EP0509540A1 - Dye-fixing element - Google Patents

Dye-fixing element Download PDF

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Publication number
EP0509540A1
EP0509540A1 EP92106696A EP92106696A EP0509540A1 EP 0509540 A1 EP0509540 A1 EP 0509540A1 EP 92106696 A EP92106696 A EP 92106696A EP 92106696 A EP92106696 A EP 92106696A EP 0509540 A1 EP0509540 A1 EP 0509540A1
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EP
European Patent Office
Prior art keywords
dye
fixing element
fixing
layer
nonionic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP92106696A
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German (de)
English (en)
French (fr)
Inventor
Toshiaki Aono
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0509540A1 publication Critical patent/EP0509540A1/en
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Classifications

    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42—Structural details
    • G03C8/52—Bases or auxiliary layers; Substances therefor
    • G03C8/56—Mordant layers
    • 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
    • G03C1/81—Photosensitive materials characterised by the base or auxiliary layers characterised by anticoiling means
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
    • G03C8/4046—Non-photosensitive layers
    • G03C8/4066—Receiving layers

Definitions

  • the present invention relates to a dye-fixing element, which is used in a method of forming a color photographic image by imagewise development, especially heat-development, followed by transfer and fixation of the formed image on the element.
  • photographic methods using silver halides are superior to other photographic methods such as electro-photographic methods and diazo-photographic methods with regard to photographic characteristics such as sensitivity and gradation adjustment, they have heretofore been utilized most widely in the technical field.
  • the above method has a drawback in that the color image that is formed is often turbid because an image of reduced silver and a color image are formed simultaneously in the exposed and heat-developed area of the material.
  • JP-A as used herein means an "unexamined published Japanese patent application".
  • a hydrophilic binder is employed in the dye-fixing layer of the dye-fixing element that is used in such image forming methods, the element often curls towards the dye-fixing layer under low humidity conditions. Therefore, in general, a backing layer consisting essentially of a hydrophilic binder is provided on the back surface of the element so as to attain curling balance in the element.
  • a water-soluble plasticizer such as glycerin
  • the effect of using a water-soluble plasticizer is not sufficient.
  • the use of a water-soluble plasticizer tends to cause precipitation of the base or base precursor. It also tends to cause an increase in the stickiness of the surface of the element, and it may cause re-transfer of the once-transferred image when transferred prints are stored in a stack (pile). (Such re-transfer is hereinafter referred to as "contact color migration").
  • a first object of the present invention is to provide a dye-fixing element which hardly curls under any humidity condition, which does not require a backing layer containing a hydrophilic binder for curling balance adjustment, and which is free from the above-mentioned problems in conventional elements.
  • a second object of the present invention is to provide a dye-fixing element which hardly curls under any humidity condition and which is free from various problems relating to precipitation of salts (for example, salts of the base or base precursor), stickiness of the coated surface, and contact color migration during storage.
  • salts for example, salts of the base or base precursor
  • a dye-fixing element having a dye-fixing layer to which is transferred and fixed a mobile dye that is formed or released by development, especially heat-development, of a photographic element comprising a light-sensitive silver halide, a hydrophilic binder and a dye providing compound capable of forming or releasing a mobile dye in correspondence or reverse correspondence with the amount of exposure, after or simultaneously with imagewise exposure of the photographic element, in the presence of a base and/or a base precursor;
  • the dye-fixing element being characterized in that the element does not have a backing layer composed of 1 g/m2 or more of a hydrophilic binder on the side opposite to the dye-fixing layer, and in that the dye-fixing layer contains a mordant and a dispersion of a polymer having a glass transition point of 25°C or lower, and in that the polymer dispersion is stabilized with a nonionic stabilizer.
  • a dye-fixing element having a dye-fixing layer to which is transferred and fixed a mobile dye that is formed or released by heat-development of a photographic element comprising a light-sensitive silver halide, a hydrophilic binder and a dye providing compound capable of forming or releasing a mobile dye in correspondence or reverse correspondence with the amount of exposure, after or simultaneously with imagewise exposure of the photographic element, in the presence of a base and/or a base precursor;
  • the dye-fixing element being characterized in that the element does not have a backing layer composed of 1 g/m2 or more of a hydrophilic binder on the side opposite to the dye-fixing layer, and in that the dye-fixing layer contains a part or all of a base and/or a base precursor, a mordant, a nonionic water-soluble polysaccharide and a dispersion of a polymer having a glass transition point of 25°C or lower.
  • the dye-fixing element of the present invention is used as an image-receiving material in the method of obtaining a color photographic image in which a silver halide photographic material is developed to form or release a diffusive dye and the dye is transferred to the image-receiving material.
  • This image forming method may be divided into a so-called wet color diffusion transfer method where development is effected with a processing solution at about room temperature, and a so-called heat-development diffusion transfer method where development is effected under heat.
  • the dye-fixing element of the present invention is suitably applicable to both methods.
  • the dye-fixing element of the present invention is used in the heat-development diffusion transfer method, which will be explained in detail below.
  • the following explanation also applies to the wet color diffusion transfer method, except the parts intrinsic to heat-development, such as organic silver salts and the heat-development system itself.
  • the polymer dispersion for use in the present invention includes not only a so-called latex prepared by emulsion polymerization but also a dispersion prepared by dissolving a polymer in an organic solvent followed by emulsifying and dispersing the resulting solution and optionally removing the solvent from the dispersion.
  • a base or base precursor into the photographic element or the dye-fixing element.
  • a mordant described below, into the dye-fixing layer of the dye-fixing element. The mordant also helps prevent the formed color images from becoming blurred under high humidity conditions.
  • a polymer dispersion is incorporated into the coating liquid composition containing the above-mentioned base or base precursor, coagulation of the liquid composition would often occur.
  • the polymer since a polymer dispersion is frequently stabilized by imparting anionic charges to the surface of the polymer, the polymer would often coagulate in the dye-fixing layer coating liquid composition containing a large amount of salts and/or cationic compounds (e.g., the mordant).
  • the present inventor investigated a method of preparing a coating composition which does not coagulate and, as a result, has found that the problem could be solved by employment of a polymer dispersion stabilized with a nonionic stabilizer such as a nonionic surfactant or a nonionic protective colloid.
  • a nonionic stabilizer such as a nonionic surfactant or a nonionic protective colloid.
  • the amount of the hydrophilic binder in the dye-fixing layer and/or the adjacent layer(s) thereto it is preferred to minimize the amount of the hydrophilic binder in the dye-fixing layer and/or the adjacent layer(s) thereto. If the amount of hydrophilic binder is minimized, however, salts tend to precipitate. Precipitation of salts may be retarded somewhat by the addition of a polymer dispersion to the layers, but the effect of this is not sufficient.
  • the method of the present inventor's own prior JP-A-62-47639 addition of nonionic water-soluble polysaccharides, especially dextran and pullulan to the dye-fixing layer and/or the adjacent layer(s) thereto has been shown to be effective. In general, however, addition of such polysaccharides to the layer often hardens the coated layer so much that the curling balance of the element is made worse.
  • incorporation into the dye-fixing layer of a dispersion of a polymer having a glass transition temperature of 25°C or lower is effective for preventing precipitation of any base or base precursor in the layer without causing curling of the layer.
  • the polymer for use in the polymer dispersion desirably has a glass transition temperature of 25°C or lower.
  • the polymer may have a glass transition temperature higher than 25°C, provided that the polymer is used in combination with an oily plasticizer and the polymer/plasticizer combination has a glass transition temperature of 25°C or lower.
  • a plasticizer it may be added to the system in which the polymer is produced. In general, however, an emulsion of the plasticizer is added to a polymer dispersion and stirred for a certain period of time.
  • Examples of a polymer dispersion for use in the present invention include polymer latex produced by emulsion homopolymerization or emulsion copolymerization of monomer systems of vinyl acetates, ethylene-vinyl acetates, acrylic substances, vinylidene chlorides, vinyl chlorides, butadienes or butadiene derivatives, and a polymer dispersion produced by dissolving the above-mentioned polymers, polyesters or polyurethanes in an organic solvent followed by emulsifying and dispersing the solution.
  • Dispersions of polymers of vinyl acetates, ethylene-vinyl acetates, acrylic substances and styrene-butadienes are especially preferred, in view of the light fastness, heat stability, and dispersion stability of the coating compositions, and in view of their curling preventing effects and salt precipitation preventing effects.
  • Examples of monomers that may be used to make the polyemrs for the polymer dispersion for use in the present invention include acrylates, methacrylates, crotonates, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, acrylamides, methacrylamides, vinyl ethers, styrenes, dicarboxylic acids, and glycols.
  • Acrylates include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, and 2-(2-methoxyethoxy)ethyl acrylate.
  • Methacrylates include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, and 2-ethoxyethyl methacrylate.
  • Crotonates include, for example, butyl crotonate and hexyl crotonate.
  • Vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinylmethoxy acetate, and vinyl benzoate.
  • Maleic acid diesters include, for example, diethyl maleate, dimethyl maleate, and dibutyl maleate.
  • Fumaric acid diesters include, for example, diethyl fumarate, dimethyl fumarate, and dibutyl fumarate.
  • Itaconic acid diesters include, for example, diethyl itaconate, dimethyl itaconate, and dibutyl itaconate.
  • Acrylamides include, for example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, n-butylacrylamide, tert-butylacrylamide, cyclohexylacrylamdie, 2-methoxyethylacrylamide, dimethylacrylamide, diethylacrylamide, and phenylacrylamide.
  • Methacrylamides include, for example, methylmethacrylamide, ethylmethacrylamide, n-butylmethacrylamide, tert-butylmethacrylamide, 2-methoxymethacrylamide, dimethylmethacrylamide, and diethylmethacrylamide.
  • Vinyl ethers include, for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, and dimethylaminoethyl vinyl ether.
  • Styrenes include, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, chloromethylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinylbenzoate, and 2-methylstyrene.
  • Dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, succinic acid, sebacic acid, and adipic acid.
  • Glycols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, and bisphenol A-ethylene oxide adduct.
  • the polymers to be made from such monomers are preferably polymers of acrylates, copolymers of acrylates and methacrylates, copolymers of acrylates and acrylic acid or methacrylic acid, homopolymers or copolymers of vinyl acetate, styrene-butadiene copolymers, and polyurethanes.
  • Free radical polymerization of ethylenic unsaturated solid monomers is initiated by addition of free radicals formed by pyrolysis of a chemical initiator or by action of a reducing agent to an oxidative compound (redox initiator) or by physical action such as irradiation using ultraviolet rays or other high energy radiations of application of high frequency waves, to monomer molecules.
  • Typical chemical initiators usable for free radical polymerization include, for example, water-soluble compounds such as persulfates (e.g., ammonium or potassium persulfate), hydrogen peroxide and 4,4'-azobis(4-cyano-valerianic acid); and water-insoluble compounds such as azoisobutyronitrile, benzoyl peroxide, and chlorobenzoyl peroxide.
  • water-soluble compounds such as persulfates (e.g., ammonium or potassium persulfate), hydrogen peroxide and 4,4'-azobis(4-cyano-valerianic acid)
  • water-insoluble compounds such as azoisobutyronitrile, benzoyl peroxide, and chlorobenzoyl peroxide.
  • Ordinary redox initiators include hydrogen peroxide-iron(II) salts, potassium persulfate-potassium bisulfite, and cerium salts of alcohols.
  • Emulsifiers include surface-active anionic, nonionic, cationic or betaine compounds as well as high molecular weight protective colloids. Examples of these compounds and their functions are described in Belgische Chemische Industrie , Vol. 28, pages 16 to 20 (1963).
  • a latex of a polymer having a glass transition temperature of 25°C or lower is especially preferred for use in the present invention.
  • various other commercial latexes and emulsions may be used. These include Nipol LX811, 814, 820 to 823, 825, 826, 842, 851, 852, 854, 855, 857, 860, 874, 110, 112, 119, 139, 206, 209, 600, 415A, 426, 430, 432A, 433, 435, 436, 438C, 472, 473, 479, 511, 513, 517, 518, 531 and 407F (all products of Nippon Zeon Co., Ltd.); various latexes and emulsions of vinyl acetates, vinyl acetate/acrylic substances, acrylates, vinyl acetate/VeoVa, styrene/acrylic substances and ethylene/vinyl acetates, as sold commercially under the trade name Polysol by Showa Highpolymer Co.; and VONDIC 1040, 1050, 1310F, 1320NS, 1340, 15
  • the amount of the polymer latex used in the dye-fixing layer is defined by the ratio of the total volume of the polymer in the latex added to the layer to the total volume of the hydrophilic binder in the same layer; and preferably, it is from 5 to 300 % by volume, more preferably from 10 to 200 % by volume. If it is less than 5 % by volume, the cracking preventing effect would be small. If, on the other hand, it is more than 300 % by volume, the film strength would be weak and the gloss of the surface would lower.
  • the amount of the polymer latex to be added is preferably from 0.5 g/m2 to 10 g/m2, and more preferably from 1 g/m2 to 5 g/m2, as the weight of the polymer in the latex.
  • the effect of the polymer latex used in the present invention is especially remarkable when it is combined with a polymer mordant having a high glass transition temperature, especially one having a glass transition temperature of 25°C or higher.
  • the nonionic surfactants which are used as a stabilizer for the polymer dispersion preferably contain a -(CH2CH2O) n - group, a -(CH(CH3)CH2O) n - group, a glycerol group or a saccharose group as a water-soluble component and an alkyl group or an aryl group as a hydrophobic component.
  • n is an integer of 1 or more, preferably 5 or more.
  • Ethylene oxide type nonionic surfactants where n is from 10 to 100 are especially preferred, as they display a large stabilizing effect.
  • nonionic surfactants usable in the present invention are described below.
  • nonionic protective colloids which may be used as a dispersion stabilizing agent for the polymer dispersion include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, polyamides, and polysaccharides such as dextran and pullulan. Polyvinyl alcohol, hydroxyethyl cellulose and methyl cellulose are especially preferred.
  • the dye-fixing element of the present invention is lapped over a photographic element at least for transfer of a diffusive dye to the former element from the latter element.
  • the dye-fixing element is to be kept in contact with the photographic element in such a way that the dye-fixing layer of the former element faces to the light-sensitive layer of the latter element, at least for transfer of a diffusive dye to the former from the later.
  • the dye-fixing element of the present invention may be either in a separate form where a dye-fixing element and a photographic element are separately coated on different supports or in a combined form where the two elements are coated on the same support.
  • the disclosure of column 57 of U.S. Patent 4,500,626 may be referred to.
  • the dye-fixing element of the present invention is in the separate form where it is coated on an independent (different) support separate from the photographic element.
  • the dye-fixing element of the present invention has a dye-fixing layer on a support, and if desired, it may have other auxiliary layers such as a protective layer, a peeling layer, a curling preventing layer or a subbing layer. Provision of a protective layer in the element is especially effective.
  • a protective layer in the element is especially effective.
  • One or more of these layers may contain a hydrophilic heat solvent, a plasticizer, an anti-fading agent, UV absorbent, a lubricant, a mat agent or an antioxidant.
  • the dye-fixing element of the present invention preferably does not have a backing layer containing a hydrophilic binder.
  • a backing layer is coated on the element for the purpose of improving the antistatic property and the paper-feeding property (for easy conveyance of papers including the element)
  • the amount of the hydrophilic binder coated in the backing layer is 1 g/m2 or more, water-soluble low molecular weight compounds in the dye-fixing layer, such as bases or base precursors, would migrate to the adjacent backing layer, especially when a plurality of such dye-fixing elements are stored in a stack (pile) under high humidity conditions. As a result, because of the unevenness of the coated compound, any image formed on the element would be uneven also.
  • the dye-fixing element of the present invention contains a polymer mordant capable of fixing a mobile dye released by development.
  • polymer mordant as used herein includes a polymer having tertiary amino groups and a polymer having nitrogen-containing heterocyclic moieties, as well as a polymer containing quaternary amino groups derived from them. These polymers are preferably combined with some other hydrophilic polymer (e.g., gelatin).
  • polymers having tertiary amino groups or heterocyclic moieties are preferred as a mordant, because the color image fixed with such a mordant has an excellent light fastness.
  • these polymers have the advantage that dispersions of such polymers (e.g., latexes) do not tend to coagulate.
  • the polymer mordant especially polymers having tertiary amino groups or tertiary imidazole groups, is preferably a water-soluble one, in view of the light fastness and the transferred density of the image fixed therewith and the easy producibility of the polymers.
  • polymers containing tertiary amine group-having vinyl monomer units are described in JP-A-60643 and 60-57836; and specific examples of polymers containing tertiary imidazole group-having vinyl monomer units are described in JP-A-60-118834, 60-122941, 62-244043 and 62-244036, and U.S. Patents 4,282,305, 4,115,124 and 3,148,061.
  • the molecular weight of the mordant is preferably from 1,000 to 1,000,000, especially preferably from 10,000 to 200,000.
  • the polymer mordant is incorporated into the dye-fixing layer of the dye-fixing element of the present invention, along with a hydrophilic colloid as a binder which will be described below.
  • the proportion of the polymer mordant to the hydrophilic colloid as well as the amount of the polymer mordant to be coated may be determined easily by anyone of ordinary skill in the art, in accordance with the amount of dye to be mordanted, the kind and composition of the polymer mordant used, and the image forming method in which the element is used.
  • the ratio of mordant/hydrophilic colloid may be from 20/80 to 80/20 (by weight); and the amount of the mordant to be coated may be from about 0.2 g/m2 to about 15 g/m2, preferably from 0.5 to 8 g/m2.
  • the dye-fixing layer containing the polymer mordant may contain various surfactants to improve the coatability of the layer.
  • the dye-fixing element of the present invention contains a water-soluble base and/or base precursor, to enhance the simple and rapid processability of the element and to improve its storage stability.
  • bases usable in the present invention include inorganic bases of alkali metals or quaternary alkylammonium hydroxides, carbonates, bicarbonates, borates, secondary or tertiary phosphates and metaborates; and organic bases of aliphatic amines, aromatic amines, heterocyclic amines, amidines, cyclic amidines, guanidines and cyclic guanidines, as well as carbonates, bicarbonates, borates and secondary or tertiary phosphates of them.
  • Base precursors for use in the present invention include precursors of the above-mentioned organic bases.
  • base precursor as used herein means a substance capable of releasing a basic component by pyrolysis or electrolysis.
  • base precursors include salts of pyrolyzing organic acids, such as trichloroacetic acid, cyanoacetic acid, acetacetic acid or ⁇ -sulfonylacetic acid, and the above-mentioned organic bases; and salts with 2-carboxycarboxamides as described in U.S. Patent 4,088,496.
  • the base precursors described in British Patent 998,945, U.S. Patent 3,220,846 and JP-A-50-22625 may also be used.
  • Electrolysis of various fatty acid salts is one example of using electrolytic oxidation.
  • carbonates of alkali metals as well as those of organic bases such as guanidines or amidines may be obtained very efficiently.
  • methods of using electrolytic reduction include formation of amines by reduction of nitro compounds or nitroso compounds; formation of amines by reduction of nitriles; and formation of p-aminophenols, p-phenylenediamines or hydrazines by reduction of nitro compounds, azo compounds or azoxy compounds.
  • p-Aminophenols, p-phenylenediamines and hydrazines may be used not only as a base but also directly as a color image-forming substance. It is also possible to form alkali components by electrolysis of water in the presence of various inorganic salts.
  • a method of forming a water-soluble base by reacting a compound, which may be complexed with a metal ion capable of forming a sparingly soluble metal salt compound (e.g., zinc oxide, basic zinc carbonate, calcium carbonate) and water, for example guanidine pyrophosphate or the like, and the sparingly soluble metal salt compound, as described in U.S. Patent 4,740,445.
  • a metal ion capable of forming a sparingly soluble metal salt compound (e.g., zinc oxide, basic zinc carbonate, calcium carbonate) and water, for example guanidine pyrophosphate or the like, and the sparingly soluble metal salt compound, as described in U.S. Patent 4,740,445.
  • the base and/or base precursor can be used either singly or in a combination of two or more of them.
  • the amount of base and/or base precursor to be used in the present invention is from 5 x 10 ⁇ 4 to 5 x 10 ⁇ 1 mol/m2, preferably from 2.5 x 10 ⁇ 3 to 2.5 x 10 ⁇ 2 mol/m2.
  • the photographic element to be used with the dye-fixing element of the present invention may be either a wet type that is processed at about room temperature under wet conditions or a heat-developing type processed under heat.
  • the dye-fixing element of the present invention is preferably used with the heat-developing type photographic element.
  • the photographic element which may be used with the dye-fixing element of the present invention basically contains a light-sensitive silver halide, a dye providing compound (which may be a reducing agent, as will be described below), and a binder on a support, and it may contain an organic metal salt oxidizing agent. These components are in most cases incorporated into the same layer, but they may be added separately to different layers provided that they are reactive with each other.
  • a colored dye providing compound is in the layer below a silver halide emulsion layer, it is effective for preventing lowering of the sensitivity of the emulsion layer.
  • a reducing agent is preferably incorporated into the photographic element.
  • it may be supplied to the photographic element from an external source such as the dye-fixing element by diffusing it thereinto from the dye-fixing element, as will be described below.
  • a combination of at least three silver halide emulsion layers each having a light-sensitivity in a different spectral region is used.
  • a combination of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer may be used, or a combination of a green-sensitive layer, a red-sensitive layer and an infrared sensitive layer may be used.
  • the respective light-sensitive layers may be arranged in any desired sequence as generally employed in ordinary color photographic materials. These layers each may have two or more layers each having a different sensitivity.
  • the heat-developing photographic material may have various other auxiliary layers, such as a protective layer, a subbing layer, an interlayer, a yellow filter layer, an anti-halation layer, and a backing layer.
  • auxiliary layers such as a protective layer, a subbing layer, an interlayer, a yellow filter layer, an anti-halation layer, and a backing layer.
  • the silver halide for use in the present invention may be any one of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide.
  • the silver halide emulsion for use in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion.
  • the internal latent image type emulsion is used as a direct reversal emulsion, in combination with a nucleating agent or with light fogging.
  • the emulsion may also be a so-called core/shell emulsion in which the inside phase and the surface phase of each grain are different from each other.
  • the silver halide emulsion may be either a monodispersed one or a polydispersed one. A mixture of monodispersed emulsions may also be used.
  • the grain size of the emulsion grains may be from 0.1 to 2 ⁇ m, especially preferably from 0.2 to 1.5 ⁇ m.
  • the crystal habit of the silver halide grains may be any one of a cubic, octahedral or tetradecahedral shape, or a tabular shape having a high aspect ratio.
  • the silver halide emulsions may be used as primitive emulsions. In general, however, they are chemically sensitized before use. For instance, any known sulfur sensitization, reduction sensitization, noble metal sensitization or selenium sensitization, which are generally applied to emulsions of ordinary photographic materials, can be employed singly or in combination. Such chemical sensitization may also be effected in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).
  • the amount of light-sensitive silver halide to be coated in preparing the photographic material for use in the present invention may be from 1 mg/m2 to 10 g/m2 as silver.
  • the silver halides to be used in the present invention may be spectrally sensitized with methine dyes or other dyes.
  • Suitable dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • sensitizing dyes described in U.S. Patent 4,617,257, JP-A-59-180550 and JP-A-60-140335, and RD No. 17029 (1978), pages 12 and 13.
  • sensitizing dyes may be used singly or in combination. Combinations of sensitizing dyes are often used for the purpose of supersensitization.
  • Dyes which do not have a spectral sensitizing activity by themselves or compounds which do not substantially absorb visible rays but which show a supersensitizing activity may be incorporated into the emulsions along with sensitizing dyes.
  • Such dyes and compounds include those described in U.S. Patent 3,615,641 and JP-A-63-23145.
  • the time of adding such sensitizing dyes into the emulsions may be before or after chemical ripening of the emulsions. As the case may be, it may be before or after the formation of nuclei of the silver halide grains, in accordance with U.S. Patents 4,183,756 and 4,225,666.
  • the amount of the dyes to be added is generally from about 10 ⁇ 8 to 10 ⁇ 2 mol, per mol of silver halide.
  • the photographic element in the system may contain an organic metal salt, as an oxidizing agent, along with a light-sensitive silver halide.
  • organic metal salt organic silver salts are especially preferred.
  • Organic compounds to be used for forming such organic silver salt oxidizing agents include benzotriazoles, fatty acids and other compounds described in U.S. Patent 4,500,626 (columns 52 to 53).
  • silver salts of alkynyl group-containing carboxylic acids such as silver phenylpropiolate, as described in JP-A-60-113235, as well as acetylene silver as described in JP-A-61-249044 are also useful. Two or more kinds of organic silver salts may be employed in combination.
  • the organic silver salt may be added to the emulsion in an amount of from 0.01 to 10 mols, preferably from 0.01 to 1 mol, per mol of the light-sensitive silver halide in the emulsion.
  • the total amount of the light-sensitive silver halide and the organic silver salt to be coated is suitably from 50 mg/m2 to 10 g/m2, as silver.
  • antifoggants and photographic stabilizers may be used in the present invention.
  • examples include the azoles and azaindenes described in RD No. 17643 (1978), pages 24 and 25; the nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442; the mercapto compounds and metal salts thereof described in JP-A-59-11166; and the acetylene compounds described in JP-A-62-87957.
  • any one which is known in the field of photographic materials can be employed.
  • the reducing agents include the dye providing compounds having a reducing property, which will be described below.
  • any other reducing agent can be used, if desired, in combination with such a reducing dye providing compound.
  • reducing agent precursors which do not have a reducing property by themselves but which exhibit a reducing capacity with the aid of a nucleophilic reagent or under heat during development procedures may also be employed.
  • Examples of the reducing agents which can be employed in the present invention include the reducing agents and reducing agent precursors described in U.S. Patents 4,500,626 (columns 49 and 50), 4,483,914 (columns 30 and 31), 4,330,617 and 4,590,152, JP-A-60-140355 (pages 17 and 18), JP-A-57-40245, JP-A-56-138736, JP-A-59-178458, JP-A-59-53831, JP-A-59-182449, JP-A-59-182450, JP-A-60-119555, JP-A-60-128436 through JP-A-60-128439, JP-A-60-198540, JP-A-60-181742, JP-A-61-259253, JP-A-62-244044, JP-A-62-131253 through JP-A-62-131256 and European Patent 220,746A2 (pages 78 to 96).
  • an electron transfer agent and/or an electron transfer agent precursor can be used, if desired, in combination with the reducing agent to accelerate the movement of electrons between the non-diffusive reducing agent and the developable silver halide.
  • the electron transfer agent or precursor thereof can be selected from the above-mentioned reducing agents and precursors thereof.
  • the electron transfer agent or precursor thereof preferably has a higher mobility than the non-diffusive reducing agent (electron donor).
  • Especially useful electron transfer agents are 1-phenyl-3-pyrazolidones and aminophenols.
  • An electron transfer agent is an easily diffusive and mobile compound. Therefore, such an electron transfer agent is especially effective for preventing unfavorable coloration of the dye-fixing element of the present invention because of the rapid movement of the agent to the element.
  • the non-diffusive reducing agent (electron donor) to be employed in combination with the electron transfer agent may be any one of the above-mentioned reducing agents which are not substantially mobile in the layers of a photographic element.
  • electron donors include hydroquinones, sulfonamidophenols, sulfonamidonaphthols, and the compounds described in JP-A-53-110827, as well as the non-diffusive and reducing dye providing compounds which will be described below.
  • the amount of the reducing agent to be added preferably is from 0.01 to 20 mols, especially preferably from 0.1 to 10 mols, per mol of silver.
  • a dye providing compound capable of forming or releasing a mobile dye in correspondence or reverse correspondence with the amount of exposure is used.
  • Examples of dye providing compounds which can be employed in the present invention include compounds (couplers) capable of forming a dye by an oxidation-coupling reaction.
  • the coupler may be either a 4-equivalent one or a 2-equivalent one.
  • 2-Equivalent couplers which have a non-diffusive group as the split-off group and which form a diffusive dye by oxidation-coupling reaction are preferred.
  • the non-diffusive group may be in the form of a polymer chain. Examples of color developing agents and couplers for use in the present invention are described in detail in T.H.
  • a further example of a dye providing compound which can be used is a compound adapted to imagewise release or form a diffusive dye.
  • Compounds of this type can be represented by the formula (LI): wherein Dye represents a dye group, or a dye group or dye precursor group whose wavelength has been shortened temporarily; Y represents a chemical bond or a linking group; Z represents a group which either causes an imagewise differential in the diffusibility of the compound in correspondence or reverse correspondence with the light-sensitive silver salt carrying a latent image or releases the Dye and causes a differential in diffusibility between the released Dye and ; and n represents 1 or 2, and when n is equal to 2, the two Dye-Y groups may be same as or different from each other.
  • the following compounds (1) through (5) are mentioned.
  • Compounds (1) through (3) are those capable of forming a diffusive color image (positive color image) in reverse correspondence with development of silver halide; and compounds (4) and (5) are those capable of forming a diffusive color image (negative color image) in correspondence with the development of silver halide.
  • Dye providing compounds other than the above-mentioned couplers and the compounds of the formula (LI) include dye-silver compounds comprising an organic silver salt and a dye bonded to each other (RD of May 1978, pages 54 to 58), azo dyes employable in a heat-developing silver dye bleaching method (U.S. Patent 4,235,957, RD of April 1976, pages 30 to 32) and leuco dyes (U.S. Patents 3,985,565 and 4,022,617). These dye donor compounds can also be employed in the present invention.
  • the dye providing compound, non-diffusive reducing agent and other hydrophobic additives are incorporated into the layers of the photographic material by any known method, for example, by the method described in U.S. Patent 2,322,027.
  • high boiling point organic solvents such as those described in JP-A-59-83154, JP-A-59-178451, JP-A-59-178452, JP-A-59-178453, JP-A-59-178454, JP-A-59-178455 and JP-A-59-178457 can be used optionally together with low boiling point organic solvents having a boiling point of from 50°C to 60°C.
  • the amount of the high boiling point organic solvent to be used in the above method is 10 g or less, preferably 5 g or less, per gram of the dye providing compound used. It is suitably one cc or less, more suitably 0.5 cc or less, especially suitably 0.3 cc or less, per gram of the binder.
  • a dispersion method with a polymer as described in JP-B-51-39853 and JP-A-51-59943, may also be employed.
  • the compound to be incorporated into the layers is substantially insoluble in water, it may be dispersed in the binder in the form of fine grains, apart from the above-mentioned methods.
  • hydrophobic compound is dispersed in a hydrophilic colloid
  • various surfactants may be used.
  • the surfactants mentioned in JP-A-59-157636, pages 37 to 38 may be used for this purpose.
  • the photographic material of the present invention can contain a compound having a function of activating the developability thereof and of stabilizing the image formed.
  • a compound having a function of activating the developability thereof and of stabilizing the image formed are described in U.S. Patent 4,500,626, columns 51 to 52.
  • the binder to be used in the layers constituting the photographic element and the dye-fixing element of the present invention is preferably a hydrophilic one.
  • hydrophilic binders include those mentioned in JP-A-62-253159 (pages 26 to 28).
  • transparent or semi-transparent hydrophilic binders are preferred, which include natural compounds, for example, proteins such as gelatin and gelatin derivatives, polysaccharides such as cellulose derivatives, starch, gum arabic, dextran and pullulan; and other synthetic high molecular weight compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers.
  • the highly water-absorbing polymers described in JP-A-62-245260 such as homopolymers of vinyl monomers having -COOM or -SO3M groups (where M is a hydrogen atom or an alkali metal), or copolymers of such vinyl monomers or copolymers of such vinyl monomers along with other vinyl monomers (e.g., sodium methacrylate, ammonium methacrylate, Sumikagel L-5H produced by Sumitomo Chemical Co., Ltd.) may also be used.
  • Such binders may be used in combinations of two or more of them.
  • the photographic material preferably contains a highly water-absorbing polymer whereby absorption of the water may be effected rapidly. It is preferred to incorporate the said highly water-absorbing polymer into the dye-fixing layer and the protective layer therefor, whereby re-transfer of the once-transferred dye to any other material from the dye-fixing element is prevented.
  • the amount of the binder to be coated is preferably 20 g or less, especially 10 g or less, more preferably 7 g or less, per m2.
  • the layers constituting the light-sensitive photographic element and the dye-fixing element can contain a hardening agent.
  • hardening agents are described in U.S. Patent 4,678,739 (column 41) and JP-A-59-116655, JP-A-62-245261 and JP-A-61-18942.
  • aldehyde hardening agents e.g., formaldehyde
  • aziridine hardening agents epoxy hardening agents
  • vinylsulfone hardening agents e.g., N,N'-ethylene-bis(vinylsulfonylacetamino)ethane
  • N-methylol hardening agents e.g., dimethylolurea
  • high molecular weight hardening agents e.g., compounds described in JP-A-62-234157.
  • epoxy hardening agents are especially preferred in view of the coatability (precisely, an epoxy hardening agent-containing composition is stable for a long period of time and an epoxy hardening agent is reactive with the adjacent layer), the quality of the hardened film (precisely, the storage stability of raw films is good when an epoxy hardening agent is used and the quality of the hardened film is also good when the agent is used), and the photographic properties (precisely, the transferred density of the image formed is high when an epoxy hardening agent is used).
  • the light-sensitive photographic element and/or the dye-fixing element can contain an image formation accelerator.
  • the image formation accelerators include those which promote the redox reaction between a silver salt oxidizing agent and a reducing agent, those which promote the reactions of forming a dye from a dye providing substance or decomposing a dye or releasing a diffusive dye, and those which promote the migration of a dye from the light-sensitive layer to the dye-fixing layer.
  • the image formation accelerators can be classified into bases or base precursors, nucleophilic compounds, high boiling point organic solvents (oils), heat solvents, and surfactants and compounds which interact with silver or silver ions, for instance.
  • each of these substances generally has plural functions and provides several of the above-mentioned effects. A detailed discussion on these substances can be found in U.S. Patent 4,678,739, columns 38 to 40.
  • the light-sensitive photographic element and/or the dye-fixing element of the present invention can contain various development stopping agents for the purpose of always obtaining constant images despite fluctuation of the development temperature and the processing time in development.
  • development stopping agent means a compound which, after proper development, quickly neutralizes a base or reacts with a base to lower the base concentration in the layer and thereby stops the development, or a compound which interacts with silver and a silver salt to arrest development.
  • acid precursors which release an acid under heat
  • electrophilic compounds which react with the existing base by displacement reaction under heat
  • nitrogen-containing heterocyclic compounds mercapto compounds and precursors thereof. More precisely, specific examples of these compounds are described in JP-A-62-253159 (pages 31 to 32).
  • Layers (including the backing layer) constituting the light-sensitive photographic element may contain various polymer latexes for the purpose of improving the film properties of the element, for example, for preventing curling, surface blocking, cracking and formation of pressure marks (due to decrease or increase of sensitivity under pressure) on the element.
  • polymer latexes usable for these purposes are the polymer latexes described in JP-A-62-245258, JP-A-62-136648 and JP-A-62-110066, as well as the above-mentioned polymer dispersions to be used in the dye-fixing element of the present invention.
  • the layers constituting the light-sensitive photographic element and the dye-fixing element can contain a high boiling point organic solvent as a plasticizer, a sliding agent, or an agent to improve peeling apart of the photographic element and the dye-fixing element.
  • a high boiling point organic solvent as a plasticizer, a sliding agent, or an agent to improve peeling apart of the photographic element and the dye-fixing element.
  • silicone oils which may be all types of silicone oils including dimethylsilicone oil and modified silicone oils formed by introducing various organic groups into dimethylsiloxane
  • examples of such silicone oils include the various modified silicone oils described in Technical Reference of Modified Silicone Oils (published by Shin-Etsu Silicone Co., Ltd.), page 6-18B.
  • carboxy-modified silicone oil (trade name: X-22-3701) is effective.
  • silicone oils described in JP-A-62-215958 and JP-A-63-46449 are also useful.
  • the light-sensitive photographic element and the dye-fixing element can contain an anti-fading agent.
  • anti-fading agents include antioxidants and ultraviolet absorbents as well as various kinds of metal complexes.
  • antioxidants examples include chroman compounds, coumaran compounds, phenol compounds (e.g., hindered phenols), hydroquinone derivatives, hindered amine derivatives and spiroindane compounds.
  • chroman compounds e.g., chroman compounds
  • coumaran compounds e.g., hindered phenols
  • hydroquinone derivatives e.g., hindered phenols
  • hindered amine derivatives e.g., spiroindane compounds.
  • JP-A-61-159644 examples include chroman compounds, coumaran compounds, phenol compounds (e.g., hindered phenols), hydroquinone derivatives, hindered amine derivatives and spiroindane compounds.
  • the compounds described in JP-A-61-159644 are also effective.
  • Examples of the ultraviolet absorbent include benzotriazole compounds (U.S. Patent 3,533,794), 4-thiazolidone compounds (U.S. Patent 3,352,681), benzophenone compounds (JP-A-46-2784) and other compounds described in JP-A-54-48535, JP-A-62-136641 and JP-A-61-88256. Further, the ultraviolet-absorbing polymers described in JP-A-62-260152 are also effective.
  • metal complexes examples include the compounds described in U.S. Patents 4,241,155, 4,245,013 (columns 3 to 36) and 4,254,195 (columns 3 to 8), JP-A-62-174741 and JP-A-61-88256 (pages 27 to 29), JP-A-63-199248, JP-A-1-75568 and JP-A-1-74272.
  • the anti-fading agent for preventing the dye which has been transferred to the dye-fixing element from fading may previously be incorporated into the dye-fixing element or, alternatively, it maybe supplied to the dye-fixing element from a source external to the light-sensitive photographic material.
  • antioxidant, ultraviolet absorbent and metal complex can be employed in the present invention in the form of a combination thereof.
  • the light-sensitive photographic element and the dye-fixing element can contain a fluorescent brightening agent.
  • a fluorescent brightening agent in the dye-fixing element or to supply it to the dye-fixing element from a source external to the light-sensitive photographic element.
  • brightning agents the compounds described in K. Veenkataraman, The Chemistry of Synthetic Dyes , Vol. V, Chap. 8, and JP-A-61-143752 are referred to. Specifically, there are mentioned stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds and carbostyryl compounds.
  • the fluorescent brightening agent can be employed in combination with an anti-fading agent.
  • the layers constituting the light-sensitive photographic element and the dye-fixing element can contain various surfactants for various purposes, such as to aid coating, improve peeling properties, improve slide properties, prevent static charges, and enhance developability. Specific examples of such surfactants are described in JP-A-62-173463 and JP-A-62-183457.
  • the layers constituting the light-sensitive photographic element and the dye-fixing element can contain organic fluorine compounds to improve sliding properties, prevent static charges, and improve peeling properties.
  • organic fluorine compounds include the fluorine surfactants described in JP-B-57-9053 (columns 8 to 17) and JP-A-61-20944 and JP-A-62-135826, as well as hydrophobic fluorine compounds such as fluorine oils and similar oily fluorine compounds, tetrafluoroethylene resins, and similar solid fluorine compound resins.
  • the light-sensitive photographic element and the dye-fixing element can contain a mat agent.
  • a mat agent there are mentioned silicone dioxide and the compounds described in JP-A-61-88256 (page 29) such as polyolefins or polymethacrylates, as well as the compounds described in JP-A-63-274944 and JP-A-63-274952 such as benzoguanamine resin beads, polycarbonate resin beads and AS resin beads.
  • the layers constituting the light-sensitive photographic element and the dye-fixing element may further contain a heat solvent, a defoaming agent, a microbicidal, fungicidal agent, a colloidal silica and other additives. Examples of such additives are described in JP-A-61-88256 (pages 26 to 32).
  • the support which may be used to prepare the light-sensitive photographic element and the dye-fixing element of the present invention may be any support that withstands the processing temperature.
  • paper and synthetic high molecular weight films are used as the support.
  • the support includes films of polyethylene terephthalate, polycarbonates, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (e.g., triacetyl cellulose) and those films containing a pigment such as titanium oxide; synthetic paper made of polypropylene by filming method; mixed paper made of a synthetic resin pulp (e.g., polyethylene) and a natural pulp; as well as Yankee paper, baryta paper, coated paper (especially cast-coated paper), metals, cloths and glasses.
  • a synthetic resin pulp e.g., polyethylene
  • coated paper especially cast-coated paper
  • These supports may be used directly as they are or they may be coated with a synthetic high molecular weight substance (e.g., polyethylene) on one surface or both surfaces.
  • a synthetic high molecular weight substance e.g., polyethylene
  • the surface of the support may be coated with a hydrophilic binder and a semiconductive metal oxide (e.g., alumina sol or tin oxide) or an antistatic agent such as carbon black.
  • a semiconductive metal oxide e.g., alumina sol or tin oxide
  • an antistatic agent such as carbon black.
  • various methods can be employed, which include, for example, a method of directly photographing the scene or portrait with a camera; a method of exposing an image through a reversal film or negative film by the use of a printer or an enlarger; a method of scanning and exposing an original through a slit by the use of an exposing device of a duplicator; a method of exposing the image information via the corresponding electric signal by emitting the information with an emitting diode or various lasers; and a method of outputting the image information with an image display device such as a CRT, a liquid crystal display, an electroluminescence display or a plasma display and then exposing the same directly or via some optical system.
  • an image display device such as a CRT, a liquid crystal display, an electroluminescence display or a plasma display and then exposing the same directly or via some optical system.
  • the light source to be used for recording an image on the photographic element those described in U.S. Patent 4,500,626 (column 56), such as natural light, tungsten lamps, light-emitting diodes, laser rays and CRT rays can be employed, as mentioned above.
  • the image information applied to the photographic material of the present invention may include image signals obtained from a video camera or an electronic still camera; television signals standardized by Nippon Television Signal Standard Code (NTSC); image signals obtained by dividing an original into pixels with a scanner; and image signals formed by the use of a computer such as CG or CAD.
  • NTSC Nippon Television Signal Standard Code
  • the heating temperature in the heat-development step varies, depending upon the film pH value to be adjusted by the base or base precursor therein and it may be from about 25°C to about 250°C. Preferably, it is from about 50°C to about 200°C, especially preferably from about 70°C to about 180°C.
  • the step of diffusing and transferring the dye formed by the development may be effected simultaneously with the heat-development step or after it. In the latter case, the heating temperature in the transfer step may be from the temperature in the previous heat-development step to room temperature. Preferably, it is from 50°C to a temperature lower than the temperature in the heat-development step by about 10°C.
  • Migration of the dye formed may be effected only by heat, but a solvent may be used for the purpose of accelerating the migration of the dye.
  • a method where development and transfer are carried out in the presence of a small amount of a solvent (especially, water) under heat, either at the same time or in a continuous sequence can be advantageously utilized.
  • the heating temperature is preferably not lower than 50°C and not higher than the boiling point of the solvent used.
  • the temperature is desirably from 50°C to 100°C.
  • Examples of the solvents to be used to accelerate development and/or migration of the diffusive dye formed to the dye-fixing element include water and an aqueous basic solution containing an inorganic alkali metal salt or an organic base.
  • bases those mentioned hereinbefore for the image formation accelerators can be employed.
  • a low boiling point solvent, or a mixed solution comprising a low boiling point solvent and water or an aqueous basic solution can also be used.
  • surfactants and antifoggants as well as sparingly soluble metals and complex-forming compounds can be incorporated into the solvents.
  • the solvent can be used by applying it to either the dye-fixing element or the light-sensitive photographic element or to both of them.
  • the amount of solvent used may be a small amount.
  • a small amount means an amount less than the weight of the solvent corresponding to the maximum swollen volume of the total coated layers (especially less than the amount obtained by subtracting the weight of the total coated layers from the weight of the solvent corresponding to the maximum swollen volume of the total coated layers).
  • the solvent can be incorporated into either the light-sensitive photographic element or the dye-fixing element or into both of them in the form of solvent-containing microcapsules.
  • a method of incorporating a hydrophilic heat solvent which is solid at room temperature but may melt at a high temperature into the light-sensitive photographic element or into the dye-fixing element may also be employed in the present invention.
  • the hydrophilic heat solvent may be incorporated into either the light-sensitive photographic element or the dye-fixing element or into both of them.
  • the layer to which the solvent is added may be any of the emulsion layer, interlayer, protective layer and dye-fixing layer, but the solvent is preferably added to the dye-fixing layer and/or the adjacent layer(s).
  • heat solvent to be employed in the method examples include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocyclic compounds.
  • a high boiling point organic solvent may be incorporated into the light-sensitive photographic material and/or the dye-fixing element.
  • the material and/or the element may be contacted with a heated block or plate, or heated with a hot plate, hot presser, hot roller, halogen lamp heater or infrared or far-infrared lamp heater, or the material may be passed through a high temperature atmosphere.
  • the photographic element and/or the dye-fixing element of the present invention may have a heating element layer provided therein, in which the layer is electrically charged so as to heat the elements.
  • the one disclosed in JP-A-61-145544 may be referred to.
  • any general heat-developing apparatus can be utilized.
  • the apparatus described in JP-A-59-75247, JP-A-59-177547, JP-A-59-181353 and JP-A-60-18951, JP-U-A-62-25944 are preferably employed.
  • First Layer Red-Sensitive Emulsion Layer Red-sensitive Silver Halide Emulsion 230 mg/m2 as Ag Cyan Dye Providing Compound (3) 343 mg/m2 Gelatin 330 mg/m2 Electron Donor (1) 163 mg/m2 High Boiling Point Solvent (1) 172 mg/m2 Electron Transfer Agent (1) 28 mg/m2 Electron Transfer Agent Precursor (1) 17 mg/m2 Antifoggant (3) 0.7 mg/m2
  • Second Layer Interlayer Gelatin 790 mg/m2 Zinc Hydroxide 300 mg/m2 Electron Donor (2) 130 mg/m2 High Boiling Point Solvent (1) 73 mg/m2 Surfactant (2) 100 mg/m2 Active Charcoal 25 mg/m2
  • Third Layer Green-Sensitive Emulsion Layer Green-Sensitive Silver Halide Emulsion 220 mg/m2 as Ag Magenta Dye Providing Compound (2) 365 mg/m2 Gelatin
  • a dye-fixing element sample having the layer constitution mentioned in Table 1-A below was prepared, in which a support having the layer constitution given in Table 1-D was coated with a surface layer described in Table 1-B and a backing layer described in Table 1-C.
  • the fluorescent brightening layer in the surface layer was introduced thereinto by an oil-protect method using high boiling point solvent (1), ethyl acetate and sodium dodecylbenzenesulfonate in the same layer.
  • the sample thus prepared was designated dye-fixing element Sample No. 01.
  • Benzoguanamine Resin (mean grain size 15 ⁇ m)
  • Water-soluble Polymer (1) Sumikagel L5-H (product of Sumitomo Chemical Co., Ltd.)
  • dye-fixing element Sample No. 02 was prepared in the same manner as Sample No. 01, except that no backing layer was provided.
  • dye-fixing element Sample Nos. 03 to 16 were prepared in the same manner as Sample No. 02, except that the second layer (mordant layer) of the surface layer (1) (Table 1-B) was changed described below.
  • Gelatin 1.40 g/m2 Mordant (1) 2.40 g/m2 Guanidine Picolinate 2.20 g/m2 Fluorescent Brightening Agent (1) 0.055 g/m2 Stain Inhibitor (1) 0.06 g/m2 High Boiling Point Organic Solvent (1) 1.40 g/m2 Surfactant (4) 0.025 g/m2
  • Gelatin 0.8 g/m2 Water-soluble Polymer (3) 0.6 g/m2 Nipol LX814 (as solid) 2.0 g/m2 Mordant (1) 2.40 g/m2 Guanidine Picolinate 2.20 g/m2 Fluorescent Brightening Agent (1) 0.055 g/m2 Stain Inhibitor (1) 0.06 g/m2 High Boiling Point Organic Solvent (1) 1.40 g/m2 Surfactant (4) 0.025 g/m2
  • Samples Nos. 07 and 08 were same as Sample Nos. 05 and 06, respectively, except that a nonionic surfactant C6H5O(CH2CH2O)30H was added.
  • Sample Nos. 14 and 15 were prepared in the same manner as Sample No. 05, except that the amount of Nipol LX814 (as solids content) was changed to 4.0 g/m2 and 0.5 g/m2, respectively.
  • the photographic element sample was exposed with an original (a test chart with wedges of yellow, magenta, cyan and gray each having a continuously varying color density) through a slit by a scanning exposure, the exposed sample was dipped in water kept at 35°C for about 5 seconds, this was squeezed with rollers and then immediately attached to a dye-fixing element sample in such a way that the coated top surfaces of the two faced each other, and the combined samples were heated with heat rollers for 15 seconds in such a way that the water-applied surfaces were heated up to 80°C. Then, the photographic element sample was peeled apart from the dye-fixing element sample, whereupon a sharp color image well corresponding to the original was formed on the dye-fixing element sample.
  • an original a test chart with wedges of yellow, magenta, cyan and gray each having a continuously varying color density
  • the developed and transferred dye-fixing element sample was cut into a size of 10 cm x 10 cm, which was then stored under one of the following conditions (A) to (C) for 2 hours whereupon the degree of curling of the sample was measured in such a way that the curled sample was put on a flat rack and the height (unit: mm) of each of the four edges of the sample (from the surface of the rack) was measured and the four measured values were averaged.
  • All the non-processed dye-fixing element samples were tempered under the condition of 25°C and 80% RH for 2 hours, and they were stacked (piled up) in such a way that the front surface (with dye-fixing layer) of one sample was kept in contact with the back surface of another sample.
  • a weight of 20 g/cm2 was applied to the stack (pile), which was thus stored for 3 days under an ambient condition of 60°C and 80% RH.
  • Each of the thus stored dye-fixing element samples was combined with the previously prepared photographic element Sample No. 01 and processed with an image recording processor as described in the above-mentioned Japanese Patent Application No. 63-137104 using an original of a completely uniformly black paper.
  • the degree of unevenness of the thus formed black image was evaluated on the basis of the following three ranks A, B and C.
  • the surface gloss of each sample was measured on the basis of JIS-Z-8741 (reflection to 20 degree-mirror surface).
  • a non-exposed photographic element Sample No. 01 or a photographic element Sample No. 01 fully exposed with a white light was combined with one of the prepared dye-fixing element samples and then processed to form developed samples each with a black solid image or a white solid image. These were tempered under the condition of 25°C and 80% RH for 1 hour and then stacked (piled up) in such a way that the front surface (with black image) of one sample was kept in contact with the front surface (with white image) of another sample, under a load of 500 g/200 cm2 and an ambient condition of 25°C and 80% RH for 3 days. Then, the two samples were peeled apart, whereupon the degree of the dye re-transferred from the black image sample to the white image sample was measured. The contact color migration of the tested samples was evaluated on the basis of the following three ranks A, B and C.
  • Non-processed dye-fixing element samples were subjected to an alternating heat cycle of 40°C-80% RH-8 hours and 0°C-20% RH-12 hours 14 times, whereupon the crystalline precipitate, if any, formed on the surface of the sample was checked. The sample was then evaluated on the basis of the following three ranks A, B and C.
  • Non-processed dye-fixing element samples were tempered under the condition of 25°C and 60% RH and then stacked (piled up) in such a say that the front surface (with dye-fixing layer) of one sample was kept in contact with the back surface of another sample under a load of 500 g/100 cm2 and an ambient condition of 60°C and 60% RH for 3 days. Then, the samples were peeled apart, whereupon the degree of surface blocking (adhesion) was examined. The tested sample was then evaluated on the basis of the following three ranks A, B and C.

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EP92106696A 1991-04-19 1992-04-16 Dye-fixing element Withdrawn EP0509540A1 (en)

Applications Claiming Priority (2)

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JP115587/91 1991-04-19
JP11558791A JPH04321045A (ja) 1991-04-19 1991-04-19 色素固定要素

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EP0509540A1 true EP0509540A1 (en) 1992-10-21

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EP92106696A Withdrawn EP0509540A1 (en) 1991-04-19 1992-04-16 Dye-fixing element

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EP (1) EP0509540A1 (ja)
JP (1) JPH04321045A (ja)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN107209450A (zh) * 2014-10-20 2017-09-26 加州大学评议会 可重写介质的氧化还原成像纳米材料的光催化颜色切换

Citations (2)

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Publication number Priority date Publication date Assignee Title
EP0123166A2 (en) * 1983-03-30 1984-10-31 Fuji Photo Film Co., Ltd. Process for forming color images
EP0219101A2 (en) * 1985-10-16 1987-04-22 Konica Corporation Silver halide photographic material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0123166A2 (en) * 1983-03-30 1984-10-31 Fuji Photo Film Co., Ltd. Process for forming color images
EP0219101A2 (en) * 1985-10-16 1987-04-22 Konica Corporation Silver halide photographic material

Non-Patent Citations (6)

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Title
PATENT ABSTRACTS OF JAPAN vol. 10, no. 358 (P-522)(2415) 2 December 1986 & JP-A-61 156 045 ( FUJI PHOTO FILM ) 15 July 1986 *
PATENT ABSTRACTS OF JAPAN vol. 11, no. 230 (P-599)(2677) 28 July 1987 & JP-A-62 043 641 ( FUJI PHOTO FILM ) 25 February 1987 *
PATENT ABSTRACTS OF JAPAN vol. 12, no. 119 (P-689)(2966) 14 April 1988 & JP-A-62 245 258 ( FUJI PHOTO FILM ) 26 October 1987 *
PATENT ABSTRACTS OF JAPAN vol. 13, no. 93 (P-838)(3441) 6 March 1989 & JP-A-63 274 953 ( FUJI PHOTO FILM ) 11 November 1988 *
RESEARCH DISCLOSURE. no. 195, July 1980, HAVANT GB pages 301 - 310; 'Photographic applications of latices' *
RESEARCH DISCLOSURE. no. 308, December 1989, HAVANT GB pages 993 - 1015; 'Photographic silver halide emulsions, preparation' *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107209450A (zh) * 2014-10-20 2017-09-26 加州大学评议会 可重写介质的氧化还原成像纳米材料的光催化颜色切换
US10534254B2 (en) 2014-10-20 2020-01-14 The Regents Of The University Of California Photocatalytic color switching of redox imaging nanomaterials of rewritable media

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