EP0287073B1 - Method for processing a silver halide photographic material - Google Patents

Method for processing a silver halide photographic material 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
European Patent Office
Prior art keywords
group
light
bleaching
processing
sensitive material
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EP88105892A
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German (de)
French (fr)
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EP0287073A2 (en
EP0287073A3 (en
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/en
Priority claimed from JP9543287A external-priority patent/JPS63261359A/en
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0287073A2 publication Critical patent/EP0287073A2/en
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.

Description

    FIELD OF THE INVENTION
  • 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.
    • BACKGROUND OF THE INVENTION
  • In general, the processing of a color light-sensitive material essentially consists of a color developing step and a desilvering step. In the color developing step, silver halide which has been exposed to light is reduced by a color developing agent to produce silver. At the same time, 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. Examples of such auxiliary steps include a hardening step, a stopping step, an image stabilizing step, and a washing step.
  • In recent years, the industry has seen a growing demand for rapid processing, i.e., shorter time required for processing, especially at the desilvering step, which accounts for the majority of the total processing time.
  • As bleaching agents there have generally been known red prussiate, bichromate, ferric chloride, ferric aminopolycarboxylate complex, and persulfate.
  • However, 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.
  • However, it cannot always be said that ferric aminopolycarboxylate has a sufficient bleaching capability.
  • As a means of expediting the desilvering process there has heretofore been known a combined blixing solution containing ferric aminopolycarboxylate and thiosulfate as described in West German Patent 866,605. However, such a combined blixing solution has a disadvantage in that the coexistence of a ferric aminopolycarboxylate complex, which has a weak oxidizing power (bleaching power), with a thiosulfate having a reducing power provides a much weaker bleaching power, making it extremely difficult to fully desilver a color light-sensitive material for photography having a high sensitivity and a high silver content, in particular.
  • Furthermore, if 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, in order to protect the environment, save costs, and simplify the processing, 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. Thus, it was found that a reduction in the amount of replenisher of the processing solution to be used in the desilvering process causes many difficulties.
  • On the other hand, as a method of improving the bleaching power there has been proposed a method which comprises adding various bleaching accelerators to the bleaching bath, blixing bath, or previous bath (prebath) thereof. Examples of such 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. 9854/78, isothiourea derivatives as described in Japanese Patent Application (OPI) No. 94927/78, thiourea derivatives as described in Japanese Patent Application (OPI) No. 8506/70, and Japanese Patent Publication No. 26586/74, thioamide compounds as described in Japanese Patent Publication No. 42349/74, dithiocarbamate as described in Japanese Patent Application (OPI) No. 26506/80, and arylenediamine compounds as described in U.S. Patent 4,552,834.
  • It is certain that among these bleaching agents, those showing a bleach accelerating effect are present. However, 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.
  • Furthermore, if 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.
  • Thus, 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.
  • Furthermore, 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.
  • As described above, the use of such a mercapto bleaching accelerator in the processing solution or its prebath to be used in the desilvering process has many limitations.
  • On the other hand, there has been known a process which comprises processing a light-sensitive material containing such a mercapto compound or its precursor as described in Japanese Patent Application (OPI) Nos. 135834/87 and 80649/87. However, if such a mercapto compound is contained in a light-sensitive material, it may greatly affect the photographic properties, and silver halide contained in unexposed portions in the light-sensitive material and such a mercapto compound form a sparingly soluble salt. Thus, this approach leaves much to be desired.
    • SUMMARY OF THE INVENTION
  • 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.
  • These objects of the present invention are accomplished by providing 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:
    • (a) said silver halide color photographic light-sensitive material contains a compound which reacts with an oxidation product of an aromatic primary amine color developing agent to release a bleaching accelerator,
    • (b) said desilvering step is conducted with a processing solution containing a ferric complex salt of an organic acid, and
    • (c) the total amount of replenisher of the processing solution to be used in said desilvering step satisfies either of the following conditions (i) or (ii):
      • (i) the total amount of replenisher is from 100 to 700 ml per m² of said light-sensitive material if the coated amount of silver per m² of said light-sensitive material is from 2.0 to 20 g;
      • (ii) the total amount of replenisher is from 50 to 300 ml per m² of said light-sensitive material if the coated amount of silver per m² of said light-sensitive material is from 0,3 to less than 2.0 g.
    DETAILED DESCRIPTION OF THE INVENTION
  • 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.
  • Further, the present inventors found that these objects of the present invention are accomplished by 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.
  • On the other hand, Research Disclosure, RD Nos. 24242 and 11449, and Japanese Patent Application (OPI) No. 201247/86 describe methods using bleaching accelerator-releasing couplers. In the above described processing method, however, the light-sensitive material is bleached and then fixed after being color-developed. Since such a bleaching accelerator is stable in a bleaching solution so long as the replenished amount of the bleaching solution is in the normal range, the effect of the bleaching accelerator in the case where such a bleaching accelerator-releasing compound is used is similar to that of the case where such a bleaching accelerator is incorporated in the bleaching solution. Thus, the above described method provides no special effects. Furthermore, there has been no teaching that the use of a high molecular weight ferric aminopoly-carboxylate complex salt providing a stable blixing solution as described herein can further eliminate the deterioration in the blixing capability, particularly in the fixing capability.
  • 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. However, it was found that 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.
  • When a light-sensitive material containing the present bleaching accelerator-releasing coupler is color-developed, 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. If such a light-sensitive material which has been color-developed is washed with water, and then processed with a processing solution having a blixing capability, the bleach accelerating effect is disadvantageously eliminated. In order to prevent such an elimination of the bleach accelerating effect when the light-sensitive material is not 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 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. In the present invention, 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. In the present invention, 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).
  • Examples of such a combination include the following:
    • (1) Bleaching-Fixing
    • (2) Bleaching-Blixing
    • (3) Blixing
    • (4) Fixing-Blixing
    • (5) Bleaching-Blixing-Fixing
    • (6) Blixing-Bleaching
    • (7) Blixing-Fixing

    In view of the rapid processing, preferred among these combinations is the combination (2) as described in Japanese Patent Application (OPI) No. 143755/86. Also, the combination (3) having less steps may be preferably used for the purpose of simplifying the processing.
  • In the present invention, 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-(L1)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.
  • In the formulae (I) and (I′), A₀ and A₁ particularly represent coupler residual groups or oxidation reduction groups.
  • As such coupler residual groups represented by A₀ and A₁, known coupler residual groups can be used. Examples of such 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. Other preferred examples of such 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.
  • Preferred examples of the 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.
    Figure imgb0001
    Figure imgb0002
    Figure imgb0003
    Figure imgb0004
    Figure imgb0005
    Figure imgb0006
    Figure imgb0007
    Figure imgb0008
    Figure imgb0009
    Figure imgb0010
  • In these formulae, the free bond stemming from the coupling position represents the position at which a coupling-off group is bonded to the coupler.
  • In these formulae, if 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. If 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.
  • The substituents R₅₁ to R₆₃ and the suffixes d and e are further described hereinafter. 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
    Figure imgb0011
    group, an
    Figure imgb0012
    group, an
    Figure imgb0013
    group, an R₄₁S- group, an R₄₃O- group, an
    Figure imgb0014
    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
    Figure imgb0015
    group, or an
    Figure imgb0016
    group, R₅₈ represents the same group as R₄₁. R₅₉ represents the same group as R₄₁ or represents an
    Figure imgb0017
    group, an
    Figure imgb0018
    group, an
    Figure imgb0019
    group, an
    Figure imgb0020
    group, an R₄₁O- group, an R₄₁S- group, a halogen atom, or an
    Figure imgb0021
    group. The suffix d represents an integer of 0 to 3. When d is a plural number, 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:
    Figure imgb0022
    Figure imgb0023
    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
    Figure imgb0024
    group, an
    Figure imgb0025
    group, an R₄₃O- group, an R₄₁S- group, a halogen atom, or an
    Figure imgb0026
    group. R₆₃ represents the same group as R₄₁ or represents an
    Figure imgb0027
    group, an
    Figure imgb0028
    group, an
    Figure imgb0029
    group, an
    Figure imgb0030
    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.
  • In the foregoing description, 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.
  • When the above described aliphatic hydrocarbon group, aromatic group and heterocyclic group contain substituents, typical examples of such substituents include halogen atoms, an R₄₇O- group, an R₄₆S- group, an
    Figure imgb0031
    group, an
    Figure imgb0032
    group, an
    Figure imgb0033
    group, an
    Figure imgb0034
    group, an
    Figure imgb0035
    group, an R₄₆SO₂- group, an R₄₇OCO- group, an
    Figure imgb0036
    group, a group having the same meaning as R₄₆, an
    Figure imgb0037
    group, an R₄₆COO- group, an R₄₇OSO₂- group, a cyano group, and a nitro group. In the above described formulae, R₄₆ represents an aliphatic group, an aromatic group or a heterocyclic group, and 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.
  • Preferred examples of R₅₁ to R₆₃, and d and e will be described hereinafter.
  • 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
    Figure imgb0038
    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.
    In the formula (Cp-6), 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. In the formula (Cp-7), R₅₉ is preferably an R₄₁CONH- group. In the formula (Cp-7), the suffix d is preferably 1. R₆₁ is preferably an aliphatic group or an aromatic group. In the formula (Cp-8), 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. In the formula (Cp-9), R₆₃ is preferably an R₄₁CONH- group, an R₄₁SO₂NH- group, an
    Figure imgb0039
    group, an R₄₁SO₂- group, an
    Figure imgb0040
    group, a nitro group or a cyano group. In the formula (Cp-10), R₆₃ is preferably an
    Figure imgb0041
    group, an R₄₃CCO- group or an R₄₃CO- group.
  • Typical examples of R₅₁ to R₆₃ will be described hereinafter.
  • Examples of R₅₁ 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. Examples of R₅₂ and R₅₃ 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-dichlorophenyl group, a 2-chloro-5-(1-dodecyloxycarbonylethoxycarbonyl)phenyl group, a 2-chlorophenyl group and a 2-ethoxyphenyl group.
  • Examples of R₅₄ 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. Preferred examples of R₅₅ 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. Examples of R₅₆ 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. Examples of R₅₇ 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]ethyl group and a dodecylthio group. Examples of R₅₈ 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. Examples of R₅₉ 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. Examples of R₆₀ 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. Examples of R₆₁ 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. Examples of R₆₂ 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. Examples of R₆₃ 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.
  • If A₀ in the formula (I) represents an oxidation reduction group, the present compound is specifically represented by the formula (II):

            A₁₁-P-(X=Y)n-Q-A₁₂   (II)


    wherein P and Q each independently represents an oxygen atom or a substituted or unsubstituted imino group; at least one of n number of X and Y represents a methine group containing -(L₁)a-(L₂)b-Z₁ as a substituent and the other X and Y each represents a substituted or unsubstituted methine group or a nitrogen atom; n represents an integer of 1 to 3 (n number of X and Y may be the same or different); and A₁₁ and A₁₂ each represents a hydrogen atom or a group removable by an alkali. 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. For example, (X=Y)n may form a benzene ring or a pyridine ring.
  • When 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.
  • In this case, P and Q are each represented by the following formulae:
    Figure imgb0042
    Figure imgb0043
    wherein the mark * represents the position at which the imino group is bonded to A₁₁ or A₁₂ and the mark ** represents the position at which the imino group is bonded to one of the free bonds of (̵X=Y
    Figure imgb0044
    .
  • In the above described formulae, 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 and a benzochienyl group.
  • In the formula (II), P and Q preferably each independently represents an oxygen group or a group represented by the formula (N-1).
  • When A₁₁ and A₁₂ each represents a group removable by an alkali (hereinafter referred to as "precursor group"), preferred examples of such 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.
  • In the formula (II), P is preferably an oxygen atom, and A₁₂ is preferably a hydrogen atom.
  • In the formula (II), 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):
    Figure imgb0045
    Figure imgb0046
    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. Examples of such a cyclic structure 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
    Figure imgb0047
    group, an R₄₃OOC- group, an R₄₁SO₂- group, an
    Figure imgb0048
    group, an
    Figure imgb0049
    group, an
    Figure imgb0050
    group, R₄₃CO- group, an R₄₁COO- group, an
    Figure imgb0051
    group, a cyano group and an
    Figure imgb0052
    group.
  • In the above described formulae, 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 represented by the formula:
    Figure imgb0053
  • In the formulae (III) and (IV), P and Q each preferably represents an oxygen atom.
  • In the formulae (III) and (IV), A₁₁ and A₁₂ each preferably represents a hydrogen atom.
  • In the formula (I′), 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. When L₁ and L₂ each represents a timing group, examples of such a timing group include the following known connecting groups:
    • (1) Group using hemiacetal cleavage reaction:
      Examples of such a group include those represented by the undermentioned formula (T-1) as described in U.S. Patent 4,146,396 and Japanese Patent Application (OPI) Nos. 249148/85 and 249149/85. The mark * represents the position at which the group is bonded to the left hand of the group of the formula (II), and the mark ** represents the position at which the group is bonded to the right hand of the group of the formula (II).
      Figure imgb0054
       wherein W represents an oxygen atom, a sulfur atom, or an
      Figure imgb0055
       group; R₆₅ and R₆₆ each represents a hydrogen atom or a substituent; R₆₇ represents a substituent; and t represents an integer of 1 or 2. When t is 2, the two groups
      Figure imgb0056
       may be the same or different. Typical examples of the substituents represented by R₆₅, R₆₆ and R₆₇ include an R₆₉ group, an R₆₉CO- group, an R₆₉SO₂- group, an
      Figure imgb0057
       group and an
      Figure imgb0058
       group. In these formulae, R₆₉ represents the same group as R₄₁ in the formulae (I) and (I′), and R₇₀ represents the same group as R₄₃ in the formulae (I) and (I′). R₆₅, R₆₆ and R₆₇ may be divalent groups which are connected to each other to form a cyclic structure. Specific examples of the group represented by the formula (T-1) include the following groups:
      Figure imgb0059
      Figure imgb0060
      Figure imgb0061
    • (2) Group which uses an intramolecular nucleophilic substitution reaction to cause a cleavage reaction:
      Examples of such a group include timing groups as described in U.S. Patent 4,248,962. Such timing groups can be represented by the formula (T-2):

              *-Nu-Link-E-**   (T-2)

      wherein the mark * represents the position at which the timing group is bonded to the left hand of the group of the formula (II); the mark ** represents the position at which the timing group is bonded to the right hand of the group of the formula (II); Nu represents a nucleophilic group containing as a nucleophilic atom an oxygen atom or a sulfur atom; E represents an electrophilic group capable of cleaving its connection with the mark ** upon a nucleophilic attack by Nu; and Link represents a connecting group which gives a steric relation between Nu and E such that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by the formula (T-2) include the following groups:
      Figure imgb0062
      Figure imgb0063
      Figure imgb0064
      Figure imgb0065
    • (3) Group which uses electronic migration through a conjugated system to cause a cleavage reaction:
      Examples of such a group include those represented by the undermentioned formula (T-3) as described in U.S. Patents 4,409,323 and 4,421,845.
      Figure imgb0066
       wherein the marks * and **, W, R₆₅, R₆₆ and t have the same meanings as described with reference to the formula (T-1). Specific examples of the group represented by the formula (T-3) include the following groups:
      Figure imgb0067
      Figure imgb0068
      Figure imgb0069
      Figure imgb0070
      Figure imgb0071
    • (4) Group using a cleavage reaction by hydrolysis of ester:
      Examples of such a group include connecting groups as described in West German Patent Application (OLS) No. 2,626,315. These connecting groups may be epresented by the following formulae:
      Figure imgb0072
      Figure imgb0073
       wherein the marks * and ** have the same meanings as described with reference to the formula (T-1).
    • (5) Group using a cleavage reaction of iminoketal:
      Examples of such a group include connecting groups represented by the undermentioned formula (T-6) as described in U.S. Patent 4,546,073.
      Figure imgb0074
       wherein the marks * and **, and W have the same meanings as described with reference to the formula (T-1); and R₆₈ has the same meaning as R₆₇. Specific examples of the group represented by the formula (T-6) include the following groups:
      Figure imgb0075
      Figure imgb0076
  • In the formula (I′), when the group represented by L₁ represents a group which undergoes a reaction with an oxidation product of a developing agent after cleavage from A₁ to cause cleavage of the (L₂)b-Z₁ bond, it specifically represents a group which becomes a coupler or an oxidation reduction group after cleavage from A₁. Similarly, when the group represented by L₂ represents a group which undergoes a reaction with an oxidation product of a developing agent after cleavage from A₁-(L₁)b to cause cleavage of the connection with Z₁, it specifically represents a group which becomes a coupler or an oxidation reduction group after cleavage from A₁-(L₁)b.
  • In such a group which becomes, for example, a phenolic coupler, it is bonded to A₁- or A₁-(L₁)b- at the oxygen atom of a hydroxyl group free of the hydrogen atom. In such a group which becomes a 5-pyrazolone type coupler, it is bonded to A₁- or A₁-(L₁)b- at the oxygen atom of hydrogen free hydroxyl group in tautomerism with 5-hydroxypyrazole. In these cases, such a group is separated from A₁- or A₁-(L₁)b- to become a phenolic coupler or a 5-pyrazolone type coupler. These coupling positions have (L₂)b-Z₁ or Z₁.
  • Preferred examples of L₁ and L₂ which each represents a group which becomes a coupler include groups represented by the undermentioned formulae (V), (VI), (VII) and (VIII). In these formulae, the mark * represents the position at which the group is bonded to the left hand of the group of the formula (I) and the mark ** represents the position at which the group is bonded to the right hand of the group of the formula (I).
    Figure imgb0077
    Figure imgb0078
    Figure imgb0079
    Figure imgb0080
    wherein 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
    Figure imgb0081
    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
    Figure imgb0082
  • V₁ preferably represents an R₇₁ group. Preferred examples of V₂ include an R₇₂ group, an R₇₂CO- group, an
    Figure imgb0083
    group, an R₇₂SO₂- group, an R₇₂S- group, an R₇₂O- group and an
    Figure imgb0084
    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.
  • Preferred examples of V₇ include a halogen atom, an R₇₁ group, an R₇₁CONH- group, an R₇₁SO₂NH- group, an R₇₃O- group, an R₇₁S- group, an
    Figure imgb0085
    group, an
    Figure imgb0086
    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
    Figure imgb0087
    include indole, imidazolinone, 1,2,5-thiazoline-1,1-dioxide, 3-pyrazoline-5-one, 3-isooxazoline-5-one and
    Figure imgb0088
  • Preferred examples of V₁₀ include a R₇₃- group, an R₇₃O- group, an
    Figure imgb0089
    group, an
    Figure imgb0090
    group and an R₇₁S- group.
  • In the foregoing description, R₇₁ and R₇₂ each represents an aliphatic group, an aromatic group or a heterocyclic group, and 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:
    Figure imgb0091
    Figure imgb0092
    Figure imgb0093
    Figure imgb0094
    Figure imgb0095
    Figure imgb0096
  • Typical examples of the group represented by the formula (VI) include the following groups:
    Figure imgb0097
    Figure imgb0098
    Figure imgb0099
    Figure imgb0100
    Figure imgb0101
  • Typical examples of the group represented by the formula (VIII) include the following groups:
    Figure imgb0102
    Figure imgb0103
    Figure imgb0104
    Figure imgb0105
    Figure imgb0106
  • Typical examples of the group represented by the formula (VIII) include the following groups:
    Figure imgb0107
    Figure imgb0108
    Figure imgb0109
    Figure imgb0110
    Figure imgb0111
    Figure imgb0112
  • In the formula (I′), when the group represented by L₁ and L₂ represents a group which becomes an oxidation reduction group, it preferably is a group represented by the formula (IX):

            *-P′-(X′=Y′)n′-Q′-A′₂   (IX)


    wherein the mark * represents the position at which the group is bonded to the left hand of the group of the formula (I′); A′₂, P′, Q′ and n′ have the same meanings as described in A₁₂, P, Q and n in the formula (II); and at least one of n′ number of X′ and Y′ represents a methine group containing (̵L₂)-Z₁ or Z₁ as a substituent and the other X′ and Y′ each represents a substituted or unsubstituted methine group or nitrogen atom. 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.
  • In the formula (IX), P′ preferably represents an oxygen atom, and Q′ preferably represents an oxygen atom or a group represented by the undermentioned formulae. In these formulae, the mark * represents the position at which the group is bonded to (X′=Y′)n′, and the mark ** represents the position at which the group is bonded to A′₂.
    Figure imgb0113
    Figure imgb0114
    wherein 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
    Figure imgb0115
  • Particularly preferred among the groups represented by the formula (IX) are those represented by the following formulae (X) and (XI):
    Figure imgb0116
    Figure imgb0117
    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.
  • Particularly preferred examples of 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 sulfamoyl group such as an N-propylsulfamoyl group and a sulfamoyl group; an acyl group such as an acetyl group and a benzoyl group; a hydroxyl group and a carboxyl group. Typical examples of the cyclic structure formed by the connection of two R₇₆ include a group represented by the following formula:
    Figure imgb0118
    wherein the marks * and ** have the same meaning as described with reference to the formula (XI).
  • In the formula (I′), the group represented by Z₁ specifically represents a known bleaching accelerator residual group. Examples of such 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. 8506/70 and 26586/74; thioamide compounds as described in Japanese Patent Application (OPI) No. 42349/74; dithiocarbamates as described in Japanese Patent Application (OPI) No. 26506/80; and arylenediamine compounds as described in U.S. Patent 4,552,834. These compounds are preferably bonded to A₁-(L₁)a-(L₂)b- in the formula (I′) at a substitutable hetero atom contained in the molecule.
  • Particularly preferred examples of the group represented by Z₁ include groups represented by the following formulae (XII), (XIII) and (XIV):
    Figure imgb0119
    Figure imgb0120
    Figure imgb0121
    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-,
    Figure imgb0122
    Figure imgb0123
    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, a sulfo group or a salt thereof, a hydroxyl group, a phosphonic acid group or a salt thereof, an amino group which may be substituted by an aliphatic group having from 1 to 4 carbon atoms, or an -NHSO₂-R₅ or -SO₂NH-R₅ group (the term "salt" as used herein means a sodium salt, a potassium salt or an ammonium salt); Y₂ represents a hydrogen atom or a group having the same meaning as described with reference to Y₁; r represents an integer of 0 or 1; ℓ represents an integer of 0 to 4; m represents an integer of 1 to 4; and u represents an integer of 0 to 4, with the proviso that m number of Y₁ are bonded to each substitutable position in R₁-{(X₁)r-R₂}ℓ and X₂-{(X₁)r-R₂}ℓ, that u number of Y₁ are bonded to each substitutable position in X₃-{(X₁)r-R₂}ℓ, that when m is a plural number, m number of Y₁ may be the same or different, and that when ℓ is a plural number, ℓ number of {(X₁)r-R₂} may be the same or different. In the above formulae, 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. Examples of 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. Examples of such 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. Examples of 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,
    Figure imgb0124
       -SCH₂CH₂NH₂,
    Figure imgb0125
    Figure imgb0126
       -SCH₂CH₂NHCOCH₃
       -S(CH₂)₄CO₂H,
    Figure imgb0127
       -SCH₂CONHCH₂CO₂H,
       -SCH₂CH₂OCH₂CO₂H,
       -SCH₂COOCH₂CH₂OH,
       -SCH₂CH₂OCH₂CH₂OCH₂CH₂OH,
    Figure imgb0128
       -SCH₂CH₂SCH₂CO₂H,
       -SCH₂CH₂CH₂CO₂H,
    Figure imgb0129
  • Specific examples of the group represented by the formula (XIII) include the following groups:
    Figure imgb0130
    Figure imgb0131
    Figure imgb0132
    Figure imgb0133
    Figure imgb0134
  • Specific examples of the group represented by the formula (XIV) include the following groups:
    Figure imgb0135
    Figure imgb0136
    Figure imgb0137
    Figure imgb0138
    Figure imgb0139
    Figure imgb0140
    Figure imgb0141
    Figure imgb0142
    Figure imgb0143
    Figure imgb0144
  • 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.
    Figure imgb0145
    Figure imgb0146
    wherein 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.
  • In the formula (XV) or (XVI), 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; and a sulfonyl group such as a methylsulfonyl group. When two or more of these substituents are contained in the alkylene group, the aralkylene group or the arylene group represented by A₂₃, they may be the same or different.
  • Examples of the noncoloring ethylenic monomer incapable of coupling with an oxidation product of an aromatic primary amine developing agent include an acrylic acid, an α-chloroacrylic acid, an α-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.
  • In the formula (I′), 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:
    Figure imgb0147
    Figure imgb0148
    Figure imgb0149
  • Particularly preferred among these bonding hands is one represented by the formula (XVII):
    Figure imgb0150
    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〈,
    Figure imgb0151
    and -S-CH〈 groups.
  • Specific examples of the bleaching accelerator-releasing compound to be used in the present invention will be described hereinafter, but the present invention should not be construed as being limited thereto.
    Figure imgb0152
    Figure imgb0153
    Figure imgb0154
    Figure imgb0155
    Figure imgb0156
    Figure imgb0157
    Figure imgb0158
    Figure imgb0159
    Figure imgb0160
    Figure imgb0161
    Figure imgb0162
    Figure imgb0163
    Figure imgb0164
    Figure imgb0165
    Figure imgb0166
    Figure imgb0167
    Figure imgb0168
    Figure imgb0169
    Figure imgb0170
    Figure imgb0171
    Figure imgb0172
    Figure imgb0173
    Figure imgb0175
    Figure imgb0176
    Figure imgb0177
    Figure imgb0178
    Figure imgb0179
    Figure imgb0180
    Figure imgb0181
    Figure imgb0182
    Figure imgb0183
    Figure imgb0184
    Figure imgb0185
    Figure imgb0186
    Figure imgb0187
    Figure imgb0188
    Figure imgb0189
    Figure imgb0190
    Figure imgb0191
    Figure imgb0192
    Figure imgb0193
    Figure imgb0194
    Figure imgb0195
    Figure imgb0196
    Figure imgb0197
    Figure imgb0198
    Figure imgb0199
    Figure imgb0200
    Figure imgb0201
    Figure imgb0202
    Figure imgb0203
    Figure imgb0204
  • Other examples of the bleaching accelerator-releasing compound which can be used in the present invention include those described in Research Disclosure, RD Nos. 24241 and 11449, Japanese Patent Application (OPI) No. 201247/86, and Japanese Patent Application Nos. 252847/86, 268870/86 and 268871/86.
  • The synthesis of the bleaching accelerator-releasing compound to be used in the present invention may be easily accomplished in accordance with the description in the above described patents.
  • 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.
  • The processing solution of the present invention having a blixing capability is described hereinafter. Examples of a bleaching agent to be used for the processing solution of the present invention having a blixing capability 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. 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:
    • A- 1:
    Diethylenetriaminepentaacetic acid
    A- 2:
    Pentasodium diethylenetriaminepentaacetate
    A- 3:
    Ethylenediamine-N-(β-oxyethyl)-N,N′,N′-triacetic acid
    A- 4:
    Trisodium ethylenediamine-N-(β-oxyethyl)-N,N′,N′-triacetate
    A- 5:
    Triammonium ethylenediamine-N-(β-oxyethyl)-N,N′,N′-triacetate
    A- 6:
    1,2-Diaminopropanetetraacetic acid
    A- 7:
    Disodium 1,2-diaminopropanetetraacetate
    A- 8:
    Nitrilotriacetic acid
    A- 9:
    Sodium nitrilotriacetate
    A-10:
    Cyclohexanediaminetetraacetic acid
    A-11:
    Disodium cyclohexanediaminetetraacetate
    A-12:
    N-Methyliminodiacetic acid
    A-13:
    Iminodiacetic acid
    A-14:
    Dihydroxyethyl glycine
    A-15:
    Ethyletherdiaminetetraacetic acid
    A-16:
    Glycoletherdiaminetetraacetic acid
    A-17:
    Ethylenediaminetetrapropionic acid
    A-18:
    1,3-Diaminepropanetetraacetic acid
    A-19:
    Ethylenediaminetetraacetic acid
    A-20:
    1,2-Propylenediaminetetraacetic acid, or alkaline metal salts or ammonium salts thereof
    A-21:
    Triethylenetetraminehexaacetic acid, or alkaline salts or ammonium salts thereof
    A-22:
    1,4-Diaminobutanetetraacetic acid or alkaline salts or ammonium salts thereof
    A-23:
    2-Propanoldiaminetetraacetic acid or alkaline salts or ammonium salts thereof
    A-24:
    1,3-Butylenediaminetetraacetic acid or alkaline salts or ammonium salts thereof
  • The present invention should not be construed as being limited to these exemplary compounds.
  • Among these, 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. Alternatively, 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. When the ferric salt is used in the form of a complex salt, one or more complex salts may be used. On the other hand, when a ferric salt and an aminopolycarboxylic acid are used to form a complex salt in a solution, one or more ferric salts may be used. Furthermore, 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.
  • Alternatively, a combination of at least one of 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. Other examples of 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.
  • 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. The added amount of such a fixing agent is preferably 3 mol or less, and particularly preferably 2 mol, per liter of the processing solution having a bleaching capability.
  • 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).
  • Furthermore, 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.
  • In the present invention, 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.
  • In the present invention, as such 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.
  • In the present invention, such a bleaching accelerator may further be incorporated into the light-sensitive material. In this case, 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. Similarly, 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. Such a processing bath may preferably contain a salt. Examples of such 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. 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 in accordance with the present invention 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. More surprisingly, such an improvement in color restoration becomes more remarkable when a ferric aminopolycarboxylate complex salt is used as a bleaching agent than when a ferric ethylenediaminetetraacetate is used. Such an improvement in color restoration enables a further rapid blixing processing. Furthermore, the combined use of the cyan dye-forming coupler enables an improvement in image stability.
    Figure imgb0205
    wherein 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; and n₁ represents an integer of 0 or 1.
    Figure imgb0206
    wherein 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; and 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 R₁₁₂ may be the same or different or may be connected to each other to form a ring, and (d) R₁₁₂ and R₁₁₃ or R₁₁₃ and X₁₀ may be connected to each other to form a ring.
  • The present cyan dye-forming coupler represented by the formula (L-I) is further described hereinafter.
  • 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 methanesulfonamide group and a butylsulfamoyl group; a sulfamide group such as a dipropylsulfamoylamino group; an imide group such as a succinimide group and a hydantoinyl group; a ureido group such as phenylureido group and a dimethylureido group; an aliphatic or aromatic sulfonyl group such as a methanesulfonyl group and a phenylsulfonyl group; an aliphatic or aromatic thio group such as an ethylthio group and a phenylthio group; a hydroxy group; a cyano group; a carboxy group; a nitro group; a sulfo group; and a halogen atom.
  • 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.
  • The suffix n represents an integer of 0 or 1.
  • In the formula (L-I), Z₁₀ represents a hydrogen atom or coupling-releasable group. Examples of such 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 dichloroacetylamino group, a heptafluorobutylamino group, a methanesulfonylamino group and a toluenesulfonylamino group; an alkoxycarbonyloxy group such as an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group; an aryloxycarbonyloxy group such as a phenoxycarbonyloxy group; an aliphatic or aromatic thio group such as an ethylthio group, a phenylthio group and a tetrazolylthio group; an imide group such as a succinimide group and a hydantoinyl group; and an aromatic azo group such as a phenylazo group. These coupling-releasable groups may contain a photographically useful group.
  • In the formula (L-I), preferred examples of 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.
  • In the formula (L-I), 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.
  • In the formula (L-I), preferred examples of Z₁₀ include a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group and a sulfonamide group.
  • In the formula (L-I), when n₁ is 0, 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.
  • Specific examples of the compound represented by the formula (L-I) are shown hereinafter, but the present invention should not be construed as being limited thereto.
    Figure imgb0207
    Figure imgb0208
    Figure imgb0209
    Figure imgb0210
    Figure imgb0211
    Figure imgb0212
    Figure imgb0213
    Figure imgb0214
    Figure imgb0215
    Figure imgb0216
    Figure imgb0217
    Figure imgb0218
    Figure imgb0219
    Figure imgb0220
    Figure imgb0221
    Figure imgb0222
    Figure imgb0223
    Figure imgb0224
    Figure imgb0225
    Figure imgb0226
    Figure imgb0227
    Figure imgb0228
    Figure imgb0229
    Figure imgb0230
    Figure imgb0231
    Figure imgb0232
    Figure imgb0233
    Figure imgb0234
    Figure imgb0235
    Figure imgb0236
    Figure imgb0237
    Figure imgb0238
    Figure imgb0239
    Figure imgb0240
    Figure imgb0241
    Figure imgb0242
    Figure imgb0243
    Figure imgb0244
    Figure imgb0245
    Figure imgb0246
    Figure imgb0247
  • The substituents contained in the formula (L-II) are further described hereinafter.
  • 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 m₁ is 2, examples of the cyclic group represented by R₁₁₂ include a dioxymethylene group.
  • R₁₁₃ represents a monovalent organic group. Such a monovalent organic group is preferably represented by the following formula (L-III):

            R₁₁₈(Y₁₀)n2 -   (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,
    Figure imgb0248
    -CO₂R₁₂₁, -SO₂R₁₂₁ or -SO₂R₁₂₁ in which R₁₁₉, R₁₂₀ and R₁₂₁ have the same meanings as R₁₁₅, R₁₁₆ and R₁₁₇, respectively.
  • In R₁₁₁ or R₁₁₈, R₁₁₅ and R₁₁₆ in
    Figure imgb0249
    and R₁₁₉ and R₁₂₀ in
    Figure imgb0250
    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,
    Figure imgb0251
    -NHCOR₁₂₅, -NHSR₁₂₅,
    Figure imgb0252
    Figure imgb0253
    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. In the above described formulae, 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.
  • Similarly, the 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.
  • Furthermore, the 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.
  • Preferred examples of suitable substituents for the formula (L-II) are described hereinafter. 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.
  • The suffix m₁ is most preferably 0. That is, the group represented by the formula (L-II) is not substituted by R₁₁₂. Alternatively, R₁₁₂ may be a halogen atom, an aliphatic group having from 1 to 30 carbon atoms, a carbonamide group or a sulfonamide group.
  • In the formula (L-III), n₂ is preferably 0. That is, the group represented by the formula (L-III) preferably has no Y₁₀. Examples of 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, a benzenesulfonyl group, a toluenesulfonyl group and a p-chlorobenzenesulfonyl group; -CONR₁₁₉R₁₂₀ such as an N,N-dimethylcarbamoyl group, an N,N-diethylcarbamoyl group, an N,N-dibutylcarbamoyl group, a morpholinocarbonyl group, a piperidinocarbonyl group, a 4-cyanophenylcarbonyl group, a 3,4-dichlorophenylcarbamoyl group and a 4-methanesulfonylphenylcarbamoyl group; and -SO₂NR₁₁₉R₁₂₀ such as an N,N-dimethylsulfamoyl group, an N,N-diethylsulfamoyl group and an N,N-dipropylsulfamoyl group. Among these groups, -COOR₁₁₉, -COR₁₁₉ and -SO₂R₁₂₁ are more preferred. Most preferred among these groups is -COOR₁₁₉.
  • 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-1,2,3,4-tetrazolyl-1-thio group; and an aromatic azo group such as a 4-dimethylaminophenylazo group, a 4-acetamidophenylazo group, a 1-naphthylazo group, a 2-ethoxycarbonylphenylazo group and a 2-methoxycarbonyl-4,5-dimethoxyphenylazo group.
  • 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. In this case, the total number of carbon atoms contained in each substituent may be beyond the specified limit.
  • If 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. 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.
    Figure imgb0254
    wherein 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; and 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; α-chloroacrylic acid; α-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 β-hydroxymethacrylate; vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate; acrylonitrile; methacrylonitrile; aromatic vinyl compounds such as styrene and derivatives thereof (e.g., vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinylalkylether (e.g., vinylethylether), maleic ester, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- and 4-vinylpyridine.
  • Among these compounds particularly preferred are 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.
  • As is well known in the field of polymer couplers, 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.
  • Specific examples of couplers represented by the formula (L-II) are shown hereinafter, but the present invention should not be construed as being limited thereto. In the following formulae, (t)C₅H₁₁ and (t)C₈H₁₇ represent -C(CH₃)₂C₂H₅ and -C(CH₃)₂CH₂C(CH₂)₃, respectively.
    Figure imgb0255
    Figure imgb0256
    Figure imgb0257
    Figure imgb0258
    Figure imgb0259
    Figure imgb0260
    Figure imgb0261
    Figure imgb0262
    Figure imgb0263
    Figure imgb0264
    Figure imgb0265
    Figure imgb0266
    Figure imgb0267
    Figure imgb0268
    Figure imgb0269
    Figure imgb0270
    Figure imgb0271
    Figure imgb0272
    Figure imgb0273
    Figure imgb0274
    Figure imgb0275
    Figure imgb0276
    Figure imgb0277
    Figure imgb0278
    Figure imgb0279
    Figure imgb0280
    Figure imgb0281
    Figure imgb0282
    Figure imgb0283
    Figure imgb0284
    Figure imgb0285
    Figure imgb0286
    Figure imgb0287
    Figure imgb0288
    Figure imgb0289
  • 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. Examples of such 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. In the 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. Examples of such a high boiling point organic solvent are described in U.S. Patent 2,322,027. The dispersion may be accompanied by phase inversion. If desired, 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-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-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.
  • Examples of 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.
  • Other examples of color developing agents which can be used in the present invention include those described in L.F.A. Mason, Photographic Processing Chemistry, Focal Press, pp. 226 to 229, U.S. Patents 2,193,015 and 2,592,364, and Japanese Patent Application (OPI) No. 64933/73. If desired, two or more color developing agents may be used in combination.
  • 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. 2,622,950, sulfite, and bisulfite; 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; competing couplers; nucleating agents 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 (OPI) No. 195845/83, organic phosphonic acid as described in Research Disclosure, RD No. 18170 (May, 1979), aminophosphonic acid (e.g., aminotris(methylenephosphonic acid), and ethylenediamine-N,N,N′,N′-tetramethylenephosphonic acid), and phosphonocarboxylic acid as described in Research Disclosure, RD No. 18170 (May, 1975).
  • 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. In a multistage countercurrent system, 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).
  • In a multistage countercurrent system as described in the foregoing literature, the amount of water to be used in the washing process can be greatly decreased. However, such a multistage countercurrent system is disadvantageous in that an increase in the time of retention of watr in the tanks causes the propagation of bacteria which produce suspended matter that may be attached to the light-sensitive material. In the processing of the present color light-sensitive material, such a problem can be extremely effectively solved by decreasing calcium and magnesium as described in Japanese Patent Application (OPI) No. 288838/87 (corresponding to European Patent Application No. 248450A). Such a problem can also be solved by the use of isothiazolone compounds and thiabendazole as described in Japanese Patent Application (OPI) No. 8542/82, chlorine bactericides such as sodium chlorinated isocyanurate, or 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.
  • Furthermore, the present light-sensitive material may be processed directly with a stabilizing solution rather than by washing with water. In such 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. Particularly, 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.
  • 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. Alternatively, 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. Alternatively, 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.
  • 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. In the present invention, 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.
  • In the process of formation or physical ripening of the silver halide grain, 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.
  • Examples of known photographic additives which can be used in the present invention are described in these citations. The table shown below also contains the places where such a description is found.
    Figure imgb0290
  • As a 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. Particularly, 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.
  • Various 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. α-Pivaloylacetanilide couplers are excellent in the fastness of color-forming dye, particularly in the fastness to light. On the other hand, α-benzoylacetanilide couplers can provide a high color density.
  • Examples of 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.
  • As 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. 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. Typical examples of such 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. Furthermore, metal complexes such as (bissalicylaldoximate)nickel complex and (bis-N,N-dialkyldithiocarbamate)nickel complex may be used.
  • In the present photographic light-sensitive material, 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.
  • The present invention will be further illustrated in the following examples, but the present invention should not be construed as being limited thereto.
  • Unless otherwise specified, all ratios, percents, etc., are by weight.
    • EXAMPLE I-1
  • 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.
    • Composition of Light-Sensitive Layer
  • 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.
    • First Layer: Antihalation Layer
  • Figure imgb0291
    Figure imgb0292
    • Second Layer: Interlayer
  • Figure imgb0293
    • Third Layer: Low Sensitivity Red-Sensitive Emulsion Layer
  • Figure imgb0294
    Figure imgb0295
    • Fourth Layer: High Sensitivity Red-Sensitive Emulsion Layer
  • Figure imgb0296
    • Fifth Layer: Interlayer
  • Figure imgb0297
    • Sixth Layer: Low Sensitivity Green-Sensitive Emulsion Layer
  • Figure imgb0298
    • Seventh Layer: High Sensitivity Green-Sensitive Emulsion
  • Figure imgb0299
    • Eighth Layer: Interlayer
  • Figure imgb0300
    • Ninth Layer: Donor Layer Having a Multilayered Effect on Red-Sensitive Layer
  • Figure imgb0301
    • Tenth Layer: Yellow Filter Layer
  • Figure imgb0302
    • Eleventh Layer: Low Sensitivity Blue-Sensitive Emulsion Layer
  • Figure imgb0303
    • Twelfth Layer: High Sensitivity Blue-Sensitive Emulsion Layer
  • Figure imgb0304
    • Thirteenth Layer: First Protective Layer
  • Figure imgb0305
    • Fourteenth Layer: Second Protective Layer
  • Figure imgb0306
    Figure imgb0307
  • Besides the above described components, 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.
    Figure imgb0308
    Figure imgb0309
    Figure imgb0310
    Figure imgb0311
    Figure imgb0312
       Solv-1: Tricresyl phosphate
       Solv-2: Dibutyl phthalate
    Figure imgb0313
    Figure imgb0314
    Figure imgb0315
    Figure imgb0316
    Figure imgb0317
    Figure imgb0318
    Figure imgb0319
    Figure imgb0320
    Figure imgb0321
    Figure imgb0322
    Figure imgb0323
    Figure imgb0324
    Figure imgb0325
    Figure imgb0326
    Figure imgb0327
    Figure imgb0328
    Figure imgb0329
    Figure imgb0330
    Figure imgb0331
    Figure imgb0332
    Figure imgb0333
    Figure imgb0334
    Figure imgb0335
    Figure imgb0336
    Figure imgb0337
    Figure imgb0338
    Figure imgb0339
    Figure imgb0340
    Figure imgb0341
    Figure imgb0342
    Figure imgb0343
    Figure imgb0344
    Figure imgb0345
    Figure imgb0346
  • 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.
    Figure imgb0347
  • 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).
    Figure imgb0348
  • The replenished amount of replenisher is represented in terms of the amount replenished per m² of the light-sensitive material.
  • The composition of the processing solutions were as follows:
    • Color Developing Solution:
  • Figure imgb0349
    • Bleaching Solution (mother liquor was also used as replenisher):
  • Figure imgb0350
    • Blixing Solution (mother liquor was also used as replenisher):
  • Figure imgb0351
    • 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. Sodium bichlorinated isocyanurate and sodium sulfate were added to the water in amounts of 20 mg/liter and 1.5 g/liter, respectively.
  • 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):
  • Figure imgb0352
  • The above described specimens were then subjected to a continuous processing. The amount of the bleaching solution and blixing solution replenished were changed as shown in Table I-2 (Processing A).
  • 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).
    • Bleaching Accelerator
  • Figure imgb0353
  • 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).
    • Bleaching Accelerator
  • Figure imgb0354
  • The added amount of this bleaching accelerator was 5 × 10⁻³ mol/liter-the bleaching solution. At the beginning and the end of each continuous processing, 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.
    • EXAMPLE I-2
  • 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.
  • 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.
    Figure imgb0355
    Figure imgb0356
    Figure imgb0357
  • The results thus obtained were similar to those of Example I-1. Table I-3 shows that the light-sensitive material specimens having 3.5 to 10.2 g of silver coated per m² provide excellent results.
    • EXAMPLE I-3
  • 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).
    Figure imgb0358
  • The replenished amount of replenisher is represented by the value per unit length of the specimen (1 m).
  • The 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.
    • Fixing Solution (mother liquor was also used as replenisher):
  • Figure imgb0359
  • The results are shown in Table I-4.
    Figure imgb0360
    Figure imgb0361
  • The results thus obtained were similar to those of Example I-1.
    • EXAMPLE I-4
  • 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).
    Figure imgb0362
  • The replenished amount of replenisher is represented by the amount supplied per unit length of the specimen (1 m).
  • The composition of the processing solutions is described hereinafter.
  • All the processing solutions were prepared in the same manner as in Example I-1.
  • The results are shown in Table I-5.
    Figure imgb0363
    Figure imgb0364
  • Table I-5 shows that the results thus obtained were similar to those of Example I-1.
    • EXAMPLE I-5
  • 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.
    • Composition of Light-Sensitive Layer:
  • 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.
    • First Layer:
  • Figure imgb0365
    • Second Layer: Antihalation Layer
  • Figure imgb0366
    • Third Layer: Low Sensitivity Red-Sensitive Layer
  • Figure imgb0367
    Figure imgb0368
    • Fourth Layer: High Sensitivity Red-Sensitive Layer
  • Figure imgb0369
    • Fifth Layer: Interlayer
  • Figure imgb0370
    • Sixth Layer: Low Sensitivity Green-Sensitive Layer
  • Figure imgb0371
    Figure imgb0372
    • Seventh Layer: High Sensitivity Green-Sensitive Layer
  • Figure imgb0373
    • Eighth Layer: Yellow Filter Layer
  • Figure imgb0374
    • Ninth layer: Low Sensitivity Blue-Sensitive Layer
  • Figure imgb0375
    • Tenth Layer: High Sensitivity Blue-Sensitive Layer
  • Figure imgb0376
    • Eleventh Layer: Ultraviolet Absorbing Layer
  • Figure imgb0377
    • Twelfth Layer: Protective Layer
  • Figure imgb0378
    Figure imgb0379
    Figure imgb0380
  • 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.
    Figure imgb0381
  • 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.
    Figure imgb0382
  • 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).
  • The composition of the processing solutions were as follows:
    • First Developing Solution:
  • Figure imgb0383
    • First Washing Solution:
  • Figure imgb0384
    • Color Developing Solution:
  • Figure imgb0385
    • Bleaching Solution:
  • Figure imgb0386
    • Blixing Solution:
  • Figure imgb0387
    • 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. Sodium dichlorinated isocyanurate and sodium sulfate were added to the water in amounts of 20 mg/liter and 1.5 g/liter, respectively. The pH of the solution was in the range of 6.5 to 7.5.
  • The above described specimens which had been exposed to light of 3,200°K 100 CMS through an optical wedge were measured for the amount of residual silver at the minimum density portion and maximum density portion of yellow image and observed for the condition of the bleaching solution and the blixing solution at the beginning, middle and end of the continuous processing. Furthermore, these specimens were subjected to various continuous processings with different supply amount of the bleaching solution and the blixing solution. The results are shown in Table I-7.
  • 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.
    Figure imgb0388
    Figure imgb0389
    • EXAMPLE II-1
  • 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.
    • Composition of Light-Sensitive Material
  • 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.
    • First Layer: Antihalation Layer
  • Figure imgb0390
    • Second Layer: Interlayer
  • Figure imgb0391
    • Third Layer: First Red-Sensitive Emulsion Layer
  • Figure imgb0392
    • Fourth Layer: Second Red-Sensitive Emulsion Layer
  • Figure imgb0393
    Figure imgb0394
    • Fifth Layer: Third Red-Sensitive Emulsion Layer
  • Figure imgb0395
    • Sixth Layer: Interlayer
  • Figure imgb0396
    • Seventh Layer: First Green-Sensitive Emulsion Layer
  • Figure imgb0397
    Figure imgb0398
    • Eighth Layer: Second Green-Sensitive Emulsion Layer
  • Figure imgb0399
    • Ninth Layer: Third Green-Sensitive Emulsion Layer
  • Figure imgb0400
    • Tenth Layer: Yellow Filter Layer
  • Figure imgb0401
    • Eleventh Layer: First Blue-Sensitive Emulsion Layer
  • Figure imgb0402
    Figure imgb0403
    • Twelfth Layer: Second Blue-Sensitive Emulsion Layer
  • Figure imgb0404
    • Thirteenth Layer: First Protective Layer
  • Figure imgb0405
    • Fourteenth Layer: Second Protective Layer
  • Figure imgb0406
    Figure imgb0407
  • Besides the above described components, a surface active agent was added to each layer as a coating aid.
  • The chemical structural formula and chemical name of the compounds used in this example are described below.
    Figure imgb0408
    Figure imgb0409
       Oil-1: Tricresyl phosphate
       Oil-2: Dibutyl phthalate
       Oil-3: Bis(2-ethylhexyl) phthalate
    Figure imgb0410
    Figure imgb0411
    Figure imgb0412
    Figure imgb0413
    Figure imgb0414
    Figure imgb0415
    Figure imgb0416
    Figure imgb0417
    Figure imgb0418
    Figure imgb0419
    Figure imgb0420
    Figure imgb0421
    Figure imgb0422
    Figure imgb0423
    Figure imgb0424
    Figure imgb0425
    Figure imgb0426
    Figure imgb0427
    Figure imgb0428
    Figure imgb0429
    Figure imgb0430
    Figure imgb0431
    Figure imgb0432
    Figure imgb0433
    Figure imgb0434
    Figure imgb0435
    Figure imgb0436
    Figure imgb0437
  • 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.
    Figure imgb0438
    Figure imgb0439
  • Specimens 301 to 316 thus prepared were processed in the following manner:
    • Processing (A):
  • Figure imgb0440
  • In the above described processing steps, the 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.
    • Color Developing Solution:
  • Figure imgb0441
    • Blixing Solution:
  • Figure imgb0442
    • Stabilizing Solution (washing solution):
  • Figure imgb0443
  • The specimens were processed with the above described processing solutions and washing solution in the above described processing steps. The results were compared.
    • Washing Solution:
  • City water was passed through a mixed bed column filled with a strongly acidic H type cation exchange resin (Diaion SK-1B, manufactured by Mitsubishi Chemical Industries, Ltd.) and a strongly basic OH type anion exchange resin (Diaion SA-10A, manufactured by Mitsubishi Chemical Industries, Ltd.) so that the water having the undermentioned composition was obtained. Sodium dichlorinated isocyanurate was added to the water as a disinfectant in an amount of 20 mg/liter.
    Figure imgb0444
    • Processing (B):
  • 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):
  • 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):
  • 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):
  • 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):
  • 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.
  • After being subjected to the above described Processings (A), (B), (C), (D), (E) and (F), the light-sensitive material specimens were examined for the amount of residual silver. The results are shown in Table II-2.
  • Table II-2 shows many interesting results. For the examination of the blixing capability, 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. On the other hand, an unexpected result was obtained in the examination of the fixing capability in Processings (C) and (D). Particularly, if no bleaching accelerator-releasing couplers are used, 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). It was also found that the fixing capability is further deteriorated when the blixing solution contains a known bleaching accelerator. On the contrary, it was found that the light-sensitive materials comprising the present bleaching accelerator-releasing couplers give a surprising result. Particularly, 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. Furthermore, it was found that the specimens comprising the cyan dye-forming couplers represented by the formulae (L-I) and (L-II) further improve their fixing capability These results are probably because DTPA·Fe(III) complex salt has a larger molecular weight than EDTA Fe(III) complex salt and therefore tends to interact with gelatin, coupler, etc., in the emulsion layer in the specimens, deteriorating the diffusibility of the fixing agent (S₂O₃²⁻ salt) in the emulsion layer. It is believed that such interaction can be relaxed by the bleaching accelerator-releasing compound of the present invention.
    Figure imgb0445
    Figure imgb0446
    • EXAMPLE II-2
  • 500 mℓ of each blixing solution to be used in Processings (A) and (B) was put into a 1 liter beaker and allowed to stand open at a temperature of 25°C. The two blixing solutions were compared for the number of days they produced sulfur particles (sulfurization). The results were as follows.
    Figure imgb0447
  • Thus, it was found that 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-3
  • 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.
    Figure imgb0448
    • EXAMPLE II-4
  • 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.
    • First Layer: Antihalation Layer
  • Figure imgb0449
    • Second Layer: Interlayer 1
  • Figure imgb0450
    • Third Layer: Interlayer 2
  • Figure imgb0451
    • Fourth Layer: First Red-Sensitive Emulsion Layer
  • Figure imgb0452
    Figure imgb0453
    • Fifth Layer: Second Red-Sensitive Emulsion Layer
  • Figure imgb0454
    • Sixth Layer: Third Red-Sensitive Emulsion Layer
  • Figure imgb0455
    • Seventh Layer: Interlayer 3
  • Figure imgb0456
    • Eighth Layer: Interlayer 4
  • Figure imgb0457
    • Ninth Layer: First Green-Sensitive Emulsion Layer
  • Figure imgb0458
    Figure imgb0459
    • Tenth Layer: Second Green-Sensitive Emulsion Layer
  • Figure imgb0460
    • Eleventh Layer: Third Green-Sensitive Emulsion Layer
  • Figure imgb0461
    • Twelfth Layer: Interlayer 5
  • Figure imgb0462
    • Thirteenth Layer: Yellow Filter Layer
  • Figure imgb0463
    • Fourteenth Layer: First Blue-Sensitive Emulsion Layer
  • Figure imgb0464
    • Fifteenth Layer: Second Blue-Sensitive Emulsion Layer
  • Figure imgb0465
    • Sixteenth Layer: Third Blue-Sensitive Emulsion Layer
  • Figure imgb0466
    • Seventeenth Layer: First Protective Layer
  • Figure imgb0467
    • Eighteenth Layer: Second Protective Layer
  • Figure imgb0468
    Figure imgb0469
  • Besides the above described components, Gelatin Hardener H-1′ and a surface active agent were added to each layer.
    Figure imgb0470
    Figure imgb0471
    Figure imgb0472
    Figure imgb0473
    Figure imgb0474
    Figure imgb0475
       Oil-1′: Ditutyl phthalate
    Figure imgb0476
    Figure imgb0477
    Figure imgb0478
    Figure imgb0479
    Figure imgb0480
    Figure imgb0481
    Figure imgb0482
    Figure imgb0483
    Figure imgb0484
    Figure imgb0485
    Figure imgb0486
    Figure imgb0487
    Figure imgb0488
    Figure imgb0489
    Figure imgb0490
    Figure imgb0491
    Figure imgb0492
    Figure imgb0493
    Figure imgb0494
    Figure imgb0495
    Figure imgb0496
    Figure imgb0497
  • 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.
    Figure imgb0498
  • 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.
    • Processing Step (G):
  • Figure imgb0499
  • The composition of the processing solutions used were as follows:
    • First Developing Solution:
  • Figure imgb0500
    • First Washing Solution:
  • Figure imgb0501
    • Reversing Solution:
  • Figure imgb0502
    • Color Developing Solution:
  • Figure imgb0503
    • Blixing Solution:
  • Figure imgb0504
    • Second Washing Solution:
  • 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. Sodium dichlorinated isocyanurate and sodium sulfate were added to the water thus processed in amounts of 20 mg/liter and 1.5 g/liter, respectively. The washing solution thus prepared had a pH value of 6.5 to 7.5.
    • Processing Step (H):
  • 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):
  • 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):
  • 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.
    Figure imgb0505
  • 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.
  • In accordance with 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.
  • Furthermore, 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.

Claims (10)

  1. A method for processing a silver halide color photographic material comprising a silver bromoiodide emulsion layer having a silver iodide content of 40 mol% or 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:
    (a) said silver halide color photographic light-sensitive material contains a compound which reacts with an oxidation product of an aromatic primary amine color developing agent to release a bleaching accelerator,
    (b) said desilvering step is conducted with a processing solution containing a ferric complex salt of an organic acid, and
    (c) the total amount of replenisher of the processing solution to be used in said desilvering step satisfies either of the following conditions (i) or (ii):
    (i) the total amount of replenisher is from 100 to 700 ml per m² of said light-sensitive material if the coated amount of silver per m² of said light-sensitive material is from 2.0 to 20 g;
    (ii) the total amount of replenisher is from 50 to 300 ml per m² of said light-sensitive material if the coated amount of silver per m² of said light-sensitive material is from 0,3 to less than 2.0 g.
  2. The method of claim 1, wherein said desilvering step is conducted with a processing solution having a bleaching capability or a subsequent processing solution having a blixing capability.
  3. The method of claim 1, wherein said desilvering step is conducted with a processing solution having a blixing capability.
  4. The method of claim 3, wherein the processing solution having a blixing capability contains a ferric aminopolycarboxylate complex salt derived from an aminopolycarboxylic acid having a molecular weight of 300 or more in the form of a free acid.
  5. The method of claim 1, wherein said silver halide color photographic material contains at least one cyan dye-forming coupler selected from the group consisting of compounds represented by formulae (L-I) and (L-II):
    Figure imgb0506
     wherein 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, an aryl group, 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 a coupling-releasable group; and n₁ represents an integer of 0 or 1;
    Figure imgb0507
     wherein R₁₁₁ represents -CONR₁₁₅R₁₁₆, -NHCOR₁₁₅, -NHCOOR₁₁₇, -NHSO₂R₁₁₇, -NHCONR₁₁₅R₁₁₆ or -NHSO₂NR₁₁R₁₁₆; 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; and X₁₀ represents a hydrogen atom or a group which can be released by a coupling reaction with an oxidation product or an aromatic primary amine developing agent, with the proviso that:
    (a) R₁₁₅ and R₁₁₆ may be the same or different and each independently represents a hydrogen atom, an aliphatic group, an aromatic group 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 R₁₁₂ may be the same or different or may be connected to each other to form a ring, and
    (d) R₁₁₂ and R₁₁₃ or R₁₁₃ and X₁₀ may be connected to each other to form a ring.
  6. The method of claim 4, wherein the ferric complex salt is a ferric diethylenetriaminepentaacetate complex salt.
  7. The method of claim 1, wherein the compound for releasing the bleaching accelerator 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.
  8. The method of claim 1, wherein the compound for releasing the bleaching accelerator is a compound represented by the formula (I′):

            A₁-(L₁)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; L 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 to 1.
  9. The method of claim 1, wherein the silver iodide content of said silver bromoiodide emulsion layer is 20 mol% or less.
  10. The method of claim 1, wherein the silver iodide content of said silver bromoiodide emulsion layer is 10 mol% or less.
EP88105892A 1987-04-14 1988-04-13 Method for processing a silver halide photographic material Expired - Lifetime EP0287073B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP89821/87 1987-04-14
JP8982187A JPS63256953A (en) 1987-04-14 1987-04-14 Method for processing silver halide color photographic sensitive material
JP9543287A JPS63261359A (en) 1987-04-20 1987-04-20 Processing method for silver halide color photographic sensitive material
JP95432/87 1987-04-20

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EP0287073A3 EP0287073A3 (en) 1989-11-29
EP0287073B1 true EP0287073B1 (en) 1995-03-08

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Publication number Priority date Publication date Assignee Title
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 (en) * 1983-07-20 1985-02-06 Fuji Photo Film Co Ltd Method for processing color photosensitive silver halide material
DE3580785D1 (en) * 1984-05-10 1991-01-17 Fuji Photo Film Co Ltd COLOR PHOTOGRAPHIC LIGHT SENSITIVE SILVER HALOGENIDE MATERIAL.
JPS60250344A (en) * 1984-05-26 1985-12-11 Fuji Photo Film Co Ltd Color photographic sensitive material
JPS6161160A (en) 1984-08-31 1986-03-28 Fuji Photo Film Co Ltd Processing method of silver halide color photosensitive material
CA1287765C (en) * 1985-02-28 1991-08-20 Eastman Kodak Company Dye-forming photographic material and process comprising bleach accelerator releasing compound
JPH07120028B2 (en) 1985-12-13 1995-12-20 富士写真フイルム株式会社 Processing method of silver halide color photographic light-sensitive material

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EP0287073A2 (en) 1988-10-19
USH789H (en) 1990-06-05
DE3853222D1 (en) 1995-04-13
EP0287073A3 (en) 1989-11-29

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