EP0460550B1 - Matériau photographique à l'halogénure d'argent - Google Patents

Matériau photographique à l'halogénure d'argent Download PDF

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Publication number
EP0460550B1
EP0460550B1 EP91108953A EP91108953A EP0460550B1 EP 0460550 B1 EP0460550 B1 EP 0460550B1 EP 91108953 A EP91108953 A EP 91108953A EP 91108953 A EP91108953 A EP 91108953A EP 0460550 B1 EP0460550 B1 EP 0460550B1
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EP
European Patent Office
Prior art keywords
group
dye
alkyl group
silver halide
layer
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EP91108953A
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German (de)
English (en)
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EP0460550A1 (fr
Inventor
Yoshihiro C/O Fuji Photo Film Co. Ltd. Jimbo
Yoko C/O Fuji Photo Film Co. Ltd. Idogaki
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • G03C1/832—Methine or polymethine dyes

Definitions

  • the present invention relates to a silver halide photographic material comprising a dyed hydrophilic colloidal layer. More particularly, the present invention relates to a silver halide photographic material comprising a hydrophilic colloidal layer containing a dye which is photochemically inert and can be easily decolored and/or eluted in photographic processing steps.
  • photographic emulsion layers and other hydrophilic colloidal layers are often colored for the purpose of absorbing light having a specific wavelength.
  • a colored layer may be provided farther from the support than the photographic emulsion layer.
  • a colored layer is called a filter layer. If there are a plurality of photographic emulsion layers, the filter layer may be located between these photographic emulsion layers.
  • a colored layer called an anti-halation layer may be provided between the photographic emulsion layer and the support or on the surface of the support opposite the photographic emulsion layer. If there are a plurality of photographic emulsion layers, an anti-halation layer may be provided between these photographic emulsion layers.
  • the photographic emulsion layer may be colored.
  • such a colored layer is a filter layer or an anti-halation layer provided on the same side of the support as the photographic emulsion layer, it is often necessary that these layers be selectively colored so that other layers are not substantially colored.
  • a failure to employ selective coloration may exert adverse spectral effects on other layers and may also reduce the filtering or anti halation effect.
  • the dye when a layer in which a dye is incorporated contacts other hydrophilic layers in a wet state, the dye often partially diffuses from the former into the latter. In order to inhibit such diffusion, many efforts have heretofore been made.
  • JP-A-56-12639 JP-A-55-155350, JP-A-55-155351, JP-A-63-27838, JP-A-63-197943 and JP-A-52-92716
  • JP-A means an "unexamined published Japanese patent application”
  • European Patents 15601, 276566, 274723, 276566 and 299435 European Patents 15601, 276566, 274723, 276566 and 299435
  • WO88/04794 which comprises using a water-insoluble solid dye to dye a specific layer.
  • EP-A-0391405, EP-A-0401709 and EP-A-0430186 all of which are considered as comprised in the state of the art in the sense of Article 54 (3)(4) EPC, disclose silver halide photographic materials comprising dyes in the form of a dispersion of finely divided solid grains.
  • EP-A-0401709 and EP-A-0430186 mention as specific examples of dyes the following compounds: and
  • a silver halide photographic material comprising at least one compound represented by general formula (I) in the form of a dispersion of finely divided solid grains: wherein X represents a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, COOR 1 or CONR 1 R 2 ; Y represents a carboxyphenyl group or a group containing an aliphatic carboxylic acid; Z represents a hydrogen atom, an alkyl group, a cyano group, CONR 3 R 4 , COOR 3 , COR 3 , SO 2 R 3 , -NR 3 SO 2 R 4 or a nitro group; L 1 , L 2 and L 3 each represents a methine group; Q represents a phenyl group or a heterocyclic group represented by general formula (IV) wherein R 11 , R 12 , R 13 and R 14 each represents a hydrogen atom, an alkyl group or an aryl group, and R 13 and R
  • the phenyl group represented by Q in general formula (I) is a 4-dialkylaminophenyl group.
  • the alkyl group represented by X may contain substituents.
  • the alkyl group represented by X is preferably a C 1-6 alkyl group.
  • Preferred examples of the alkyl group represented by X include an unsubstituted alkyl group (e.g., methyl, ethyl, isopropyl, t-butyl) and a substituted alkyl group (e.g., carboxymethyl, ethoxycarbonylmethyl, benzyl).
  • the aryl group represented by X may contain substituents.
  • the aryl group represented by X is preferably a C 6-12 aryl group.
  • Preferred examples of the aryl group represented by X include a substituted aryl group (e.g., 4-methoxyphenyl, 4-chlorophenyl, 4-carboxyphenyl).
  • Preferred examples of the carboxyphenyl group represented by Y include 4-carboxyphenyl, 3-carboxyphenyl, 2-carboxyphenyl, 3,5-dicarboxyphenyl, 5-carboxy-2-methoxyphenyl, 5-carboxy-2-hydroxyphenyl, and 3,5-dicarboxyphenyl.
  • Preferred examples of the group containing an aliphatic carboxylic acid represented by Y include an alkyl group containing a carboxylic acid (e.g., carboxymethyl, 2-carboxylethyl, 1-carboxyethyl, 5-carboxypentyl, 2-(2-carboxy-4-cyclohexene-1-ylcarbonyloxy)ethyl, 2-(3-carboxy-5-norbornene-2-ylcarbonyloxy)-ethyl), and an aryl group containing an aliphatic carboxylic acid (e.g., 4-carboxymethoxyphenyl, 4-(2-carboxyethoxy)phenyl).
  • a carboxylic acid e.g., carboxymethyl, 2-carboxylethyl, 1-carboxyethyl, 5-carboxypentyl, 2-(2-carboxy-4-cyclohexene-1-ylcarbonyloxy)ethyl, 2-(3-
  • the alkyl group represented by Z is preferably a C 1-4 alkyl group.
  • Preferred examples of such an alkyl group include an unsubstituted alkyl group (e.g., methyl, ethyl) and a substituted alkyl group (e.g., carboxymethyl, ethoxycarbonylmethyl, 2-hydroxyethyl).
  • the methine group represented by L 1 , L 2 or L 3 is preferably an unsubstituted methine group.
  • the methine group represented by L 1 , L 2 or L 3 may contain substituents (e.g., methyl, benzyl).
  • the phenyl group represented by Q is preferably a 4-dialkylaminophenyl group represented by the following general formula (II):
  • Preferred examples of such a 4-dialkylaminophenyl group include 4-dimethylaminophenyl, 2-carboxy-4-dimethylaminophenyl, 4-dimethylamino-2-methylphenyl, 4-(N-ethyl-N- ⁇ -methanesulfonamidoethylamino)-2-methylphenyl, and 4-(N-ethyl-N- ⁇ -hydroxyethylamino)-2-methylphenyl.
  • the phenyl group represented by Q may also preferably be a 4-hydroxyphenyl group or a 4-alkoxyphenyl group represented by the following general formula (III): Preferred examples of such a phenyl group include 4-methoxyphenyl, 3,4-methylenedioxyphenyl and 4-butoxyphenyl.
  • R 21 , R 22 , R 23 and R 24 each represents a hydrogen atom, an alkyl group (e.g., methyl, ethyl, ethoxycarbonylmethyl, methoxycarbonylethyl) or an alkoxy group (e.g., methoxy, ethoxy, ethoxycarbonylmethoxy, 2-ethoxyethoxy),
  • R 25 and R 26 each represents an alkyl group (e.g., methyl, ethyl, ethoxycarbonylmethyl, methoxycarbonylethyl), and
  • R 27 represents a hydrogen atom or an alkyl group (e.g., methyl, ethyl, ethoxycarbonylmethyl, methoxycarbonylethyl).
  • the heterocyclic group represented by Q is a group represented by the following general formula (IV): wherein R 11 , R 12 , R 13 and R 14 each represents a hydrogen atom, an alkyl group or an aryl group.
  • the alkyl group and the aryl group each may contain substituents.
  • the alkyl group represented by R 11 , R 12 , R 13 or R 14 is preferably a C 1-10 alkyl group.
  • Preferred examples of such an alkyl group include an unsubstituted alkyl group (e.g., methyl, ethyl, butyl, 2-ethylhexyl, cyclohexyl) and a substituted alkyl group (e.g., 2-hydroxyethyl, carboxymethyl, dimethylaminoethyl).
  • the aryl group represented by R 11 , R 12 , R 13 or R 14 is preferably a C 6-10 aryl group.
  • aryl group examples include an unsubstituted aryl group (e.g., phenyl, naphthyl) and a substituted aryl group (e.g., 3-carboxyphenyl, 5-carboxy-2-methoxyphenyl, 5-carboxy-2-4-dimethylaminophenyl, 4-ethoxycarbonylphenyl).
  • R 13 and R 14 may together form a 6-membered ring (e.g., indole).
  • the alkyl group represented by R 1 , R 2 , R 3 or R 4 may contain substituents.
  • the alkyl group represented by R 1 , R 2 , R 3 or R 4 is preferably a C 1-10 alkyl group.
  • Preferred examples of such an alkyl group include an unsubstituted alkyl group (e.g., methyl, ethyl, butyl, 2-ethylhexyl) and a substituted alkyl group (e.g., 2-chloroethyl, 2-hydroxyethyl, 2-methanesulfonamidoethyl, 2-acetamidoethyl, 2-carboxyethyl, 2-N,N-dimethylaminoethyl, 2-ethoxyethyl, carboxymethyl, ethoxycarbonylmethyl, allylbenzyl, methoxysulfonylethyl).
  • R 1 and R 2 , or R 3 and R 4
  • the aryl group represented by R 1 , R 2 , R 3 or R 4 may contain substituents.
  • the aryl group represented by R 1 , R 2 , R 3 or R 4 is preferably a C 6-10 aryl group.
  • Preferred examples of such an aryl group include an unsubstituted aryl group (e.g., phenyl) and a substituted aryl group (e.g., 2,5-dichlorophenyl, 4-methylphenyl, 4-hydroxyphenyl, 4-cyanophenyl, sulfamoylphenyl).
  • Particularly preferred among compounds represented by the general formula (I) are those wherein X is a hydrogen atom or a methyl group and Z is a cyano group or a carbamoyl group.
  • Two molecules of the compound represented by general formula (I) may be connected to each other via a group represented by X, Y, Z, R 1 , R 2 , R 3 , R 4 , R 5 or R 6 to form a dimer.
  • the compound of general formula (I) may be used in an amount of 1 to 1,000 mg, preferably 1 to 800 mg per m 2 of light-sensitive material.
  • the compound of formula (I) when used as a filter dye or an anti-halation dye, it may be used in any effective amount, preferably in such an amount that the resulting optical density is from 0.05 to 3.5.
  • the addition of the compound may be effected at any step before coating.
  • the compound of general formula (I) can be incorporated in any emulsion layer or other hydrophilic colloidal layer.
  • the fine dispersion of the compound of general formula (I) can be prepared by a method which comprises precipitating the compound in the form of a dispersion and/or a method which comprises subjecting the compound to grinding in the presence of a dispersant by a known means such as a ball mill (e.g., ball mill, oscillation ball mill, planetary ball mill), sand mill, colloid mill, jet mill or roller mill (in this case, a solvent such as water and alcohol may be present in the system).
  • a microcrystalline powder of the compound may be precipitated by adding a poor solvent for the compound to the solution.
  • a dispersing surfactant may be used.
  • the compound can be first dissolved in a solvent by controlling the pH thereof, and then precipitated as a microcrystalline powder by changing the pH.
  • the average diameter of microcrystalline grains of the compound used in the present invention in the dispersion is 10 ⁇ m or less, preferably 2 ⁇ m or less, more preferably, 0.5 ⁇ m or less, optionally 0.1 ⁇ m or less.
  • Gelatin is typically used as the hydrophilic colloid.
  • Other examples of hydrophilic colloids which can be used in the present invention are those which have been well known for use in photography.
  • silver halide emulsions which can be used in the present invention include silver bromide, silver bromoiodide, silver bromochloroiodide, silver bromochloride and silver chloride.
  • the silver halide grains to be used in the present invention may be so-called regular grains having a regular crystal form, such as cubic and octahedral or those having an irregular crystal form such as spherical and tabular, or those having a complex crystal forms thereof.
  • silver halide grains comprising a mixture of grains in various crystal forms can be used.
  • regular crystal forms are used.
  • the silver halide grains to be used in the present invention may have either a homogeneous structure or a heterogeneous structure composed of a core and a shell differing in phase.
  • the silver halide grains which can be used in the present invention may be those which form latent images mainly on the surface thereof (e.g., negative emulsion) or those which form latent images mainly inside the grains (e.g., internal latent image type emulsion, previously fogged direct type emulsion).
  • grains which form latent images mainly on the surface thereof are used in the present invention.
  • the silver halide emulsion to be used in the present invention may be an emulsion of tabular grains wherein the silver halide grains having a thickness of 0.5 ⁇ m or less, preferably 0.3 ⁇ m or less, preferably having a diameter of 0.6 ⁇ m or less, and having an average aspect ratio of 5 or more account for 50% or more of all the grains calculated in terms of projected area, or the emulsion may be a monodisperse emulsion having a statistical coefficient of fluctuation S/ d ⁇ (obtained by dividing the standard deviation S by the diameter d ⁇ in the distribution of diameter in case where projected area is made to resemble circle) of 20% or less. Two or more tabular grain emulsions and monodisperse emulsions may be used in admixture.
  • the preparation of the photographic emulsion to be used in the present invention can be accomplished by any suitable method as described in P. Glafkides, Chimie et Physique Photographeque , Paul Montel, 1967; G.F. Duffin, Photographic Emulsion Chemistry , Focal Press, 1966; and V.L. Zelikman et al., Making and Coating Photographic Emulsion , Focal Press, 1964.
  • a silver halide solvent there may be used ammonia, potassium thiocyanate, ammonium thiocyanate, a thioether compound as described in U.S. Patents 3,271,157, 3,574,628, 3,704,130, 4,297,439 and 4,276,374, a thione compound as described in JP-A-53-144319, JP-A-53-82408 and JP-A-55-77737, an amine compound as described in JP-A-54-100717, or the like.
  • cadmium salt zinc salt, thallium salt, iridium salt or complex salts thereof, rhodium salt or complex salts thereof, iron salt or complex salts thereof may be present in the system.
  • Gelatin can be used advantageously as a binder or protective colloid to be incorporated in the emulsion layer or interlayer in the light-sensitive material of the present invention.
  • Other hydrophilic colloids can be used also.
  • proteins such as gelatin derivatives, graft polymers of gelatin with other high molecular compounds, albumin and casein, saccharide derivatives such as cellulose derivatives (e.g., hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate ester), sodium alginate and starch derivatives, homopolymers or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinyl pyrazole, and various other synthetic hydrophilic high molecular weight compounds.
  • gelatin there may be used acid-treated gelatin or enzyme-treated gelatin as described in Bulletin of Society of Scientific Photography of Japan, No. 16, page 30, 1966, besides commonly used lime-treated gelatin.
  • a hydrolyzate of gelatin can be used.
  • the light-sensitive material of the present invention may include an inorganic or organic hardener in any hydrophilic colloidal layer constituting a photographic light-sensitive layer or a backing layer.
  • a hardener include chromium salt, aldehydes (e.g., formaldehyde, glyoxal, glutaraldehyde), and N-methylol compounds (e.g., dimethylol urea).
  • Active halogen compounds e.g., 2,4-dichloro-6-hydroxy-1,3,5-triazine and sodium salt
  • active vinyl compounds e.g., 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonyl methyl)ether, vinyl polymer containing vinylsulfonyl group in side chains
  • active vinyl compounds e.g., 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonyl methyl)ether, vinyl polymer containing vinylsulfonyl group in side chains
  • N-carbamoylpyridinium salts e.g., (l-morpholinocarbonyl-3-pyridinio) methanesulfonate
  • haloamidinium salts e.g., 1-(1-chloro-1-pyridinomethylene)pyrrolidinium-2-naphthalene sulfonate
  • the photographic emulsion to be used in the present invention may be subjected to spectral sensitization with a methine dye or the like.
  • a methine dye or the like examples include cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, hemicyanine dye, styryl dye and hemioxonol dye.
  • Particularly preferred among these dyes are cyanine dye, merocyanine dye and complex merocyanine dye. Any of the nuclei which are commonly used as the basic heterocyclic nuclei for cyanine dye can be used in these dyes.
  • nuclei examples include pyrroline nuclei, oxazoline nuclei, thiazoline nuclei, pyrrole nuclei, oxazole nuclei,. thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei and nuclei obtained by fusion of alicyclic hydrocarbon rings to these nuclei or nuclei obtained by fusion of aromatic hydrocarbon rings to these groups, e.g., indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthooxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benzimidazole nuclei and quinoline nuclei. These nuclei may contain a substituent on carbon
  • Suitable nuclei which can be used in merocyanine dyes or complex merocyanine dyes include those having a ketomethylene structure such as a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazoline-2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus.
  • a ketomethylene structure such as a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazoline-2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus.
  • sensitizing dyes can be used singly or in combination. Such a combination of sensitizing dyes is often used particularly for the purpose of super-sensitization.
  • a dye which does not exhibit a spectral sensitizing effect or a substance which does not substantially absorb visible light but exhibits a super-sensitizing effect may be incorporated in the emulsion together with such a sensitizing dye.
  • aminostilbene compounds substituted by a nitrogen-containing heterocyclic group as described in U.S. Patents 2,933,390 and 3,635,721, aromatic organic acid-formaldehyde condensates as described in U.S.
  • Patent 3,743,510 cadmium salts, azaindene compounds or the like may be incorporated in the emulsion. Combinations as described in U.S. Patents 3,615,613, 3,615,641, 3,617,295, and 3,635,721 are particularly useful.
  • the silver halide photographic emulsion to be used in the present invention may comprise various compounds for the purpose of inhibiting fogging during the preparation, storage or photographic processing of the light-sensitive material or for stabilizing the photographic properties of the light-sensitive material.
  • examples of such compounds which may be incorporated in the photographic emulsion include many compounds known as fog inhibitors or stabilizers, such as azoles, e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, thioketo compounds, e.g
  • the light-sensitive material of the present invention may comprise one or more surfactants for the purpose of facilitating coating and emulsion dispersion, inhibiting electric charging and adhesion, improving smoothness and photographic properties (e.g., acceleration of development, higher contrast, sensitization) or like purposes.
  • the light-sensitive material according to the present invention may contain a water-soluble dye in addition to the dye in the hydrophilic colloid layer as a filter dye or for the purpose of inhibiting irradiation or halation or other various purposes.
  • a water-soluble dye in addition to the dye in the hydrophilic colloid layer as a filter dye or for the purpose of inhibiting irradiation or halation or other various purposes.
  • Preferred examples of such a dye include an oxonol dye, a hemioxonol dye, a styryl dye, a merocyanine dye, an anthraquinone dye, and an azo dye.
  • Other useful examples of such a dye include a cyanine dye, an azomethine dye, a triarylmethane dye, and a phthalocyanine dye.
  • a oil-soluble dye may be emulsified by an oil-in-water dispersion method and then incorporated in the hydrophilic colloidal layer.
  • the present invention can be applied to a multi-layer multi-color photographic light-sensitive material having at least two different spectral sensitivities on a support.
  • the multi-layer natural color photographic light-sensitive material normally comprises at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive layer on a support. The order of arrangement of these layers can be properly selected as necessary.
  • the order of arrangement of layers is red-sensitive emulsion layer, green-sensitive emulsion layer and blue-sensitive emulsion layer; blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer; or blue-sensitive emulsion layer, red-sensitive emulsion layer and green-sensitive emulsion layer, as viewed from the support side.
  • An emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the resulting sensitivity.
  • a three-layer structure may be employed to improve graininess.
  • a light-insensitive layer may be provided between two or more emulsion layers having the same color sensitivity.
  • An emulsion layer having another color sensitivity may be inserted between emulsion layers having the same color sensitivity.
  • a reflective layer comprising finely divided silver halide grains may be provided under a high sensitivity layer, particularly a high sensitivity blue-sensitive layer, to improve sensitivity.
  • the red-sensitive emulsion layer contains a cyan-forming coupler
  • the green-sensitive emulsion layer contains a magenta-forming coupler
  • the blue-sensitive emulsion layer contains a yellow-forming coupler.
  • Different combinations may be employed as necessary.
  • infrared-sensitive emulsion layers may be combined to provide a photographic light-sensitive material for false color photography or exposure by semiconductor laser.
  • the photographic emulsion layer and other layers are coated on a flexible support commonly used for photographic light-sensitive material such as plastic film, paper or cloth or on a rigid support such as glass, earthenware or metal.
  • flexible supports include films made of semisynthetic or synthetic high molecular weight compounds such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate, and papers on which a baryta layer or ⁇ -olefin polymer (e.g., polyethylene, polypropyrene, ethylene-butene copolymer) is coated or laminated.
  • a baryta layer or ⁇ -olefin polymer e.g., polyethylene, polypropyrene, ethylene-butene copolymer
  • the support may be colored with a dye or pigment.
  • the support may be blackened for the purpose of screening light.
  • the surface of the support is normally undercoated to facilitate adhesion of the photographic emulsion layer.
  • the surface of the support may be subjected to glow discharge, corona discharge, irradiation with ultraviolet light, flame treatment or the like before or after being subjected to undercoating.
  • the coating of the photographic emulsion layers and other hydrophilic colloidal layers can be accomplished by any coating method such as a dip coating method, a roller coating method, a curtain coating method and an extrusion coating method.
  • a number of layers may be coated simultaneously on a support by the coating method described in U.S. Patents 2,681,294, 2,761,791, 3,526,528, and 3,508,947 as necessary.
  • the present invention can be applied to various color and black-and-white light-sensitive materials.
  • Typical examples of such light-sensitive materials include color negative films for general purpose use and motion pictures, color reversal films for slides and television, color papers, color positive films, color reversal papers, color diffusion transfer type light-sensitive materials, and heat-developable color light-sensitive materials.
  • the present invention can be applied to black-and-white light-sensitive materials for X-rays and the like.
  • the present invention can be also applied to plate-making films such as lithographic films and scanner films, X-ray films for direct or indirect medical use or industrial use, negative black-and-white films for picture taking, black-and-white photographic papers, COM or ordinary microfilms, silver salt diffusion transfer type light-sensitive materials, and print-out type light-sensitive materials.
  • plate-making films such as lithographic films and scanner films, X-ray films for direct or indirect medical use or industrial use, negative black-and-white films for picture taking, black-and-white photographic papers, COM or ordinary microfilms, silver salt diffusion transfer type light-sensitive materials, and print-out type light-sensitive materials.
  • the photographic element of the present invention When the photographic element of the present invention is applied to a color diffusion transfer photographic process, it can be used in the form of a peel-apart film unit, an integrated type film unit as described in JP-B-46-16356 and JP-B-48-33697 (the term "JP-B” as used herein means an "examined Japanese patent publication"), JP-A-50-13040, and British Patent 1,330,524, or a non-peel apart type film unit as described in JP-A-57-119345.
  • a polymeric acid layer protected by a neutralization timing layer may be advantageously used so that the tolerance of the processing temperature can be widened. If the light-sensitive material of the present invention is applied to color diffusion transfer photography, such a polymeric acid may be incorporated in any layer in the light-sensitive material. Alternatively, a polymeric acid may be contained in the processing solution vessel as a developing component.
  • the light-sensitive material of the present invention may be exposed by various means. Any light source which emits radiation having a wavelength corresponding to the sensitive wavelength of the light-sensitive material can be used as an illuminating or recording light source.
  • natural light unshine
  • incandescent lamps halogen lamps
  • mercury vapor lamps mercury vapor lamps
  • fluorescent tubes fluorescent tubes
  • flash lights such as stroboscopes and metal combustion flash bulbs
  • light sources which emit light having a wavelength ranging from the ultraviolet region to the infrared region such as gas, dye solution or semiconductor lasers, light-emitting diodes and plasma light sources can be used as the recording light source.
  • fluorescent screens which emit light from a fluorescent substance excited by electronic rays
  • liquid crystal displays LCD
  • an exposure means obtained by combining a microshutter array utilizing lanthanum-doped titanium lead zirconiumate (PLZT) with a linear or planar light source can be used. If necessary, the spectral distribution used for exposure can be adjusted by a color filter.
  • the color developer to be used for the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing as a main component an aromatic primary amine color developing agent.
  • an aromatic primary amine color developing agent effective use can be made of an aminophenolic compound, preferably a p-phenylenediamine compound.
  • Typical examples of such compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, and sulfates, hydrochlorides and p-toluenesulfonates thereof.
  • These diamines are normally more stable and thus can be preferably used in the form of a salt rather than in the free state.
  • the color developer to be used in the present invention normally contains a pH buffer such as a carbonate, a borate or a phosphate of an alkaline metal and may also contain a development or fog inhibitor such as a bromide, iodide, benzimidazole, benzothiazole or mercapto compound.
  • a pH buffer such as a carbonate, a borate or a phosphate of an alkaline metal
  • a development or fog inhibitor such as a bromide, iodide, benzimidazole, benzothiazole or mercapto compound.
  • the color developer may also contain a preservative such as hydroxylamine, dialkylhydroxylamine, hydrazine, triethanolamine, triethylenediamine or sulfite; an organic solvent such as triethanolamine or diethylene glycol; a development accelerator such as benzyl alcohol, polyethylene glycol, quaternary ammonium salt, or amine; a dye-forming coupler; a competing coupler; a nucleating agent such as sodium boron hydride; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a viscosity builder; various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid; an oxidation inhibitor as described in West German Patent Application (OLS) 2,622,950; or the like.
  • a preservative such as hydroxylamine, dialkylhydroxylamine, hydrazine, triethanolamine, triethylenediamine or sulfite
  • black-and-white development is normally effected before color development.
  • the black-and-white developer may comprise known black-and-white developing agents such as dihydroxybenzene (e.g., hydroquinone), 3-pyrazolidone (e.g., 1-phenyl-3-pyrazolidone) and aminophenol (e.g., N-methyl-p-amionophenol), singly or in combination.
  • any color developer and any photographic developing method can be applied to the light-sensitive material of the present invention.
  • the developing agent to be incorporated in the developer include a dihydroxybenzene developing agent, a 1-phenyl-3-pyrazolidone developing agent, and a p-aminophenolic developing agent. These developing agents can be used singly or in combination (e.g., a combination of 1-phenyl-3-pyrazolidone and dihydroxybenzene or a combination of p-aminophenol and dihydroxybenzene).
  • the light-sensitive material of the present invention may be processed with an infectious developer comprising hydroquinone and a sulfurous ion buffer such as carbonyl bisulfite.
  • Examples of dihydroxybenzene developing agents include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, and 2,5-dimethylhydroquinone.
  • Examples of 1-phenyl-3-pyrazolidone developing agents include 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, and 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone.
  • Examples of p-aminophenolic developing agents include p-aminophenol, and N-methyl-p-aminophenol.
  • the developer to be used in the present invention may include a compound which releases free sulfurous ions as a preservative, such as sodium sulfite, potassium sulfite, potassium metabisulfite and sodium bisulfite.
  • the infectious developer if one is used, may include a formaldehyde-sodium bisulfite condensation product, which contains little or no free sulfurous ions therein.
  • alkaline agents which may be incorporated in the developer include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, diethanolamine, and triethanolamine.
  • the pH value of the developer is normally adjusted to 9 or more, preferably 9.7 or more.
  • the developer may include an organic compound known as a fog inhibitor or development inhibitor.
  • organic compounds include azoles such as benzothiazolium, nitroindazole, nitrobenzimidazole, chlorobenzimidazole, bromobenzimidazole, mercaptothiazole, mercaptobenzothiazole, mercaptobenzimidazole, mercaptothiadiazole, aminotriazole, benzotriazole, nitrobenzotriazole, and mercaptotetrazole (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidine, mercaptotriazine, thioketo compounds such as oxazolinethione, azaindenes such as triazaindene, tetrazaindene (particularly 4-hydroxy-substituted (1,3,3a,7)tetrazaindene), and pentazaindene, benzenethiosulfonic acid, benzenes
  • the developer to be used in the present invention may include as a development inhibitor a polyalkylene oxide as described above, for example a polyethylene oxide having a molecular weight of 1,000 to 10,000 in an amount of 0.1 to 10 g/l.
  • the developer to be used in the present invention may include as a water hardener nitrilotriacetic acid, ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, diethylenetriaminepentaacetic acid, or the like.
  • the developer to be used in the present invention may include a compound as described in JP-A-56-24347 as a silver stain inhibitor, a compound as described in JP-A-62-212651 as an uneven development inhibitor, and a compound as described in JP-A-61-267759 as a dissolution aid.
  • the developer to be used in the present invention may include as a buffer boric acid as described in JP-A-62-186259, and saccharides (e.g., saccharose), oxims (e.g., acetoxim), phenols (e.g., 5-sulfosalicylic acid), and tribasic phosphate (e.g., sodium salt, potassium salt) as described in JP-A-60-93433.
  • saccharides e.g., saccharose
  • oxims e.g., acetoxim
  • phenols e.g., 5-sulfosalicylic acid
  • tribasic phosphate e.g., sodium salt, potassium salt
  • development accelerator Any known development accelerator may be used in the present invention. These compounds may be incorporated in the light-sensitive material or in any of the processing solutions.
  • Preferred examples of development accelerators include amine compounds, imidazole compounds, imidazoline compounds, phosphonium compounds, sulfonium compounds, hydrazide compounds, thioether compounds, thione compounds, certain kinds of mercapto compounds, mesoionic compounds, and thiocyanates.
  • development accelerators are needed if rapid development is to be effected in a short time. They are preferably incorporated in the color developer. However, these development accelerators are also preferably incorporated in the light-sensitive material depending on the kind of compounds and on the position on the support of the light-sensitive layer to be development-accelerated. Thus, the development accelerators may be incorporated both in the color developer and in the light-sensitive material. If necessary, the color developing bath may be provided with a prebath in which development accelerators are incorporated.
  • amino compounds useful as development accelerators include inorganic amines such as hydroxylamines and organic amines.
  • organic amines include aliphatic amines, aromatic amines, cyclic amines, aliphatic-aromatic mixed amines, and heterocyclic amines.
  • Primary, secondary and tertiary amines and quaternary ammonium compounds are all effective.
  • the photographic emulsion layer which has been subjected to color development is normally then subjected to bleaching.
  • the bleaching may be effected simultaneously with or separately from fixing. In order to further expedite the processing, the bleaching may be followed by blixing.
  • As bleaching agents there may be used compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II), peracids, quinones, nitroso compounds or the like.
  • bleaching agents include ferricyanides, bichromates, complex salts of iron (III) or cobalt (III) with organic acids such as aminopolypolycarboxylic acid (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid), citric acid, tartaric acid and malic acid, persulfates, manganates, and nitrosophenols.
  • aminopolypolycarboxylic acid e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid
  • citric acid tartaric acid and malic acid
  • persulfates manganates
  • manganates nitrosophenols.
  • ferric ethylenediaminetetraacetate, ferric diethylenetriaminepentaacetate and persulfate may be preferably used in view of the rapidity of processing and environmental protection. Furthermore, ferric ethylenediaminetetraacetate complex is particularly useful for either a single bleaching bath or a combined bleach and fixing bath.
  • the bleaching solution, blix solution and their prebaths may include a bleach accelerator as necessary.
  • useful bleach accelerators include compounds containing a mercapto group or a disulfide group as described in U.S. Patent 3,893,858, West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-65732, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, and JP-A-53-28426, and Research Disclosure No.
  • Patent 3,870,520 JP-A-53-94927, JP-A-54-35727, JP-A-55-26506, and JP-A-58-163940, iodine ions, and bromine ions.
  • these bleach accelerators compounds containing a mercapto group or a disulfide group are preferably used in view of their accelerating effect.
  • the compounds described in U.S. Patent 3,893,858, West German Patent 1,290,812, and JP-A-53-95630 are preferably used.
  • the compounds described in U.S. Patent 4,552,834 are preferably used.
  • These bleach accelerators may be incorporated in the light-sensitive material. When a color light-sensitive material for picture taking is subjected to blixing, these bleach accelerators are particularly effective.
  • fixing agents to be used in the present invention include thiosulfates, thiocyanates, thioether compounds, thioureas, and iodide (to be used in a large amount).
  • Thiosulfates are normally used.
  • As a preservative for the blix solution or fixing solution there may be preferably used sulfites, bisulfites or carbonyl-bisulfurous acid adducts.
  • the blix or fixing step is normally followed by rinse and stabilizing steps.
  • various known compounds may be incorporated in the rinsing bath and stabilizing bath.
  • a water softener to inhibit precipitation such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid and organic phosphoric acid; a germicide or anti-fungal agent for the inhibition of proliferation of various bacteria, algae or mold; a metallic salt such as magnesium salt, aluminum salt and bismuth salt; a surfactant for the inhibition of drying load or unevenness; and various hardeners, may be used as necessary.
  • a water softener to inhibit precipitation such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid and organic phosphoric acid
  • a germicide or anti-fungal agent for the inhibition of proliferation of various bacteria, algae or mold
  • a metallic salt such as magnesium salt, aluminum salt and bismuth salt
  • surfactant for the inhibition of drying load or unevenness
  • the rinsing step is normally effected in two or more baths wherein the rinsing water flows countercurrently to save water.
  • a multi-stage countercurrent stabilizing step as described in JP-A-57-8543 can be employed. In this case, two to nine baths wherein the processing solution flows countercurrently are needed.
  • the stabilizing bath may include various compounds for the purpose of stabilizing images. Typical examples of these compounds include various buffers for adjusting the pH value of the film to e.g., 3 to 9.
  • buffers examples include borates, metaborates, boraxs, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, in combination, and aldehydes such as formalin.
  • chelating agents e.g., inorganic phosphoric acids, aminopolycarboxylic acids, organic phosphoric acids, aminopolysulfonic acids, phosphonocarboxylic acids
  • germicides benzoisothiazolinone, isothiazolone, 4-thiazolinebenzimidazole, halogenated phenol, sulfanylamide, benzotriazole
  • surfactants brightening agents, and hardeners
  • pH adjustors for processed films there can be preferably used various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.
  • ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.
  • the rinse-stabilization step which is normally effected after fixing may be replaced by the above mentioned stabilizing step and rinsing step (water saving).
  • the stabilizing bath may be free of formalin.
  • the rinsing and stabilizing time depends on the type of light-sensitive material and the processing conditions and is normally in the range of 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes.
  • the silver halide color light-sensitive material of the present invention may include a color developing agent for the purpose of simplifying and expediting processing.
  • a color developing agent may be preferably incorporated in the form of precursor.
  • precursors include indoaniline compounds as described in U.S. Patent 3,342,597, Schiff base type compounds as described in U.S. Patent 3,342,599 and Research Disclosure Nos. 14850 and 15159, aldol compounds as described in Research Disclosure No. 13924, metal complexes as described in U.S.
  • the silver halide color light-sensitive material of the present invention may comprise various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development as necessary. Typical examples of such compounds are described in JP-A-56-64339, JP-A-57-144547, JP-A-57-211147, JP-A-58-50532, JP-A-58-50536, JP-A-58-50533, JP-A-58-50534, JP-A-58-50535, and JP-A-58-115438.
  • the various processing solutions are used at a temperature of 10°C to 50°C. While the processing solution temperature is normally in the range of 33°C to 38°C, a high temperature may be used to accelerate the processing and thus reduce the processing time or a lower temperature may be used to improve the picture quality or the stability of the processing solutions.
  • processing using cobalt intensification or hydrogen peroxide intensification as described in West German Patent 2,226,770 and U.S. Patent 3,674,499 may be employed.
  • a heater, temperature sensor, level sensor, circulating pump, filter, floating cover, squeegee or the like may be provided.
  • the various processing solutions may be replenished to reduce fluctuation in the composition of the solutions, providing a constant finish.
  • the replenishment rate may be reduced to half or less of the standard value to reduce cost.
  • a color paper When a color paper is used in the invention, it may be processed normally. When a color photographic material for picture taking is used, it may be subjected to blix processing as necessary.
  • Subbing Layer 1 having Formulation 1 and Subbing Layer 2 having Formulation 2 were coated sequentially.
  • the Formulation 2 coating solution was coated on Subbing Layer 1 in such an amount that the amount of gelatin per one side reached 0.16 g/m 2 after being dried at a temperature of 170°C for 2 minutes.
  • Formulation 3 (Electrically-conductive layer) SnO 2 /Sb (9/1 weight ratio; average grain diameter: 0.25 ⁇ m) 300 mg/m 2 Gelatin 170 mg/m 2 Compound c 7 mg/m 2 Sodium dodecylbenzenesulfonate 10 mg/m 2 Sodium dihexyl- ⁇ -sulfosuccinate 40 mg/m 2 Sodium polystyrenesulfonate 9 mg/m 2 Formulation 4 (Backing layer) Gelatin 1.8 g/m 2 Compound d 300 mg/m 2 Compound e 50 mg/m 2 Compound f 50 mg/m 2 Compound c 6 mg/m 2 Sodium dodecylbenzenesulfonate 50 mg/m 2 Sodium dibenzyl- ⁇ -sulfosuccinate 10 mg/m 2 1,2-Bis(vinylsulfony
  • Emulsion A (Br: 1 mol%; grain size: 0.20 ⁇ m; Rh: 1.0 ⁇ 10 -5 mol/mol Ag) was prepared from Solution I, Solution II and Solution III by the following method.
  • Solution II and Solution III were simultaneously added to Solution I at a constant rate over 20 minutes while the latter was kept at a temperature of 40°C.
  • Soluble salts were removed from the emulsion by a method well known in the art.
  • Gelatin- was then added to the emulsion.
  • the emulsion was not subjected to chemical ripening.
  • 2-Methyl-4-hydroxy-1,3,3a,7-tetraazaindene was then added to the emulsion as stabilizer.
  • 1 kg of an emulsion having an average grain size of 0.20 ⁇ m and a gelatin content of 60 g was obtained.
  • a hydrazine compound (Hz) of the following general formula: was added to the emulsion in an amount of 4 ⁇ 10 -2 mol/mol Ag.
  • An ultraviolet absorbent (UV absorbent) of the following general formula: was added to the emulsion in an amount of 100 mg/m 2 .
  • a polyethyl acrylate latex was added to the emulsion in a solid content of 30 wt% based on gelatin.
  • 1,3-Bis(vinylsulfonyl)-2-propanol was added to the emulsion as a hardener. The emulsion was then coated on the support as described above in such an amount that the amount of silver and gelatin reached 2.5 g/m 2 and 1.18 g/m 2 , respectively.
  • Gelatin was then coated on the upper layer in an amount of 0.9 g/m 2 as a protective layer to prepare Specimen 1-1.
  • Specimens 1-2 to 1-7 were prepared in the same manner as described above except that yellow dyes were incorporated in the protective layer as set forth in Table 1.
  • the dyes incorporated in Specimens 1-4 to 1-7 were solid dispersions prepared in the following manner. 20 g of the dye and beads of zirconium oxide were added to a 6.7% solution of 53 g of Triton X-200® surfactant (available from Rohm & Hass Co.) in 434 ml of water. The mixture was then ground in a ball mill for 4 days. The beads were later removed by filtration. Table 1: protective layer for each specimen Specimen No.
  • Specimens 1-1 to 1-7 thus prepared were exposed to light from a Type P-607 ultrahigh voltage mercury vapor lamp (ORC-CHM-1000 available from Dainippon Screen Mfg. Co., Ltd.) through a neutral density filter (ND filter) in such a manner that they were subjected to the same exposure-second. These specimens were then processed with Developer A at a temperature of 38°C for 12 seconds (dry-to-dry: about 50 seconds) by means of an automatic developing machine FG-310PTS (available from Fuji Photo Film Co., Ltd.). GR-Fl (available from Fuji Photo Film Co., Ltd.) was used as the fixing solution.
  • Specimens 1-1 to 1-7 were then evaluated for color remaining and safety to safelight.
  • Specimens 1-1 to 1-7 were processed in the same manner as described above by means of the automatic developing machine except that they were not exposed prior to processing. The specimens thus processed were then evaluated by eye for color remaining. The results are set forth in Table 2.
  • the evaluation criteria are as follows:
  • Table 2 shows that Specimens 1-6 and 1-7 according to the present invention exhibit no color remaining perceived. Specimens 1-6 and 1-7 also exhibit an excellent safety to safelight. Table 2 also shows that Specimens 1-6 and 1-7, even though they comprise a small amount of a dye, suppress safelight fog as compared to Specimens 1-2 and 1-3, which incorporated a water-soluble dye.
  • a 175- ⁇ m thick biaxially-oriented blue-dyed polyethyleneterephthalate film was subjected to corona discharge treatment.
  • the following compositions were coated on the both surfaces of the thus-treated film by means of a wire bar coater.
  • the material was then dried at a temperature of 175°C for 1 minute.
  • the latex solution contained as an emulsion dispersant the following compound in an amount of 0.4 wt% based on latex solid content:
  • compositions were coated on the both surfaces of the material by means of a wire bar coater.
  • the material was then dried at a temperature of 175°C for 1 minute.
  • compositions were coated on the material by means of a wire bar coater.
  • the material was dried at a temperature of 175°C for 1 minute.
  • the support thus prepared was designated Support 1.
  • Support 2 was prepared in the same manner as Support 1 except that Dye 1 of the present invention was replaced by Dye i of the following structural formula: (corresponding to Compound 102 in JP-A-55-155351)
  • Each dye was dispersed in water with a surfactant by means of a ball mill to prepare a dispersion of solid dye in the same manner as in Specimens 1-4 to 1-7 in Example 1.
  • An aqueous solution containing 8.33 g of silver nitrate was added to the system over 7 minutes and 30 seconds in such a manner that the flow rate at the end of the addition was twice that at the beginning of the addition.
  • An aqueous solution of 153.34 g of silver nitrate and a mixed aqueous solution of potassium bromide and potassium iodide were added to the system over 25 minutes by a controlled double jet process while the potential thereof was kept at a pAg value of 8.1. The flow rate was accelerated so that it became eight-fold at the end of the addition. 15 ml of a 2N solution of potassium thiocyanate was added to the system.
  • the system was then heated to a temperature of 56°C. 175 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 625 mg of a sensitizing dye of the following structural formula were then added to the system. After 10 minutes, 5.5 mg of sodium thiosulfate pentahydrate, 163 mg of potassium thiocyanate and 3.6 mg of chloroauric acid were added to the system. After 5 minutes, the system was rapidly cooled so that it was solidified.
  • the emulsion thus obtained comprised grains wherein those having an aspect ratio of 3 or more account for 93% of all grains as calculated in terms of projected area. All grains having an aspect ratio of 2 or more had an average diameter of 0.95 ⁇ m as calculated in terms of projected area (standard deviation: 23%), an average thickness of 0.155 ⁇ m and an aspect ratio of 6.1.
  • the above described coating solution for the emulsion layer was coated on both surfaces of Supports 1 and 2 in the same manner to prepare Photographic Specimens 2-1 and 2-2, respectively.
  • a surface protective layer was then coated over the emulsion layer, on both sides.
  • the amount of the emulsion layer and surface protective layer coated per one surface were as follows: Emulsion layer Silver 1.9 g/m 2 Gelatin 1.5 g/m 2
  • 1,2-bis(vinylsulfonylacetamido)-ethane was coated in an amount of 56 mg/m 2 per one surface.
  • Photographic Specimens 2-1 and 2-2 were subjected to X-ray sensitometry with a GRENEX orthochromatic screen HR-4 (available from Fuji Photo Film Co., Ltd.) closely contacted to both surfaces thereof in a cassette. The exposure was adjusted by altering the distance between the X-ray bulb and the cassette. After the exposure, the specimens were developed with the following developer and fixing solution by means of an automatic developing machine. Development 35°C 9.5 sec. Fixing 31°C 10 sec. Rinse 15°C 6 sec. Squeeze 6 sec. Drying 50°C 12 sec. Dry-to-dry processing time 45 sec.
  • the developer and fixing solution used had the following formulations: Fixing solution Ammonium thiosulfate (70 wt/vol%) 200 ml Disodium ethylenediaminetetraacetate dihydrate 0.02 g Sodium sulfite 15 g Boric acid 10 g Sodium hydroxide 6.7 g Glacial acetic acid 15 g Aluminum sulfate 10 g 36 N sulfuric acid 3.9 g Water to make 1 l pH 4.25
  • the photographic specimens which had not been exposed were developed by means of the automatic developing machine in the same manner as described above, and then measured for green light transmission density.
  • a blue-dyed polyethylene terephthalate support which had not been undercoated was measured for green light transmission density. The latter value was subtracted from the former value to obtain the denisty of the color remaining.
  • MTF as obtained by the combination of the HR-4 screen and the automatic developing machine was determined. In the measurement, an aperture of 30 ⁇ m ⁇ 500 ⁇ m was employed. For evaluation, the MTF value with a space frequency of 1.0 cycles/mm was measured at an optical density of 1.0.
  • Table 3 shows that the present invention can provide a light-sensitive material which exhibits a high dye decoloration rate and little color remaining.
  • the dye to be incorporated in the dye layer exhibits a proper spectral absorption and selectively dyes the dye layer.
  • the dye can also easily decolor and elute upon photographic processing, providing a low Dmin.
  • the silver halide photographic material of the present invention provides an image having an improved sharpness and shows no drop in sensitivity.
  • the silver halide photographic material also shows no deterioration in photographic properties even after prolonged storage.

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Claims (4)

  1. Matériau photographique à l'halogénure d'argent comprenant au moins un composé représenté par la formule générale (I) sous la forme d'une dispersion de grains solides finement divisé :
    Figure imgb0107
     où X représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe hydroxyle, COOR1 ou CONR1R2; Y représente un groupe carboxyphényle ou un groupe contenant un acide carboxylique aliphatique ; Z représente un atome d'hydrogène, un groupe alkyle, un groupe cyano, CONR3R4, COOR3, COR3, SO2R3,
    Figure imgb0108
     -NR3SO2R4, ou un groupe nitro ; L1, L2 et L3 représentent chacun un groupe méthine ; Q représente un groupe groupe hétérocyclique représenté par la formule générale (IV):
    Figure imgb0109
     où R11, R12, R13 et R14 représentent chacun un atome d'hydrogène, un groupe alkyle ou un groupe aryle, et R13 et R14 peuvent former ensemble un cycle indole, n représente 0 ou 1 ; et R1, R2, R3 et R4 représentent chacun un atome d'hydrogène, un groupe alkyle ou un groupe aryle ;
    à la condition que quand Q est un groupe 4-dialkylaminophényle représenté par la formule générale (II), le matériau photographique à l'halogénure d'argent comprenant le composé représenté par la formule générale (I) n'est pas un matériau photographique couleur à l'halogénure d'argent ;
    Figure imgb0110
     où R21, R22, R23 et R24 représentent chacun un atome d'hydrogène, un groupe alkyle ou un groupe alcoxy ; et R25 et R26 représentent chacun un groupe alkyle ;
    et à la condition que ledit composé représenté par la formule (I) n'est pas
    Figure imgb0111
     ou
    Figure imgb0112
  2. Matériau photographique à l'halogénure d'argent selon la revendication 1, où le groupe phényle représenté par Q dans la formule générale (I) est un groupe 4-dialkylaminophényle.
  3. Matériau photographique à l'halogénure d'argent selon la revendication 1, où Q est un groupe 4-dialkylaminophényle représenté par la formule générale suivante (II) :
    Figure imgb0113
     où R21, R22, R23 et R24 représentent chacun un atome d'hydrogène, un groupe alkyle ou un groupe alcoxy, et R25 et R26 représentent chacun un groupe alkyle.
  4. Matériau photographique à l'halogénure d'argent selon la revendication 1, où Q est un groupe 4-hydroxyphényle ou un groupe 4-alcoxyphényle représenté par la formule générale suivante (III) :
    Figure imgb0114
     où R21, R22, R23 et R24 représentent chacun un atome d'hydrogène, un groupe alkyle ou un groupe alcoxy, et R27 représente un atome d'hydrogène ou un groupe alkyle.
EP91108953A 1990-06-04 1991-05-31 Matériau photographique à l'halogénure d'argent Expired - Lifetime EP0460550B1 (fr)

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JPH0833610B2 (ja) * 1987-08-10 1996-03-29 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
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EP0391405A2 (fr) * 1989-04-06 1990-10-10 Fuji Photo Film Co., Ltd. Matériau photographique à halogénure d'argent et méthode de traitement
EP0401709A2 (fr) * 1989-06-05 1990-12-12 Fuji Photo Film Co., Ltd. Matériel photographique sensible aux rayons X
EP0430186A1 (fr) * 1989-11-27 1991-06-05 Fuji Photo Film Co., Ltd. Matériaux photographiques à l'halogénure d'argent sensibles à la lumière

Also Published As

Publication number Publication date
EP0460550A1 (fr) 1991-12-11
DE69127138D1 (de) 1997-09-11
DE69127138T2 (de) 1997-12-11
JPH0437841A (ja) 1992-02-07

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