EP0287073B1 - Procédé de traitement d'un matériau photographique à l'halogénure d'argent - Google Patents

Procédé de traitement d'un matériau photographique à l'halogénure d'argent Download PDF

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Publication number
EP0287073B1
EP0287073B1 EP88105892A EP88105892A EP0287073B1 EP 0287073 B1 EP0287073 B1 EP 0287073B1 EP 88105892 A EP88105892 A EP 88105892A EP 88105892 A EP88105892 A EP 88105892A EP 0287073 B1 EP0287073 B1 EP 0287073B1
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EP
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Prior art keywords
group
light
bleaching
processing
sensitive material
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EP88105892A
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German (de)
English (en)
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EP0287073A3 (en
EP0287073A2 (fr
Inventor
Shinji Ueda
Kei Sakanoue
Seiji Ichijima
Hidetoshi Kobayashi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP8982187A external-priority patent/JPS63256953A/ja
Priority claimed from JP9543287A external-priority patent/JPS63261359A/ja
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Publication of EP0287073A2 publication Critical patent/EP0287073A2/fr
Publication of EP0287073A3 publication Critical patent/EP0287073A3/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/44—Regeneration; Replenishers

Definitions

  • the present invention relates to a method for processing (hereinafter referred to as "processing") an exposed silver halide color photographic material (hereinafter referred to as "color light-sensitive material”). More particularly, the present invention relates to a method for rapidly processing a color light-sensitive material having an improved desilvering capability.
  • the processing of a color light-sensitive material essentially consists of a color developing step and a desilvering step.
  • the color developing step silver halide which has been exposed to light is reduced by a color developing agent to produce silver.
  • the color developing agent which has been oxidized reacts with a color forming agent (coupler) to provide color images.
  • the silver thus produced is oxidized by a bleaching agent in a subsequent desilvering step and then acted on by a fixing agent to become a soluble silver complex which is then dissolved and removed.
  • the practical developing process comprises various auxiliary steps besides the above described basic steps in order to maintain photographic and physical qualities of the images or improve the preservability of the images.
  • auxiliary steps include a hardening step, a stopping step, an image stabilizing step, and a washing step.
  • bleaching agents there have generally been known red prussiate, bichromate, ferric chloride, ferric aminopolycarboxylate complex, and persulfate.
  • red prussiate and bichromate have a disadvantage in that these salts can give cyanide or hexavalent chromium pollution and thus require a special treatment facility.
  • Ferric chloride has a disadvantage in that it produces iron hydroxide or stain at the subsequent washing process, thereby impeding the practical use thereof.
  • Persulfate has a disadvantage in that it requires a remarkably long period of time to finish bleaching due to its very weak bleaching effect.
  • Ferric aminopolycarboxylate complex salts (particularly ferric ethylenediaminetetraacetate complex salts) have less pollution problems and no storage problem as for persulfate and are therefore most widely put into practical use as bleaching agents.
  • ferric aminopolycarboxylate has a sufficient bleaching capability.
  • the processing is conducted with a reduced amount of replenisher of the processing solutions (i.e., bleaching solution, blixing solution and/or fixing solution) to be used in the desilvering of the silver halide color photographic material
  • a reduced amount of replenisher of the processing solutions i.e., bleaching solution, blixing solution and/or fixing solution
  • silver halide eluted from the light-sensitive material is accumulated in a high concentration as a silver complex in these processing solutions. This causes more precipitate to be produced or reduces the activity of the processing solutions, further weakening the bleaching power thereof.
  • a reduction in the amount of replenisher of the processing solution to be used in the desilvering process causes many difficulties.
  • bleaching accelerators include various mercapto compounds as described in U.S. Patent 3,893,858, British Patent 1,138,842, and Japanese Patent Application (OPI) No. 141623/78 (the term "OPI” as used herein refers to a "published unexamined Japanese patent application"), compounds containing disulfide bonds as described in Japanese Patent Application (OPI) No. 95630/78, thiazolidine derivatives as described in Japanese Patent Publication No.
  • bleaching agents those showing a bleach accelerating effect are present.
  • those bleaching accelerators leave much to be desired in practicality. For example, some bleaching accelerators are expensive or have insufficient stability in a bath having a bleaching capability.
  • the light-sensitive material is processed in a bleaching bath, blixing bath, or prebath thereof containing these various bleaching accelerators, and these bleaching accelerators are compounds containing mercapto groups
  • these mercapto compounds produce a sparingly soluble silver salt with unexposed silver halide or silver halide produced by the bleaching reaction in the emulsion layer of the light-sensitive material.
  • Such a sparingly soluble silver salt cannot be solubilized by a fixing agent, possibly causing poor fixation.
  • the inventors have found that the reduction of the amount of replenisher of the processing solution to be used in the desilvering process causes more silver ions to be accumulated in the desilvering bath, and these silver ions form a sparingly soluble silver salt with the mercapto compound, further reducing the bleach accelerating effect to an insufficient level.
  • the inventors have also found that the presence of iodide ions in the desilvering solution promotes such a reaction.
  • the above described mercapto compounds include those which react with sulfite ions in the processing solution to undergo decomposition ( Sulfur Dioxide , L.C. Schroeter, Pergamon Press (1966)).
  • the ordinary blixing solution comprising a thiosulfate as a fixing agent contains a sulfite in combination. Therefore, such a mercapto compound is susceptible to decomposition in the blixing solution.
  • One object of the present invention is to provide a method for processing a silver halide color photographic material which enables rapid desilvering even with a reduced amount of replenisher of a desilvering solution.
  • Another object of the present invention is to provide a method for processing a color light-sensitive material which is excellent in the blixing capability, particularly in the fixing capability.
  • a further object of the present invention is to provide a rapid desilvering step which enables the stabilization of the blixing solution.
  • Still another object of the present invention is to provide a rapid desilvering step which causes fewer pollution problems.
  • Still a further object of the present invention is to provide a rapid desilvering step which costs less and is more practical than those currently available.
  • a method for processing a silver halide color photographic material comprising a silver bromoiodide emulsion layer having a silver iodide content of 40 mol% of less, which method comprises imagewise exposing the silver halide color-photographic light-sensitive material to light, color developing the light-sensitive material, and then desilvering the light-sensitive material, wherein:
  • bleaching accelerator-releasing compound When a compound which reacts with an oxidation product of an aromatic primary amine color developing agent to release a bleaching accelerator (hereinafter referred to as "bleaching accelerator-releasing compound") is contained in a light-sensitive material in accordance with the present invention, the result is surprising in that very rapid desilvering can be made to occur even under the above described conditions (i) or (ii) wherein a very small amount of the processing solution is replenished.
  • a method for the processing of a silver halide color photographic material which comprises imagewise exposing the silver halide color photographic material to light, color-developing the silver halide color photographic material and then desilvering the light-sensitive material with a processing solution having a blixing capability, wherein the silver halide color photographic material contains a compound which reacts with an oxidation product of an aromatic primary amine color developing agent to release a bleaching accelerator, and the processing solution having a blixing capability contains preferably a ferric aminopolycarboxylate complex salt having a molecular weight of 300 or more in the form of a free acid.
  • Another method has been proposed which comprises washing a light-sensitive material containing such a bleaching accelerator-releasing compound after being color-developed, and then subjecting the light-sensitive material to blixing.
  • this method has a disadvantage in that the bleaching accelerator is washed out from the light-sensitive material in the washing bath, thereby impeding the expected bleach accelerating effect.
  • a bleaching accelerator is released in the vicinity of metal produced by development (hereinafter referred to as "developed silver") in an amount proportional to the amount of developed silver. Since such a bleaching accelerator is transferred to the subsequent desilvering process while being adsorbed by metal, it presumably prevents the reaction with silver ions and/or iodide compound ions which produces precipitates. Therefore, a light-sensitive material containing the present bleaching accelerator-releasing coupler which has been color-developed is preferably immediately processed with a processing solution having a blixing capability or a processing solution having a fixing capability and then with a processing solution having a blixing capability.
  • the bleach accelerating effect is disadvantageously eliminated.
  • the light-sensitive material which has been color-developed is preferably immediately processed with a processing solution having a salt concentration of 2 ⁇ 10 ⁇ 3 mol/l or more, and then processed with a processing solution having a blixing capability.
  • the condition (i) wherein the coated amount of silver per m2 of the silver halide photographic material is from 2.0 to 20 g can be applied to color negative film, color reversal film, color negative film for motion picture, color internegative film, etc.
  • the total amount of replenisher of the processing solution to be used in the desilvering of such light-sensitive materials can be remarkably reduced to from 100 to 700 ml, per m2 of the light-sensitive material.
  • the condition (ii) wherein the coated amount of silver per m2 of the silver halide photographic material is from 0.3 to less than 2.0 g can e.g. be applied to color paper, reversal color paper, automatic positive color paper, color positive paper for motion picture.
  • the total amount of replenisher of the processing solution to be used in the desilvering of such light-sensitive materials can be remarkably reduced to from 50 to 300 ml per m2 of the light-sensitive material.
  • the desilvering step as mentioned herein normally consists of one or a combination of two or three of processing with a processing solution having a bleaching capability (bleaching), processing with a processing solution having a blixing capability (blixing), and processing with a prccessing solution having a fixing capability (fixing).
  • the total amount of replenisher of the processing solution to be used in the desilvering means the replenished amount of the processing solution if the desilvering process consists of only one desilvering process as in the combination (3) or the total of the replenished amount of two or more desilvering solutions if the desilvering process consists of two or more desilvering steps as in the combinations (1), (2), (4), (5), (6) and (7).
  • a preferred example of the bleaching accelerator-releasing compound of the present invention is a compound represented by the formula (I): A0-(L0) p -Z0 (I) wherein A0 represents a group which undergoes a reaction with an oxidation product of a developing agent to cause cleavage of the (L0) p -Z0 bond; L0 represents a timing group or a group which undergoes a reaction with an oxidation product of a developing agent to cause cleavage of the connection with Z0; Z0 represents a group which exhibits the effect of accelerating bleaching upon cleavage of its connection with A0-(L0); and p represents an integer of 0 to 3, with the proviso that when p is a plural number, the plurality of L0 may be the same or different.
  • Another preferred example of the bleaching accelerator-releasing compound of the present invention is a compound represented by the formula (I′): A1-(L 1)a -(L2) b -Z1 (I′) wherein A1 represents a group which undergoes a reaction with an oxidation product of a developing agent to cause cleavage of the (L1) a -(L2) b -Z1 bond; L1 represents a timing group or a group which undergoes a reaction with an oxidation product of a developing agent to cause cleavage of the (L2) b -Z1 bond; L2 represents a timing group or a group which undergoes a reaction with an oxidation product of a developing agent to cause cleavage of the connection with Z1; Z1 represents a group which exhibits the effect of accelerating bleaching upon cleavage of its connection with A1-(L1) a -(L2) b ; and a and b each represents an integer of 0 or 1.
  • A0 and A1 particularly represent coupler residual groups or oxidation reduction groups.
  • coupler residual groups represented by A0 and A1 known coupler residual groups can be used.
  • coupler residual groups include yellow coupler residual groups such as open chain ketomethylene type coupler residual groups; magenta coupler residual groups such as the 5-pyrazolone type, pyrazoloimidazole type and pyrazolotriazole type coupler residual groups; cyan coupler residual groups such as the phenol type and naphthol type coupler residual groups; and colorless coupler residual groups such as the indanone type and acetophenone type coupler residual groups.
  • coupler residual groups include heterocyclic coupler residual groups as described in U.S. Patents 4,315,070, 4,183,752, 3,961,959 and 4,171,223.
  • Coupler residual groups represented by A1 in the formula (I′) include coupler residual groups represented by the following formulae (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8), (Cp-9) and (Cp-10). These couplers advantageously have a high coupling rate.
  • the free bond stemming from the coupling position represents the position at which a coupling-off group is bonded to the coupler.
  • R51, R52, R53, R54, R55, R56, R57, R58, R59, R60, R61, R62 or R63 contains a nondiffusible group, it is selected such that the total number of carbon atoms contained therein is from 8 to 40, and preferably from 10 to 30, and if it contains no nondiffusible group, it is selected such that the total number of carbon atoms contained therein is preferably 15 or less.
  • the formulae (I) and (I′) are a bis, telomer or polymer type coupler, any one of the above described substituents R51 to R63 represents a divalent group which connects repeating units. In this case, the total number of carbon atoms contained in the coupler may not be within the above specified limit.
  • R41 represents an aliphatic, aromatic or heterocyclic group.
  • R42 represents an aromatic or heterocyclic group.
  • R43, R44 and R45 each represents a hydrogen atom, an aliphatic group or a heterocyclic group.
  • R51 represents the same group as R41.
  • R52 and R53 each represents the same group as R42.
  • R54 represents the same group as R41 or represents an group, an group, an group, an R41S- group, an R43O- group, an group, or an N ⁇ C- group.
  • R55 represents the same group as R41.
  • R56 and R57 each represents the same group as R43 or represents an R41S- group, an R43O- group, an group, or an group,
  • R58 represents the same group as R41.
  • R59 represents the same group as R41 or represents an group, an group, an group, an R41O- group, an R41S- group, a halogen atom, or an group.
  • the suffix d represents an integer of 0 to 3.
  • the plurality of R59 may be the same or different or may be divalent groups which connect each other to form a cyclic structure.
  • Typical examples of such divalent groups include the following compounds: wherein f represents an integer of 0 to 4; and g represents an integer of 0 to 2.
  • R60 represents the same group as R41.
  • R61 represents the same group as R41.
  • R62 represents the same group as R41 or represents an R41CONH- group.
  • R62 represents the same group as R41 or represents an R41OCONH- group, an R41SO2NH- group, an group, an group, an R43O- group, an R41S- group, a halogen atom, or an group.
  • R63 represents the same group as R41 or represents an group, an group, an group, an group, an R41SO2- group, an R43OCO- group, an R43O-SO2- group, a halogen atom, a nitro group, a cyano group or an R43CO- group.
  • the suffix e represents an integer of 0 to 4. When there are a plurality of R62 or R63, these may be the same or different.
  • the aliphatic group is a saturated or unsaturated, chain or cyclic, straight chain or branched, substituted or unsubstituted aliphatic hydrocarbon group (having from 1 to 32 carbon atoms and preferably from 1 to 22 carbon atoms).
  • Typical examples of such an aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, an i-butyl group, a t-amino group, a hexyl group, a cyclohexyl group, a 2-ethylhexyl group, an octyl group, a 1,1,3,3-tetramethylbutyl group, a decyl group, a dodecyl group, a hexadecyl group and an octadecyl group.
  • the above described aromatic group is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, having from 6 to 20 carbon atoms.
  • the above described heterocyclic group is preferably a 3- to 5-membered substituted or unsubstituted heterocyclic group (having from 1 to 20 carbon atoms and preferably from 1 to 7 carbon atoms) containing atoms selected from nitrogen, oxygen and sulfur as hetero atoms.
  • Typical examples of such a heterocyclic group include a 2-pyridyl group, a 2-chienyl group, a 2-furyl group, a 1-imidazolyl group, a 1-indolyl group, a phthalimide group, a 1,3,4-thiadiazole-2-yl group, a 2-quinolyl group, a 2,4-dioxo-1,3-imidazolidine-5-yl group, a 2,4-dioxo-1,3-imidazolidine-3-yl group, a succinimide group, a 1,2,4-triazole-2-yl group and a 1-pyrazolyl group.
  • substituents include halogen atoms, an R47O- group, an R46S- group, an group, an group, an group, an group, an R46SO2- group, an R47OCO- group, an group, a group having the same meaning as R46, an group, an R46COO- group, an R47OSO2- group, a cyano group, and a nitro group.
  • R46 represents an aliphatic group, an aromatic group or a heterocyclic group
  • R47, R48 and R49 each represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom.
  • the aliphatic groups, aromatic groups or heterocyclic groups have the same meanings as described above.
  • R51 is preferably an aliphatic group or an aromatic group.
  • R52, R53 and R55 each is preferably an aromatic group.
  • R54 is preferably an R41CONH- group or an group.
  • R56 and R57 each is preferably an aliphatic group, an R41O- group or an R41S- group.
  • R58 is preferably an aliphatic group or an aromatic group.
  • R59 is preferably a chlorine atom, an aliphatic group or an R41CONH- group.
  • the suffix d is preferably 1 or 2.
  • R60 is preferably an aromatic group.
  • R59 is preferably an R41CONH- group.
  • the suffix d is preferably 1.
  • R61 is preferably an aliphatic group or an aromatic group.
  • the suffix e is preferably 0 or 1.
  • R62 is preferably an R41OCONH- group, an R41CONH- group or an R41SO2NH- group. These substituents preferably substitute the hydrogen atom in the 5-position of the naphthol ring.
  • R63 is preferably an R41CONH- group, an R41SO2NH- group, an group, an R41SO2- group, an group, a nitro group or a cyano group.
  • R63 is preferably an group, an R43CCO- group or an R43CO- group.
  • R51 examples include a t-butyl group, a 4-methoxyphenyl group, a phenyl group, a 3-[2-(2,4-di-t-amylphenoxy)butanamido]phenyl group and a methyl group.
  • R52 and R53 examples include a 2-chloro-5-dodecyloxycarbonylphenyl group, a 2-chloro-5-hexadecylsulfonamidophenyl group, a 2-chloro-5-tetradecanamidophenyl group, a 2-chloro-5-[4-(2,4-di-t-amylphenoxy)butanamido]phenyl group, a 2-chloro-5-[2-(2,4-di-t-amylphenoxy)butanamido]phenyl group, a 2-methoxyphenyl group, a 2-methoxy-5-tetradecyloxycarbonylphenyl group, a 2-chloro-5-(1-ethoxycarbonylethoxycarbonyl)phenyl group, a 2-pyridyl group, a 2-chloro-5-octyloxycarbonylphenyl group, a 2,4-dichlorophen
  • R54 examples include a 3-[2-(2,4-di-t-amylphenoxy)butanamido]benzamide group, a 3-[4-(2,4-di-t-amylphenoxy)butanamido]benzamide group, a 2-chloro-5-tetradecanamidoaniline group, a 5-(2,4-di-t-amylphenoxyacetamido)benzamide group, a 2-chloro-5-dodecenylsuccinimidoanilino group, a 2-chloro-5-[2-(3-t-butyl-4-hydroxyphenoxy)tetradecanamido]anilino group, a 2,2-dimethylpropanamide group, a 2-(3-pentadecylphenoxy)butanamide group, a pyrrolidino group and an N,N-dibutylamino group.
  • R55 examples include a 2,4,6-trichlorophenyl group, a 2-chlorophenyl group, a 2,5-dichlorophenyl group, a 2,3-dichlorophenyl group, a 2,6-dichloro-4-methoxyphenyl group, a 4-[2-(2,4-di-t-amylphenoxy)butanamido]phenyl group and a 2,6-dichloro-4-methanesulfonylphenyl group.
  • R56 examples include a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a 3-phenylureido group and a 3-(2,4-di-t-amylphenoxy)propyl group.
  • R57 examples include a 3-(2,4-di-t-amylphenoxy)propyl group, a 3-[4- ⁇ 2-[4-(4-hydroxyphenylsulfonyl)phenoxy]tetradecanamido ⁇ phenyl]propyl group, a methoxy group, a methylthio group, an ethylthio group, a methyl group, a 1-methyl-2- ⁇ 2-octyloxy-5-[2-octyloxy-5-(1,1,3,3-tetramethylbutyl)phenylsulfonamido]phenylsulfonamido ⁇ ethyl group, a 3-[4-(4-dodecyloxyphenylsulfonamido)phenyl]propyl group, a 1,1-dimethyl-2-[2-octyloxy-5-(1,1,3,3-tetramethylbutyl)phenylsulfonamido]eth
  • R58 examples include a 2-chlorophenyl group, a pentafluorophenyl group, a heptafluoropropyl group, a 1-(2,4-di-t-amylphenoxy)propyl group, a 3-(2,4-di-t-amylphenoxy)propyl group, a 2,4-di-t-amylmethyl group and a furyl group.
  • R59 examples include a chlorine atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a 2-(2,4-di-t-amylphenoxy)butanamide group, a 2-(2,4-di-t-amylphenoxy)hexanamide group, a 2-(2,4-di-t-octylphenoxy)octanamide group, a 2-(2-chlorophenoxy)tetradecanamide group, a 2-[4-(4-hydroxyphenylsulfonyl)phenoxy]tetradecanamide group and a 2-[2-(2,4-di-t-amylphenoxyacetamido)phenoxy]butanamide group.
  • R60 examples include a 4-cyanophenyl group, a 2-cyanophenyl group, a 4-butylsulfonylphenyl group, a 4-propylsulfonylphenyl group, a 4-chloro-3-cyanophenyl group, a 4-ethoxycarbonylphenyl group and a 3,4-dichlorophenyl group.
  • R61 examples include a dodecyl group, a hexadecyl group, a cyclohexyl group, a 3-(2,4-di-t-amylphenoxy)propyl group, a 4-(2,4-di-t-amylphenoxy)butyl group, a 3-dodecyloxypropyl group, a t-butyl group, a 2-methoxy-5-dodecyloxycarbonylphenyl group and a 1-naphthyl group.
  • R62 examples include an isobutyloxycarbonylamino group, an ethoxycarbonylamino group, a phenylsulfonylamino group, a methanesulfonamide group, a benzamide group, a trifluoroacetamide group, a 3-phenylureido group, a butoxycarbonylamino group and an acetamide group.
  • R63 examples include a 2,4-di-t-amylphenoxyacetamide group, a 2-(2,4-di-t-amylphenoxy)butanamide group, a hexadecylsulfonamide group, an N-methyl-N-octadecylsulfamoyl group, an N,N-dioctylsulfamoyl group, a 4-t-octylbenzoyl group, a dodecyloxycarbonyl group, a chlorine atom, a nitro group, a cyano group, an N-[4-(2,4-di-t-amylphenoxy)butyl]carbamoyl group, an N-3-(2,4-di-t-amylphenoxy)propylsulfamoyl group, a methanesulfonyl group and a hexadecylsulfonyl group.
  • A0 in the formula (I) represents an oxidation reduction group
  • Any two substituents of P, X, Y, Q, A11 and A12 may be divalent groups which are connected to each other to form a cyclic structure.
  • P and Q each represents a substituted or unsubstituted imino group, they are each preferably an imino group substituted by a sulfonyl group or an acyl group.
  • preferred examples of the group represented by G include straight chain or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic groups, having from 1 to 32 carbon atoms and preferably from 1 to 22 carbon atoms such as a methyl group, an ethyl group, a benzyl group, a phenoxybutyl group and an isopropyl group, a substituted or unsubstituted aromatic group having from 6 to 10 carbon atoms such as a phenyl group, a 4-methylphenyl group, a 1-naphthyl group and a 4-dodecyloxyphenyl group, and 4- to 7-membered heterocyclic groups containing as a hetero atom an atom selected from a nitrogen atom, a sulfur atom and an oxygen atom such as a 2-pyridyl group, a 1-phenyl-4-imidazolyl group, a 2-furyl group
  • P and Q preferably each independently represents an oxygen group or a group represented by the formula (N-1).
  • A11 and A12 each represents a group removable by an alkali (hereinafter referred to as "precursor group")
  • a precursor group include hydrolyzable groups such as an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfonyl group, precursor groups of the type using the reverse Michael reaction as described in U.S. Patent 4,009,029, precursor groups of the type using as an intramolecular nucleophilic group an anion produced upon a ring cleavage reaction as described in U.S.
  • Patent 4,310,612 precursor groups which undergo electronic migration of anions through a conjugated system to cause a ring cleavage reaction as described in U.S. Patents 3,674,478, 3,932,480 and 3,993,661, precursor groups which undergo electronic migration of anions after a ring cleavage reaction to cause a cleavage reaction, and precursor groups using an imidomethyl group as described in U.S. Patents 4,363,865 and 4,410,618.
  • P is preferably an oxygen atom
  • A12 is preferably a hydrogen atom
  • the other X and Y which is not a methine group having an -(L1) a -(L2) b -Z1 group each is preferably a substituted or unsubstituted methine group.
  • Particularly preferred among groups represented by the formula (II) are those represented by the formulae (III) or (IV): wherein the mark * represents the position at which it is bonded to -(L1) a -(L2) b -Z1; P, Q, A11 and A12 have the same meanings as described with reference to the formula (II); R64 represents a substituent; and q represents an integer of 0 to 3. When q is 2 or 3, the two or more R64 may be the same or different. When the two R64 are substituents on adjacent carbon atoms, they may be divalent groups which are connected to each other to form a cyclic structure.
  • cyclic structures examples include benzene condensed rings such as naphthalene, benzonorholunene, chroman, indole, benzothiophene, quinoline, benzofuran, 2,3-dihydrobenzofuran, indane and indene. These cyclic structures may further contain one or more substituents.
  • Preferred examples of such substituents and R64 containing no condensed rings include an R41 group, a halogen atom, an R43O- group, an R43S- group, an group, an R43OOC- group, an R41SO2- group, an group, an group, an group, R43CO- group, an R41COO- group, an group, a cyano group and an group.
  • R41, R43, R44 and R45 represent the same meanings as in the above described formulae (I) and (I′).
  • Typical examples of R64 include a methyl group, an ethyl group, a t-butyl group, a methoxy group, a methylthio group, a dodecylthio group, a 3-(2,4-di-t-amylphenoxy)propylthio group, an N-3-(2,4-di-t-amylphenoxy)propylcarbamoyl group, an N-methyl-N-octadecyloxycarbamoyl group, a methoxycarbonyl group, a dodecyloxycarbonyl group, a propylcarbamoyl group, a hydroxyl group, and an N,N-dioctylcarbamoyl group.
  • Examples of a cyclic structure formed by two R64 include a group,
  • P and Q each preferably represents an oxygen atom.
  • A11 and A12 each preferably represents a hydrogen atom.
  • the group represented by L1 or L2 may or may not be used in the present invention. Such a group is preferably not used in the present invention but may be optionally used depending on the purpose.
  • L1 and L2 each represents a timing group
  • examples of such a timing group include the following known connecting groups:
  • L1 and L2 which each represents a group which becomes a coupler include groups represented by the undermentioned formulae (V), (VI), (VII) and (VIII).
  • the mark * represents the position at which the group is bonded to the left hand of the group of the formula (I)
  • the mark ** represents the position at which the group is bonded to the right hand of the group of the formula (I).
  • V1 and V2 each represents a substituent
  • V3, V4, V5 and V6 each represents a nitrogen atom or a substituted or unsubstituted methine group
  • V7 represents a substituent
  • x represents an integer of 0 to 4
  • V8 represents a -CO- group, an -SO2- group, an oxygen atom or a substituted imino group
  • V9 represents nonmetallic atomic groups which form a 5- to 8-membered ring together with and
  • V10 represents a hydrogen atom or a substituent, with the proviso that when x is a plural number, the plurality of V7 may be the same or different or two V7 may be connected to each other to form a cyclic structure, and that V1 and V2 may be divalent groups which are connected to each other to form a 5- to 8-membered ring together with
  • V1 preferably represents an R71 group.
  • Preferred examples of V2 include an R72 group, an R72CO- group, an group, an R72SO2- group, an R72S- group, an R72O- group and an group.
  • Examples of the cyclic ring formed by the connection of V1 and V2 include indene, indole, pyrazole and benzothiophene.
  • Preferred examples of the substituents represented by V3, V4, V5 and V6 which represent a substituted methine group include an R71 group, an R73O- group, an R71S- group and an R71CONH- group.
  • V7 include a halogen atom, an R71 group, an R71CONH- group, an R71SO2NH- group, an R73O- group, an R71S- group, an group, an group, an R71CO- group and an R73OOC group.
  • Examples of the cyclic structure formed by the linkage of a plurality of V7 include naphthalene, quinoline, oxyindole, benzodiazepine-2,4-dione, benzimidazole-2-one-and benzothiophene.
  • Preferred examples of the substituted imino group represented by V8 include an R73N ⁇ group.
  • Preferred examples of the cyclic structure which is formed by V9 together with include indole, imidazolinone, 1,2,5-thiazoline-1,1-dioxide, 3-pyrazoline-5-one, 3-isooxazoline-5-one and
  • V10 include a R73- group, an R73O- group, an group, an group and an R71S- group.
  • R71 and R72 each represents an aliphatic group, an aromatic group or a heterocyclic group
  • R73, R74 and R75 each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
  • the aliphatic group, the aromatic group and the heterocyclic group have the same meanings as described with reference to R41 in the formulae (I) and (I′), with the proviso that the total number of carbon atoms contained in each of these groups preferably 10 or less.
  • Typical examples of the group represented by the formula (V) include the following groups:
  • Typical examples of the group represented by the formula (VI) include the following groups:
  • Typical examples of the group represented by the formula (VIII) include the following groups:
  • Typical examples of the group represented by the formula (VIII) include the following groups:
  • Any two substituents selected from A′2, P′, Q′, X′ and Y′ may be divalent groups which are connected to each other to form a cyclic structure.
  • Examples of such a cyclic structure include a benzene ring and a pyridine ring.
  • P′ preferably represents an oxygen atom
  • Q′ preferably represents an oxygen atom or a group represented by the undermentioned formulae.
  • the mark ** represents the position at which the group is bonded to A′2.
  • G′ has the same meaning as described in G in the formulae (N-1) and (N-2).
  • Q′ is particularly preferably an oxygen atom or a group represented by
  • Particularly preferred among the groups represented by the formula (IX) are those represented by the following formulae (X) and (XI): wherein the mark * represents the position at which the group is bonded to the left hand of the group of the formula (I); the mark ** represents the position at which the group is bonded to the right hand of the group of the formula (I); R76 has the same meaning as R64 in the formulae (III) or (IV); and y represents an integer of 0 to 3, with the proviso that when y is a plural number, the plurality of R76 may be the same or different or two of these R76 may be connected to each other to form a cyclic structure.
  • R76 include an alkoxy group such as a methoxy group and an ethoxy group; an acylamino group such as an acetamide group and a benzamide group; a sulfonamide group such as a methanesulfonamide group and a benzenesulfonamide group; an alkylthio group such as a methylthio group and an ethylthio group; a carbamoyl group such as an N-propylcarbamoyl group, an N-t-butylcarbamoyl group and an N-i-propylcarbamoyl group; an alkoxycarbonyl group such as a methoxycarbonyl group and a propoxycarbonyl group; an aliphatic group such as a methyl group and a t-butyl group; a halogen atom such as a fluorine atom and a chlorine atom; a sulfamo
  • the group represented by Z1 specifically represents a known bleaching accelerator residual group.
  • a bleaching accelerator residual group include various mercapto compounds as described in U.S. Patent 3,893,858, British Patent 1,138,842, and Japanese Patent Application (OPI) No. 141623/78; compounds containing a disulfide bond as described in Japanese Patent Application (OPI) No. 95630/78; thiazolidine derivatives as described in Japanese Patent Publication No. 9854/78; isothiourea derivatives as described in Japanese Patent Application (OPI); No. 94927/78; thiourea derivatives as described in Japanese Patent Publication Nos.
  • Particularly preferred examples of the group represented by Z1 include groups represented by the following formulae (XII), (XIII) and (XIV): wherein the mark * represents the position at which the group is bonded to A-(L1) a -(L2) b -; R1 represents a divalent aliphatic group having from 1 to 8 carbon atoms and preferably from 1 to 5 carbon atoms; R2 has the same meaning as R1 or represents a divalent aromatic group or a 3- to 8-membered, preferably 5- or 6-membered divalent heterocyclic group having from 6 to 10 carbon atoms; X1 represents -O-, -S-, -COO-, -SO2-, X2 represents an aromatic group having from 6 to 10 carbon atoms; X3 represents a 3- to 8-membered, preferably 5- or 6-membered heterocyclic group containing at least one carbon atom bonded to S in the ring; Y1 represents a carboxyl group or a salt thereof,
  • R3, R4 and R5 each represents a hydrogen atom or an aliphatic group having from 1 to 8 carbon atoms and preferably from 1 to 5 carbon atoms.
  • the aliphatic group represented by R1 or R5 may be a chain or cyclic, straight chain or branched, saturated or unsaturated, substituted or unsubstituted, preferably unsubstituted aliphatic group.
  • substituents for the substituted aliphatic group represented by R1 or R5 include a halogen atom, an alkoxy group such as a methoxy group and an ethoxy group; and an alkylthio group such as a methylthio group and an ethylthio group.
  • the aromatic group represented by X2 or R2 may contain substituents. Examples of such substituents include those described with reference to the aliphatic group represented by R1 or R5.
  • the heterocyclic group represented by X3 or R2 is a saturated or unsaturated, substituted or unsubstituted heterocyclic group containing as a hetero atom an oxygen atom, a sulfur atom or a nitrogen atom.
  • a heterocyclic group include a pyridine ring, an imidazole ring, a piperidine ring, an oxirane ring, a sulforane ring, an imidazolidine ring, a thiazepine ring and a pyrazole ring.
  • substituents for such heterocyclic groups include those described with reference to the aliphatic group represented by R1 or R5.
  • Specific examples of the group represented by the formula (XII) include the following groups: -SCH2CH2CO2H, -SCH2CO2H, -SCH2CH2NH2, -SCH2CH2NHCOCH3 -S(CH2)4CO2H, -SCH2CONHCH2CO2H, -SCH2CH2OCH2CO2H, -SCH2COOCH2CH2OH, -SCH2CH2OCH2CH2OCH2CH2OH, -SCH2CH2SCH2CO2H, -SCH2CH2CH2CO2H, -SCH2CH2CH2CO2H,
  • Examples of the compound represented by the formula (I′) include bis, telomer, and polymer compounds.
  • Examples of such a polymer compound include a polymer containing repeating units represented by the formula (XVI) derived from a monomer represented by the formula (XV) and a copolymer of one or more noncoloring monomers containing at least one ethylene group incapable of coupling with an oxidation product of an aromatic primary amine developing agent. Two or more monomers represented by the formula (XV) may be polymerized at the same time.
  • R represents a hydrogen atom, a lower alkyl group having from 1 to 4 carbon atoms or a chlorine atom;
  • A21 represents -CONH-, -NHCONH-, -NHCOO-, -COO-, -SO2-, -CO-, -NHCO-, -SO2NH-, -NHSO2-, -OCO-, -OCONH-, -NH- or -O-;
  • A22 represents -CONH- or -COO-; and
  • A23 represents a substituted or unsubstituted alkylene group, an aralkylene group or an arylene group.
  • Such an alkylene group may be a straight chain or branched group.
  • Examples of such an alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene and decylmethylene.
  • Examples of the aralkylene group represented by A23 include benzylidene.
  • Examples of the arylene group represented by A23 include phenylene and naphthylene.
  • QQ represents a residual group of the compound represented by the formula (I′). QQ may be bonded to the main body of the group represented by the formula (XV) or (XVI) at any position in the substituent as described with reference to the residual group of the compound represented by the formula (I′) except for the group represented by Z1.
  • the suffixes i, j and k each represents 0 or 1 but are not 0 at the same time.
  • Examples of the substituents for the alkylene group, the aralkylene group or the arylene group represented by A23 include an aryl group such as a phenyl group; a nitro group; a hydroxyl group; a cyano group; a sulfo group; an alkoxy group such as a methoxy group; an aryloxy group such as a phenoxy group; an acyloxy group such as an acetoxy group; an acylamino group such as an acetylamino group; a sulfonamide group such as a methanesulfonamide group; a sulfamoyl group such as a methylsulfamoyl group; a halogen atom such as fluorine, chlorine and bromine; a carboxyl group; a carbamoyl group such as a methylcarbamoyl group; an alkoxycarbonyl group such as a methoxycarbonyl group;
  • noncoloring ethylenic monomer incapable of coupling with an oxidation product of an aromatic primary amine developing agent examples include an acrylic acid, an ⁇ -chloroacrylic acid, an ⁇ -alkylacrylic acid and ester or amide derived from these acrylic acids, methylenebisacrylamide, a vinyl ester, acrylonitrile, an aromatic vinyl compound, maleic acid derivatives and vinylpyridines. Two or more of these noncoloring ethylenically unsaturated monomers may be used at the same time.
  • any two of the groups represented by A1, L1, L2 and Z1 may optionally contain bonding hands other than the bonding hand represented by the formula (I′).
  • This second bonding hand can provide the effects of the present invention without being severed upon development. Examples of such a bonding hand include the following bonding hands:
  • Particularly preferred among these bonding hands is one represented by the formula (XVII): wherein L2, b, Z1, R58 and R59 have the same meanings as in the formula (I′) described above; h and v each represents an integer of 0 or 1; and A34 represents a divalent organic residual group which forms a 5- to 8-membered ring.
  • Examples of the divalent organic residual group represented by A34 include -O-CH ⁇ , and -S-CH ⁇ groups.
  • the amount of the bleaching accelerator-releasing compound of the present invention to be added to the light-sensitive material is preferably in the range of from 1 ⁇ 10 ⁇ 7 to 1 ⁇ 10 ⁇ 1 mol, particularly from 1 ⁇ 10 ⁇ 6 to 5 ⁇ 10 ⁇ 2 mol, per m2 of the light-sensitive material.
  • the bleaching accelerator-releasing compound may be incorporated into any layers in the light-sensitive material but is preferably incorporated into a light-sensitive emulsion layer. The more light-sensitive emulsion layers the present compound is incorporated in, the more remarkable the effects of the present invention become.
  • the desilvering step of the present invention may be two steps in which the bleaching step and fixing step are separately carried out, but is preferably one step (one bath) in which only bleach-fixing step is carried out.
  • a bleaching agent to be used for the processing solution of the present invention having a blixing capability examples include oxidizing agents such as a ferric complex salt, e.g., an iron ferricyanide complex salt and a ferric citrate complex salt, persulfate, and peroxide, e.g., hydrogen peroxide.
  • oxidizing agents such as a ferric complex salt, e.g., an iron ferricyanide complex salt and a ferric citrate complex salt, persulfate, and peroxide, e.g., hydrogen peroxide.
  • Preferred examples of such a bleaching agent include a ferric aminopolycarboxylate complex salt, and a complex of ferric ion with an aminopolycarboxylic acid or a salt thereof.
  • Particularly preferred bleaching agents to be used for the processing solution of the present invention having a blixing capability is a ferric aminopolycarboxylate complex salt having a molecular weight of generally 300 or more, preferably from 300 to 600, and particularly preferably from 300 to 500, in the form of a free acid.
  • Typical examples of such an aminopolycarboxylic acid and a salt thereof include the following compounds:
  • preferred compounds are A-1, A-2, A-6, A-7, A-10, A-11, A-12, A-16 and A-18.
  • a particularly preferred compound is diethylenetriaminepentaacetic acid (A-1).
  • Such a ferric aminopolycarboxylate complex salt may be used in the form of a complex salt.
  • a ferric salt such as ferric sulfate, ferric chloride, ferric ammonium sulfate and ferric phosphate may be used with an aminopolycarboxylic acid to form a ferric ion complex salt in the solution.
  • one or more complex salts may be used.
  • one or more ferric salts may be used.
  • one or more aminopolycarboxylic acids may be used. In any case, an aminopolycarboxylic acid may be used in an excess amount beyond the amount required to form a ferric ion complex salt.
  • ferric aminopolycarboxylate complex salts except for A-19 and a ferric ethylenediaminetetraacetate complex salt may be used.
  • the processing solution capable of blixing containing the above described ferric complex salt may contain a complex salt of a metal ion other than a ferric ion such as cobalt, nickel and copper.
  • the content of bleaching agent per liter of the present processing solution having a blixing capability is in the range of 0.1 to 1 mol and preferably 0.2 to 0.5 mol.
  • the pH value of the bleaching bath is preferably in the range of 4.0 to 8.0 and particularly preferably 5.0 to 7.5.
  • the processing bath of the present invention having a blixing capability may contain a rehalogenizing agent such as bromide, e.g., potassium bromide, sodium bromide and ammonium bromide; and chloride, e.g., potassium chloride, sodium chloride and ammonium chloride besides a bleaching agent and the above described compounds.
  • a rehalogenizing agent such as bromide, e.g., potassium bromide, sodium bromide and ammonium bromide
  • chloride e.g., potassium chloride, sodium chloride and ammonium chloride besides a bleaching agent and the above described compounds.
  • compounds which may be incorporated into the present processing bath include various known additives such as inorganic acids, organic acids and salts thereof having a pH buffering capability, e.g., nitrates such as sodium nitrate, ammonium nitrate, etc, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate and tartaric acid.
  • nitrates such as sodium nitrate, ammonium nitrate, etc
  • boric acid borax
  • sodium metaborate acetic acid
  • sodium acetate sodium carbonate
  • potassium carbonate potassium carbonate
  • phosphorous acid phosphoric acid
  • sodium phosphate citric acid
  • citric acid sodium citrate and tartaric acid.
  • the processing bath of the present invention having a blixing capability may contain as a fixing agent any known compound commonly used in a blixing solution such as thiosulfate (e.g., sodium thiosulfate, ammonium thiosulfate, ammonium sodium thiosulfate and potassium thiosulfate); thiocyanate (e.g., ammonium thiocyanate and potassium thiocyanate); thiourea; and thioether.
  • thiosulfate e.g., sodium thiosulfate, ammonium thiosulfate, ammonium sodium thiosulfate and potassium thiosulfate
  • thiocyanate e.g., ammonium thiocyanate and potassium thiocyanate
  • thiourea thioether
  • the processing solution of the present invention having a bleaching capability may contain a so-called sulfite ion-releasing compound such as sulfite (e.g., sodium sulfite and ammonium sulfite), bisulfite, and an addition product of an aldehyde and bisulfite (e.g., carbonyl bisulfite).
  • sulfite e.g., sodium sulfite and ammonium sulfite
  • bisulfite e.g., sodium sulfite and ammonium sulfite
  • an aldehyde and bisulfite e.g., carbonyl bisulfite
  • the processing solution of the present invention having a blixing capability may contain an organic phosphate compound such as an aminopolycarboxylic acid represented by A-1 to A-24, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentakismethylenephosphonic acid, 1,3-diaminopropanetetrakismethylenephosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid and 1-hydroxyethylidene-1,1′-diphosphonic acid.
  • an organic phosphate compound such as an aminopolycarboxylic acid represented by A-1 to A-24, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentakismethylenephosphonic acid, 1,3-diaminopropanetetrakismethylenephosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid and 1-hydroxyethylidene-1,1′-diphosphonic acid.
  • the processing solution having a blixing capability may contain at least one bleaching accelerator selected from compounds having a mercapto group or a disulfide bond, isothiourea derivatives and thiazolidine derivatives.
  • the content of such a bleaching accelerator per liter of the processing solution having a blixing capability is preferably in the range of from 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 1 mol and particularly preferably from 1 ⁇ 10 ⁇ 4 to 5 ⁇ 10 ⁇ 2 mol.
  • a bleaching accelerator to be incorporated into the processing solution having a blixing capability there may be used any compound having a bleach accelerating effect selected from compounds having a mercapto group or a disulfide bond, thiazolidine derivatives, thiourea derivatives and isothiourea derivatives.
  • Preferred examples of such a bleaching accelerators include compounds represented by formulae as described in Japanese Patent Application No. 313598/86 (pp. 63-77).
  • These compounds may be normally incorporated into the processing solution in the form of a solution in water, alkali, organic acid, organic solvent, etc. However, these compounds may be directly added to the bleaching bath without affecting its bleach accelerating effect.
  • such a bleaching accelerator may further be incorporated into the light-sensitive material.
  • the bleaching accelerator may be incorporated into any emulsion layer selected from blue-sensitive, green-sensitive and red-sensitive emulsion layers, or a gelatin layer such as the top layer, interlayer and bottom layer.
  • the processing bath of the present invention having a blixing capability may consist of one tank or two or more tanks. Such a group of tanks may be replenished with a processing solution in a multistage countercurrent process. Alternatively, the processing solution may be circulated among these tanks to provide a uniform processing solution. In this case, a replenisher of the processing solution may be replenished to only one of these tanks. In any case, the total amount of replenisher of the processing solution to be supplied is within the range specified herein.
  • the processing solution of the present invention having a bleaching capability may contain a bleaching agent which can be used in the processing solution of the present invention having a blixing capability.
  • the processing solution of the present invention having a bleaching capability may contain a bleaching accelerator and other all compounds which can be used in the processing solution having a blixing capability.
  • the pH value of the processing solution having a bleaching capability is preferably in the range of 4.0 to 8.0.
  • Another processing bath may be provided between the color developing bath and the processing bath having a blixing capability.
  • a processing bath may preferably contain a salt.
  • a salt include organic carboxylic acids such as phosphate, carbonate, sulfite, thiosulfate, borate, hydrochloride, sulfate, citrate, and acetate; organic aminocarboxylates such as ethylenediaminetetraacetate; and organic phosphates or sulfonates such as ethylenediaminetetrakisphosphate and 1-hydroxyethylidene-1,1-diphosphate.
  • organic carboxylic acids such as phosphate, carbonate, sulfite, thiosulfate, borate, hydrochloride, sulfate, citrate, and acetate
  • organic aminocarboxylates such as ethylenediaminetetraacetate
  • organic phosphates or sulfonates such as ethylenediaminete
  • These salts may be preferably incorporated as cations in the form of an alkaline metal salt such as a sodium salt and a potassium salt; an alkaline earth metal salt; an ammonium salt; or a free acid. These salts may be used alone or in combination.
  • the total amount of these salts to be incorporated in the processing solution is preferably in the range of 2 ⁇ 10 ⁇ 3 mol or less, and particularly preferably from 1 ⁇ 10 ⁇ 2 to 2 mol, per liter of the processing solution.
  • the pH value of the processing bath is not specifically limited but is preferably the same as that of the subsequent blixing bath.
  • the method for processing a silver halide color photographic material containing a compound which releases a bleaching accelerator (i.e., a bleaching accelerator-releasing compound) with a processing solution containing a specific ferric complex salt and having a blixing capability enables an improvement in the solution stability and rapid processing with an excellent blixing capability. It was also found that the deterioration in color restoration of cyan images which becomes remarkable with increasing processing speed can be eliminated by incorporating at least one cyan dye-forming coupler represented by the formulae (L-I) or (L-II) in the light-sensitive material.
  • R101 and R102 each independently represents an aliphatic group, an aryl group or a heterocyclic group
  • R103 represents a hydrogen atom, a halogen atom, an aliphatic group having from 5 to 25 carbon atoms, an aryl group having from 5 to 25 carbon atoms, an acylamino group, or nonmetallic atomic groups which form a 5- or 6-membered nitrogen-containing ring together with R102
  • Z10 represents a hydrogen atom or coupling-releasable group
  • n1 represents an integer of 0 or 1.
  • R111 represents -CONR115R116, -NHCOR115, -NHCOOR117, -NHSO2R117, -NHCONR115R116 or -NHSO2NR115R116;
  • R112 represents a group which can be substituted by a naphthol ring;
  • m1 represents an integer of 0 to 3;
  • R113 represents a monovalent organic group;
  • X10 represents a hydrogen atom or a group which can be released by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, with the provisos that: (a) R115 and R116 may be the same or different and each independently represents a hydrogen atom, an aliphatic group having from 5 to 25 carbon atoms, an aromatic group having from 5 to 25 carbon atoms, or a heterocyclic group, (b) R117 represents an aliphatic group, an aromatic group or a heterocyclic group, (c) when m1 is a plural number, the plurality of R11
  • R101 and R102 each represents an aliphatic group having from 1 to 32 carbon atoms such as a methyl group, a butyl group, a tridecyl group, a cyclohexyl group and an allyl group; an aryl group such as a phenyl group and a naphthyl group; or a heterocyclic group such as a 2-pyridyl group, a 2-imidazolyl group, a 2-furyl group and a 6-quinolyl group.
  • These groups may be substituted by groups selected from an alkyl group; an aryl group; a heterocyclic group; an alkoxy group such as a methoxy group and a 2-methoxyethoxy group; an aryloxy group such as a 2,4-di-tert-amylphenoxy group, a 2-chlorophenoxy group and a 4-cyanophenoxy group; an alkenyloxy group such as a 2-propenyloxy group; an acyl group such as an acetyl group and a benzoyl group; an ester group such as a butoxycarbonyl group, a phenoxycarbonyl group, an acetoxy group, a benzoyloxy group, a butoxysulfonyl group and a toluenesulfonyloxy group; an amide group such as an acetylamino group, an ethylcarbamoyl group, a dimethylcarbamoyl group, a
  • R103 represents a hydrogen atom, a halogen atom, an aliphatic group having from 1 to 25 carbon atoms, an aryl group having from 1 to 25 carbon atoms, an acylamino group, or nonmetallic atomic groups which form a 5- or 6-membered nitrogen-containing ring together with R102.
  • R103 may have substitutable substituents which may be substituted by substituents as described with reference to R101.
  • n an integer of 0 or 1.
  • Z10 represents a hydrogen atom or coupling-releasable group.
  • a coupling-releasable group include a halogen atom such as fluorine, chlorine and bromine; an alkoxy group such as an ethoxy group, a dodecyloxy group, a methoxyethylcarbamoylmethoxy group, a carboxypropyloxy group and a methylsulfonylethoxy group; an aryloxy group such as a 4-chlorophenoxy group, a 4-methoxyphenoxy group and a 4-carboxyphenoxy group; an acyloxy group such as an acetoxy group, a tetradecanoyloxy group and a benzoyloxy group; a sulfonyloxy group such as a methanesulfonyloxy group and a toluenesulfonyloxy group; an amide group such as a dichlorophenoxy group, a
  • R101 include an aryl group and a heterocyclic group.
  • the aryl group may be preferably substituted by a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group or a cyano group.
  • R102 when R103 and R102 do not form a ring, R102 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group.
  • R103 is preferably a hydrogen atom.
  • Z10 include a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group and a sulfonamide group.
  • Z10 is preferably a halogen atom and particularly preferably fluorine or chlorine.
  • the cyan dye-forming coupler represented by the formula (L-I) is normally incorporated in a silver halide emulsion layer and particularly preferably in a red-sensitive emulsion layer.
  • the amount of such a cyan dye-forming coupler to be added is in the range of from 2 ⁇ 10 ⁇ 3 to 5 ⁇ 10 ⁇ 1 mol/mol-Ag and preferably 1 ⁇ 10 ⁇ 2 to 5 ⁇ 10 ⁇ 1 mol/mol-Ag.
  • the synthesis of the cyan dye-forming coupler represented by the formula (L-I) can be easily accomplished by any suitable method as described in U.S. Patents 3,772,002, 4,334,011, 4,327,173 and 4,427,767.
  • R111 has the same meaning as described above.
  • R115, R116 and R117 each represents an aliphatic group having from 1 to 30 carbon atoms, an aromatic group having from 6 to 30 carbon atoms or a heterocyclic group having from 2 to 30 carbon atoms.
  • R112 represents a group (or atom) which can substitute for a naphthol ring.
  • Typical examples of such a group or atom include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic group, a cyano group, an aromatic group, a heterocyclic group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group, an acyl group, an acyloxy group, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group, an aromatic thio group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group and an imide group.
  • the group represented by R112 contains 0 to 30 carbon atoms. When m
  • R113 represents a monovalent organic group.
  • a monovalent organic group is preferably represented by the following formula (L-III): R118(Y10) n 2 - (L-III) wherein Y10 represents ⁇ NH, ⁇ CO or ⁇ SO2; n2 represents an integer of 0 or 1; and R118 represents a hydrogen atom, an aliphatic group having from 1 to 30 carbon atoms, an aromatic group having from 6 to 30 carbon atoms, a heterocyclic group having from 2 to 30 carbon atoms, -OR119, -COR119, -CO2R121, -SO2R121 or -SO2R121 in which R119, R120 and R121 have the same meanings as R115, R116 and R117, respectively.
  • R115 and R116 in and R119 and R120 in may be connected to each other to form a nitrogen-containing heterocyclic group such as a morpholine ring, a piperidine ring and a pyrrolidine ring.
  • X10 represents a hydrogen atom or coupling-releasable group (or atom).
  • Typical examples of such a coupling-releasable group include a halogen atom, -OR125, -SR125, -NHCOR125, -NHSR125, an aromatic azo group having from 6 to 30 carbon atoms, and a heterocyclic group having from 1 to 30 carbon atoms connected to the coupling active position of a coupler through a nitrogen atom such as a succinic imide group, a phthalimide group, a hydantoinyl group, a pyrazolyl group and a 2-benzotriazolyl group.
  • R125 represents an aliphatic group having from 1 to 30 carbon atoms, an aromatic group having from 6 to 30 carbon atoms and a heterocyclic group having from 2 to 30 carbon atoms.
  • the aliphatic groups in the formula (L-II) may be saturated or unsaturated, substituted or unsubstituted, straight chain, branched or cyclic groups.
  • Typical examples of such an aliphatic group include a methyl group, an ethyl group, a butyl group, a cyclohexyl group, an allyl group, a propargyl group, a methoxyethyl group, an n-decyl group, an n-dodecyl group, an n-hexadecyl group, a trifluoromethyl group, a heptafluoropropyl group, a dodecyloxypropyl group, a 2,4-di-tert-amylphenoxypropyl group and a 2,4-di-tert-amylphenoxybutyl group.
  • aromatic groups in the formula (L-II) may be substituted or unsubstituted groups.
  • Typical examples of such an aromatic group include a phenyl group, a tolyl group, a 2-tetradecyloxyphenyl group, a pentafluorophenyl group, a 2-chloro-5-dodecyloxycarbonylphenyl group, a 4-chlorophenyl group, a 4-cyanophenyl group and a 4-hydroxyphenyl group.
  • heterocyclic group in the present invention may be a substituted or unsubstituted group.
  • Typical examples of such a heterocyclic group include a 2-pyridyl group, a 4-pyridyl group, a 2-furyl group, a 4-chienyl group and a quinolinyl group.
  • R111 is preferably -CONR115R116.
  • Specific examples of the group represented by -CONR115R116 include a carbamoyl group, an ethylcarbamoyl group, a morpholinocarbonyl group, a dodecylcarbamoyl group, a hexadecylcarbamoyl group, a decyloxypropyl group, a dodecyloxypropyl group, a 2,4-di-tert-amylphenoxypropyl group and a 2,4-di-tert-amylphenoxybutyl group.
  • R112 may be a halogen atom, an aliphatic group having from 1 to 30 carbon atoms, a carbonamide group or a sulfonamide group.
  • n2 is preferably 0. That is, the group represented by the formula (L-III) preferably has no Y10.
  • R118 include -COR119 such as a formyl group, an acetyl group, a trifluoroacetyl group, a chloroacetyl group, a benzoyl group, a pentafluorobenzoyl group and a p-chlorobenzoyl group; -COOR119 such as a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a decyloxycarbonyl group, a methoxyethoxycarbonyl group and a phenoxycarbonyl group; -SO2R121 such as a methanesulfonyl group, an ethanesulfonyl group, a butanesulfonyl group, a hexadecanesulfonyl group,
  • Preferred examples of X10 include a hydrogen atom, a halogen atom, an aliphatic oxy group having from 1 to 30 carbon atoms such as a methoxy group, a 2-methanesulfonamidoethoxy group, a 2-methanesulfonylethoxy group, a carboxymethoxy group, a 3-carboxypropyloxy group, a 2-carboxymethylthioethoxy group, a 2-methoxyethoxy group and a 2-methoxyethylcarbamoylmethoxy group; an aromatic oxy group such as a phenoxy group, a 4-chlorophenoxy group, a 4-methoxyphenoxy group, a 4-tert-octylphenoxy group and a 4-carboxyphenoxy group; a heterocyclic thio group such as a 5-phenyl-1,2,3,4-tetrazolyl-1-thio group and a 5-ethyl-1,2,3,
  • the couplers represented by the formula (L-II) may be connected to each other at the substituent R111, R112, R113 or X10 through a divalent or polyvalent group to form a dimer, oligomer or higher polymer.
  • the total number of carbon atoms contained in each substituent may be beyond the specified limit.
  • the coupler represented by the formula (L-II) forms a polymer
  • typical examples of such a polymer include a monopolymer or copolymer of addition polymerizable ethylenically unsaturated compounds (cyan dye-forming monomer) containing a cyan dye-forming coupler residual group.
  • cyan dye-forming monomer containing a cyan dye-forming coupler residual group.
  • Such a polymer contains repeating units represented by the formula (L-IV).
  • One or more cyan dye-forming repeating units represented by the formula (L-IV) may be contained in such a polymer.
  • Such a polymer may be a copolymer containing one or more noncoloring ethylenic monomers as copolymer components.
  • R10 represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms or a chlorine atom;
  • A10 represents -CONH-, -COO- or a substituted or unsubstituted phenylene group;
  • B10 represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group;
  • L10 represents -CONH-, -NHCONH-, -NHCOO-, -NHCO-, -OCONH-, -NH-, - COO-, -OCO-, -CO-, -O-, -SO2-, -NHSO2- or -SO2NH-;
  • a1, b1 and c1 each represents an integer of 0 or 1;
  • Q10 represents a cyan coupler residual group obtained by elimination of a hydrogen atom other than that in the hydroxyl group at the 1-position from the compound represented by the formula (L-II).
  • Preferred examples of such a polymer include a copolymer of a cyan dye-forming monomer providing a coupler unit represented by the formula (L-IV) and a noncoloring ethylenic monomer copolymer as described below.
  • Examples of a noncoloring ethylenic monomer which does not undergo coupling with an oxidation product of an aromatic primary amine developing agent include acrylic acid; ⁇ -chloroacrylic acid; ⁇ -alkylacrylic acid such as methacrylic acid; esters or amides derived from these acrylic acids such as acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetonacrylamide, methylacrylate, ethylacrylate, n-propylacrylate, n-butylacrylate, t-butylacrylate, isobutylacrylate, 2-ethylhexylacrylate, n-octylacrylate, laurylacrylate, methylmethacrylate, ethylmethacrylate, n-butylmethacrylate and ⁇ -hydroxymethacrylate; vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate; acrylonitrile;
  • acrylic ester methacrylic ester and maleic ester.
  • Two or more of such noncoloring ethylenic monomers may be used in combination. Examples of such a combination include methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid and methyl acrylate and diacetonacrylamide.
  • the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the compound of the formula (L-IV) can be selected such that it gives a favorable effect on physical and/or chemical properties of the copolymer formed, e.g., solubility, compatibility with binder for photographic colloidal composition such as gelatin, softening point, flexibility and heat stability.
  • the preparation of the cyan polymer coupler to be used in the present invention can be accomplished by dissolving in an organic solvent a lipophilic polymer coupler obtained by polymerization of vinyl monomers providing a coupler unit of the formula (L-IV), and then emulsion-dispersing the solution in an aqueous solution of gelatin in the form of a latex, or subjecting such a lipophilic polymer coupler to a direct emulsion polymerization.
  • the emulsion dispersion of such a lipophilic polymer coupler in an aqueous solution of gelatin in the form of a latex may be accomplished by any suitable method as described in U.S. Patent 3,451,820.
  • the emulsion polymerization of such a lipophilic polymer coupler may be accomplished by any suitable method as described in U.S. Patents 4,080,211 and 3,370,952.
  • couplers represented by the formula (L-II) are shown hereinafter, but the present invention should not be construed as being limited thereto.
  • (t)C5H11 and (t)C8H17 represent -C(CH3)2C2H5 and -C(CH3)2CH2C(CH2)3, respectively.
  • the synthesis of the coupler represented by the formula (L-II) can be accomplished by any suitable method as described in Japanese Patent Application(OPI) Nos. 237448/85, 153640/86, and 145557/86.
  • the coupler represented by the formula (L-II) may be normally incorporated in a silver halide emulsion layer.
  • the amount of the coupler to be added is preferably in the range of from 3 ⁇ 10 ⁇ 3 to 1 mol/mol-Ag, more preferably from 5 ⁇ 10 ⁇ 3 to 0.5 mol/mol-Ag, and particularly preferably from 0.01 to 0.25 mol/mol-Ag.
  • the incorporation of the present coupler and other couplers which can be used in combination therewith in the light-sensitive material can be accomplished by any known dispersion method.
  • dispersion methods include a solid dispersion method and an alkali dispersion method.
  • a preferred dispersion method is a latex dispersion method.
  • Typical examples of particularly preferred dispersion methods are an oil-in-water dispersion method.
  • the coupler is dissolved in either or a mixture of a high boiling point organic solvent having a boiling point of 175°C or more and a low boiling point solvent, i.e., auxiliary solvent, and the solution is then finely dispersed in water or an aqueous solvent such as an aqueous solution of gelatin in the presence of a surface active agent.
  • a high boiling point organic solvent such as an aqueous solution of gelatin in the presence of a surface active agent.
  • auxiliary solvent such as an aqueous solution of gelatin in the presence of a surface active agent.
  • the dispersion may be accompanied by phase inversion.
  • the auxiliary solvent may be removed or reduced by distillation, noodle rinsing, or ultrafiltration before the coupler is coated on the support.
  • the color developing solution to be used for the development of the present light-sensitive material is an alkaline aqueous solution comprising an aromatic primary amine color developing agent as a main component.
  • a useful example of such a color developing agent is an aminophenolic compound.
  • Preferably used is a p-phenylenediamine compound.
  • Typical examples of such a compound include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, and sulfates, hydrochlorides, phosphates, p-toluenesulfonates, tetraphenylborates, and p-(t-octyl)benzenesulfonates thereof.
  • These diamines are more stable in the form of salts than in the free state. Therefore, these diamines are preferably used in the form of salts.
  • aminophenolic derivatives which may be used in the present invention include o-aminophenol, p-aminophenol, 4-amino-2-methylphenyl, 2-amino-3-methylphenol and 2-oxy-3-amino-1,4-dimethylbenzene.
  • the color developing solution of the present invention may contain pH buffering agents such as carbonates, borates and phosphates of alkali metals; development inhibitors or antifoggants such as bromide, iodide, benzimidazoles, benzothiazoles and mercapto compounds; preservatives such as hydroxylamine, triethanolamine, compounds as described in West German Patent Application (OLS) No.
  • pH buffering agents such as carbonates, borates and phosphates of alkali metals
  • development inhibitors or antifoggants such as bromide, iodide, benzimidazoles, benzothiazoles and mercapto compounds
  • preservatives such as hydroxylamine, triethanolamine, compounds as described in West German Patent Application (OLS) No.
  • organic solvents such as diethylene glycol
  • development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, thiocyanate and 3,6-thiaoctane-1,8-diol
  • color-forming couplers such as sodium boron hydride
  • auxiliary developing agents such as 1-phenyl-3-pyrazolidone
  • tackifiers and chelating agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, aminopolycarboxylic acid and 1-hydroxyethylidene-1,1′-diphosphonic acid as described in Japanese Patent Application
  • the content of such a color developing agent to be incorporated in the normal color developing solution is in the range of about 0.1 g to about 30 g, and preferably about 1 g to about 15 g, per liter of the color developing solution.
  • the pH of the color developing solution is normally in the range of 7 or more and particularly about 9 to about 13.
  • the present silver halide color photographic material is normally subjected to washing and/or stabilization after being subjected to desilvering such as fixing or blixing.
  • the amount of water to be used in the washing process can be widely selected depending on the properties (different with components such as coupler) and use of the light-sensitive material, washing water temperature, number of washing tanks (stages), replenishing system of a replenisher (e.g., counter-current or cocurrent), and other various conditions.
  • a replenisher e.g., counter-current or cocurrent
  • the relationship between the number of washing tanks and the amount of water to be used in the washing process can be determined in accordance with a method as described in Journal of the Society of Motion Picture and Television Engineers , Vol. 64, pp. 248 to 253 (May, 1955).
  • chlorine bactericides such as sodium chlorinated isocyanurate
  • bactericides such as benzotriazole as described in Hiroshi Horiguchi, Chemistry of Bactericide and Antifungal Agents , Association of Sanitary Engineering, Sterilization of Microorganism, and Sterilization and Antifungal Engineering , and Japan Sterilization and Antifungal Association, Dictionary of Bactericide and Antifungal Agents .
  • the pH value of the washing water to be used in the processing of the present light-sensitive material is in the range of 4 to 9 and preferably 5 to 8.
  • the temperature of washing water and the washing time can be freely determined depending on the properties and application of the light-sensitive material.
  • the optimum washing time is normally between 20 seconds and 10 minutes at a temperature of 15 to 45°C, and preferably between 30 seconds and 5 minutes at a temperature of 25 to 50°C.
  • the present light-sensitive material may be processed directly with a stabilizing solution rather than by washing with water.
  • a stabilizing process known methods as described in Japanese Patent Application (OPI) Nos. 8543/82, 14834/83, 184343/84, 220345/85, 238832/85, 239784/85, 239749/85, 4054/86 and 118749/86 can all be used.
  • a stabilizing bath containing 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazoline-3-one, a bismuth compound, an ammonium compound, etc. may be preferably used in the present invention.
  • the washing process may be followed by a stabilizing process such as a stabilizing bath containing formalin and a surface active agent used as a final processing bath for color light-sensitive material for photography.
  • a stabilizing process such as a stabilizing bath containing formalin and a surface active agent used as a final processing bath for color light-sensitive material for photography.
  • the silver halide color photographic material to be used in the present invention is described hereinafter.
  • the emulsion layer in the light-sensitive material comprises silver bromoiodide having a content of silver iodide in the range of 40 mol% or less, preferably 20 mol% or less, an particularly 10 mol% or less.
  • the processing method of the present invention is further advantageous in that the bleaching of the light-sensitive material can be effectively accelerated even if the light-sensitive material contains silver iodide, which easily produces precipitation.
  • the above described particulate silver halide may have a regular crystal structure such as a cube, an octahedron and a tetradecahedron, an irregular crystal structure such as a sphere, a crystal structure having a crystal defect such as twinning plane, or a composite thereof. Alternatively, a mixture of grains of various crystal structure may be used.
  • the above described silver halide may be in the form of a monodispersed emulsion having a narrow distribution or a polydispersed emulsion having a wide distribution.
  • the above described emulsion layer may comprise tabular grains having an aspect ratio of 5 or more.
  • the crystal structure of the present silver halide grains may be uniform, or such that the halide composition varies between the inner portion and the outer portion thereof, or may be a layer.
  • These emulsion grains are disclosed in British Patent 1,027,146, U.S. Patents 3,505,068, 4,444,877, and 4,668,614.
  • silver halides having different compositions may be connected to each other by an epitaxial junction or by any suitable compound other than silver halide such as silver thiocyanate and zinc oxide.
  • the above described emulsion grains may be those of a surface latent image type in which latent images are formed mainly in the surface portion thereof or those of an internal latent image type in which latent images are formed mainly in the interior thereof.
  • the above described emulsion grains may have the interior thereof chemically sensitized.
  • a silver halide photographic emulsion which can be used in the present invention can be produced by well known methods, for example, methods as described in Research Disclosure , RD No. 17643, Vol. 176, pages 22 and 23, "Emulsion Preparation and Types” (December, 1978) and Research Disclosure , RD No. 18716, Vol. 187, page 648 (November, 1979).
  • the preparation of a silver halide photographic emulsion which can be used in the present invention can be accomplished by using various silver halide solvents such as ammonia, potassium thiocyanate, and thioether and thione as described in U.S. Patent 3,271,157 and Japanese Patent Application (OPI) Nos. 12360/76, 82408/78, 144319/78, 100717/79 and 155828/79.
  • various silver halide solvents such as ammonia, potassium thiocyanate, and thioether and thione as described in U.S. Patent 3,271,157 and Japanese Patent Application (OPI) Nos. 12360/76, 82408/78, 144319/78, 100717/79 and 155828/79.
  • a typical monodispersed emulsion is an emulsion of silver halide grains having an average grain diameter of more than about 0.1 »m in which the grain diameter of at least 95% by weight thereof falls within ⁇ 40% of the average grain diameter.
  • an emulsion of silver halide grains having an average grain diameter of 0.25 to 2 »m in which the grain diameter of at least 95% by weight or number of grains falls within ⁇ 20% of the average grain diameter may be used.
  • cadmium salts zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, or iron salts or complex salts thereof may coexist.
  • the emulsion to be used in the present invention may be normally subjected to physical ripening and then to chemical ripening and spectral ripening before use.
  • Examples of additives to be used in such processes are described in Research Disclosure , RD Nos. 17643 (December, 1978) and 18716 (November, 1979). The places where such a description is found are summarized in the table below.
  • spectral sensitizer for the present color photographic light-sensitive material there may be used any suitable spectral sensitizer selected from the above described known compounds.
  • exemplary compounds represented by the formula (IV) or (V) described in Japanese Patent Application No. 313598/86 (pp. 90-110) may be preferably used in the present processing process.
  • color couplers can be used in the present invention. Specific examples of such color couplers are described in patents cited in Research Disclosure , RD No. 17643 (VII-C to G).
  • An important dye-forming coupler is a coupler which provides three primaries of subtractive color processes, i.e., yellow, magenta and cyan upon color development.
  • Specific examples of a nondiffusible 4- or 2-equivalent dye-forming coupler of such a type include those described hereinafter besides those described in patents cited in Research Disclosure , RD No. 17643 (VII-C and D).
  • Typical examples of yellow couplers which may be used in the present invention include known oxygen-releasing type yellow couplers and nitrogen-releasing type yellow couplers.
  • ⁇ -Pivaloylacetanilide couplers are excellent in the fastness of color-forming dye, particularly in the fastness to light.
  • ⁇ -benzoylacetanilide couplers can provide a high color density.
  • magenta couplers which may be used in the present invention include hydrophobic 5-pyrazolone and pyrazoloazole couplers containing ballast groups.
  • Such 5-pyrazolone couplers preferably contain an arylamino group or an acylamino group as a substituent in the 3-position thereof in view of hue of the color-forming dye or color density.
  • cyan couplers which may be used in the present invention, in addition to the cyan dye-forming couplers as described above, hydrophobic nondiffusible naphthonic and phenolic couples may be used. Preferred examples of such cyan couplers include oxygen-releasing type 2-equivalent naphtholic couplers.
  • a coupler which provides a color-forming dye having a proper diffusibility may be used in combination with the above described couplers to improve the graininess.
  • Specific examples of such couplers include magenta couplers as described in U.S. Patent 4,366,237, and yellow, magenta and cyan couplers as described in European Patent 96,570.
  • the above described dye-forming couplers and special couplers may form a dimer or higher polymer.
  • Typical examples of polymerized dye-forming couplers are described in U.S. Patent 3,451,820.
  • Specific examples of polymerized magenta couplers are described in U.S. Patent 4,367,282.
  • Couplers which release a photographically useful residual group may be preferably used in the present invention.
  • Useful examples of DIR couplers which release a development inhibitor are described in patents cited in Research Disclosure , RD No. 17643 (VII-F).
  • the present light-sensitive material may comprise a coupler which imagewise releases a nucleating agent or a development accelerator or a precursor thereof upon development.
  • a coupler which imagewise releases a nucleating agent or a development accelerator or a precursor thereof upon development.
  • Specific examples of such a coupler are described in British Patents 2,097,140 and 2,131,188.
  • Other examples of such a coupler which may be used in the present invention include DIR redox compound-releasing couplers as described in Japanese Patent Application (OPI) No. 185950/85, and couplers which release a dye which restores color after coupling release as described in European Patent 173,302A.
  • the incorporation of the present couplers in the light-sensitive material can be accomplished by various known dispersion methods. Examples of high boiling point solvents which can be used in an oil-in-water dispersion method are described in U.S. Patent 2,322,027. Specific examples of the process and effects of the latex dispersion method and latex for such dispersion method are described in U.S. Patent 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
  • the light-sensitive material to be used in the present invention may contain as a color antifoggants or color stain inhibitors hydroquinone derivatives, aminophenol derivatives, amine derivatives, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamidophenol derivatives or the like.
  • the light-sensitive material to be used in the present invention may comprise a known discoloration inhibitor.
  • a known discoloration inhibitor include hindered phenols such as hydroquinones, 6-hydroxycoumarones, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols or bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating phenolic hydroxyl groups thereof.
  • metal complexes such as (bissalicylaldoximate)nickel complex and (bis-N,N-dialkyldithiocarbamate)nickel complex may be used.
  • the photographic emulsion layer and other layers may be coated on a flexible support such as plastic film commonly used for photographic light-sensitive materials.
  • the coating of the photographic emulsion layer and other layers onto the support can be accomplished by any suitable method such as a dip coating method, a roller coating method, a curtain coating method and an extrusion coating method.
  • the present invention can be applied to various color light-sensitive materials, for example, color light-sensitive materials for a color negative film for a motion picture, a color reversal film for a slide or TV, a color paper, a color positive film or a color reversal paper.
  • a multilayer color light-sensitive material Specimen 101 was prepared by coating various layers of the undermentioned compositions on the undercoated cellulose triacetate film support.
  • the coated amount of silver halide and colloidal silver are represented by g/m2 in terms of silver.
  • the coated amount of coupler, additive and gelatin are represented by g/m2.
  • the coated amount of sensitizing dye is represented in terms of molar number per mol of silver halide contained in the same layer.
  • Twelfth Layer High Sensitivity Blue-Sensitive Emulsion Layer
  • Second Protective Layer Second Protective Layer
  • Emulsion Stabilizer Cpd-3 and Surface Active Agent Cpd-4 were added to each of these layers as coating aids in amounts of 0.04 g/m2 and 0.03 g/m2, respectively. Furthermore, the undermentioned Compounds Cpd-5 and Cpd-6 were added to these layers in amounts of 0.5 g/m2.
  • Solv-1 Tricresyl phosphate
  • Solv-2 Dibutyl phthalate
  • Specimens 102 to 105 were then prepared in the same manner as in Specimen 101 except that the respective couplers for the third, fourth, sixth, seventh, eleventh and twelfth layers were replaced by those shown in the following Table I-1.
  • the coated amount of silver in these Specimens 101 to 105 were all in the range of 6.05 ⁇ 0.02 g/m2.
  • Color photographic light-sensitive material Specimens 101 to 105 thus prepared were then exposed to light and processed by means of an automatic developing machine in the following manner (until the cumulative supply of the color developing solution reached three times the volume of the mother liquor tank).
  • the replenished amount of replenisher is represented in terms of the amount replenished per m2 of the light-sensitive material.
  • composition of the processing solutions were as follows:
  • Blixing Solution (mother liquor was also used as replenisher) :
  • City water was passed through a mixed bed column filled with a strongly acidic H type cation exchange resin (Amberlite 1R-120B manufactured by Rohm & Haas Co.) and an OH type anion exchange resin (Amberlite 1R-400 manufactured by Rohm & Haas Co.) so that the concentration of calcium and magnesium ions were reduced to 3 mg/liter or less.
  • a strongly acidic H type cation exchange resin Amberlite 1R-120B manufactured by Rohm & Haas Co.
  • an OH type anion exchange resin Amberlite 1R-400 manufactured by Rohm & Haas Co.
  • the pH of the washing solution thus prepared was in the range of 6.5 to 7.5.
  • Stabilizing Solution (mother liquor was also used as replenisher) :
  • Specimen 101 was subjected to a continuous processing in the same manner as in Processing A except that the undermentioned bleaching accelerator was added to the bleaching solution (Processing B).
  • the added amount of this bleaching accelerator was 5 ⁇ 10 ⁇ 3 mol/liter-the bleaching solution.
  • Specimen 101 was also subjected to a continuous processing in the same manner as in Processing A except that the undermentioned bleaching accelerator was added to the bleaching solution (Processing C).
  • the added amount of this bleaching accelerator was 5 ⁇ 10 ⁇ 3 mol/liter-the bleaching solution.
  • specimens which had been exposed to light of 4,200°K 20 CMS were processed. These specimens thus processed were measured for the amount of residual silver by a fluorescent X-ray analysis method. After the continuous processings, the bleaching solution and the blixing solution were examined for the presence of any precipitate. The results are shown in Table I-2.
  • Table I-2 shows that the present light-sensitive material specimens can provide images having a small amount of residual silver even if processed with a lesser amount of the processing solution replenished at the desilvering step. The results also show that the present light-sensitive material specimens leave a small amount of precipitate in the processing solution.
  • Specimens 106 and 107 having different coated amounts of silver from Specimen 104 were prepared in the same manner as in Specimen 104 except that the coated amount of each layer was changed. These specimens were then subjected to a continuous processing in the same manner as in Processing A of Example I-1.
  • Example I-3 In the same manner as in Example I-1, these specimens were examined for the amount of residual silver at the beginning, the middle and the end of the continuous processing. These specimens were also checked for the presence of precipitate in the bleaching solution and the blixing solution after being processed. The results are shown in Table I-3.
  • Example I-3 shows that the light-sensitive material specimens having 3.5 to 10.2 g of silver coated per m2 provide excellent results.
  • Specimens 101 to 105 prepared in Example I-1 were exposed to light and then processed by means of an automatic developing machine in the following manner (until the cumulative amount of the color developing solution reached three times the volume of the mother liquor tank).
  • the replenished amount of replenisher is represented by the value per unit length of the specimen (1 m).
  • compositions of the processing solutions are described hereinafter.
  • the color developing solution, the bleaching solution, the washing solution and the stabilizing solution were each prepared in the same manner as in Example I-1.
  • Specimens 101 to 105 prepared in Example I-1 were exposed to light and then processed by means of an automatic developing machine in the following manner (until the cumulative replenished amount of the processing solution reached three times the volume of the mother liquor tank).
  • the replenished amount of replenisher is represented by the amount supplied per unit length of the specimen (1 m).
  • composition of the processing solutions is described hereinafter.
  • a color photographic light-sensitive material Specimen 201 was prepared by coating the undermentioned first layer to twelfth layer on a paper support having polyethylene laminated on both surfaces thereof.
  • the polyethylene contains titanium white as a white pigment and a slight amount of ultramarine as a bluish dye at the side thereof on which the first layer was coated.
  • the coated amount of each composition is represented by g/m2.
  • the coated amount of silver halide is represented in terms of amount of silver.
  • Second Layer Antihalation Layer
  • Specimens 202 to 204 were prepared in the same manner as described above except that cyan coupler (*3) in the third and fourth layers, magenta coupler (*15) in the sixth and seventh layers and yellow coupler (*21) in the ninth and tenth layers were replaced by the compounds shown in Table I-6.
  • the coated amounts of silver in Specimens 201 to 204 were all in the range of 1.29 ⁇ 0.01 g per m2 of the specimen.
  • Specimen 205 was then prepared in the same manner as Specimen 204 except that the coated amount in each layer was 1.5 times that of Specimen 204 (coated amount of silver: 1.93 g/m2).
  • the silver halide color photographic material Specimens 201 to 205 thus prepared were then exposed to light and processed by means of an automatic developing machine in the following manner until the cumulative replenished amount of the color developing solution reached three times the capacity of the mother liquor tank.
  • the first washing step and the third washing step were conducted in a countercurrent system. That is, first washing solution was replenished into the first washing tank (2). The overflow from the first washing tank (2) was introduced into the first washing tank (1). Second washing solution was replenished into the second washing tank (3). The overflow from the second washing tank (3) was introduced into the second washing tank (2). The overflow from the second washing tank (2) was introduced into the second washing tank (1).
  • composition of the processing solutions were as follows:
  • Second Washing Solution (mother liquor was also used as replenisher) :
  • City water was passed through a mixed bed column filled with a strongly acidic H type cation exchange resin (Amberlite 1R-120B manufactured by Rohm & Haas Co.) and an OH type anion exchange resin (Amberlite 1R-400 manufactured by Rohm & Haas Co.) so that the concentration of calcium and magnesium ions were reduced to 3 mg/liter or less.
  • a strongly acidic H type cation exchange resin Amberlite 1R-120B manufactured by Rohm & Haas Co.
  • an OH type anion exchange resin Amberlite 1R-400 manufactured by Rohm & Haas Co.
  • Table I-7 shows that the present processing method leaves a small amount of residual silver and provides an excellent image having a low minimum density in the same manner as Example I-1. However, Specimen 205 having much silver coated thereon shows an increase in the amount of residual silver.
  • a multilayer color photographic light-sensitive material Specimen 301 was prepared by coating various layers of the undermentioned compositions on an undercoated cellulose triacetate film support.
  • the coated amount of silver halide and colloidal silver are represented by g/m2 in terms of silver.
  • the coated amount of coupler, additive and gelatin are represented by g/m2.
  • the coated amount of sensitizing dye is represented in terms of molar number per mol of silver halide contained in the same layer.
  • Second Red-Sensitive Emulsion Layer Second Red-Sensitive Emulsion Layer
  • Second Protective Layer Second Protective Layer
  • a surface active agent was added to each layer as a coating aid.
  • Oil-1 Tricresyl phosphate
  • Oil-2 Dibutyl phthalate
  • Oil-3 Bis(2-ethylhexyl) phthalate
  • Specimens 302 to 316 were prepared in the same manner as in Specimen 301 except that Coupler C-9 in the seventh, eighth and ninth layers was replaced by the couplers shown in Table II-1 and Coupler C-3 and Coupler C-4 in the third, fourth and fifth layers were replaced by the couplers shown in Table II-1.
  • the coated amount of these couplers in these specimens are represented in terms of the weight (g) per m2 of the specimen.
  • Specimens 301 to 316 thus prepared were processed in the following manner:
  • washing steps 1 and 2 were conducted in a countercurrent system in which water flows from the tank 2 to the tank 1.
  • the composition of the processing solutions used in Processing (A) will be described hereinafter.
  • the specimens were processed with the above described processing solutions and washing solution in the above described processing steps. The results were compared.
  • Processing (B) was conducted in the same manner as Processing (A) except that NH4[Fe(III) (EDTA)] and EDTA ⁇ 2Na in the blixing solution were replaced by the equimolecular amounts of NH4[Fe(III)(DTPA)] (ferric ammonium diethylenetriaminepentaacetate) and diethylenetriaminepentaacetic acid as bleaching agents.
  • Processing (C) was conducted in the same manner as Processing (A) except that ammonium iodide was added to the blixing solution in an amount of 1.20 g/liter, the light-sensitive material specimens were not exposed to light, and the blixing was conducted for 2 minutes. Thus, the fixation of unexposed silver halide was examined.
  • Processing (D) was conducted in the same manner as Processing (B) except that ammonium iodide was added to the blixing solution in an amount of 1.20 g/liter, the light-sensitive material specimens were not exposed to light, and the blixing was conducted for 2 minutes.
  • Processing (E) was conducted in the same manner as Processing (A) except that 2-mercapto-1,3,4-triazole was added to the blixing solution as a known bleaching accelerator in an amount of 0.40 g/liter.
  • Processing (F) was conducted in the same manner as Processing (E) except that ammonium iodide was added to the blixing solution in an amount of 1.2 g/liter, the light-sensitive material specimens were not exposed to light, and the blixing was conducted for 2 minutes.
  • Table II-2 shows many interesting results.
  • the use of the present bleaching accelerator-releasing couplers provides excellent images with a lesser amount of residual silver both in Processings (A) and (B) as compared to the case where the present bleaching accelerator-releasing couplers are not used.
  • an unexpected result was obtained in the examination of the fixing capability in Processings (C) and (D).
  • the blixing solution is worse in the fixing capability when it comprises a ferric diethylenetriaminepentaacetate complex salt (DTPA ⁇ Fe) as a bleaching agent than when it comprises a ferric ethylenediaminetetraacetate (EDTA ⁇ Fe).
  • DTPA ⁇ Fe ferric diethylenetriaminepentaacetate complex salt
  • the fixing capability is further deteriorated when the blixing solution contains a known bleaching accelerator.
  • the light-sensitive materials comprising the present bleaching accelerator-releasing couplers give a surprising result.
  • the light-sensitive materials comprising the present bleaching accelerator-releasing couplers exhibit a better fixing capability when DTPA ⁇ Fe is used than when no DTPA ⁇ Fe is used.
  • the blixing solution comprising a DTPA Fe (Processing (B)) is less susceptible to sulfurization and more excellent in stability than the blixing solution comprising EDTA Fe (Processing (A)).
  • Example II-1 The specimens prepared in Example II-1 were stored at a temperature of 80°C and a relative humidity of 70% for 7 days, and then examined for cyan density. On the other hand, the same specimens were rebleached with a processing solution ("CN-16 N2", manufactured by Fuji Photo Film Co., Ltd.) at a temperature of 38°C for 10 minutes, and then examined for deterioration in color restoration. The results are shown in Table II-3. Table II-3 shows that the use of the cyan dye-forming couplers represented by the formulae (L-I) and (L-III) gives excellent results in preservation of cyan images and color restoration.
  • a multilayer color light-sensitive material specimen 401 was prepared by coating various layers of the undermentioned compositions on an undercoated cellulose triacetate film support.
  • Oil-1′ Ditutyl phthalate
  • Specimens 402 to 404 were prepared in the same manner as in Specimen 401 except that Coupler C-4′ to be contained in the ninth, tenth and eleventh layers of Specimen 401 and Coupler C-5 to be contained in the fourteenth and fifteenth layers of Specimen 401 were replaced by the couplers shown in Table II-4 in equimolecular amounts.
  • Specimens 401 to 404 thus prepared were processed in the undermentioned Processing Steps (G), (H), (I) and (J). These specimens had been previously exposed to light of 100 CMS and 4,200°K.
  • composition of the processing solutions used were as follows:
  • City water was passed through a mixed bed column filled with a strongly acidic H type cation exchange resin (Amberlite 1R-120B, manufactured by Rohm & Haas Co.) and an OH type anion exchange resin (Amberlite 1R-400, manufactured by Rohm & Haas Co.) so that the concentration of calcium and magnesium ions were reduced to 3 mg/liter or less.
  • a strongly acidic H type cation exchange resin Amberlite 1R-120B, manufactured by Rohm & Haas Co.
  • an OH type anion exchange resin Amberlite 1R-400, manufactured by Rohm & Haas Co.
  • Processing Step (H) was conducted in the same manner as Processing Step (G) except that ferric ammonium ethylenediaminetetraacetate (dihydrate) to be incorporated in the blixing solution was replaced by the equimolecular amount of ferric ammonium ethylenetriaminepentaacetate.
  • Processing Step (I) was conducted in the same manner as Processing Step (G) except that ferric ammonium ethylenediaminetetraacetate (dihydrate) to be incorporated in the blixing solution was replaced by the equimolecular amount of ferric ammonium cyclohexanediaminetetraacetate.
  • Processing Step (J) was conducted in the same manner as Processing Step (G) except that ferric ammonium ethylenediaminetetraacetate (dihydrate) to be incorporated in the blixing solution was replaced by the equimolecular amount of ferric ammonium 1,2-propylenediaminetetraacetate.
  • Specimens 401 to 404 thus processed were examined for fluorescent X-ray analysis for the amount of residual silver in the light-sensitive material. The results are shown in Table II-5.
  • Table II-5 shows that Specimen 402 to 404 exhibit excellent results with a small amount of residual silver when processed in Processing Steps (H) to (J) of the present invention.
  • a method for the processing of a silver halide color photographic material which provides an excellent blixing capability,particularly fixing capability, and a high stability in the blixing solution can be accomplished.
  • the present invention enables a very rapid desilvering of a color light-sensitive material. This rapidness can be further effectively attained by the combined use of a cyan dye-forming coupler represented by the formulae (L-I) or (L-II).
  • the present invention also enables an improvement in color restoration and image stability.

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  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (10)

  1. Procédé pour le traitement d'un matériau photographique couleur à l'halogénure d'argent comprenant une couche d'émulsion de bromoiodure d'argent ayant une teneur en iodure d'argent de 40 mol % ou moins, ce procédé comprenant l'exposition du matériau photosensible photographique couleur à l'halogénure d'argent à la lumière suivant une image, le développement chromogène du matériau photosensible et ensuite l'élimination de l'argent du matériau photosensible, dans lequel :
    (a) ledit matériau photosensible photographique couleur à l'halogénure d'argent contient un composé qui réagit avec le produit d'oxydation de l'agent développateur chromogène du type amine primaire aromatique en libérant un accélérateur de blanchiment,
    (b) ladite étape d'élimination de l'argent est effectuée avec une solution de traitement contenant un sel complexe ferrique d'un acide organique et
    (c) la quantité totale de régénérateur de la solution de traitement à utiliser dans l'étape d'élimination de l'argent satisfait l'une ou l'autre des conditions (i) et (ii) suivantes :
    (i) la quantité totale de régénérateur est de 100 à 700 ml/m² dudit matériau photosensible si la quantité d'argent déposée est de 2,0 à 20 g/m² dudit matériau photosensible ;
    (ii) la quantité totale de régénérateur est de 50 à 300 ml/m² dudit matériau photosensible si la quantité d'argent déposée est de 0,3 à moins de 2.0 g/m² dudit matériau photosensible.
  2. Procédé selon la revendication 1, dans lequel ladite étape d'élimination de l'argent est effectuée avec une solution de traitement ayant une activité de blanchiment ou une solution de traitement subséquent ayant une activité de blanchiment-fixage.
  3. Procédé selon la revendication 1, dans lequel ladite étape d'élimination de l'argent est effectuée avec une solution de traitement ayant une activité de blanchiment-fixage.
  4. Procédé selon la revendication 3, dans lequel la solution de traitement ayant une activité de blanchiment-fixage contient un aminopolycarboxylate ferrique complexe dérivé d'un acide aminopolycarboxylique ayant un poids moléculaire de 300 ou plus sous la forme d'un acide libre.
  5. Procédé selon la revendication 1, dans lequel ledit matériau photographique couleur à l'halogénure d'argent contient au moins un coupleur chromogène pour cyan choisi parmi les composés représentés par les formules (L-I) et (L-II) :
    Figure imgb0510
     dans laquelle R₁₀₁ et R₁₀₂ représentent chacun un groupe aliphatique, un groupe aryle ou un groupe hétérocyclique ; R₁₀₃ représente un atome d'hydrogène, un atome d'halogène, un groupe aliphatique, un groupe aryle, un groupe acylamino ou un groupe atomique non métallique formant avec R₁₀₂ un cycle azoté à 5 ou 6 chaînons ; Z₁₀ représente un atome d'hydrogène ou un groupe éliminable par couplage ; et n₁ est égal à 0 ou 1 ;
    Figure imgb0511
     dans laquelle R₁₁₁ représente -CONR₁₁₅R₁₁₆, -NHCOR₁₁₅, NHCOOR₁₁₇, -NHSO₂R₁₁₇, -NHCONR₁₁₅R₁₁₆ ou -NHSO₂NR₁₁R₁₁₆ ; R₁₁₂ représente un groupe qui peut être substitué par un noyau naphtol ; m₁ représente un entier de 0 à 3 ; R₁₁₃ représente un groupe organique monovalent ; et X₁₀ représente un atome d'hydrogène ou un groupe qui peut être éliminé par une réaction de couplage avec le produit d'oxydation de l'agent développateur du type amine primaire aromatique, avec les conditions que :
    (a) R₁₁₅ et R₁₁₆ peuvent être les mêmes ou différents et représentent chacun indépendamment un atome d'hydrogène, un groupe aliphatique, un groupe aromatique ou un groupe hétérocyclique,
    (b) R₁₁₇ représente un groupe aliphatique un groupe aromatique ou un groupe hétérocyclique,
    (c) lorsque m₁ est supérieur à un, les restes R₁₁₂ peuvent être les mêmes ou différents ou peuvent être reliés l'un à l'autre pour former un cycle et
    (d) R₁₁₂ et R₁₁₃ ou R₁₁₃ et X₁₀ peuvent être reliés l'un à l'autre pour former un cycle.
  6. Procédé selon la revendication 4, dans lequel le sel complexe ferrique est un sel complexe de diéthylènetriaminepentaacétate ferrique.
  7. Procédé selon la revendication 1, dans lequel le composé qui libère un accélérateur de blanchiment est un composé représenté par la formule (I) :

            A₀-(L₀)p-Z₀   (I)

    dans laquelle A₀ représente un groupe qui réagit avec le produit d'oxydation de l'agent développateur en provoquant la coupure de la liaison (L₀)p-Z₀ ; L₀ représente un groupe retardateur ou un groupe qui réagit avec le produit d'oxydation de l'agent développateur en provoquant la coupure de la liaison avec Z₀ ; Z₀ représente un groupe qui a pour effet d'accélérer le blanchiment après la coupure de sa liaison avec A₀-(L₀) ; et p représente un entier de 0 à 3, avec la condition que lorsque p est supérieur à 1, les restes L₀ peuvent être les mêmes ou différents.
  8. Procédé selon la revendication 1, dans lequel le composé qui libère l'accélérateur de blanchiment est un composé représenté par la formule (I′) :

            A₁-(L₁)a-(L₂)b-Z₁   (I′)

    dans laquelle A₁ représente un groupe qui réagit avec le produit d'oxydation de l'agent développateur en provoquant la coupure de la liaison (L₁)a-(L₂)b-Z₁ ; L₁ représente un groupe retardateur ou un groupe qui réagit avec le produit d'oxydation de l'agent développateur en provoquant la coupure de la liaison (L₂)b-Z₁ ; L₂ représente un groupe retardateur ou un groupe qui réagit avec le produit d'oxydation de l'agent développateur en provoquant la coupure de la liaison avec Z₁ ; Z₁ représente un groupe qui a pour effet d'accélérer le blanchiment après coupure de sa liaison avec A₁-(L₁)a-(L₂)b ; et a et b représentent chacun 0 ou 1.
  9. Procédé selon la revendication 1, dans lequel la teneur en iodure d'argent de ladite couche d'émulsion de bromoiodure d'argent est de 20 mol % ou moins.
  10. Procédé selon la revendication 1, dans lequel la teneur en iodure d'argent de ladite couche d'émulsion de bromoiodure d'argent est de 10 mol % ou moins.
EP88105892A 1987-04-14 1988-04-13 Procédé de traitement d'un matériau photographique à l'halogénure d'argent Expired - Lifetime EP0287073B1 (fr)

Applications Claiming Priority (4)

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JP89821/87 1987-04-14
JP8982187A JPS63256953A (ja) 1987-04-14 1987-04-14 ハロゲン化銀カラ−写真感光材料の処理方法
JP9543287A JPS63261359A (ja) 1987-04-20 1987-04-20 ハロゲン化銀カラ−写真感光材料の処理方法
JP95432/87 1987-04-20

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US5352568A (en) * 1988-02-15 1994-10-04 Konica Corporation Processing method and bleaching solution for silver halide color photographic light-sensitive materials
US5234801A (en) * 1989-07-24 1993-08-10 Fuji Photo Film Co., Ltd. Processing of silver halide color photographic material
GB0206089D0 (en) 2002-03-15 2002-04-24 Eastman Kodak Co Colour photographic element containing a heterocyclic dye-forming coupler
GB0211049D0 (en) 2002-05-15 2002-06-26 Eastman Kodak Co Protection of photographic material

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US3828172A (en) 1973-06-04 1974-08-06 Eastman Kodak Co Replenishment controller for photographic processors
US4434226A (en) 1981-11-12 1984-02-28 Eastman Kodak Company High aspect ratio silver bromoiodide emulsions and processes for their preparation
JPS6023857A (ja) * 1983-07-20 1985-02-06 Fuji Photo Film Co Ltd ハロゲン化銀カラ−感光材料の処理方法
EP0161626B1 (fr) * 1984-05-10 1990-12-05 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
JPS60250344A (ja) * 1984-05-26 1985-12-11 Fuji Photo Film Co Ltd カラ−写真感光材料
JPS6161160A (ja) 1984-08-31 1986-03-28 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
CA1287765C (fr) * 1985-02-28 1991-08-20 Eastman Kodak Company Materiau photographique colorant et methode englobant un compose a decharge d'agent accelerateur de blanchiment
JPH07120028B2 (ja) 1985-12-13 1995-12-20 富士写真フイルム株式会社 ハロゲン化銀カラ−写真感光材料の処理方法

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EP0287073A2 (fr) 1988-10-19

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