90%下に 72 時間保存した後、やはり 180° 剥離強度を測定した。  A sheet-like adhesive was affixed to the easy adhesion layer side of each sample, and was affixed to a glass substrate. 180 ° peel strength was measured according to the above measurement method. In addition, after storing for 72 hours at 60% humidity and 90% humidity, the 180 ° peel strength was also measured.
評価結果を表 1に示す。  Table 1 shows the evaluation results.
また、表中、 Xは添付したフィルムがガラスから一部分剥れて浮いて欠陥が生じた ことを示す。△は添付したフィルムがガラスから「X」よりも程度が軽いが、一部分剥れ て浮いて欠陥が生じたことを示す。〇はこの問題が観察されな力 たことを示す。  In the table, X indicates that the attached film partially peeled off the glass and floated, resulting in defects. △ indicates that the attached film is lighter than “X” from the glass, but partly peeled off and floated to cause a defect. ○ indicates that this problem was not observed.
[0236] [表 1] [0236] [Table 1]
Figure imgf000085_0001
[0237] サンプル Nol.において、その導電性金属酸ィ匕物を表 2のように変更した以外は、 サンプル Nol.と同様にして金属導電膜を製造した。得られた結果を表 2に示す。な お、各種評価基準、単位などは表 1と同じである。
Figure imgf000085_0001
[0237] A metal conductive film was produced in the same manner as in Sample Nol. Except that the conductive metal oxide was changed as shown in Table 2 in Sample Nol. Table 2 shows the results obtained. Various evaluation criteria and units are the same as in Table 1.
[0238] [表 2]  [0238] [Table 2]
Figure imgf000086_0001
Figure imgf000086_0001
[0239] サンプル Nol.において、 1層目（帯電防止層）に添加するアンチモンド一プ酸ィ匕錫 のポリアクリル榭脂に対する量を下表のようにして、サンプル 2-1〜2-5を作成し、評 価した。なお、各種評価基準、単位などは表 1と同じである。  [0239] In Sample Nol., The amount of antimony monophosphate 匕 tin added to the first layer (antistatic layer) relative to the polyacrylic resin is shown in the table below. Was created and evaluated. Various evaluation criteria and units are the same as in Table 1.
[0240] [表 3] [0240] [Table 3]
サンプル 易接着眉 導電性粒子の含有量 針吠構造 黒色 剥離強度 備考Sample Easy-to-adhere eyebrows Content of conductive particles Needle hook structure Black Peel strength Remarks
No. (ァク リル樹脂及びカルポジ 酸化ス ズ スポット No. (acrylic resin and calposit oxide soot spot
ィミ ド化合物の固形分合計量 粒子（固形  Total solid content of imide compound Particles (solid
に対する量） （質量％) 分 20%)の  Amount) (mass%) min 20%)
含有量（質  Content (quality
量部）  Part)
2-1 1 アンチモンドープ酸ィ匕 45質量部 B 〇 本発明  2-1 1 Antimony doped acid 45 mass parts B 〇 This invention
錫  Tin
120 «量％  120 «Amount%
2-2 1 アンチモンドープ酸ィ匕 5ύ質量部 A 〇 本発明  2-2 1 Antimony doped acid 5% by mass A ○ The present invention
錫  Tin
170 ¾量％  170 ¾%
2-3 1 アンチモンドープ酸ィ匕 82 ¾S部 A 〇 本発明  2-3 1 Antimony doped acid 82 ¾S part A ○ The present invention
錫  Tin
220 8量％  220 8%
2-4 1 アンチモンドープ酸ィ匕 138 質量 A 〇 本発明  2-4 1 Antimony-doped acid 138 Mass A ○ The present invention
部  Part
370質量％  370% by mass
2-5 1 アンチモンドープ酸化 164 質量 A Δ 本発明  2-5 1 Antimony-doped oxidation 164 Mass A Δ The present invention
錫 部  Tin part
440 ¾量％  440 ¾%
[0241] 尚、サンプル 1でのアンチモンドープ酸化錫の添加量 (結合剤（アクリル榭脂及び力 ルボジイミドィ匕合物）の固形分に対する量）は、 222質量％である。このときの計算方 法は、 131.1質量部 X 0.2/ (30.9質量部 X 0.3 + 6.4質量部 X 0.4) X 100 = 221.6%。 [0241] The amount of antimony-doped tin oxide added in Sample 1 (the amount of the binder (acrylic resin and force rubodiimide compound) based on the solid content) was 222% by mass. The calculation method at this time is 131.1 parts by mass X 0.2 / (30.9 parts by mass X 0.3 + 6.4 parts by mass X 0.4) X 100 = 221.6%.
[0242] 上記の結果は、ハロゲンィ匕銀感光材料を用い、パターン露光と現像処理によって 導電性膜を作ることができて、 PDP用の透光性導電性膜として用いることができるこ とを示している。  [0242] The above results show that a conductive film can be produced by pattern exposure and development using a halogen silver photographic material, and can be used as a translucent conductive film for PDP. ing.
なお、従来ハロゲンィ匕銀写真感光材料で多用されてきたゼラチンを利用した易接 着層では、湿熱経時後の剥離強度の点で問題があることが分力る（サンプル 4)。これ に対し、アクリル榭脂を易接着層最上層に有するもの（サンプル 2)は、優れた剥離強 度を持つことが分かる。  The easy adhesion layer using gelatin, which has been widely used in conventional halogen silver photographic materials, has a problem in terms of peel strength after wet heat aging (Sample 4). On the other hand, it is clear that the one with acrylic resin in the top layer of the easy-adhesion layer (Sample 2) has excellent peel strength.
但し、ゼラチンを用いたサンプル 4では、メッシュ途切れを伴なつた黒色スポットの発 生頻度は少なぐ大きな問題ではな力つた。しかし、アクリル榭脂を用いたサンプル 2 では、剥離強度に優れるものの、メッシュ途切れを伴なつた黒色スポットが頻発した。 この問題に対し、本発明のサンプル 1は、メッシュ途切れ (黒色スポット）を顕著に改 善することが分力つた。尚、メッシュの開口部のいわゆるカプリ濃度は、易接着層成分 がゼラチンでもアクリル榭脂でも同程度であったことから、導電性金属酸化物の作用 効果は、単なるカプリ防止ではないと考えられる。 However, in sample 4 using gelatin, the frequency of black spots with mesh breakage was not a big problem. However, sample 2 with acrylic resin Then, although it was excellent in peeling strength, the black spot with mesh breakage occurred frequently. In response to this problem, Sample 1 of the present invention was able to remarkably improve mesh breaks (black spots). The so-called capri concentration in the mesh opening was the same regardless of whether the easy-adhesion layer component was gelatin or acrylic resin. Therefore, it is considered that the effect of the conductive metal oxide is not merely prevention of capri.
尚、従来産業上利用されるハロゲンィ匕銀感光材料の殆どは、ハロゲン化銀乳剤層 が最上層ではなぐ乳剤層上に保護層を有する感光材料である。上記実施例に対し 、乳剤層上にゼラチンカゝらなる保護層を設けることによつても、メッシュ途切れを伴な つた黒色スポットは見られな力つた。また、ハロゲンィ匕銀乳剤層の銀/バインダー体積 比が 1/4以下の感光材料では、該欠陥は見られな力つた。以上のことから、該欠陥が 、導電性金属膜を形成可能な本系に特有の問題であることが分かる。  It should be noted that most of the silver halide light-sensitive materials conventionally used in the industry are light-sensitive materials having a protective layer on the emulsion layer where the silver halide emulsion layer is not the uppermost layer. In contrast to the above examples, a black spot with mesh breakage was also observed by providing a protective layer made of gelatin on the emulsion layer. Further, in the light-sensitive material in which the silver / binder volume ratio of the halogenated silver emulsion layer was 1/4 or less, the defect was strong. From the above, it can be seen that the defect is a problem peculiar to the present system capable of forming a conductive metal film.
尚、実施例 1作成の感光材料の乳剤層側の最外層に保護層を設けると、 10 Ω /口 以上の導電性の低い部分ができやすぐ導電性金属膜や電磁波シールドフィルムを 得るという本願の目的には好ましくな力つた。また、ハロゲンィ匕銀乳剤層の銀/バイン ダー体積比が 1/4以下の感光材料では 10 Ω /口以上の導電性の低い部分ができや すぐ導電性金属膜や電磁波シールドフィルムを得るという本願の目的には好ましく なかった。  It should be noted that when a protective layer is provided on the outermost layer on the emulsion layer side of the photosensitive material prepared in Example 1, a conductive low-conductivity portion of 10 Ω / port or more can be readily obtained, and a conductive metal film or an electromagnetic shielding film can be obtained immediately. It was a good force for the purpose. In addition, a photosensitive material having a silver / binder volume ratio of 1/4 or less in the silver halide silver emulsion layer can produce a conductive metal film or an electromagnetic shielding film immediately after forming a portion with low conductivity of 10 Ω / mouth or more. It was not preferable for the purpose.
[0243] (光学フィルターの作製）  [0243] (Production of optical filter)
上記サンプル No. 1で得た透光性電磁波シールド能を有するフィルムを用い、外 縁部 20mmを除いた内側の透光性電磁波シールド膜上に、厚さ 25 mのアクリル系 透光性粘着材を介して、ガラス板を貼り合わせた。該アクリル系透光性粘着材層中に は光学フィルターの透過特性を調整する調色色素（三井化学製 PS— Red— G、 PS — Violet— RC)を含有させた。さらに、該ガラス板の反対の主面には、粘着材を介し て近赤外線カット能を有する反射防止フィルム（日本油脂 (株)製商品名リアルック 77 2UV)を貼り合わせ、光学フィルターを作製した。  Using the film with translucent electromagnetic shielding ability obtained in Sample No. 1 above, an acrylic translucent adhesive with a thickness of 25 m is formed on the inner translucent electromagnetic shielding film excluding the outer edge of 20 mm. The glass plate was bonded together. The acrylic light-transmitting pressure-sensitive adhesive layer contained a toning dye (PS-Red-G, PS-Violet-RC, manufactured by Mitsui Chemicals) that adjusts the transmission characteristics of the optical filter. Further, an antireflection film having a near-infrared cutting ability (trade name “Realak 77 2UV” manufactured by NOF Corporation) was bonded to the opposite main surface of the glass plate via an adhesive material to produce an optical filter.
[0244] 得られた光学フィルタ一は、金属メッシュが黒色であり、これをプラズマディスプレイ パネルに用いたところ、ディスプレイ画像が金属色を帯びることがなぐまた、実用上 問題な!/、電磁波遮蔽能及び近赤外線カット能を有し、反射防止層により視認性に優 れていた。また、色素を含有させることによって、調色機能を付与できており、プラズ マディスプレイ等の光学フィルタ一として好適に使用できる。 [0244] The obtained optical filter has a black metal mesh, and when this is used in a plasma display panel, the display image does not take on a metallic color, and is also problematic in practice! In addition, it has near-infrared cutting ability and excellent visibility due to the antireflection layer. It was. Further, by adding a pigment, a toning function can be imparted, and it can be suitably used as an optical filter such as a plasma display.
本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲 を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明ら かである。 本出願は 2006年 1月 27日出願の日本特許出願 (特願 2006-019640)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。  Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on January 27, 2006 (Japanese Patent Application No. 2006-019640), the contents of which are incorporated herein by reference.

Claims

請求の範囲 The scope of the claims
[I] 支持体と、  [I] a support;
前記支持体の一方の面上に設けられ、銀塩を含有する銀塩乳剤層と、 前記支持体の他方面上に設けられ、合成樹脂及び導電性粒子を含有する易接着 層と、  A silver salt emulsion layer containing a silver salt provided on one side of the support; an easy-adhesion layer containing a synthetic resin and conductive particles provided on the other side of the support;
を有することを特徴とするハロゲンィ匕銀感光材料。  A halogenated silver photographic material characterized by comprising:
[2] 前記合成樹脂が、アクリル榭脂、ポリエステル榭脂、ポリウレタン榭脂およびスチレ ンブタジエンゴム力 なる群力 選択される少なくとも 1種であることを特徴とする請求 項 1に記載のハロゲン化銀感光材料。  [2] The silver halide according to claim 1, wherein the synthetic resin is at least one selected from the group strength of acrylic resin, polyester resin, polyurethane resin, and styrene butadiene rubber. Photosensitive material.
[3] 前記合成樹脂が、アクリル榭脂であることを特徴とする請求項 1又は 2に記載のハロ ゲン化銀感光材料。 [3] The silver halide photosensitive material according to [1] or [2], wherein the synthetic resin is acrylic resin.
[4] 前記導電性粒子が、金属酸化物を含むことを特徴とする請求項 1〜3のいずれかに 記載のハロゲン化銀感光材料。  [4] The silver halide photosensitive material according to any one of [1] to [3], wherein the conductive particles contain a metal oxide.
[5] 前記金属酸化物が、 ZnO、 TiO 、 SnO 、 Al O 、 In O、 MgO、 BaO及び MoO [5] The metal oxide includes ZnO, TiO 2, SnO 2, Al 2 O 3, In 2 O, MgO, BaO, and MoO.
2 2 2 3 2 3  2 2 2 3 2 3
力 なる群力 選択される少なくとも 1種であることを特徴とする請求項 4に記載のハ The group force as a force is at least one type selected.
3 Three
ロゲン化銀感光材料。  Silver halide light-sensitive material.
[6] 前記導電性粒子が、アンチモンがドープされた SnO を含むことを特徴とする請求  [6] The conductive particles include SnO doped with antimony
2  2
項 4に記載のハロゲンィ匕銀感光材料。  Item 5. A silver halide silver photographic material according to Item 4.
[7] 前記導電性粒子が針状粒子であり、その短軸に対する長軸の比が 3〜50の範囲 にあることを特徴とする請求項 1〜6のいずれかに記載のハロゲンィ匕銀感光材料。 [7] The halogen silver halide photosensitive material according to any one of [1] to [6], wherein the conductive particles are acicular particles, and the ratio of the major axis to the minor axis is in the range of 3 to 50. material.
[8] 前記銀塩乳剤層の膨潤率が 150%以上であることを特徴とする請求項 1〜7のい ずれかに記載のハロゲン化銀感光材料。 8. The silver halide photosensitive material according to any one of claims 1 to 7, wherein the silver salt emulsion layer has a swelling ratio of 150% or more.
[9] 前記支持体が透明支持フィルムであることを特徴とする請求項 1〜8のいずれかに 記載のハロゲン化銀感光材料。 [9] The silver halide photosensitive material according to any one of [1] to [8], wherein the support is a transparent support film.
[10] 前記銀塩乳剤層は、 Ag及びバインダーを含有し、 AgZバインダー体積比が 1Z4 以上であることを特徴とする請求項 1〜9のいずれかに記載のハロゲンィ匕銀感光材料 10. The silver halide silver halide light-sensitive material according to claim 1, wherein the silver salt emulsion layer contains Ag and a binder, and an AgZ binder volume ratio is 1Z4 or more.
[II] 前記銀塩乳剤層が最外層にあることを特徴とする請求項 1〜10のいずれかに記載 のハロゲンィ匕銀感光材料。 [II] The silver salt emulsion layer according to any one of claims 1 to 10, wherein the silver salt emulsion layer is an outermost layer. Halogen silver photographic material.
[12] 支持体と、  [12] a support;
前記支持体の一方の面上に設けられ、銀塩を含有する銀塩乳剤層と、 前記支持体の他方面上に設けられ、合成樹脂を含有する易接着層と、 を有することを特徴とするハロゲンィ匕銀感光材料。  A silver salt emulsion layer containing a silver salt provided on one side of the support; and an easy-adhesion layer containing a synthetic resin provided on the other side of the support. Halogen silver photographic material.
[13] 請求項 1〜12のいずれかに記載のハロゲンィ匕銀感光材料を用いて製造されたこと を特徴とする導電性金属膜、電磁波シールドフィルム、プラズマディスプレイパネル 用光学フィルター、又は、プラズマディスプレイパネル。 [13] A conductive metal film, an electromagnetic wave shielding film, an optical filter for a plasma display panel, or a plasma display, which is manufactured using the halogenated silver photographic material according to any one of claims 1 to 12. panel.
[14] 請求項 1〜12の 、ずれかに記載のハロゲンィ匕銀感光材料の前記銀塩乳剤層に対 し、露光して現像処理を施し、現像処理工程と、 [14] The silver salt emulsion layer of the halogenated silver photographic material according to any one of claims 1 to 12, wherein the silver salt emulsion layer is exposed to a development process, and a development process step;
更に物理現像処理及び Zまたはめつき処理を施して導電性金属部を形成し、導電 性金属膜を得る導電性金属部形成工程と、  Further, a conductive metal part forming step of forming a conductive metal part by performing physical development processing and Z or staking treatment to obtain a conductive metal film,
を有することを特徴とする導電性金属膜の製造方法。  A method for producing a conductive metal film, comprising:
PCT/JP2007/051304 2006-01-27 2007-01-26 Silver halide photosensitive material, conductive metal film, translucent electromagnetic wave shielding film, optical filter and plasma display panel WO2007086523A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04149430A (en) * 1990-10-12 1992-05-22 Konica Corp Silver halide phtosensitive material and method of processing the material
JPH06161056A (en) * 1992-11-17 1994-06-07 Fuji Photo Film Co Ltd Processing method for silver halide photographic sensitive material
JPH10142738A (en) * 1996-11-12 1998-05-29 Eastman Kodak Co Image forming element
JPH1115109A (en) * 1997-06-26 1999-01-22 Fuji Photo Film Co Ltd Silver halide photographic sensitive material
JP2002144493A (en) * 2000-11-08 2002-05-21 Fuji Photo Film Co Ltd Support, photosensitive material of silver halide photograph and photosensitive transfer material
JP2004221564A (en) * 2002-12-27 2004-08-05 Fuji Photo Film Co Ltd Translucent electromagnetic wave shielding film and manufacturing method therefor
JP2006012935A (en) * 2004-06-23 2006-01-12 Fuji Photo Film Co Ltd Transparent electromagnetic wave shield film and method of manufacturing the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04149430A (en) * 1990-10-12 1992-05-22 Konica Corp Silver halide phtosensitive material and method of processing the material
JPH06161056A (en) * 1992-11-17 1994-06-07 Fuji Photo Film Co Ltd Processing method for silver halide photographic sensitive material
JPH10142738A (en) * 1996-11-12 1998-05-29 Eastman Kodak Co Image forming element
JPH1115109A (en) * 1997-06-26 1999-01-22 Fuji Photo Film Co Ltd Silver halide photographic sensitive material
JP2002144493A (en) * 2000-11-08 2002-05-21 Fuji Photo Film Co Ltd Support, photosensitive material of silver halide photograph and photosensitive transfer material
JP2004221564A (en) * 2002-12-27 2004-08-05 Fuji Photo Film Co Ltd Translucent electromagnetic wave shielding film and manufacturing method therefor
JP2006012935A (en) * 2004-06-23 2006-01-12 Fuji Photo Film Co Ltd Transparent electromagnetic wave shield film and method of manufacturing the same

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