EP0704759A2 - Image formation method - Google Patents

Image formation method Download PDF

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Publication number
EP0704759A2
EP0704759A2 EP95114681A EP95114681A EP0704759A2 EP 0704759 A2 EP0704759 A2 EP 0704759A2 EP 95114681 A EP95114681 A EP 95114681A EP 95114681 A EP95114681 A EP 95114681A EP 0704759 A2 EP0704759 A2 EP 0704759A2
Authority
EP
European Patent Office
Prior art keywords
light
sensitive material
group
dye
mordant
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Withdrawn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
EP95114681A
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German (de)
English (en)
French (fr)
Inventor
Hiroyuki C/O Fuji Photo Film Co. Ltd. Hirai
Yoshiharu c/o Fuji Photo Film Co. Ltd. Yabuki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
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 EP0704759A2 publication Critical patent/EP0704759A2/en
Withdrawn legal-status Critical Current

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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
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
    • G03C8/4033—Transferable dyes or precursors
    • 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
    • G03C8/4006—Development by heat ; Photo-thermographic processes using materials covered by the groups G03C8/04 - G03C8/06
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
    • G03C1/49854—Dyes or precursors of dyes
    • 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
    • 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
    • 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
    • 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
    • G03C2200/00—Details
    • G03C2200/23—Filter dye
    • 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

Definitions

  • the present invention relates to an image formation method using a silver halide light-sensitive material. More specifically, the present invention relates to an image formation method providing excellent color separation and sharpness. The present invention also provides a method for forming an image simply by heat development within a short period of time.
  • the silver halide light-sensitive material can provide a highly fine image having light sensitivity.
  • the material since the material is developed with a processing solution having a complicated composition, it is bound to defects such as restriction in view of environmental conservation and cumbersomeness in controlling the solution.
  • a heat developable dye transfer type light-sensitive material which requires no development processing solution and can provide simply and rapidly a high-quality color image using a slight amount of water and by heating, and an image formation apparatus using the light-sensitive material have been developed and come into sale (e.g., Pictography 2000, Pictography 3000, Pictrostat 100, Pictrostat 200, manufactured by Fuji Photo Film Co., Ltd.).
  • JP-A-62-283332 (the term "JP-A” as used herein means an "unexamined published Japanese patent application") and JP-A-63-198050 describe a heat developable silver salt diffusion-transfer type light-sensitive material.
  • the image formed by the diffusion-transferred dye or silver as in the above-described prior art techniques has been found to lack in sufficiently satisfactory sharpness in a specific use, for example, in case of a color negative film for camera work or an intermediate material for plate making.
  • colloidal silver and a filter dye are used to improve color separation or sharpness.
  • colloidal silver serves as a fog nucleus
  • the colloidal silver must be isolated from a silver halide emulsion layer and as a result, an interlayer or the like must be additionally provided to increase the film thickness to thereby diminish the effect by half.
  • the filter dye hitherto used elutes into a processing solution or is decolorized at the development processing.
  • the filter dye may transfer to the dye fixing material together with a dye for forming an image or may stain the image due to insufficient decolorization, which problems are in need of overcoming, thus an improvement has been demanded.
  • JP-A-6-337511 discloses a method for forming an image where a water-insoluble organic pigment is incorporated into a light-sensitive material as a solid fine particle dispersion and the light-sensitive material is heat-developed in the presence of water. This method is very preferred because the organic pigment does not transfer to the dye fixing material and accordingly, the dye image is not stained.
  • the object of the present invention is to provide a method for forming an image excellent in sharpness as required in the case of a color negative film for camera work or for an intermediate material for plate making, within a short period of time.
  • an image formation method comprising the steps of superimposing a silver halide light-sensitive material containing a compound represented by the following formula (I) on a mordant sheet containing a mordant in the presence of a reducing agent, a base and water after or during imagewise exposure so that the layer surfaces of the light-sensitive material and the mordant sheet face to each other, developing the light-sensitive material and transferring the compound represented by formula (I) to the mordant sheet, and then separating the mordant sheet from the light-sensitive material to obtain an image on the silver halide light-sensitive material: D-(X) y (I) wherein D represents a compound having a chromophore; X represents a dissociative proton or a group having a dissociative proton bonded to D directly or via a divalent linking group; and y represents an integer of from 1 to 7.
  • the compound having a chromophore represented by D can be selected from many known dye compounds.
  • the dye compounds include oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, azomethine dyes, triphenylmethane dyes, azo dyes, anthraquinone dyes and indoaniline dyes.
  • the dissociative proton or the group having a dissociative proton represented by X is non-dissociative and renders the compound represented by formula (I) substantially water-insoluble when the compound represented by formula (I) is added to the silver halide light-sensitive material of the present invention, but is dissociated and renders the compound represented by formula (I) substantially water-soluble in the development process of the light-sensitive material.
  • substantially water-insoluble means that solubility of a compound at pH of 4 to 6 and 25°C is 1% or less, and the term “substantially water-soluble” means that solubility of a compound at pH of 8 or more and 25°C is 10% or more.
  • the compound represented by formula (I) is more preferably a compound represented by the following formula (II), (III), (IV) or (V).
  • A1 and A2 each represents an acidic nucleus
  • B1 represents a basic nucleus
  • Q represents an aryl group or a heterocyclic group
  • L1, L2 and L3 each represents a methine group
  • m represents 0, 1 or 2
  • n and p each represents 0, 1, 2 or 3, with the proviso that the compound represented by formula (II), (III), (IV) or (V) has at least one dissociative group selected from the group consisting of a carboxyl group, a sulfonamido group, an arylsulfamoyl group, a sulfonylcarbamoyl group, a carbonylsulfamoyl group, an enol group of an oxonol dye and a phenolic hydroxyl group in one molecule, and has no water-
  • the acidic nucleus represented by A1 or A2 is preferably an acidic nucleus containing a cyclic ketomethylene compound or a compound having a methylene group interposed in electron-withdrawing groups.
  • the cyclic ketomethylene compound include 2-pyrazoline-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isooxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolopyridine, hydroxypyridine, pyrazolidinedione, 2,5-dihydrofuran-2-one and pyrroline-2-one. These groups each may have one or more substituents.
  • Examples of the basic nucleus represented by B1 include pyridine, quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole, benzimidazole, benzothiazole, oxazoline, naphthoxazole and pyrrole, which each may have one or more substituents.
  • Examples of the aryl group represented by Q include a phenyl group and a naphthyl group, which each may have one or more substituents (preferably an electron-withdrawing group).
  • a phenyl group substituted with a dialkylamino group, a hydroxyl group or an alkoxy group is most preferred.
  • heterocyclic group represented by Q examples include pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran, oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin and coumarone, which each may have one or more substituents.
  • the methine group represented by L1, L2 or L3 may have one or more substituents and the substituents may be combined with each other to form a 5- or 6-membered ring (e.g., cyclopentene, cyclohexene).
  • the substituents on the above-described groups are not particularly restricted if the substituents do not substantially dissolve the compound represented by formula (I), (II), (III), (IV) or (V) in water having a pH of from 5 to 7.
  • the substituents include a carboxyl group, a sulfonamido group having from 1 to 10 carbon atoms (e.g., methanesulfonamido, benzenesulfonamido, butanesulfonamido, n-octanesulfonamido), a sulfamoyl group having from 1 to 10 carbon atoms (e.g., unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, butylsulfamoyl), a sulfonylcarbamoyl group having from 2 to 10 carbon atoms (e.g., methane
  • the dye represented by formula (I) may be dissolved as a known emulsified dispersion in a high boiling point organic solvent and if desired, a low boiling point organic solvent having a boiling point of from 50 to 160°C. But preferably the dye is used as a solid dispersion of fine powder (fine crystal particle).
  • the fine (crystal) particle solid dispersion of the dye may be mechanically prepared by using, if desired, an appropriate solvent (e.g., water, alcohol) in the presence of a dispersant by a known pulverization method (e.g., ball mill, vibration ball mill, planet ball mill, sand mill, colloid mill, jet mill, roller mill).
  • the dye may be formed into fine (crystal) particles by a method where the dye is dissolved in an appropriate solvent using a surface active agent for dispersion and then a bad solvent for the dye is added thereto to deposit fine crystals or a method where the dye is first dissolved by controlling the pH and then finely crystallized by varying the pH.
  • the layer containing fine dye powder is provided by dispersing the fine (crystal) particle of the dye prepared as above in an appropriate binder to obtain a nearly uniform grain solid dispersion and then coating the dispersion on a desired support.
  • the layer may also be provided by a method where the dispersion and the fixing are achieved at the coating by coating the dye in a dissociated state as a salt and then overcoating an acidic gelatin thereon.
  • the above-described binder is not particularly restricted as long as it is a hydrophilic colloid capable of use in a light-sensitive emulsion layer or a light-insensitive layer, but gelatin or a synthetic polymer is commonly used to this effect.
  • the surface active agent for dispersion may be a known surface active agent and preferably, anionic, nonionic or amphoteric surface active agent is used. In particular, an anionic and/or nonionic surface active agent is preferably used.
  • the fine dye particle in the solid dispersion has an average particle size of from 0.005 to 10 ⁇ m, preferably from 0.01 to 1 ⁇ m, more preferably from 0.01 to 0.5 ⁇ m and, in some cases, preferably from 0.01 to 0.1 ⁇ m.
  • the addition amount of the fine (crystal) particle dispersion of the dye represented by formula (I) of the present invention to the light-sensitive material is from 5.0 ⁇ 10 ⁇ 5 to 5.0 g, preferably from 5.0 ⁇ 10 ⁇ 4 to 2.0 g, and more preferably from 5.0 ⁇ 10 ⁇ 3 to 1.0 g, per m2 of the light-sensitive material.
  • Two or more dyes may be incorporated into the same layer or one dye may be used in a plurality of layers. Also, known dyes and pigments other than the dye of the present invention may be used, if desired.
  • the fine (crystal) particle dispersion of the dye represented by formula (I) may be incorporated into either an emulsion layer or a light-insensitive layer to provide various hues depending on the purpose.
  • a light-insensitive layer in the case of a light-sensitive material where an antihalation layer is provided between the support and a silver halide light-sensitive layer and a plurality of light-insensitive layers are provided, for example, in the case of a color negative light-sensitive material where a yellow filter layer, a magenta filter layer and an antihalation layer are provided between a blue-sensitive silver halide light-sensitive layer and a green-sensitive silver halide light-sensitive layer, between a green-sensitive silver halide light-sensitive layer and a red-sensitive silver halide light-sensitive layer and between the support and a red-sensitive silver halide light-sensitive layer, respectively, the fine (crystal) particle dispersion of the dye represented by formula (I) of the present invention is preferably
  • the dye to be incorporated into a yellow filter layer is preferably a dye represented by the following formula (VI) or (VII): wherein R3 and R5 each represents a chained or cyclic alkyl group having from 1 to 8 carbon atoms (e.g., methyl, ethyl, isopropyl, n-butyl, n-hexyl, cyclopropyl, cyclohexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, benzyl, phenetyl, 4-carboxybenzyl, 2-diethylaminoethyl), an alkoxy group having from 1 to 8 carbon atoms (e.g., methoxy, ethoxy, butoxy), a sulfonamido group having from 1 to 8 carbon atoms (e.g., methanesulfonamido, benzenes
  • R3 and R5 each represents
  • R4, R6 and R7 each represents a hydrogen atom, a chained or cyclic alkyl group having from 1 to 8 carbon atoms (e.g., methyl, ethyl, isopropyl, butyl, hexyl, cyclohexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, benzyl, 4-carboxybenzyl), an aryl group having from 6 to 10 carbon atoms (e.g., phenyl, naphthyl, 4-carboxyphenyl, 3-carboxyphenyl, 3-methanesulfonamidophenyl, 4-hydroxyphenyl) or a heterocyclic group (e.g., pyridine ring, pyrazine ring, furan ring, thiophene ring, pyrrole ring, sulforane ring, pyrrolidine ring, pyrimidine ring).
  • Q
  • the dye represented by formula (I) may be used to provide various hues in accordance with the wavelength on exposure, and in particular, when the exposure is conducted using light having a wavelength in a near infrared region, a dye represented by the following formula (VIII), (VIX), (X), (XI) or (XII) is preferably used:
  • G1, G2 and G3 each represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyl group, an alkyl group having from 1 to 8 carbon atom (e.g., methyl, ethyl, hexyl), an aryl group having from 6 to 10 carbon atoms (e.g., phenyl, 4-carboxyphenyl), an alkoxy group having from 1 to 8 carbon atoms (e.g., ethoxy, methoxy, ethoxy), a sulfonyl having from 1 to 8
  • R4 has the same meaning as defined in formula (VI);
  • R8 represents a hydrogen atom, a chained or cyclic alkyl group having from 1 to 8 carbon atoms (e.g., methyl, ethyl, isopropyl, butyl, hexyl, cyclohexyl, 2-hydroxyethyl, benzyl, 4-carboxybenzyl), an aryl group having from 6 to 10 carbon atoms (e.g., phenyl, 4-carboxyphenyl), a heterocyclic group (e.g., pyridine ring, furan ring, thiophene ring, pyrrole ring), an acyl group having from 1 to 10 carbon atoms (e.g., acetyl, benzoyl, propanoyl) or a sulfonyl group having from 1 to 8 carbon atoms (e.g., methyl, sulfonyl,
  • T1 represents a chained or cyclic alkyl group having from 1 to 8 carbon atoms (e.g., methyl, ethyl, isopropyl, hexyl, 2-hydroxyethyl, 4-carboxybenzyl), an alkenyl group having from 1 to 8 carbon atoms (e.g., vinyl, allyl, 2-hexenyl) or an aryl group having from 6 to 10 carbon atoms (e.g., phenyl, 4-carboxyphenyl);
  • T2 represents a hydrogen atom or a mono-valent group (e.g., a substituent described as a group which each group in formulae (I) to (V) may have as a substituent);
  • E represents a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic group (which may further condensed with a benzene ring or a naphthalene ring);
  • R10 and R11 each represents a hydrogen atom, a chained or cyclic alkyl group having from 1 to 8 carbon atoms (e.g., methyl, ethyl, isopropyl, hexyl, 2-hydroxyethyl, 4-carboxybenzyl), an aryl group having from 6 to 10 carbon atoms (e.g., phenyl, 4-carboxyphenyl);
  • R12 represents a hydrogen atom, a chained or cyclic alkyl group having from 1 to 8 carbon atoms (e.g., methyl, ethyl, isopropyl, hexyl, 2-hydroxyethyl, 4-carboxybenzyl), an aryl group having from 6 to 10 carbon atoms (e.g., phenyl, 4-carboxyphenyl), a heterocyclic group (e.g., pyridine ring, furan ring, thiophene ring, pyr
  • T3 and T4 each represents a hydrogen atom, a chained or cyclic alkyl or alkenyl group having from 1 to 10 carbon atoms (e.g., methyl, ethyl, isopropyl, cyclohexyl, t-butyl, n-butyl, vinyl, allyl, benzyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, phenetyl, 4-carboxybenzyl, 2-diethylaminoethyl), an aryl group having from 6 to 10 carbon atoms (e.g., phenyl, naphthyl, 4-carboxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl, 4-butanesulfonamidophenyl), a 5- or 6-membered heterocyclic group containing oxygen, nitrogen
  • the dyes for use in the present invention can be synthesized by the methods or according to the methods as disclosed in WO 88/04794, EP-A-0274723, EP-A-276566, EP-A-299435, U.S. Patents 2,527,583, 3,486,897, 3,746,539, 3,933,798, 4,130,429, 4,040,841, JP-A-48-68623, JP-A-52-92716, JP-A-55-155350, JP-A-55-155351, JP-A-61-205934, JP-A-2-173630, JP-A-2-230135, JP-A-2-277044, JP-A-2-282244, JP-A-3-7931, JP-A-3-167546, JP-A-3-13937, JP-A-3-206443, JP-A-3-208047, JP-A-3-192157, JP-A-3-216645, JP-A-3-27404
  • the light-sensitive material of the present invention basically contains a light-sensitive silver halide and a binder on a support, and it may contain an organic metal salt oxidizing agent, a reducing agent and a dye-donating compound, if needed. These components are often incorporated into the same layer, but they may be separately added to different layers if they are reactive with each other. For instance, if a colored dye-donating compound is in a lower layer of a silver halide emulsion layer, it is effective for preventing lowering of the sensitivity.
  • the reducing agent can be incorporated into the heat-developable light-sensitive material.
  • the reducing agent may also be supplied to the photographic material from the external, for example, by diffusing it from the mordant sheet described below.
  • a combination of at least three silver halide emulsion layers each having light-sensitivity in a different spectral region is used.
  • the combination include a combination of three layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer and an infrared sensitive layer.
  • the respective light-sensitive layers may be arranged in any desired sequence generally used in conventional color light-sensitive materials. These layers may have two or more plural layers, if needed.
  • the light-sensitive material of the present invention may have various other auxiliary layers, such as a protective layer, a subbing layer, an interlayer, a yellow filter layer, an infrared 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 infrared 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 type emulsion.
  • the latter internal latent 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 core/shell emulsion in which the grain inside phase and the grain surface phase differ from each other.
  • the silver halide emulsion may be either a monodisperse emulsion or a polydisperse emulsion. A mixture of plural monodisperse emulsions may also be used.
  • the grain size of the emulsion grains is 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.
  • Silver halide emulsions may be used as primitive emulsions. In general, however, they are chemically sensitized. For instance, a sulfur sensitization method, a reduction sensitization method and a noble metal sensitization method, which are generally applied to emulsions of conventional photographic materials, can be used alone or in combination of them. Such chemical sensitization may also be carried out in the presence of a nitrogen-containing heterocyclic compound (as disclosed in JP-A-62-253159).
  • the amount of the light-sensitive silver halide for use in the present invention is from 1 mg to 10 g in terms of silver per m2 of the light-sensitive material.
  • the silver halide for use in the present invention may be spectral-sensitized with methine dyes or other dyes.
  • the dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • sensitizing dyes may be used singly or in combination. Combinations of plural sensitizing dyes are often used for the purpose of supersensitization.
  • Dyes which do not have a spectral-sensitizing activity by themselves but show a supersensitivity activity or compounds which do not substantially absorb visible rays but show a supersensitizing activity may be incorporated into the emulsions of the present invention along with sensitizing dyes (for instance, dyes or compounds as described in U.S. Patent 3,615,641 and JP-A-63-23145).
  • the time of adding these sensitizing dyes into the emulsions of the present invention may be during or before or after chemical ripening of the emulsions. It may be before or after the formation of the nuclei of the silver halide grains, in accordance with U.S. Patents 4,183,756 and 4,225,666.
  • the amount of the dyes added is usually from 10 ⁇ 8 to 10 ⁇ 2 mol per mol of silver halide.
  • Additives usable in these steps and other known additives for photographing for use in preparing the light-sensitive material and the mordant-containing sheet of the present invention are described in RD Nos. 17643, 18716 and 307105, and the relevant parts in these RD s are shown below.
  • Additive RD 17643 RD 18716 RD 307105 1. Chemical sensitizer p. 23 p. 648, right column (RC) p. 866 2. Sensitivity increasing agent ditto 3. Spectral sensitizer, Supersensitizer pp. 23-24 p. 648, RC to p. 649, RC pp. 866-868 4. Fluorecent brightening agent p. 24 p. 648, RC p.
  • Antifoggant, Stabilizer pp. 24-25 p. 649, RC pp. 868-870 6.
  • Dye image stabilizer p. 25 p. 650, LC p. 872 8.
  • Hardening agent p. 26 p. 651, LC pp. 874-875 9.
  • Binder p. 26 ditto pp. 873-874 10.
  • Plasticizer, Lubricant p. 27 P. 650, RC p. 876 11. Coating aid, Surfactant pp. 26-27 ditto p. 875-876 12.
  • organic metal salts may be used as an oxidizing agent with the light-sensitive silver halide.
  • organic silver salts are preferably used as an oxidizing agent.
  • organic compounds used for forming the organic silver salt oxidizing agents include benzotriazoles, fatty acids and other compounds described in U.S. Patent 4,500,626 (columns 52 and 53).
  • silver salts of alkynyl group-containing carboxylic acids such as silver phenylpropionate as described in JP-A-60-113235, and acetylene silver as described in JP-A-61-249044, are also useful. Two or more kinds of organic silver salts may be used in combination.
  • the above-described organic silver salt may be added to the emulsion in an amount of from 0.01 to 10 mol, preferably from 0.01 to 1 mol, per mol of the light-sensitive silver halide.
  • the total coated amount of the light-sensitive silver halide and the organic silver salt is preferably from 50 mg/m2 to 10 g/m2 in terms of silver.
  • antifoggants and photographic stabilizers may be used in the present invention.
  • examples thereof include azoles and azaindenes as described in RD No. 17643 (1978), pages 24 and 25; nitrogen-containing carboxylic acids and phosphoric acids as described in JP-A-59-168442; mercapto compounds and metal salts thereof as described in JP-A-59-111636; and acetylene compounds as described in JP-A-62-87957.
  • reducing agents used in the field of light-sensitive materials may be used in the present invention.
  • Dye-donating compounds having a reducing property described below are used.
  • another reducing agent may be used in combination.
  • reducing agent precursors which do not have a reducing property by themselves but which show a reducing capacity by a nucleating reagent or by heating during the step of development may also be used.
  • Examples of the reducing agents for use in the present invention include reducing agents and reducing agent precursors as 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, JP-A-60-128437, JP-A-60-128438, JP-A-60-128439, JP-A-60-198540, JP-A-60-181742, JP-A-61-259253, JP-A-62-244044, JP-A-62-131253, JP-A-62-131254, JP-A-62-131255, J
  • an electron-transfer ring agent and/or an electron-transferring agent precursor may be used, if desired, in combination with the reducing agent for accelerating the movement of electrons between the non-diffusible reducing agent and the heat-developable silver halide.
  • the electron-transferring agent or precursor thereof can be selected from the above-described reducing agents and precursors thereof.
  • the electron-transferring agent or precursor thereof preferably has a higher mobility than the non-diffusible reducing agent (electron donor).
  • Especially useful electron-transferring agents are 1-phenyl-3-pyrazolidones and aminophenols.
  • the non-diffusible reducing agent (electron donor) used in combination with the electron-transferring agent may be any one of the above-described reducing agents which are substantially immobile in the layers of the light-sensitive material.
  • reducing agents which are substantially immobile in the layers of the light-sensitive material.
  • Preferable examples thereof include hydroquinones, sulfonamidophenols, sulfonamidonaphthols, the compounds described in JP-A-53-110827 as electron donors, and non-diffusible and reducing dye-donating compounds described below.
  • the amount of the reducing agent or precursor thereof added is from 0.001 to 20 mol, preferably from 0.01 to 10 mol, per mol of silver.
  • silver and/or a dye is used as an image-forming material.
  • silver halide in the unexposed area can be eliminated to the mordant sheet by a silver salt diffusion-transfer method as described in JP-A-62-283332.
  • a non-diffusible dye-providing compound is incorporated into the light-sensitive material and a non-diffusible dye is formed or a diffusible dye is formed or released in correspondence or countercorrespondence to the reduction reaction of silver ion (silver halide) to silver and the dye is transferred to a mordant sheet.
  • Examples of the dye-donating compounds for use in the present invention include compounds (couplers) capable of forming a dye by an oxidation-coupling reaction.
  • the coupler may be either 4-equivalent couplers or 2-equivalent couplers.
  • the non-diffusible 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.
  • examples of the dye-donating compound include non-diffusible dye-donating compounds having a heterocyclic group containing an oxygen atom, a sulfur atom or a selenium atom (thiazolidine compounds) which releases a mobile dye by a cleavage reaction of the heterocyclic ring in the presence of a silver ion or a soluble silver complex as described in JP-A-59-180548.
  • examples of the dye-donating compound include compounds adapted to imagewise release or spread a diffusible dye.
  • the compounds can be represented by the following formula (LI): (Dye-Y) n -Z (LI) wherein Dye represents a dye group, or a dye group or dye precursor group whose wavelength has been temporarily shortened; Y represents a chemical bond or a linking group; Z represents a group which either causes a differential in the diffusibility of the compound (Dye-Y) n -Z or releases Dye and causes a differential in diffusibility between released Dye and (Dye-Y) n -Z in correspondence or reverse correspondence with photosensitive silver halide imagewise having a latent image; and n represents 1 or 2, and when n is equal to 2, the two Dye-Y groups may be the same as or different from each other.
  • dye-donating compounds represented by formula (LI) include the following compounds (1) to (5).
  • Compounds (1) to (3) release a diffusible dye in reverse correspondence with the development of silver halide and compounds (4) and (5) release a diffusible dye in correspondence with the development of silver halide.
  • dye-donating compounds other than the above-described couplers and the compounds represented by 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 for use in a heat-developable 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).
  • Hydrophobic additives such as the dye-donating compound and the non-diffusible reducing agent may be incorporated into the layers of the light-sensitive 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 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 160°C.
  • the amount added of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, per gram of the dye-donating compound. It is preferably one cc or less, more preferably 0.5 cc or less, especially preferably 0.3 cc or less, per gram of the binder.
  • JP-B-51-39853 and JP-A-51-59943 may also be used.
  • compounds are substantially insoluble in water, they may be dispersed in the binder in the form of fine grains in addition to the above-described methods.
  • hydrophobic compound When the hydrophobic compound is dispersed in a hydrophilic colloid as a binder, various surfactants may be used.
  • surfactants described in JP-A-59-157636, pages 37 and 38 and the above-described RD s may be used.
  • phosphate surfactants as described in JP-A-7-56267 and published West German Patent Application 1932299A are examples of surfactants.
  • the light-sensitive material of the present invention may contain a compound having a function of activating the developability thereof and of stabilizing the image formed at the same time.
  • a compound having a function of activating the developability thereof and of stabilizing the image formed at the same time Preferable examples of the compounds are described in U.S. Patent 4,500,626 at columns 51 and 52.
  • the mordant sheet for use in the present invention may be provided either on a support independent from the support for the light-sensitive material or on the same support of the light-sensitive material.
  • the support or the white reflection layer With respect to the interrelation between the light-sensitive material and the mordant sheet, the support or the white reflection layer, the relation described in U.S. Patent 4,500,626, column 57 can also be applied to the present invention.
  • the light-sensitive material and the mordant sheet for use in the present invention will be described below.
  • the light-sensitive material and the mordant sheet are often referred to as a "light-sensitive element” and a “mordant element”, respectively.
  • the mordant element which is preferably used in the present invention has at least one layer containing a mordant agent and a binder.
  • mordant agents in the photographic field may be used. Specific examples thereof include mordant compounds as described in U.S. Patent 4,500,626 at columns 58 and 59, and JP-A-61-88256, pages 32 to 41; and those described in JP-A-62-244043 and JP-A-62-244036.
  • dye-receptable high polymer compounds as those described in U.S. Patent 4,463,079 may be also used.
  • the mordant element may have auxiliary layers such as a protective layer, a peeling layer and a curling preventing layer, if needed.
  • a protective layer is preferably provided.
  • the binder for the layers constituting the light-sensitive element and the mordant element is preferably hydrophilic.
  • hydrophilic binders for example, natural compounds such as proteins (e.g., gelatin, gelatin derivatives), polysaccharides (e.g., cellulose derivatives, starch, gum arabic, dextran, pullulan), and synthetic polymer compounds such as polyvinyl alcohol, polyvinyl pyrrolidone and acrylamide polymers.
  • high water-absorbing polymers as described in JP-A-62-245260 may also be used, for example, homopolymers of vinyl monomers having a -COOM or -SO3M group (M represents a hydrogen atom or an alkali metal) or copolymers of the vinyl monomers or of the vinyl monomers and other vinyl monomers (e.g., sodium methacrylate, ammonium methacrylate, Sumikagel L-5H produced by Sumitomo Chemical Company, Limited). These binders may be used in combination with two or more kinds thereof.
  • the heat development of the present invention is carried out while supplying a small amount of water, use of the above-described high water-absorbing polymers is desired for rapid absorption of water. If the high water-absorbing polymer is incorporated into the mordant layer or its protective layer, re-transfer of the dye which is transferred and fixed to the mordant element to any other area can be prevented.
  • the amount of the binder coated is preferably 20 g/m2 or less, more preferably 10 g/m2 or less, and most preferably 7 g/m2 or less.
  • the layers constituting the light-sensitive element and the mordant element of the present invention may contain a plasticizer or a slipping agent.
  • a high boiling point organic solvent may be used as an agent for improving peelability between the light-sensitive element and the mordant element. Specific examples thereof include those described in JP-A-62-245253.
  • various silicone oils including all silicone oils from dimethylsilicone oil to modified silicone oils formed by introducing various organic groups into dimethylsiloxane
  • silicone oils include various modified silicone oils as described in the technical reference Modified Silicone Oils (published by Shin-Etsu Silicone Co.), particularly a carboxy-modified silicone (X-22-3710, trade name).
  • silicone oils described in JP-A-62-215953 and JP-A-63-46449 are effective.
  • the light-sensitive element and the mordant element may contain a discoloration preventive.
  • the discoloration preventive include an antioxidant, an ultraviolet absorbent and 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. Furthremore, the compounds described in JP-A-61-159644 are 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 as described in JP-A-54-48535, JP-A-62-136641 and JP-A-61-88256. Furthermore, ultraviolet-absorbing polymers described in JP-A-62-260152 are also effective.
  • metal complexes examples include compounds described in U.S. Patents 4,241,155, 4,245,018 (columns 3 to 36) and 4,254,195 (columns 3 to 8), JP-A-62-174741, JP-A-61-88256 (pages 27 to 29), JP-A-63-199248, JP-A-1-75568 and JP-A-1-74272.
  • the discoloration preventive for preventing the dye of the mordant element from fading may be previously incorporated into the light-sensitive element or it may be supplied to the light-sensitive element from an external source such as a mordant element.
  • antioxidant ultraviolet absorbent
  • metal complex may be used in combination.
  • the light-sensitive element and the mordant element may contain a fluorecent brightening agent.
  • a fluorecent brightening agent such as a fluorecent brightening agent.
  • the agent include compounds as described in K. Veenkataraman, The Chemistry of Synthetic Dyes , Vol. V, Chap. 8, and JP-A-61-143752. Specific examples thereof include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds and carbostyryl compounds.
  • the fluorecent brightening agent may be used in combination with the discoloration preventive or the ultraviolet absorbent.
  • the layers constituting the light-sensitive material and the mordant sheet may contain a hardening agent.
  • the hardening agent used in the layers constituting the light-sensitive element and the mordant element include hardening agents described in the above-described RD s, U.S. Patents 4,678,739 (column 41), 4,791,042 and JP-A-59-116655, JP-A-62-245261, JP-A-61-18942 and JP-A-4-218044.
  • aldehyde hardening agents e.g., formaldehyde
  • aziridine hardening agents epoxy hardening agents
  • vinylsulfone hardening agents e.g., N,N'-ethylene-bis(vinylsulfonylacetamide)ethane
  • N-methylol hardening agents e.g., dimethylolurea
  • high polymer hardening agents e.g., compounds described in JP-A-62-234157.
  • the hardening agent is preferably used in an amount of from 0.001 g to 1 g, more preferably 0.005 g to 0.5 g, per one g of gelatin coated.
  • the hardening agent may be incorporated in any of the layers constituting the light-sensitive element or the mordant element or may be separately incorporated in two or more layers.
  • the layers constituting the light-sensitive element or the mordant element may comprise various fog inhibitors, photographic stabilizers, or precursors thereof. Specific examples of these compounds are described in the above cited RD s, U.S. Patents 5,089,378, 4,500,627, 4,614,702, JP-A-64-13546, pages 7 to 9, pages 57 to 71, pages 81 to 97, U.S. Patents 4,775,610, 4,626,500, 4,983,494, JP-A-62-174747, JP-A-62-239148, JP-A-1-150135, JP-A-2-110557, JP-A-2-178650, and RD 17643 (1978), pages 24 to 25.
  • These compounds are preferably used in an amount of from 5 ⁇ 10 ⁇ 6 to 1 ⁇ 10 ⁇ 1 mol, more preferably from 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 2 mol, per mol of silver.
  • the layers constituting the light-sensitive element and the mordant element may contain various surfactants for various purposes of aiding coating, improvement of the peeling property, improvement of the sliding property, prevention of static charge and enhancement of developability.
  • specific examples of the surfactants include those as described in JP-A-62-173463 and JP-A-62-183457.
  • the layers constituting the light-sensitive element and the mordant element of the present invention may contain organic fluorine compounds for the purpose of improvement of sliding property, prevention of static charge and improvement of peeling property.
  • organic fluorine compounds include fluorine surfactants as described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20944, JP-A-62-135826, and hydrophobic fluorine compounds such as oily fluorine compounds (e.g., fluorine oils) and solid fluorine compound resins (e.g., ethylene tetrafluoride resins).
  • a physical development nucleus or a silver halide solvent is preferably incorporated into the mordant element.
  • a complex-forming compound described later may be used alone or in combination with known thiosulfates, thioether compounds or uracils.
  • the layers (including a backing layer) constituting the light-sensitive element or the mordant element may contain various polymer latexes for improving physical properties of the layer, such as dimension stabilization, curling prevention, adhesion prevention, layer cracking prevention, pressure sensitization/desensitization prevention. More specifically, any of polymer latexes described in JP-A-62-245258, JP-A-62-136648 and JP-A-62-110066 may be used. In particular, when a polymer latex having a low glass transition point (40°C or less) is used in the mordant layer, the mordant layer can be prevented from cracking or when a polymer latex having a high glass transition point is used in the backing layer, an effect of curling prevention can be achieved.
  • a polymer latex having a low glass transition point 40°C or less
  • the light-sensitive element and the mordant element may contain a matting agent.
  • the matting agent include silicon dioxide and compounds as described in JP-A-61-88256 (page 29) such as polyolefins or polymethacrylates, and compounds as described in JP-A-63-274944 and JP-A-63-274952 such as benzoguanamine resin beads, polycarbonate resin beads and AS (acrylonitrile-styrene) resin beads.
  • the compounds described in the above-described RD s may be used.
  • the layers constituting the light-sensitive element and the mordant element may further contain a thermal solvent, a defoaming agent, a microbicidal and fungicidal agent, and colloidal silica.
  • a thermal solvent e.g., a thermal solvent, a defoaming agent, a microbicidal and fungicidal agent, and colloidal silica. Examples of these additives are described in JP-A-61-88256 (pages 26 to 32), JP-B-3-11338 and JP-A-2-51496.
  • the light-sensitive element and/or the mordant element may contain an image formation accelerator.
  • the image formation accelerators can promote a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction of forming a dye from a dye-donating substance or decomposing a dye, a reaction of releasing a diffusible dye, and a migration of a dye from the light-sensitive layer to the mordant layer.
  • the image formation accelerators can be classified into bases or base precursors, nucleophilic compounds, high boiling point organic solvents (oils), thermal solvents, surfactants and compounds which interact with silver or silver ions.
  • each of these image formation accelerators have plural functions and provide several of the above-described effects.
  • the image formation accelerators are described in detail in U.S. Patent 4,678,739 at columns 38 to 40.
  • the base precursor examples include salts between an organic acid by heating and a base, and compounds capable of releasing an amine by an intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. Specific examples thereof are described in U.S. Patents 4,511,493 and 4,657,848.
  • the heat-development and the dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferred to incorporate the base and/or base precursor in the mordant element for the purpose of improving the storage stability of the light-sensitive element.
  • a method generating a base by using the combination of a hardly soluble (slightly soluble) metal compound and a compound capable of complexing with the metal ion which constitutes the hardly soluble metal compound (hereinafter referred to as a "complex-forming compound") as described in EP-A-210660 and U.S. Patent 4,740,445 may be adopted.
  • the hardly soluble metal compound and the complex-forming compound are separately added to the light-sensitive element and the mordant element, respectively, for preservability.
  • the light-sensitive element and/or the mordant element of the present invention may contain various development terminating agents for the purpose of always obtaining constant images despite fluctuations in processing temperature and processing time in developing.
  • development terminating 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 in which the base is present and thereby terminates the development, or a compound which interacts with silver or a silver salt to control development.
  • the development terminating agent include acid precursors which release an acid by heating, electrophilic compounds which react with the existing base by a substitution reaction by heating, nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof. More precisely, specific examples thereof are described in JP-A-62-253159 (pages 31 and 32).
  • a zinc salt of mercaptocarboxylic acid as described in Japanese Patent Application No. 6-190529 is contained in the light-sensitive element and the above-described complex-forming compound is contained in the mordant element.
  • the support of the light-sensitive material and the mordant sheet of the present invention may be any support that withstands the processing temperature.
  • paper and synthetic high polymer film
  • film such as described in Bases of Photographic Engineering , Edition of Silver Photography, pages 223 to 240 (published by Corona Publishing Co., Ltd., Japan, 1979), are used as the support.
  • the support examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonates, polyvinyl chloride, polystyrene, polypropylene, polyimide, polyarylate, celluloses (e.g., triacetyl cellulose), which each may contain a pigment such as titanium oxide; synthetic paper made of polypropylene by a filming method; mixed paper made of a synthetic resin pulp (e.g., polyethylene); Yankee paper; baryta paper; coated paper (especially cast-coated paper); metals; cloth; and glass.
  • a pigment such as titanium oxide
  • synthetic paper made of polypropylene by a filming method
  • mixed paper made of a synthetic resin pulp
  • Yankee paper baryta paper
  • coated paper especially cast-coated paper
  • metals cloth; and glass.
  • These supports may be used directly or may be laminated with a synthetic high polymer (e.g., polyethylene) on one surface or both surfaces thereof.
  • a synthetic high polymer e.g., polyethylene
  • the surface of the support may be coated with a hydrophilic binder and a semiconductive metal oxide (e.g., alumina sol, tin oxide) or an antistatic agent such as carbon black.
  • a semiconductive metal oxide e.g., alumina sol, tin oxide
  • an antistatic agent such as carbon black.
  • the supports described in JP-A-6-41281, JP-A-6-43581, JP-A-6-51426, JP-A-6-51437, JP-A-A-51442, JP-A-6-82961, JP-A-6-82960, JP-A-6-82959, JP-A-6-67346, JP-A-6-175282, JP-A-6-118561, and JP-A-6-202277 are preferred as a support for a light-sensitive material.
  • various methods can be employed, which include, for example, a method of directly photographing a scene or man with a camera; a method of exposing an image through a reversal film or negative film by using a printer or an enlarger; a method of scanning and exposing an original through a slit by using an exposing device of a duplicator; a method of exposing image information via a corresponding electric signal by emitting the same with an emitting diode or various lasers; and a method of outputting image information with an image display device such as a CRT, liquid crystal display, electroluminescence display or plasma display and then exposing the same directly or via some optical system.
  • an image display device such as a CRT, liquid crystal display, electroluminescence display or plasma display and then exposing the same directly or via some optical system.
  • the light source used for recording an image on the light-sensitive material include those as described in U.S. Patent 4,500,626 (column 56), JP-A-2-53378 and JP-A-2-54672, such as natural light, a tungsten lamp, a light-emitting diode, laser rays and CRT rays. Furthremore, the exposure methods described therein may be adopted.
  • a light source using a blue light emitting diode in combination with a green light emitting diode and a red emitting diode may be used.
  • the exposure apparatuses described in Japanese Patent Application Nos. 6-40164, 6-40012, 6-42732, 6-86919, 6-86920, 6-93421, 6-94820, 6-96628 and 6-149609 are preferably used:
  • a wavelength conversion element in which a nonlinear optical material is combined with a coherent light source such as laser may be used for imagewise exposure.
  • the nonlinear optical material is a material capable of revealing nonlinearity between polarization and electric field provided when a strong photoelectric field such as laser light is given.
  • Inorganic compounds such as lithium niobate, potassium dihydrogenphosphate (KDP), lithium iodate and BaB2O4, urea derivatives, nitroaniline derivatives, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), and the compounds described in JP-A-61-53462 and JP-A-62-210432 are preferably used.
  • Examples of wavelength conversion elements include single crystal light guide type wavelength conversion element and fiber type wavelength conversion element.
  • Examples of the above-described image information include image signals obtained from a video camera or an electronic still camera; television signals as standardized by the Nippon Television Signal Code (NTSC); image signals obtained by dividing an original into plural pixels with a scanner; and image signals formed by using a computer such as CG or CAD.
  • NTSC Nippon Television Signal Code
  • the light-sensitive material of the present invention may be used over a wide range.
  • the light-sensitive material after development transfer may be used as a positive or negative color light-sensitive material for camera work.
  • the light-sensitive material uses a black dye-providing substance and a yellow, magenta or cyan dye-providing substance by mixture, it can be used as a material for printing such as a black-and-white positive or negative light-sensitive material for camera work and a light-sensitive material for lithography or as a material for an X-ray photography.
  • a support comprising a magnetic substance layer described in, for example, JP-A-4-124645, JP-A-5-40321, and JP-A-6-35092 is preferably used so that information on photographing can be recorded.
  • the light-sensitive material after development transfer is preferably subjected to desilvering treatment.
  • a print can be made on a color paper or on a heat-developable light-sensitive material using the above-described color photographing material for camera work.
  • the printing can be made according to the methods described in JP-A-5-241251, JP-A-5-19364 and JP-A-5-19363.
  • the light-sensitive material and/or the mordant sheet of the present invention may have an electrically conductive heating element layer as a heating means for heat development and diffusion transfer of dye.
  • heating elements described in JP-A-61-145544 may be used.
  • the development and the transfer are preferably conducted simultaneously or continuously in the presence of a slight amount of water by heating as described in U.S. Patents 4,704,345 and 4,740,445 and JP-A-61-238056.
  • the heating temperature is preferably from 50 to 100°C.
  • the time for processing the light-sensitive material and the mordant sheet which are superimposed so that the layer surfaces of the light-sensitive material and the mordant sheet face to each other can be freely set but the heating temperature of the layer surfaces is preferably controlled to provide the processing time of from about 1 to about 120 seconds.
  • Examples of the solvents used for the acceleration of development and/or diffusion transfer of the dye include water and an aqueous basic solution containing an inorganic alkali metal salt or an organic base (the base includes those described in the explanation of the image formation accelerators), and a low boiling point solvent or a mixed solvent containing a low boiling point solvent and water or an aqueous basic solution may also be used. Further, surfactants, antifoggants, complex-forming compounds with hardly soluble metals, an antiputrefaction agent, and an antimicrobial agent can be incorporated into the solvents.
  • water is preferably added.
  • any ordinary water may be employed. Specific examples thereof include distilled water, city tap water, well water, and mineral water.
  • water once used may be drained off or may be circulated through the apparatus for recycle use. In the latter case, water to be circulated and re-used contains chemicals dissolved out from the processed materials.
  • the apparatuses and water described in JP-A-63-144354, JP-A-63-144355, JP-A-62-38460, and JP-A-3-210555 may also be used in processing the light-sensitive materials of the present invention.
  • the solvent may be applied to either or both of the light-sensitive material and the mordant sheet.
  • the amount of the solvent to be applied may be equal to or less than the weight of the solvent corresponding to the maximum swollen volume of all the coated layers.
  • Preferable examples of the method applying water to the material include those described in JP-A-62-253159, page 5 and JP-A-63-85544.
  • the solvent may be encapsulated in microcapsules or may be incorporated beforehand into the light-sensitive material and/or the mordant sheet in the form of hydrate.
  • the temperature of water to be applied is from 30°C to 60°C as described in JP-A-63-85544.
  • a system of incorporating a hydrophilic thermal solvent which is solid at room temperature but which can melt at a high temperature into the light-sensitive material and/or the mordant sheet may also be used in the present invention.
  • the hydrophilic thermal solvent may be incorporated into a light-sensitive silver halide emulsion layer, an interlayer, a protective layer and a dye-fixing layer, but the solvent is preferably added to the dye-fixing layer and/or layer(s) adjacent thereto.
  • hydrophilic thermal solvent examples include ureides, pyridines, amides, sulfon-amides, imides, alcohols, oximes and other heterocyclic compounds.
  • Heating methods of the materials in the development step and/or the transfer step include methods keeping the materials in contact with a heated block, a plate, a hot plate, a hot presser, a hot roller, a hot drum, a halogen lamp heater or an infrared or far-infrared lamp heater or passing the materials through a high temperature atmosphere.
  • Methods of superimposing the light-sensitive material and the mordant sheet include methods described in JP-A-62-253159 and JP-A-61-147244 (page 27).
  • any general heat-developing apparatus may be used.
  • apparatus described in JP-A-59-75247, JP-A-59-177547, JP-A-59-181353, JP-A-60-18951, JU-A-62-25944, JP-A-6-130509, JP-A-6-95338 and JP-A-6-95267 are preferably employed (the term "JU-A" as used herein means an "examined Japanese utility application").
  • Examples of commercially available heat developing apparatus include Pictrostat 100, Pictrostat 200, Pictrography 2000 and Pictrography 3000 produced by Fuji Photo Film Co., Ltd.
  • the light-sensitive material (image) after processing may be subjected to post-processing such as fixing, bleach-fixing and washing.
  • Sensitizing Dye (a) and Sensitizing Dye (b) each was a sensitizing dye having a spectral sensitivity peak at 760 nm and added at the final stage of the chemical sensitization. Also, at this time, 1 ml of a 3.5% solution of the compound represented by Chem. 30 was added as an antiseptic.
  • the yield of the emulsion was 680 g and the emulsion obtained was a monodisperse cubic emulsion having a coefficient of variation of 11.2% and an average grain size of 0.2 ⁇ m.
  • the preparation of a gelatin dispersion of a nondiffusible reducing agent (electron donor) will be described below.
  • the oil phase components shown in Table 3 were dissolved under heating at about 70°C to obtain a uniform solution and to the resulting solution, the aqueous phase components heated at about 60°C were added and mixed while stirring and then dispersed in a homogenizer for 10 minutes at 10,000 rpm. Water was added thereto and stirred to obtain a uniform dispersion.
  • the preparation of a gelatin dispersion of a fixing agent precursor will be described below.
  • Zinc thiosalicylate (10 g), 0.1 g of Surface Active Agent (2) and 0.5 g of Surface Active Agent (3) were added to 90 ml of a 3% lime-processed aqueous gelatin solution and dispersed in a mill using glass beads having an average particle size of 0.75 mm for 30 minutes. The glass beads were separated to obtain a dispersion of a fixing agent precursor.
  • Gelatin dispersions of an electron transfer agent (1,5-diphenyl-3-pyrazolidone) and of zinc hydroxide were also prepared according to the above-described method.
  • Light-Sensitive Material 101 having a structure shown in Table 4 was prepared using the materials prepared above. The preparation of a dispersion of the compound of the present invention will be described below.
  • Light-Sensitive Materials 102, 103, 104, 105 and 106 were prepared in the same manner as Light-Sensitive Material 101 except for adding Compound (VIII-4), (IX-2), (X-4), (XI-2) or (XII-1) of the present invention to the second layer of Light-Sensitive Material 101 in an amount to give a transmission density of 1.0.
  • Light-Sensitive Material 107 was prepared in the same manner as Light-Sensitive Material 101 except for using a filter dye described in JP-A-4-217243 in place of the compound of the present invention. Then, Mordant Sheet R1 was prepared to have a structure as shown in Table 5. The thus-obtained Light-Sensitive Materials 101 to 107 each was exposed under the exposure conditions shown in Table 6 using a semiconductor laser having an oscillation wavelength of 750 nm. Each of the exposed light-sensitive materials was dipped in water kept at a temperature of 40°C for 2.5 seconds, then squeezed by rollers and immediately superimposed with the mordant sheet so that the layer surfaces faced to each other.
  • the laminate was heated for 15 seconds in a heat drum of which temperature was adjusted to set the temperature of the water-absorbed layer surface to 85°C and then the mordant layer was peeled off to obtain a black-and-white image on the light-sensitive material.
  • Light-Sensitive Material 201 was prepared to have the same structure as Light-Sensitive Material 101 except for changing the additives and the coating amount thereof in the third layer (emulsion layer) of Light-Sensitive Material 101 in Example 1 as follows. Unless otherwise specified, silver halide emulsions and other materials used were the same as those used in Example 1 and the dye-providing compound was used as a coemulsion with a reducing agent or a high boiling point solvent.
  • Light-Sensitive Material 202 was prepared in the same manner as Light-Sensitive Material 201 except for adding 250 mg/m2 of Compound (VIII-1) of the present invention to the second layer of Light-Sensitive Material 201.
  • Light-Sensitive Materials 201 and 202 each was processed in the same manner as in Example 1 using Mordant Sheet R1.
  • the transmission images obtained were measured on the UV density and as a result, in both materials, the Dmax was 3.1 and the Dmin was 0.35, however, Light-Sensitive Material 202 was superior in the resolution to Light-Sensitive Material 201 and proved to be a satisfactory light-sensitive material for process printing.
  • Respective gelatin dispersions of cyan, magenta and yellow dye-providing compounds and a reducing agent (electron donor) were prepared as formulated in Table 8. More specifically, the oil phase components were dissolved under heating at about 60°C to obtain a uniform solution and the resulting solution and the aqueous phase components heated at about 60°C were mixed while stirring and dispersed in a homogenizer for 10 minutes at 10,000 rpm. Water was added to the dispersion and stirred to obtain a uniform dispersion.
  • Dye-Providing Compounds (1) to (4), Reducing Agent (3), the development inhibitor precursor, the electron transfer agent precursor, Compound (B) and High Boiling Point Solvent (3) in Table 8 are shown below. Unless otherwise indicated, the other materials were the same as used in Example 1. The preparation of a light-sensitive silver halide emulsion will be described below.
  • aqueous gelatin solution obtained by adding 20 g of gelatin, 0.5 g of potassium bromide, 3 g of sodium chloride and 30 mg of Compound (A) to 480 ml of water and kept at a temperature of 45°C) under well stirring, Solution (I) and Solution (II) shown in Table 9 were added simultaneously at the same flow rate over 20 minutes. After 5 minutes, Solution (III) and Solution (IV) shown in Table 9 were further added simultaneously at the same flow rate over 25 minutes.
  • aqueous gelatin solution obtained by adding 20 g of gelatin, 0.5 g of potassium bromide, 6 g of sodium chloride and 30 mg of Compound (A) to 783 ml of water and kept at a temperature of 65°C) under well stirring, Solution (I) and Solution (II) shown in Table 10 were added simultaneously at the same flow rate over 30 minutes. After 5 minutes, Solution (III) and Solution (IV) shown in Table 10 were further added simultaneously at the same flow rate over 15 minutes.
  • aqueous gelatin solution obtained by adding 20 g of gelatin, 0.5 g of potassium bromide, 4 g of sodium chloride and 15 mg of Compound (A) to 675 ml of water and kept at a temperature of 48°C) under well stirring, Solution (I) and Solution (II) shown in Table 11 were added simultaneously at the same flow rate over 10 minutes. After 10 minutes, Solution (III) and Solution (IV) shown in Table 11 were further added simultaneously at the same flow rate over 20 minutes.
  • aqueous gelatin solution obtained by adding 20 g of gelatin, 0.3 g of potassium bromide, 6 g of sodium chloride and 15 mg of Compound (A) to 675 ml of water and kept at a temperature of 55°C) under well stirring, Solution (I) and Solution (II) shown in Table 12 were added simultaneously at the same flow rate over 20 minutes. After 10 minutes, Solution (III) and Solution (IV) shown in Table 12 were further added simultaneously at the same flow rate over 20 minutes.
  • aqueous gelatin solution obtained by adding 20 g of gelatin, 0.5 g of potassium bromide, 4 g of sodium chloride and 15 mg of Compound (A) to 675 ml of water and kept at a temperature of 50°C) under well stirring, Solution (I) and Solution (II) shown in Table 13 were added simultaneously at the same flow rate over 8 minutes. After 10 minutes, Solution (III) and Solution (IV) shown in Table 13 were further added simultaneously at the same flow rate over 32 minutes.
  • aqueous gelatin solution obtained by adding 20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride and 15 mg of Compound (A) to 675 ml of water and kept at a temperature of 65°C) under well stirring, Solution (I) and Solution (II) shown in Table 14 were added simultaneously at the same flow rate over 10 minutes. After 10 minutes, Solution (III) and Solution (IV) shown in Table 14 were further added simultaneously at the same flow rate over 30 minutes.
  • Light-Sensitive Material 301 shown in Table 15 was prepared.
  • Table 15 other than those described above, Surface Active Agent (7), Antifoggants (1) and (2) and Hardening Agents (3) and (4) are shown below.
  • Light-Sensitive Materials 302 and 303 were prepared in the same manner as Light-Sensitive Material 301 except for adding Compound (VI-7) or (VII-1) of the present invention to the fourth layer of Light-Sensitive Material 301 in an amount to give a transmission density of 0.8.
  • Light-Sensitive Material 304 was prepared in the same manner as Light-Sensitive Material 301 except for adding an organic pigment described in JP-A-6-337511 in place of the compound of the present invention.
  • Light-Sensitive Materials 301 to 304 each was subjected to surface exposure through a wedge of B (blue), G (green), R (red) and gray with the densities being continuously changed and the exposed light-sensitive materials each was dipped in water kept at a temperature of 40°C for 2.5 seconds, then squeezed by rollers and immediately thereafter, superposed on Mordant Sheet R1 used in Example 1 so that the layer surfaces came into contact.
  • the laminate was heated for 17 seconds in a heat drum of which temperature was controlled to set the temperature on the water-absorbed layer surface at 80°C and then the light-sensitive material was peeled off from the mordant sheet. On the light-sensitive material, a silver image and also a negative dye image were obtained and on the mordant sheet, a positive dye image was obtained.
  • the compound of the present invention was almost 100% transferred, and onto the mordant sheet coupled with Light-Sensitive Material 304, the organic pigment was not transferred.
  • an image free of color turbidity or white spot and having excellent sharpness can be obtained simply within a short period of time.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP95114681A 1994-09-30 1995-09-18 Image formation method Withdrawn EP0704759A2 (en)

Applications Claiming Priority (2)

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JP25980594A JP3514528B2 (ja) 1994-09-30 1994-09-30 画像形成方法
JP259805/94 1994-09-30

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EP0704759A2 true EP0704759A2 (en) 1996-04-03

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1037101A1 (en) * 1999-03-18 2000-09-20 Fuji Photo Film Co., Ltd. Silver halide color photographic photosensitive material and method for forming image
EP1422550A2 (en) * 2002-11-20 2004-05-26 Eastman Kodak Company Thermally bleachable filter dye compositions comprising barbituric acid arylidene dyes and base precursors for use in a photothermographic element

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1037101A1 (en) * 1999-03-18 2000-09-20 Fuji Photo Film Co., Ltd. Silver halide color photographic photosensitive material and method for forming image
US6489086B1 (en) 1999-03-18 2002-12-03 Fuji Photo Film Co., Ltd. Silver halide color photographic photosensitive material and method for forming image
EP1422550A2 (en) * 2002-11-20 2004-05-26 Eastman Kodak Company Thermally bleachable filter dye compositions comprising barbituric acid arylidene dyes and base precursors for use in a photothermographic element
EP1422550A3 (en) * 2002-11-20 2004-12-15 Eastman Kodak Company Thermally bleachable filter dye compositions comprising barbituric acid arylidene dyes and base precursors for use in a photothermographic element

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JP3514528B2 (ja) 2004-03-31

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