EP0530828B1 - Photographische Verarbeitungszusammensetzung und Verarbeitungsverfahren - Google Patents

Photographische Verarbeitungszusammensetzung und Verarbeitungsverfahren Download PDF

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Publication number
EP0530828B1
EP0530828B1 EP19920115176 EP92115176A EP0530828B1 EP 0530828 B1 EP0530828 B1 EP 0530828B1 EP 19920115176 EP19920115176 EP 19920115176 EP 92115176 A EP92115176 A EP 92115176A EP 0530828 B1 EP0530828 B1 EP 0530828B1
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EP
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Prior art keywords
group
processing
formula
solution
silver halide
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EP19920115176
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English (en)
French (fr)
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EP0530828A1 (de
Inventor
Tadashi C/O Fuji Photo Film Co. Ltd. Inaba
Hisashi C/O Fuji Photo Film Co. Ltd. Okada
Hiroyuki C/O Fuji Photo Film Co. Ltd. Seki
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP3252745A external-priority patent/JP3042640B2/ja
Priority claimed from JP3252775A external-priority patent/JP2889999B2/ja
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Publication of EP0530828A1 publication Critical patent/EP0530828A1/de
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26Processes using silver-salt-containing photosensitive materials or agents therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/40Chemically transforming developed images
    • G03C5/44Bleaching; Bleach-fixing
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407Development processes or agents therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • the present invention relates to a processing composition for silver halide photographic materials and a processing method using the processing composition, and more particularly to a processing composition containing a novel chelating agent for masking metal ions harmful for photographic processing and a processing method using the same. Furthermore, the invention relates to a photographic processing composition containing a novel bleaching agent for a bleach step in color development processing and a processing method using the same.
  • a silver halide black and white photographic material is, after imagewise-exposure, processed by the processing steps of black and white development, fixing, washing, etc.
  • a silver halide color photographic material (hereinafter, referred to as "color photographic material") is, after imagewise-exposure, processed by the processing steps of color development, desilvering, washing, stabilization, etc.
  • a silver halide color reversal photographic material is, after imagewise exposure, processed by the processing steps of black and white development, reversal processing, color development, desilvering, washing, stabilization, etc.
  • exposed silver halide grains are converted into silver by being reduced with a color developing agent and at the same time, the oxidation product of the color developing agent formed reacts with couplers to form dye images.
  • auxiliary steps are added for the purposes of keeping the photographic and physical qualities of dye images and keeping the stability of photographic processing. For example, there are a wash step, a stabilization step, a hardening step, a stop step, etc.
  • metal ions enter the processing solution through various routes.
  • calcium ions, magnesium ions, and, in some cases, iron ions enter the processing solution through water being used for preparing the processing solution or calcium ions contained in the gelatin of silver halide photographic materials enters the processing solution.
  • iron ions enter the processing solution through water being used for preparing the processing solution or calcium ions contained in the gelatin of silver halide photographic materials enters the processing solution.
  • an iron chelate contained in the blix solution enters a developer which is the preceding bath.
  • metal ions contained in a preceding bath are carried in by photographic films impregnated with the solution in the preceding bath.
  • the influences by the intermixed metal ions differ according to the kinds of the metal ions and the processing solution.
  • ⁇ ions and magnesium ions in a developer react with a carbonate, which is used as a buffer in the developer, and form precipitates and sludges, which cause the problems of clogging a filter in a circulation system of an automatic processor and in staining photographic films so processed.
  • the entrance of transition metal salts such as iron ions, in a color developer or a black and white developer causes decomposition of a paraphenylenediamine color developing agent, a black and white developing agent, such as hydroquinone, monol (monomethyl-p-aminophenol sulfate), or a preservative, such as hydroxylamine, a sulfite. This results in greatly lowering the photographic characteristics.
  • transition metal ions such as iron ions, etc.
  • the stability of the bleach solution is greatly lowered. This causes the problems of inferior bleaching.
  • a stabilization solution prepared using hard water containing a large amount of calcium and magnesium bacteria grow using calcium and magnesium as a nutrient. This makes the solution turbid and stains the photographic films so processed. Also, when transition metal ions, such as iron ions enter a stabilization solution, the metal ions remain on the surface of a photographic film so processed, thereby the storage stability of the photographic film after processing is deteriorated.
  • chelating agents capable of masking metal ions have been used.
  • chelating agents there are, for example, the aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) described in JP-B-48-30496 and JP-B-44-30232 (the term “JP-B” as used herein means an "examined Japanese patent publication”), the organic phosphonic acids described in JP-A-56-97347 (the term “JP-A” as used herein means an "unexamined published Japanese patent application"), JP-B-56-39359, and West German Patent 2,227,639, the phosphonocarboxylic acids described in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, JP-A-55-126241, and JP-A-55-65956, and the compounds described in JP-
  • ethylenediaminetetraacetic acid shows a large masking ability to calcium ions, but when the compound is added to a developer, it accelerates the decomposition of a developing agent and a preservative for the developing agent in the presence of iron ions which causes the deterioration of the photographic characteristics such as lowering of the image density and an increase of the formation of fog.
  • alkylidenediphosphonic acid does not cause such a bad action even in the presence of iron ions but, when this compound is added to a processing solution prepared using hard water having a large content of calcium, solid matters are formed in the solution. This causes a problem for an automatic processor.
  • ethylenediaminetetraacetic acid ferric complex salt which is conventionally used as a bleaching agent for a bleach step and/or a blix step in processing of color photographic materials, has a fundamental fault in that the oxidative power is weak.
  • a bleach accelerator e.g., the addition of the mercapto compound described in U.S. Patent 1,138,842
  • quick bleaching has not yet been attained.
  • potassium ferricyanide As a bleaching agent capable of attaining quick bleaching, potassium ferricyanide, iron chloride, bromates are known.
  • potassium ferricyanide can not be widely used because of environmental concerns
  • iron chloride can not be widely used because of its inconvenience in handling, such as the corrosion of metals, and bromates can not be widely used because of the problem of instability of the processing solution.
  • a bleaching agent capable of attaining quick bleaching having a good handling property without causing the problem at discharging the waste solution has been desired.
  • 1,3-diaminopropanetetraacetic acid ferric complex salt has been disclosed as a bleaching agent.
  • the foregoing bleaching agent has a problem in performance, such as bleach fog forming with bleaching.
  • a method of reducing the formation of the bleach fog it is disclosed to add a buffer to the bleach solution as described, e.g., in JP-A-1-213657.
  • the improvement level is not sufficiently satisfactory.
  • a developer having a high activity is used in quick processing wherein the color development is carried out within 3 minutes, large bleach fog occurs even in the case of using such a buffer.
  • FR-A-2083830 describes a photographic bleach-fixing composition comprising a bleaching agent, which is a salt, wherein the anion is a Fe (III)complex with a ligand of formula: wherein L, L 1 , L 2 and L 3 each represents a carboxy residue or phosphono residue; G, G 1 , G 2 and G 3 represent a divalent residue selected from the group consisting of alkylene groups, arylene groups, and heterocyclene groups; and Z represents a divalent organic group.
  • the first object of the present invention is, therefore, to provide a photographic processing composition without forming precipitates and sludges by the intermixing of metal ions, and a processing method using the composition.
  • the second object of the present invention is to provide a stable photographic processing composition without causing a decrease of the effective components in the processing solution and the formation of components giving bad photographic action even by intermixing of metal ions, and a processing method using the composition.
  • the third object of the present invention is to provide a photographic processing composition capable of preventing lowering of the storage stability of images caused by remaining metal ions of the processing components in the photographic light-sensitive material processed, and a processing method using the composition.
  • the fourth object of the present invention is to provide a photographic processing composition which can be handled easily and does not cause an environmental problem by the waste solution, and a processing method using the composition.
  • the fifth object of the present invention is to provide a photographic processing composition having a bleaching power excellent in the desilvering property, and a processing method using the composition.
  • the sixth object of the present invention is to provide a photographic processing composition having a bleaching power and giving less bleaching fog, and a processing method using the composition.
  • the seventh object of the present invention is to provide a photographic processing composition having a bleaching power and causing less stains on photographic light-sensitive materials processed over the passage of time, and a processing method using the composition.
  • the eighth object of the present invention is to provide a photographic processing composition capable of stably keeping the above-described perfomances even in continuous processing, and a method using the composition.
  • a photographic processing composition containing at least one compound represented by formula (I); wherein X 1 , X 2 , and X 3 each represents a hydrogen atom, -L-COOM, or Z represents a carbon atomic group necessary for forming an aryl group; R 1 represents a hydrogen atom or a substituent group; R 2 represents an alkyl group, an alkoxy group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group
  • a method for processing a silver halide photographic material which comprises processing an imagewise exposed silver halide photographic material with a processing solution containing at least one compound represented by formula (I); wherein X 1 , X 2 , and X 3 each represents a hydrogen atom, -L-COOM, or Z represents a carbon atomic group necessary for forming an aryl group; R 1 represents a hydrogen atom or a substituent group; R 2 represents an alkyl group, an alkoxy group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an alkylsulfonyl group, an arylsulfonyl group
  • a photographic processing composition for a silver halide color photographic material said composition containing at least one of Fe(III), Mn(III), Co(III), Rh(II), Rh(III), Au(II), Au(III) and Ce(IV) chelate compounds of a compound represented by formula (I); wherein X 1 , X 2 , and X 3 each represents a hydrogen atom, -L-COOM, or Z represents a carbon atomic group necessary for forming an aryl group; R 1 represents a hydrogen atom or a substituent group; R 2 represents an alkyl group, an alkoxy group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoyl group, a carbamoyl group,
  • a method for processing a silver halide color photographic material which comprises processing an imagewise exposed silver halide color photographic material with a processing solution containing at least one of Fe(III), Mn(III), Co(III), Rh(II), Rh(III), Au(II), Au(III) and Ce(IV) chelate compounds of a compound represented by formula (I); wherein X 1 , X 2 , and X 3 each represents a hydrogen atom, -L-COOM, or Z represents a carbon atomic group necessary for forming an aryl group; R 1 represents a hydrogen atom or a substituent group; R 2 represents an alkyl group, an alkoxy group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a s
  • a group having an acyl moiety represents a group having an aliphatic acyl moiety or an aromatic acyl moiety
  • an aryl group represents a group having a phenyl group or a naphthyl group.
  • Z represents a carbon atomic group necessary for forming an aryl group.
  • aryl group a monocyclic or dicyclic aryl group is preferred, a phenyl group is more preferable. Examples include a phenyl group and a naphthyl group, and a phenyl group is preferred.
  • R 1 represents a hydrogen atom or a substituent.
  • substituent shown by R 1 there are e.g. an alkyl group, an aralkyl group, an alkenyl group, an alkinyl group, an alkoxy group, an aryl group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an aryloxy group, a sulfamoyl group, a carbamoyl group, -SM 3 , an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a hydroxy group, a halogen atom,
  • R 1 there are e.g. an alkyl group (e.g., methyl and ethyl), an aralkyl group (e.g., phenylmethyl), an alkenyl group (e.g., allyl), an alkinyl group (e.g., ethinyl group), an alkoxy group (e.g., methoxy and ethoxy), an aryl group (e.g., phenyl and p-methylphenyl), an amino group (e.g., amino, dimethylamino, and dihydroxyamino), an acylamino group (e.g., acetylamino and benzamido), an alkyl- and aryl-sulfonylamino group (e.g., methanesulfonylamino), an ureido group (e.g., ureido and methylureido), an alkyl group (e.g.,
  • the carbon atom number (in the present invention the carbon number of a group includes the number of the substituent(s) if the group has any) is preferably from 1 to 10, more preferably from 1 to 4.
  • R 1 is preferably an alkoxy group, an amino group, an acylamino group, an alkyl- and aryl- sulfonylamino group, an alkoxy- and aryloxy-carbonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a hydroxy group, -SO 3 M 3 , -COOM 3 , -PO 3 M 3 M 4 , a nitro group, or a hydroxamic acid group, more preferably a hydroxy group, -SO 3 M 3 , -COOM 3 , or a nitro group, and particularly preferably -COOM 3 .
  • R 2 represents an alkyl group, an alkoxy group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a hydroxy group, a halogen atom, a cyano group, -SO 3 M 1 , -COOM 1 , -PO 3 M 1 M 2 , an acyl group, an alkoxycarbonyl group, an acyloxy group, a nitro group, or a hydroxamic acid group.
  • R 2 represents an alkyl group (e.g., methyl and ethyl), an alkoxy group (e.g., methoxy and ethoxy), an acylamino group (e.g., acetylamino), an alkyl- and aryl-sulfonyl amino group (e.g., methanesulfonylamino), an ureido group (e.g., ureido and methylureido), an alkoxy- and aryloxy-carbonylamino group (e.g., methoxycarbonylamino), a sulfamoyl group (e.g., methylsulfamoyl), a carbamoyl group (e.g., carbamoyl and methylcarbamoyl), an alkylthio group (methylthio), an alkyl- and aryl-sulfonyl group (e.g., methanesul
  • R 2 is preferably an alkoxy group, an acylamino group, an alkyl- and aryl- sulfonylamino group, an ureido group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a hydroxy group, -SO 3 M 1 , -COOM 1 , -PO 3 M 1 M 2 , a nitro group, or a hydroxamic acid group, and more preferably a hydroxy group, -SO 3 M 1 , -COOM 1 , or a nitro group.
  • n represents 0 or an integer of from 1 to 7, preferably an integer of from 0 to 2, more preferably 0 or 1, and particularly preferably 0.
  • At least one or two of X 1 , X 2 and X 3 preferably one or two of them, more preferably one of them represents
  • the alkylene group shown by L may be straight chain or branched, and is preferably an alkylene group having from 1 to 6 carbon atoms.
  • L When formula (I) has plural Ls, the plural Ls may be the same or different. Also, L may have at least one substituent, such as those shown by R 1 . L is preferably methylene or ethylene.
  • M, M 1 , M 2 , M 3 and M 4 there are e.g. an alkali metal (e.g., lithium, sodium, and potassium), an ammonium (e.g., ammonium and tetraethylammonium), pyridinium.
  • an alkali metal e.g., lithium, sodium, and potassium
  • an ammonium e.g., ammonium and tetraethylammonium
  • the divalent linkage group shown by W can be preferably shown by following formula (W); -(W 1 -D) m -W 2 - wherein W 1 and W 2 , which may be the same or different, each represents a straight chain or branched alkylene group (preferably an alkylene group having from 2 to 8 carbon atoms), a cycloalkylene group (preferably a cycloalkylene group having from 5 to 10 carbon atoms), an arylene group (preferably an arylene group having from 6 to 10 carbon atoms), or an aralkylene group (preferably an aralkylene group having from 7 to 10 carbon atoms), and D represents -O-, -S-, -N(R W )-, or a divalent nitrogen-containing heterocyclic group.
  • W 1 and W 2 which may be the same or different, each represents a straight chain or branched alkylene group (preferably an alkylene group having from 2 to 8 carbon atoms), a cycloalkylene
  • R W represents a hydrogen atom, an alkyl group (preferably an alkyl group having from 1 to 8 carbon atoms) or an aryl group (preferably an aryl group having from 6 to 10 carbon atoms) each group may be substituted with -COOM 2 , -PO 3 M 3 M 4 , -OH, or -SO 3 M 5 (wherein M 2 , M 3 , M 4 , and M 5 each has the same meaning as M in formula (I)).
  • the linkage group shown by W may have at least one substituent at W 1 , R w and/or W 2 such as the substituent shown by R 1 .
  • W When W has two substituents, they may be bonded to form a 5- or 6-membered condenced ring, for example 5- or 6-membered saturated or unsaturated hydrocarbon ring.
  • a 5- or 6-membered heterocyclic ring having 1 to 4 hetero atoms that is, at least one nitrogen atom and at least one of nitrogen atom, oxygen atom and sulfur atom, as the hetero atom(s) is preferred.
  • the heterocyclic group which is bonded to W 1 and W 2 with adjacent carbon atoms in the heterocyclic ring is more preferable.
  • an alkylene group having from 2 to 4 carbon atoms is preferred.
  • m represents an integer of from 0 to 3, and when m is 2 or 3, said (W 1 -D)s may be the same or different. Furthermore, m is preferably from 0 to 2, more preferably 0 or 1, and particularly preferably 0.
  • Preferred compounds in the compounds shown by formula (I) described above are the compounds represented by following formula (II) or (III); wherein X 11 represents a hydrogen atom, -L 13 -COOM 13 , or X 11 is preferably -L 13 -COOM 13 ; Z 11 and Z 11 ' each has the same meaning as Z in formula (I); R 11 and R 11 ' each has the same meaning as R 1 in formula (I); R 12 and R 12 ' each has the same meaning as R 2 in formula (I); n 1 and n 1 ' each has the same meaning as n in formula (I); W 1 has the same meaning as W in formula (I); L 11 , L 12 , and L 13 each has the same meaning as L in formula (I); and M 11 , M 12 , and M 13 each has the same meaning as M in formula (I): wherein Z 21 and Z 21 ' each has the same meaning as Z in formula (I); R 21 and R 21 ' each has the same meaning as R 1 in formula (I); R
  • the particularly preferred compounds of formula (I) are the compound shown by formula (II) wherein R 11 is -COOM 33 (wherein M 33 has the same meaning as M in formula (I)) and the compound shown by formula (III) wherein R 21 and R 22 ' each is -COOM 43 (wherein M 43 has the same meaning as M in formula (I)).
  • the most preferred compounds are those which are shown by formula (II) wherein R 11 represents -COOM 33 and X 11 represents -L 13 COOM 13 .
  • X, X' Halogen atom (such as F, Cl, Br and I) L, R 1 , R 2 , n, M, W and Z are same as in formula (I).
  • the compound shown by formula (I) can be obtained by substituting the halogen atom of the halogen-substituted aromatic derivative with a diamine derivative, reacting the compound thus obtained with an inorganic acid (preferably hydrochloric acid) and reacting the compound thus obtained with a halogen-substituted alkylcarboxylic acid.
  • an inorganic acid preferably hydrochloric acid
  • alkali for the reaction of the halogen-substituted aromatic derivative and the diamine derivative, it is preferred to use an alkali and a catalyst.
  • alkali being used for the reaction are potassium carbonate and sodium carbonate.
  • the catalyst are a copper powder, CuCl, CuBr, CuI, and CuO.
  • a solvent may be used or may not be used.
  • any solvents which do not take part in the reaction can be used.
  • the solvent are alcohols (e.g., methanol, ethanol, isopropanol, butanol, and pentanol), dioxane, and dimethylformamide.
  • a solvent for the reaction of the halogen-substituted alkylcarboxylic acid, it is preferred to use a solvent.
  • the solvent are water, alcohols (e.g., methanol, ethanol and isopropanol) and dioxane.
  • a base for the reaction. Examples of the base are sodium hydroxide, potassium hydroxide, tertiary amines (e.g., triethylamine), and pyridine.
  • a method for production 3a is also disclosed in Allen Young and Thomas R. Sweet, J. Amer. Chem. Soc., 80 , 800 (1958).
  • a method for production of 4a is also disclosed in the same literature as that for 3a.
  • the compound represented by formula (I) can be applied to all sorts of processing compositions for processing silver halide black and white photographic materials or silver halide color photographic materials.
  • processing compositions for black and white photographic materials to which the foregoing compound can be applied there are an ordinary black and white developer, an infectious developer for lith films, a fixing solution, wash water, etc.
  • processing solutions for color photographic materials there are a color developer, a bleaching solution, a fixing solution, a blix solution, a compensating solution, a stop solution, a hardening solution, wash water, a stabilization solution, a rinse solution, a fogging solution, a toner, etc.
  • the processing composition to which the compound of formula (I) can be applied is not limited to the aforesaid compositions.
  • the addition amount of the compound shown by formula (I) depends upon the kind of the processing composition to which the composition is added but is generally used in the range of from 10 mg to 50 g per liter of the processing composition.
  • a preferred amount thereof is from 0.5 g to 10 g, and particularly from 0.5 g to 5 g per liter of the developer.
  • the amount is preferably from 0.1 g to 20 g, and particularly preferably from 0.1 g to 5 g per liter of the bleach solution.
  • the amount is preferably from 1 g to 40 g, and particularly preferably from 1 g to 20 g per liter of the processing solution.
  • the amount is preferably from 50 mg to 1 g, and particularly preferably from 50 mg to 300 mg per liter of the stabilization solution.
  • the compounds shown by formula (I) may be used alone or as a combination thereof.
  • the compound By forming a metal chelate compound of the compound shown by formula (I) and a salt of a metal selected from Fe(III), Mn(III), Co(III), Rh(II), Rh(III), Au(II), Au(III) and Ce(IV), the compound has an effect as a bleaching agent for silver halide color photographic materials.
  • the processing composition containing the metal chelate compound used in the present invention by color developing an imagewise exposed silver halide color photographic material and thereafter processing the color photographic material with a processing composition containing at least the metal chelate compound used in the present invention, bleaching of developed silver is carried out very quickly without causing severe bleaching fog occurred in the case of using a conventional bleaching agent capable of carrying out quick bleaching.
  • the effect is particularly remarkable when processing with the processing composition containing the metal chelate compound used in the present invention subsequent to a quick color development of a processing time of 3 minutes or shorter.
  • the storage stability of color images after processing is good and thus it is preferred to handle the processed color images.
  • the metal salt constituting the metal chelate compound for use in this invention is the salt of a metal selected from Fe(III), Mn(III), Co(III), Rh(II), Rh(III), Au(II), Au(III) and Ce(IV), preferably the salt of Fe(III), Mn(III) or Ce(IV), and particularly preferably the salt of Fe(III).
  • the Fe(III) chelate compound is preferable because it can be easily made to exhibit the function to obtain the effects of the present invention, there is less problem with respect to coloring, it is easily available and cheap, and it has excellent aging stability.
  • the metal chelate compound for use in the present invention may be formed in a solution by reacting the compound shown by formula (I) and the foregoing metal salt (e.g., ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate, and ferric phosphate) in the solution.
  • the foregoing metal salt e.g., ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate, and ferric phosphate
  • the molar ratio of the compound shown by formula (I) to the metal ion is at least 1.0.
  • the ratio is preferably as large as possible in the case that the stability of the metal chelate compound is low, and is usually used in the range of from 1 to 30.
  • the metal chelate compound may be used as an isolated metal chelate compound.
  • the specific examples of the metal chelate compound for use in the present invention are illustrated below but the invention is not limited to these compounds.
  • the compound shown by formula (I) and the metal salt may be present, alternatively the metal complex set thereof may be present.
  • the metal chelate compound for use in this invention may be incorporated in a fixing solution or an intermediate bath between a color development and a desilvering step in a small amount (preferably 1 m mol/l to 0.01 mol/l; in order to accelerate a rapid process) thereof, but by adding from 0.01 to 1 mol of the metal chelate compound per liter of a processing solution, the compound is effective as a bleaching agent for a bleaching solution or a blixing solution.
  • the metal chelate compound for use in this invention is effective as a bleaching agent for the processing solution having a bleaching ability when the solution contains the compound in an amount of from 0.01 to 1 mol per liter of the solution as described above, and the amount of the metal chelate compound is more preferably from 0.05 to 0.5 mol, and particularly preferably from 0.1 to 0.5 mol per liter of the processing solution.
  • the metal chelate compound used in this invention when used as a bleaching agent for the processing solution having a bleaching ability, the compound may be used together with another known bleaching agent in a range of giving the effect of the present invention.
  • a known bleaching agent there are the Fe(III), Co(III), or Mn(III) chelate bleaching agents of the compounds shown below and persulfates (e.g., peroxodisulfate), hydrogen peroxide, bromates, etc.
  • ethylenediaminetetraacetic acid diethylenetriaminepentaacetic acid, ethylenediamine-N-( ⁇ -hydroxyethyl)-N,N',N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyl ether diaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diaminopropanol-N,N,N',N'-tetramethylenephosphonic acid, ethylenediamine-N,N,N',N'
  • the processing solution containing the metal chelate compound for use in this invention as a bleaching agent and having a bleaching ability further contains a halide, such as a chloride, a bromide, an iodide, etc., as a rehalogenating agent for accelerating the oxidation of silver.
  • the processing solution may contain an organic ligand forming a sparingly soluble silver salt in place of the halide.
  • the halide is added to the processing solution as an alkali metal salt, an ammonium salt, or a salt of guanidine, amine, etc.
  • the amount of the rehalogenating agent is properly not more than 2 mols/liter, preferably from 0.01 to 2.0 mols/liter, and more preferably from 0.1 to 1.7 mols/liter.
  • the blix solution containing the metal chelate compound for use in this invention further contains a fixing agent (shown below) and, if necessary, can further contain the foregoing rehalogenating agent.
  • the amount thereof is from 0.001 to 2.0 mols/liter, and preferably from 0.001 to 1.0 mol/liter.
  • the bleach solution or the blix solution being used in the present invention may, if necessary, contain a bleach accelerator, a corrosion inhibitor inhibiting the corrosion of the processing bath, a buffer for keeping the necessary pH of the solution, an optical whitening agent, a defoaming agent, etc.
  • the bleach accelerator which can be used in this invention there are the compounds having a mercapto group or a disulfide group described in U.S. Patent 3,893,858, West German Patent 1,290,812, U.S. Patent 1,138,842, JP-A-53-95630, and Research Disclosure , No. 17129 (1978); the thiazolidine derivatives described in JP-A-50-140129; the thiourea derivative described in U.S. Patent 3,706,561; the polyethylene oxides described in West German Patent 2,748,430; the polyamine compounds described in JP-B-45-8836; and the imidazole compounds described in JP-A-49-40493. Of these compounds, the mercapto compounds described in U.S. Patent 1,138,842 are preferable.
  • a nitrate is preferably used and ammonium nitrate, sodium nitrate, potassium nitrate, etc., is used.
  • the addition amount thereof is from 0.01 to 2.0 mols/liter, and preferably from 0.05 to 0.5 mol/liter.
  • the ammonium ion concentration can be reduced to 0.3 mol/liter or lower. This embodiment is preferable from the view point of the environmental preservation and, if necessary, in the present invention the concentration can be reduced to 0.1 mol/liter or lower.
  • the pH of the bleach solution or the blix solution for use in this invention is from 2.0 to 8.0, and preferably from 3.0 to 7.5.
  • a color photographic material for photographing when the photographic material is bleached or blixed immediately after color development, it is better to use the processing solution at a pH of 7.0 or lower, and preferably 6.4 or lower.
  • the pH thereof is preferably from 3.0 to 5.0. If the pH is lower than 2.0, the metal chelate compound for use in this invention becomes unstable and hence the pH of the processing solution is preferably from 2.0 to 6.4.
  • the pH of the processing solution is preferably in the range of from 3 to 7.
  • any buffers which are reluctant to be oxidized with the bleaching agent and show a buffer action in the foregoing pH range can be used.
  • organic acids such as acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid, ureidopropionic acid, etc.
  • organic bases such as pyridine, dimethylpyrazole, 2-methyl-o-oxazoline, aminoacetonitrile, etc.
  • organic acids such as acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid, ureidopropionic acid, etc.
  • organic bases such as pyridine, dimethylpyrazole, 2-methyl-o-oxazoline, aminoacetonitrile, etc.
  • an organic acid having a pKa of from 2.0 to 5.5 is preferably used as the buffer and, in particular, the use of acetic acid
  • the amount of the buffer is properly 3.0 mols or less, and preferably from 0.5 to 2.0 mols per liter of the processing solution having a bleaching ability.
  • an alkali agent e.g., aqueous ammonia, potassium hydroxide, sodium hydroxide, imidazole, monoethanolamine, and diethanolamine
  • aqueous ammonia is preferable.
  • the bleaching step or the blixing step is carried out in the temperature range of from 30°C to 60°C, and preferably from 35°C to 50°C.
  • the processing time of the bleaching and/or the blixing step is in the range of from 10 seconds to 7 minutes, and preferably from 10 seconds to 2 minutes in a light-sensitive material for photographing. Also, the processing time thereof is from 5 seconds to 70 seconds, preferably from 5 seconds to 60 seconds, and more preferably from 10 seconds to 45 seconds in a photographic light-sensitive material for printing. In these preferred processing conditions, good results of quick processing and having no increase of stains are obtained.
  • a known fixing agent may be used.
  • the fixing agent there are thiosulfates, thiocyanates, thioethers, amines, mercaptos, thiones, thioureas, iodides, mesoions, etc. Practical examples thereof are ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, potassium thiocyanate, dihydroxyethyl thioether, 3,6-dithia-1,8-octanediol, and imidazole.
  • thiosulfates in particular, ammonium thiosulfate is preferred for carrying out quick fixing.
  • the fixing agents by using two or more kinds of the fixing agents, more quick fixing can be carried out.
  • a combination of ammonium thiosulfate and foregoing ammonium thiocyanate, imidazole, thiourea, thioether, can be preferably used, and in this case, as the secondary fixing agent, it is preferred to use the secondary fixing agent in the range of from 0.01 to 100 mol% to ammonium thiosulfate.
  • the amount of the fixing agent is from 0.1 to 3.0 mols, and preferably from 0.5 to 2.0 mols per liter of the blix solution or the fixing solution.
  • the pH of the fixing solution depends upon the kind of the fixing agent but is generally from 3.0 to 9.0. In particular, in the case of using a thiosulfate, the pH of the fix solution is preferably from 6.5 to 8.0 for obtaining a stable fixing performance.
  • the blix solution or the fixing solution can contain a preservative for increasing the stability of the solution with the passage of time.
  • a preservative for increasing the stability of the solution with the passage of time.
  • a blix solution or a fixing solution containing a thiosulfate, sulfites and/or hydroxylamine, hydrazine, bisulfite addition products of an aldehyde (e.g., bisulfite addition products of acetaldehyde and, particularly preferably, the bisulfite addition products of aromatic aldehydes described in JP-A-1-298935), etc. are effective as the preservatives.
  • the sulfinic acid compounds described in JP-A-62-143048 are preferably used as the preservatives.
  • a buffer for keeping the pH of the blix solution or the fixing solution at a constant value, it is preferable to add a buffer to the solution.
  • the buffer are phosphates; imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imisdazole, 1-ethyl-imidazole, etc., triethanolamine; N-allylmorpholine; and N-benzoylpiperazine.
  • the stability of the solution can be improved by adding thereto various chelating agents to mask iron ions carried in from a bleaching solution.
  • preferred chelating agents are 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,2-propanediaminetetraacetic acid, and the compound shown by foregoing formula (I) for use in the present invention.
  • the fixing step is carried out in the temperature range of from 30°C to 60°C, and preferably from 35°C to 50°C.
  • the processing time for the fixing step is from 15 seconds to 2 minutes, and preferably from 25 seconds to 1 minute and 40 seconds for a light-sensitive material for photographing and from 8 seconds to 80 seconds and preferably from 10 seconds to 45 seconds for a photographic light-sensitive material for print.
  • the desilvering step in this invention is carried by the combinations of a bleaching step, a fixing step, and a blixing step, and typical examples of these combinations are as follows.
  • the combination (1), (2), (3), or (4) is preferable, and the combination (1), (2) or (3) is more preferable.
  • the combination (5) is preferable.
  • the present invention can be applied to a desilvering processing through, for example, a stop bath and a wash bath, after color development processing.
  • the processing solution is stirred as strong as possible for more efficiently obtaining the effect of the present invention.
  • the processing process of the present invention is carried out using an automatic processor.
  • the transporting method of photographic light-sensitive materials in such an automatic processor is described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259. Also, for carrying out quick processing in an automatic processor, it is preferable to shorten the crossover between the processing baths.
  • the automatic processor wherein the crossover time is 5 seconds or shorter is described in JP-A-1-319038.
  • each replenisher it is preferred to supply each replenisher to each processing solution in accordance with the amount of photographic light-sensitive materials processed for compensating the loss of the components of each processing solution with the processing of the photographic light-sensitive materials, and also for preventing the accumulation of undesirable components dissolved out from the photographic light-sensitive materials processed in each processing solution.
  • two or more processing tanks may be employed for each processing step and in this case, it is preferred to employ a countercurrent system of supplying the replenisher from the post-bath tank to the preceding bath tank.
  • a cascade-type countercurrent system of from 2 to 4 stages is preferably used.
  • the amount of each replenisher is preferably low if the change of the composition in the processing solution does not cause troubles for the photographic performance and staining of the solution.
  • the amount of the replenisher for a color developer is from 100 ml to 3,000 ml, and preferably from 100 ml to 2,200 l per square meter of a photographic light-sensitive material being processed in the case of a color photographic material and is from 20 ml to 500 ml, and preferably from 30 ml to 350 ml per square meter of a photographic light-sensitive material in the case of a color print material.
  • the amount of the replenisher for a bleaching solution is from 10 ml to 1,000 ml, and preferably from 50 ml to 550 ml per square meter of a photographic light-sensitive material being processed in the case of a color photographic material and is from 20 ml to 500 ml, and preferably from 50 ml to 300 ml per square meter of a photographic light-sensitive material in the case of a print material.
  • the amount of the replenisher for a blix solution is from 200 ml to 3,000 ml, and preferably from 250 ml to 1,300 ml per square meter of a photographic light-sensitive material in the case of a color photographic material and is from 20 ml to 300 ml, and preferably from 50 ml to 200 ml per square meter of a photographic light-sensitive material in the case of a print material.
  • the replenisher for a blix solution may be replenished as one solution or may be replenished separately as a bleaching composition and a fixing composition. Also, a mixture of the overflow solutions from bleaching baths and/or fixing baths may be used as a replenisher for a blix solution.
  • the amount of the replenisher for the fixing solution is from 300 ml to 3,000 ml, and preferably from 300 ml to 1,200 ml per square meter of a photographic light-sensitive material in the case of a color photographic material and is from 20 ml to 300 ml, and preferably from 50 ml to 200 ml per square meter of a photographic light-sensitive material in the case of a print material.
  • the amount of the replenisher for wash water or a stabilization solution is from 1 to 50 times, preferably from 2 to 30 times, and more preferably from 2 to 15 times the amount of the solution carried from the preceding bath per unit area of a photographic light-sensitive material.
  • each processing solution may be practiced while circulating the processing solution in an automatic processor or after once recovering the processing solution from the processing tank and applying thereto a proper regeneration treatment, the solution may be supplied again to the processing bath as the replenisher.
  • a metal chelate bleaching agent in a bleaching solution and/or a blix solution is converted to a reduced state with bleaching processing, it is preferred to employ a continuous regeneration method for the bleaching solution and/or the blix solution in corporation with processing. Practically, it is preferred to blow air into the bleaching solution and/or the blix solution by means of an air pump and reoxidizing (or so-called aerating) the metal chelate in a reduced state with oxygen. Furthermore, by adding an oxidizing agent, such as hydrogen peroxide, a persulfate and a bromate, to the bleaching solution and/or the blix solution, the processing solution can be also regenerated.
  • an oxidizing agent such as hydrogen peroxide, a persulfate and a bromate
  • the regeneration of a fixing solution and a blix solution is carried out by electrolytically reducing accumulated silver ions. Furthermore, it is preferred for keeping the fixing ability to remove accumulating halogen ions with an anion exchange resin.
  • an ion exchange or an ultrafiltration is used, and the use of an ultrafiltration is particularly preferred.
  • the color developer being used in this invention contains a conventionally known aromatic primary amine color developing agent.
  • Preferred color developing agents are p-phenylenediamine derivatives and specific examples thereof are 4-amino-N-ethyl-N-( ⁇ -hydroxyethyl)-3-methylaniline, 4-amino-N-ethyl-N-( ⁇ -hydroxypropyl)-3-methylaniline, 4-amino-N-ethyl-N-(4-hydroxybutyl)-3-methylaniline, 4-amino-N-ethyl-N-( ⁇ -methanesulfonamidoethyl)-3-methylaniline, 4-amino-N-(3-carbamoylpropyl)-N-n-propyl-3-methylaniline, and 4-amino-N-ethyl-N-( ⁇ -hydroxyethyl)-3-methoxyaniline.
  • salts of these p-phenylenediamine derivatives and sulfates, hydrochlorides, sulfites, naphthalene-disulfonic acid, or p-toluenesulfonic acid may be used as the color developing agent.
  • the amount of the aromatic primary amine developing agent used is preferably from 0.0002 mol to 0.2 mol, and more preferably from 0.001 mol to 0.1 mol per liter of the developer.
  • the color developer can contain, if necessary, a sulfite, such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonylsulfite addition product as the preservative.
  • a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonylsulfite addition product as the preservative.
  • various hydroxylamines such as the compounds shown by JP-A-63-5341 and JP-A-63-106655, are preferred and of these compounds, the compounds having a sulfo group or a carboxy group are particularly preferred.
  • hydroxamic acids described in JP-A-63-43138 can be preferably added to the color developer.
  • the hydrazines and hydrazides described in JP-A-63-146041 can be preferably added to the color developer.
  • the phenols described in JP-A-63-44657 and JP-A-63-58443 can be preferably added to the color developer.
  • the color developer may contain the various metals described in JP-A-57-44148 and JP-A-57-53749, the salicylic acids described in JP-A-59-180588, the alkanolamines described in JP-A-54-3582, the polyethyleneimines described in JP-A-56-94349, or the aromatic polyhydroxy compounds described in U.S. Patent 3,746,544 as other preservatives.
  • the addition of the aromatic polyhydroxy compounds is particularly preferable.
  • the addition amount of the foregoing preservative is from 0.005 mol to 0.2 mol, and preferably from 0.01 mol to 0.05 mol per liter of the color developer.
  • the pH of the color developer being used in this invention is in the range of from 9.0 to 12.0, and preferably from 9.5 to 11.5.
  • the color developer for use in this invention can further contain compounds conventionally known as components for color developers.
  • the buffer is sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tri-sodium phosphate, tri-potassium phosphate, di-sodium phosphate, di-potassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
  • the invention is not limited to these compounds.
  • the addition amount of the buffer to the color developer is preferably not less than 0.1 mol/liter, and particularly preferably from 0.1 to 0.4 mol/liter.
  • the color developer can further contain the compounds shown by formula (I) for use in this invention and other various chelating agents as precipitation inhibitors for calcium and magnesium or for improving the stability of the color developer.
  • organic acid compounds are preferable and, for example, there are aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.
  • aminopolycarboxylic acids organic phosphonic acids
  • phosphonocarboxylic acids include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine o-hydroxyphenylacetic acid, 2-phosphono-butane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and N,N'-bis(2-
  • These chelating agents may be used, if desired, as a mixture of two or more kinds thereof.
  • the addition amount of the chelating agent may be one sufficient for blocking metal ions in the color developer and, for example, from 0.001 mol to 0.05 mol, and preferably from 0.003 mol to 0.02 mol per liter of the color developer.
  • the color developer can further contain, if desired, a development accelerator.
  • a development accelerator examples include the thioether compounds described in JP-B-37-16088, JP-B-37-5987, JP-B-38-7826, JP-B-44-12380, JP-B-45-9019, U.S. Patent 3,818,247; the p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554; the quaternary ammonium salts described in JP-A-50-137726, JP-B-44-30074, JP-A-56-156826, JP-A-52-43429; the amine compounds described in U.S.
  • the 1-phenyl-3-pyrazolidones described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438 are preferably added to the color developer as auxiliary developing agents for quickening the color development.
  • the color developer for use in this invention can contain, if desired, an optional antifoggant.
  • an optional antifoggant alkali metal halides, such as sodium chloride, potassium bromide, potassium iodide and organic antifoggants can be used.
  • organic antifoggant are nitrogen-containing heterocyclic compounds, such as benzotriazole, 6-nitrobenzimidazole, 5-nitrosioindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine, and adenine.
  • the color developer being used in this invention may contain an optical whitening agent.
  • an optical whitening agent 4,4'-diamino-2,2'-disulfostilbene compounds are preferably used.
  • the addition amount thereof is from 0 to 5 g/liter, and preferably from 0.1 g/liter to 4 g/liter.
  • various surface active agents such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, aromatic carboxylic acids, may be added to the color developer.
  • the processing temperature for the color developer being used in this invention is preferably from 20°C to 55°C, and more preferably from 30°C to 55°C.
  • the processing time preferably is from 20 seconds to 5 minutes, more preferably from 30 seconds to 3 minutes and 20 seconds, and particularly preferably from 1 minute to 2 minutes and 30 seconds for a color photographic material for photographing, and preferably from 10 seconds to 1 minute and 20 seconds, more preferably from 10 seconds to 60 seconds, and particularly preferably from 10 seconds to 40 seconds for a print material.
  • the processing process of the present invention can be applied to color reversal processing.
  • the black and white developer being used in color reversal processing is an ordinary known black and white primary developer which is used for reversal processing for a color photographic light-sensitive material.
  • the black and white primary developer can contain various additives well known as the additives for a black and white developer being used for developing a black and white silver halide photographic material.
  • developing agents such as 1-phenyl-3-pyrazolidone, Metol, and hydroquinone
  • preservatives such as sulfites
  • accelerators such as sodium hydroxide, sodium carbonate, potassium carbonate
  • inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzothiazole
  • water softeners such as polyphosphates
  • development inhibitors such as a slight amount of an iodide and mercapto compounds.
  • Wash water being used for a wash step and/or the stabilization solution can contain various surface active agents for preventing the occurrence of water spots when drying the photographic light-sensitive material after processing.
  • surface active agents there are polyethylene glycol type nonionic surface active agents, polyhydric alcohol type nonionic surface active agents, alkylbenzenesulfonate type anionic surface active agents, higher alcohol sulfuric acid ester salt type anionic surface active agents, alkylnaphthalenesulfonate type anionic surface active agents, quaternary ammonium salt type cationic surface active agents, amine salt type cationic surface active agents, amino acid type amphoteric surface active agents, and betaine type amphoteric surface active agents.
  • nonionic surface active agents are preferably used, and in particular, alkylphenol-ethylene oxide addition products are preferably used.
  • alkylphenol octyl, nonyl, dodecyl, and dinonylphenol are preferred, and the addition mol number of the ethylene oxide is particularly preferably from 8 to 14 mols.
  • silicone surface active agents having a high defoaming effect are preferably used.
  • wash water and/or the stabilization solution can contain various antibacterial agents or antifungal agents for preventing the formation of furs, and the generation of fungi in the photographic light-sensitive materials after processing.
  • antibacterial agents and antifungal agents are the thiazolylbenzimidazole compounds as described in JP-A-57-157244 and JP-A-58-105145; the isothiazolone compounds as described in JP-A-54-27424 and JP-A-57-8542; chlorophenol compounds, such as trichlorophenol; bromophenol compounds; organotin compounds and organozinc compounds; thiocyanic acid or isothiocyanic acid compounds; acid amide compounds; diazine and triazine compounds, thiourea compounds; benzotriazole alkylguanizine compounds; quaternary ammonium salts, such a benzammonium chloride; antibiotics, such as penicillin; and the ordinary antibacterial agents described in Journal of Antibacterial and Antifungus Agents , Vol. 1, No. 5, 207-223(1983).
  • JP-A-48-83820 various germicides described in JP-A-48-83820 can be used.
  • wash water and/or the stabilization solution can further contain various chelating agents in the range of not reducing the effect of the compound shown by formula (I) for use in this invention.
  • aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid
  • organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid
  • maleic anhydride polymers described in European Patent 345172A1.
  • the foregoing preservative which can be incorporated in the fixing solution and the blix solution is incorporated in wash water.
  • a processing solution for stabilizing dye images is used.
  • a processing solution for stabilizing dye images there are an organic acid or a solution having a buffering ability of a pH of from 3 to 6 and a solution containing an aldehyde (e.g., formalin and glutaraldehyde), hexahydrotriazine, hexamethylenetetramine, or an N-methylol compound (e.g., dimethylolurea, N-methylolpyrazole, and N-methylol-1,2,4-triazole) as an image stabilizer.
  • an aldehyde e.g., formalin and glutaraldehyde
  • hexahydrotriazine hexamethylenetetramine
  • an N-methylol compound e.g., dimethylolurea, N-methylolpyrazole, and N-methylol-1,2,4-triazole
  • the stabilization solution can further contain a saturated cyclic amine (e.g., morpholine and piperazine), an ammonium compound, such as ammonium chloride, ammonium sulfite, a metal compound, such as a Bi compound, an Al compound, an optical brightening agent, a hardening agent, and the alkanolamine described in U.S. Patent 4,786,583.
  • a saturated cyclic amine e.g., morpholine and piperazine
  • a multistage countercurrent system is preferably employed and the stage number is preferably from 2 to 4 stages.
  • the amount of the replenisher for the processing solution is from 1 to 50 times, preferably from 2 to 30 times, and more preferably from 2 to 15 times the amount of the processing solution carried by the photographic light-sensitive material from the preceding bath per unit area of the light-sensitive material.
  • city water may be used but water which is subjected to a deionizing treatment with ion exchange resins to lower the concentrations of calcium and magnesium to 5 mg/liter or lower and water sterilized with a halogen, ultraviolet sterilizing lamp are preferably used.
  • city water may be used, but foregoing deionized water or sterilized water, which is preferably used for the foregoing wash step or stabilization step is preferably used.
  • the amount of waste liquids can be reduced.
  • black and white silver halide photographic materials e.g., black and white light-sensitive materials for photographing, X-ray black and white light-sensitive materials, and black and white light-sensitive materials for printing
  • ordinary multi layer silver halide color photographic materials e.g., color negative photographic films, color reversal photographic films
  • the photographic light-sensitive material being processed by the processing composition of the present invention can have various layer structures (e.g., silver halide emulsion layers each having a light-sensitive to red, green, or blue, a subbing layer, an antihalation layer, a filter layer, interlayers, and surface protective layer(s)) and layer dispositions on one surface or both the surfaces thereof according to the purpose of the photographic light-sensitive materials.
  • layer structures e.g., silver halide emulsion layers each having a light-sensitive to red, green, or blue, a subbing layer, an antihalation layer, a filter layer, interlayers, and surface protective layer(s)
  • the supports of the photographic light-sensitive materials the coating methods, the kinds of silver halide being used for the silver halide emulsion layers and surface protective layers (e.g., silver iodobromide, silver iodochlorobromide, silver bromide, silver chlorobromide, and silver chloride); the grain forms of the silver halide grains (e.g., cubic, tabular, and spherical); the grain sizes thereof; the variation coefficients thereof; the crystal structures (e.g., core/shell structure, multiphase structure, and uniform phase structure); the production method thereof (e.g., a single jet method and a double jet method); binders (e.g., geratin); hardening agents; antifoggants; metal doping agents; silver halide solvents; thickeners; emulsion precipitating agents; dimensional stabilizers; adhesion inhibitors; stabilizers; color mixing inhibitors; stain inhibitors; dye image stabilizer
  • the dry thickness of the entire constituting layers is preferably not thicker than 20.0 ⁇ m, and more preferably not thicker than 18.0 ⁇ m in the case of the color photographic material for photographing and is not thicker than 16.0 ⁇ m, and more preferably not thicker than 13.0 ⁇ m in the case of a print material.
  • the bleach fog caused by the color developing agent remaining after color development and stains after processing are liable to increase.
  • the occurrence of the bleach fog and stains is caused by a green-sensitive emulsion layer, and as the result thereof, the increase of magenta color becomes larger than the increases of cyan color and yellow color.
  • the lower limit in the foregoing range of the layer thickness is preferably as thin as possible in the range of not greatly reducing the performance of the color photographic material.
  • the lower limit of the total dry layer thickness of the entire constituting layers, excluding the support of the color photographic material, the subbing layer, and the back layer, is 12.0 ⁇ m in the case of a color photographic material and is 7.0 ⁇ m in the case of a print material .
  • a layer is usually disposed between the lowermost light-sensitive emulsion layer and the subbing layer on the support and the lower limit of the total dry thickness of the layer (the layer may be plural) is 1.0 ⁇ m. Also, the reduction of the layer thickness may be practiced for light-sensitive emulsion layers and/or the light-insensitive layers.
  • the layer thickness of a multilayer color photographic material is measured by the following method.
  • the color photographic material being measured is stored for 7 days after the preparation thereof under the condition of 25°C and 50% RH.
  • the total thickness of the color photographic material is measured, then, after removing the coated layers on the support, the thickness thereof is measured again, and the difference between the former thickness and the latter thickness is defined as the layer thickness of the entire coated layers of the color photographic material excluding the support.
  • the thickness can be measured by using, for example, a film thickness measuring apparatus by a contact-type piezoelectric conversion element (K-402B Stand., trade name, manufactured by Anritsu electric Co., Ltd.).
  • the coated layers on the support can be removed using an aqueous solution of sodium hypochloride.
  • the cross section of the foregoing color photographic material is photographed using a scanning type electron microscope (the magnification is preferably at least 3,000 magnifications) to measure actually the thickness of the entire layers on the support and the thickness of each layer, and by comparing the measured results with the measured value (the absolute value of the actually measured thickness) of the total thickness by the foregoing film thickness measuring apparatus, the thickness of each layer can be calculated.
  • the magnification is preferably at least 3,000 magnifications
  • the swelling ratio [(A - B)/B ⁇ 100; A: the equilibrium swelled layer thickness in water at 25°C; B: the dry total layer thickness at 25°C, 55% RH] in the color photographic material being processed by the process of this invention is preferably from 50 to 200%, and more preferably from 70 to 150%.
  • the swelling ratio is outside the foregoing range, the remaining amount of a color developing agent is increased and also the photographic performance, the image quality, such as the desilvering property, etc., and the film properties, such as the film strength, etc., are deteriorated.
  • the swelling speed of the color photographic material being processed by the process of the present invention is as follows. That is, when 90% of the maximum swelled layer thickness of the color photographic material in a color developer (30°C, 3 minutes and 15 seconds) is defined as a saturated swelled layer thickness and the time required for reaching 1/2 of the saturated swelled layer thickness is defined as swelling speed T1 ⁇ 2, T1 ⁇ 2 is preferably 15 seconds or lower, and more preferably 9 seconds or lower.
  • the silver halide contained in the silver halide photographic emulsion layers of the color photographic material being processing by the process of this invention may have any silver halide composition.
  • silver iodobromide, silver iodochloride or silver iodochlorobromide each containing from 0.1 mol% to 30 mol% silver iodide is preferred.
  • silver iodobromide containing 1 mol% to 25 mol% silver iodide is preferred.
  • silver bromide or silver chlorobromide is preferred and also silver chloride is preferred for carrying out quick processing.
  • silver chloride or silver chlorobromide is preferred and in particular, silver chlorobromide having a silver chloride content of at least 80 mol%, more preferably at least 95%, and most preferably at least 98 mol% is preferred.
  • Suitable supports which can be used for the color photographic materials being processed by the process of this invention are also described, e.g., in foregoing Research Disclosure , No. 17643, page 28 and ibid. , No. 18716 from page 647, right column to page 648, left column.
  • the present invention can be applied to various kinds of color photographic light-sensitive materials. Typical examples thereof are general or cine color negative photographic films, color reversal photographic films for slide or television, color photographic papers, direct positive color photographic papers, color positive photographic films, and color reversal photographic papers.
  • the color reversal film may be of a type of containing couplers in the color photographic material (coupler-in-emulsion type)or of a type of containing couplers in the developers (coupler-in-developer type).
  • City water was passed through a mixed bed type column filled with an H-type strong acidic cation exchange resin (Amberlite® IR-120B, trade name, made by Rohm and Haas Company) and an OH-type strong basic anion exchange resin (Amberlite® IRA-400) to lower the concentration of calcium and magnesium below 3 mg/liter, and then 20 mg/liter of sodium dichloroisocyanurate and 150 mg/liter of sodium sulfate were added to the water.
  • the pH of the solution was in the range of from 6.5 to 7.5.
  • ferric chloride at 5 ppm as a ferric ion and calcium nitrate at 150 ppm as a calcium ion to provide samples 101 to 107.
  • the multilayer color photographic material sample 105 described in Example 1 of JP-A-2-89045 was sliced in a width of 35 mm and wedge-exposed of 5 CMS at a color temperature of 4800 K.
  • the color photographic material was processed by the following processing steps using each of Samples 101 to 107 directly after preparation (new solution) and after the test with the passage of time as the color developer.
  • Step Processing Time Processing Temperature (°C) Color Development 3 min. and 15 sec. 37.8 Bleach 50 sec. 38.0 Fix 100 sec. 38.0 Wash (1) 30 sec. 38.0 Wash (2) 20 sec. 38.0 Stabilization 20 sec. 38.0
  • the residual ratios of the developing agent and hydroxylamine in the color developer after 30 days were obtained by analysis. Furthermore, for each color developer after 30 days, the presence of precipitates was visually determined.
  • Example 1 To the fixing solution used in Example 1 was added 3 g/liter of each of Compounds 1, 3, 4, and 20 of formula (I) used in this invention and further 100 ml/liter of the bleaching solution described in Example 1 was added to the fixing solution to provide Samples 201 to 204. Also, for the sake of comparison, the fix solution of Example 1 without having added the compound of formula (I) but added with the bleaching solution only was prepared to provide Sample 205.
  • the addition amount of the bleaching solution corresponds to the general amount of bleaching solution attached to the color photographic material processed and carried into a fixing solution and accumulated to equilibrium.
  • the stabilization solution as in Example 1 was used as Comparison Sample 301 and by adding 100 mg/liter of each of Compounds 1, 3 and 4 of formula (I) to the stabilization solution Samples 302 to 303 were provided.
  • Example 1 The multilayer color photographic material as in Example 1 was processed by the same manner as in Example 1 using each of the stabilization solutions and the fresh solutions of the color developer (Sample 101) and others in Example 1.
  • the multilayer color photographic material was stored for one week under the wet and heat conditions of 80°C and 70% RH. Then, the stain increase ( ⁇ Dmin) of magenta before and after processing was determined.
  • a bleaching solution having the following composition was prepared. Hydrogen Peroxide (30%) 50 ml Potassium Bromide 28 g Potassium Hydrogenphosphate 10 g Water to make 1 liter pH 3.5
  • This bleaching solution was used as Comparison Sample 401 and by adding 100 g/liter of each of the Comparison compound and Compounds 1, 3, and 4 of formula (I) to the bleaching solution, Samples 402 to 405 were prepared.
  • Example 1 For determining the bleaching ability of each sample, the multilayer color photographic material as in Example 1 was processed using Sample 101 in Example 1 as the color developer and the fixing solution, the stabilization solution, and wash water as in Example 1.
  • III-10 was used in place of III-23 described in the above patent application as the bisphenol compound, the yellow coupler (ExY), the cyan coupler (ExC), the dye image stabilizer (Cpd-8), the solvent (Solv-6), and the oxonol dyes were changed with the following compounds, and also the following antiseptics (antibacterial and antifungal agent) was further used to provide multilayer color photographic paper B.
  • each sample was stored in a beaker for 20 days at 39°C in a state that the open ratio was 0.10 cm -1 .
  • the foregoing multilayer color photographic paper B was subjected to a gradation exposure of a sensitometric 3 color separation filter using a sensitometer (Type FWH, made by Fuji Photo Film Co., Ltd.). The exposure was carried out such that the exposure amount became 250 CMS by the exposure time of 0.1 second.
  • the color photographic paper was processed by the following steps using the foregoing color developer immediately after preparation (fresh solution) or the color developer stored for 20 days (stored solution). (Processing Steps) Step Temperature Time Color Development 38°C 45 sec. Blix 35°C 25 sec. Rinse (1) 35°C 20 sec. Rinse (2) 35°C 20 sec. Rinse (3) 35°C 20 sec. Drying 80°C 60 sec.
  • Ion-exchanged water concentration of calcium and magnesium each was less than 3 ppm.
  • the residual amount of the color developing agent in the stored color developer was determined by a high-speed liquid chromatography. Also, the occurrence of precipitations in the stored color developer was visually observed.
  • Example 1 of JP-A-2-58041 When disodium ethylenediaminetetraacetate in Developer (A) in Example 1 of JP-A-2-58041 was replaced with the same amount of Compound 3 of formula (I) for use in the present invention to provide Developer (B) and after storing the developer for 4 days at 40°C, Sample 1 in Example 1 of JP-A-2-58041 was subjected to running processing using the developer, the formation of precipitates was restrained.
  • a multilayer color photographic material A having the layers of the following compositions on a cellulose triacetate film support having a subbing layer was prepared.
  • the coating amount was shown by a g/m 2 unit of silver for a silver halide in an emulsion and colloidal silver, by a g/m 2 unit for couplers, additives and gelatin, and by mol number per mol of silver halide in the same layer for a sensitizing dye.
  • Layer 1 Antihalation layer Black Colloidal Silver 0.20 as Ag Gelatin 2.20 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 ⁇ 10 -2 Cpd-2 1.9 ⁇ 10 -2 Solv-1 0.30 Solv-2 1.2 ⁇ 10 -2
  • Layer 2 Interlayer Fine Grain Silver Iodobromide (AgI 1.0 mol%, sphere-corresponding diameter 0.07 ⁇ m) 0.15 as Ag Gelatin 1.00 ExC-4 6.0 ⁇ 10 -2 Cpd-3 2.0 ⁇ 10 -2
  • Layer 3 1st Red-Sensitive Emulsion Layer Silver Iodobromide in Emulsion (AgI 5.0 mol%, surface high AgI type, sphere-corresponding diameter 0.9 ⁇ m, variation coeff.
  • the sample further contained 1,2-benzisothizaolin-3-one (200 ppm in average to gelatin), n-butyl-p-hydroxybenzoate (1,000 ppm to gelatin), and 2-phenoxyethanol (10,000 ppm to gelatin). Furthermore, the sample contains B-4, B-5, W-2, W-3, F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, an iron salt, a lead salt, a gold salt, a platinum salt, an iridium salt, and a rhodium salt.
  • the multilayer color photographic material A thus prepared was sliced into width of 35 mm, subjected to a wedge exposure of white light (color temperature of the light source 4800 K), and processed by the following processing steps using an cine automatic processor. In this case, however, the multilayer color photographic material A for evaluating the performance was processed after processing an imagewise-exposed sample until the accumulated amount of the replenisher for the color developer became thrice the tank volume.
  • Wash was a countercurrent system from (2) to (1).
  • the carried amount of the color developer into the bleaching step and the carried amount of the fixing solution into the washing step were 2.5 ml and 2.0 ml, respectively per a meter length ⁇ 35 mm width of the color photographic material.
  • the bleaching carried was out while bubbling at 200 ml/min through a conduit portion having a large number of fine holes having a diameter of 0.2 mm equipped to the bottom of the bleaching solution tank.
  • each crossover time was 5 seconds, which was included in the processing time of the previous step.
  • the chelate compound shows an organic acid which reacts with iron nitrate ⁇ 9H 2 O to form an organic acid ferric ammonium salt acting as a bleaching agent. (The same in the following examples).
  • the residual amount of silver at the maximum color density portion was measured by a fluorescent X-ray analysis.
  • the bleaching solution was replaced with the bleaching solution having the following formula as a standard bleaching solution giving no bleaching fog and the multilayer color photographic material A was processed at a bleaching time of 390 seconds, a processing temperature of 38°C, and at a replenishing amount of 25 ml per 35 mm ⁇ 1 meter of the color photographic material, while not changing the other conditions.
  • the foregoing multilayer color photographic material A thus processed was stored under the following condition and the increase of stains upon storing the sample after processing was determined by the density change of Dmin at the uncolored portion before and after storing.
  • the metal chelate compounds for use in this invention can reduce the residual amount of silver and show excellent effects in the bleach fog and stains upon storing color images after processing as compared with the case of using the comparison compounds.
  • Ion-exchanged water concentration of calcium and magnesium each lower than 3 ppm
  • the multilayer color photographic paper B prepared in Example 5 was processed in the following processing steps. (Processing steps) Step Temperature Time Color Development 38°C 45 sec. Blix 35°C 25 sec. Rinse (1) 35°C 20 sec. Rinse (2) 35°C 20 sec. Rinse (3) 35°C 20 sec. Drying 80°C 60 sec.
  • the multilayer color photographic paper B uniformly exposed such that the gray density became 1.5 was processed by the same manner as above and the residual silver amount in the maximum density portion of each sample was determined by a fluorescent X-ray analysis.
  • Comparison Compound A is the same Comparison Compound A in Example 8.
  • the multilayer color photographic material A as in Example 8 was exposed to white light of a color temperature of 4800 K through a wedge and processed by the following processing steps.
  • the processing was carried out until the accumulated amount of each replenisher became twice the tank volume, and at that time the processing property was evaluated.
  • the evaluation of the processing property was carried out by measuring the residual amount at the maximum color density portion, measuring the bleach fog, and measuring the increase of stains under the dark, wet, and heat condition as in Example 8.
  • the comparison compounds are the same as those in Example 8.
  • the bleaching solutions containing the metal chelate compounds for use in this invention as the bleaching agents are excellent in the desilvering property, the prevention of bleach fog, and the prevention of stains after processing as compared with the comparison bleach solutions.
  • the multilayer color photographic material prepared as in Example 8 was exposed to white light having a color temperature of 4800 K through an optical wedge and then processed by the following processing steps.
  • an automatic processor having shortened racks was used and processing for shortening processing time was also carried out.
  • Processing (1) is a process wherein the processing time for bleaching, blixing, and fixing each is 50 seconds
  • processing (2) is the process wherein the processing time for bleaching and blixing is shortened to 20 seconds and the processing time for fixing is shortened to 30 seconds.
  • Wash step was a countercurrent system of from wash (2) to wash (1) and all of the overflow liquid of wash water was introduced into the fix bath.
  • Replenishing to the blix bath was carried out as follows.
  • the upper portion of the bleach tank was connected to the bottom of the blix tank by pipe and the upper portion of the fix tank was connected to the bottom of the blix tank by pipes in the automatic processor, whereby all of the overflow liquids formed by supplying each replenisher to the bleach bath and the fix bath were introduced into the blix bath.
  • the carrying over amounts of the color developer into the bleaching step, the bleaching solution into the blixing step, the blix solution into the fixing step, and the fixing solution into the wash step were 2.5 ml, 2.0 ml, 2.0 ml, and 2.0 ml respectively per 35 mm ⁇ 1 meter of the color photographic material.
  • the crossover time in each case was 5 seconds, which was included in the processing time of the preceding step.
  • the processing was continued until the accumulated amount of each replenisher in each processing bath tank became thrice the tank volume.
  • the following processing performance was the result of processing carried out at that time.
  • to the bleach bath tank was equipped a subtank of aeration for the bleaching solution and the processing was carried out while blowing air of about 200 ml/min.
  • a 15:85 mixture of the foregoing bleach tank liquid and the following tank liquid of the fixing solution A 15:85 mixture of the foregoing bleach tank liquid and the following tank liquid of the fixing solution.
  • (Fix Solution) Mother Liquid Replenisher Ammonium Sulfite 19.0 g 57.0 g
  • Aqueous Ammonium Thiosulfate Solution (700 g/liter) 280 ml 840 ml Imidazole 28.5 g 85.5 g Ethylenediaminetetraacetic Acid 12.5 g 37.5 g Water to make 1 liter 1 liter pH (adjusted with aqueous ammonia or acetic acid) 7.40 7.45
  • the residual silver amount at the maximum density portion was measured by a fluorescent X-ray analysis method. Also, the bleach fog was evaluated as in Example 8.
  • the comparison compounds are the same as in Example 8.
  • the processing solution having a bleaching ability containing the metal chelate compound for use in this invention can reduce the residual amount of silver and also shows almost no increase of bleaching fog and stains after processing, and thus shows an excellent performance as compared with the processing solution containing the comparative compound.
  • the multilayer color photographic paper B as prepared in Example 5 was uniformly exposed such that the gray density became 2.2 and processed by the following processing steps.
  • the residual silver amount was measured by a fluorescent X-ray analysis method.
  • the multilayer color photographic paper B was subjected to a gradation exposure through a wedge and processed as above.
  • the sample after processing was stored for one week at 80°C, 70% RH and the increase of stain before and after the storage was determined.
  • Step Temp Time Replenishing Amount Tank Volume (°C) (sec.) (ml) (liter) Color Development 39 45 70 20 Blix 35 (1) 45 60 20 (2) 20 Rinse (1) 35 20 - 10 Rinse (2) 35 20 - 10 Rinse (3) 35 20 360 10 Drying 80 60
  • Example 1 For the rinse, the wash water in Example 1 was used. No. Chelate Compound Blix Time Residual Silver Amount Stain Increase ⁇ D Remarks ( ⁇ g/cm 2 ) 1201 Comparison 45 sec. 2.6 0.11 Comp. -1 Compound A 20 sec. 8.0 0.20 1202 " B 45.sec. 10.0 0.03 Comp. -2 20 sec. 20.2 0.04 1203 Compound 1 45 sec. 1.6 0.04 Inv. 20 sec. 2.1 0.05 1204 " 3 45.sec. 0.9 0.03 " 20 sec. 1.4 0.04 1205 “ 4 45 sec. 0.7 0.04 " 20 sec. 1.1 0.05 1206 " 20 45 sec. 1.4 0.04 " 20 sec. 2.0 0.05
  • the comparison compounds are the same as in Example 8.
  • the metal chelate compounds for use in this invention are excellent in the desilvering property and the formation of stains upon storage after processing as compared with the comparison compounds.
  • the effects are remarkable in the processing of shortening the blixing time. That is, when the blixing time is shortened to half, the residual silver amount is less and the formation of stain with the passage of time after processing is less even before and after running.
  • the comparison compounds when the sample was processed with the processing solution immediately after preparation, the residual silver was scarcely observed, but with the progress of running, the desilvering property was greatly reduced as shown above, and further precipitates formed.
  • Example 8 When the same procedure as processings 801 to 809 in Example 8 was followed using Fuji Color Super HG 400® (Production No. 311130, trade name, made by Fuji Photo Film Co., Ltd.) and Fuji Color REALA® (Production No. 861016, trade name, made by Fuji Photo Film Co., Ltd.), almost same results as Example 8 were confirmed.
  • the multilayer color photographic material as in Example 1 was sliced into a width of 35 mm, subjected to a light exposure of 5 CMS at a color temperature of 4800 K, and then processed by the following processing steps using the following processing solutions and a cine automatic processor.
  • samples 1401 to 1408 including comparison samples and the samples used in this invention were prepared and each sample was used for each case.
  • the time from the bleach step before drying was 8 minutes and 35 seconds.
  • the residual silver amount was measured by the following method.
  • the amount of silver remaining in each color photographic material thus processed was measured by a fluorescent X-ray analysis method.

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Claims (16)

  1. Photographische Verarbeitungszusammensetzung, enthaltend mindestens eine Verbindung, die durch die Formel (I) dargestellt ist;
    Figure 01860001
    worin X1, X2 und X3 jeweils ein Wasserstoffatom, -L-COOM, oder
    Figure 01860002
    darstellen;
    Z eine Kohlenstoff-Atomgruppe darstellt, die zum Bilden einer Arylgruppe erforderlich ist; R1 ein Wasserstoffatom oder eine Substituentengruppe darstellt; R2 eine Alkylgruppe, eine Alkoxygruppe, eine Acylaminogruppe, eine Alkylsulfonylaminogruppe, eine Arylsulfonylaminogruppe, eine Ureidogruppe, eine Alkoxycarbonylaminogruppe, eine Aryloxycarbonylaminogruppe, eine Sulfamoylgruppe, eine Carbamoylgruppe, eine Alkylthiogruppe, eine Alkylsulfonylgruppe, eine Arylsulfonylgruppe, eine Alkylsulfinylgruppe, eine Arylsulfinylgruppe, eine Hydroxygruppe, ein Halogenatom, eine Cyanogruppe, -SO3M1, -COOM1, eine -PO3M1M2-Gruppe, eine Acylgruppe, eine Alkoxycarbonylgruppe, eine Acyloxygruppe, eine Nitrogruppe oder eine Hydroxamsäuregruppe darstellt; n 0 oder eine ganze Zahl von 1 bis 7 darstellt; L eine Alkylengruppe darstellt; M, M1 und M2 jeweils ein Wasserstoffatom oder ein Kation darstellen; und W eine zweiwertige Verbindungsgruppe darstellt, die eine Alkylengruppe und/oder eine Arylengruppe enthält,
    dadurch gekennzeichnet, daß mindestens einer der Reste X1, X2 und X3
    Figure 01870001
    darstellt.
  2. Verfahren zum Verarbeiten eines photographischen Silberhalogenidmaterials, welches das Verarbeiten eines bildmäßig belichteten photographischen Silberhalogenidmaterials mit einer Verarbeitungslösung umfaßt, welche mindestens eine Verbindung enthält, die durch die Formel (I) dargestellt ist;
    Figure 01870002
    worin X1, X2 und X3 jeweils ein Wasserstoffatom, -L-COOM oder
    Figure 01870003
    darstellen; Z eine Kohlenstoff-Atomgruppe darstellt, die zum Bilden einer Arylgruppe erforderlich ist; R1 ein Wasserstoffatom oder eine Substituentengruppe darstellt; R2 eine Alkylgruppe, eine Alkoxygruppe, eine Acylaminogruppe, eine Alkylsulfonylaminogruppe, eine Arylsulfonylaminogruppe, eine Ureidogruppe, eine Alkoxycarbonylaminogruppe, eine Aryloxycarbonylaminogruppe, eine Sulfamoylgruppe, eine Carbamoylgruppe, eine Alkylthiogruppe, eine Alkylsulfonylgruppe, eine Arylsulfonylgruppe, eine Alkylsulfinylgruppe, eine Arylsulfinylgruppe, eine Hydroxygruppe, ein Halogenatom, eine Cyanogruppe, -SO3M1, -COOM1, eine -PO3M1M2-Gruppe, eine Acylgruppe, eine Alkoxycarbonylgruppe, eine Acyloxygruppe, eine Nitrogruppe oder eine Hydroxamsäuregruppe darstellt; n 0 oder eine ganze Zahl von 1 bis 7 darstellt; L eine Alkylengruppe darstellt, M, M1 und M2 jeweils ein Wasserstoffatom oder ein Kation darstellen; und W eine zweiwertige Verbindungsgruppe darstellt, die eine Alkylengruppe und/oder eine Arylengruppe enthält;
    dadurch gekennzeichnet, daß mindestens einer der Reste X1, X2 und X3
    Figure 01880001
    darstellt.
  3. Photographische Verarbeitungszusammensetzung für ein farbphotographisches Silberhalogenidmaterial, wobei diese Zusammensetzung mindestens einen Bestandteil, ausgewählt aus Fe(III), Mn(III), Co(III), Rh(II), Rh(III), Au(II), Au(III) und Ce(lV)-Chelatverbindungen von einer Verbindung, die durch die Formel (I) dargestellt ist, enthält
    Figure 01880002
    worin X1, X2 und X3 jeweils ein Wasserstoffatom, -L-COOM oder
    Figure 01890001
    darstellen;
    Z eine Kohlenstoff-Atomgruppe darstellt, die zum Bilden einer Arylgruppe erforderlich ist; R1 ein Wasserstoffatom oder eine Substituentengruppe darstellt; R2 eine Alkylgruppe, eine Alkoxygruppe, eine Acylaminogruppe, eine Alkylsulfonylaminogruppe, eine Arylsulfonylaminogruppe, eine Ureidogruppe, eine Alkoxycarbonylaminogruppe, eine Aryloxycarbonylaminogruppe, eine Sulfamoylgruppe, eine Carbamoylgruppe, eine Alkylthiogruppe, eine Alkylsulfonylgruppe, eine Arylsulfonylgruppe, eine Alkylsulfinylgruppe, eine Arylsulfinylgruppe, eine Hydroxygruppe, ein Halogenatom, eine Cyanogruppe, -SO3M1, -COOM1, eine -PO3M1M2-Gruppe, eine Acylgruppe, eine Alkoxycarbonylgruppe, eine Acyloxygruppe, eine Nitrogruppe oder eine Hydroxamsäuregruppe darstellt, n 0 oder eine ganze Zahl von 1 bis 7 darstellt; L eine Alkylengruppe darstellt; M, M1 und M2 jeweils ein Wasserstoffatom oder ein Kation darstellen; und W eine zweiwertige Verbindungsgruppe darstellt, die eine Alkylengruppe und/oder eine Arylengruppe enthält,
    dadurch gekennzeichnet, daß mindestens einer der Reste X1, X2 und X3
    Figure 01890002
    darstellt.
  4. Verfahren zum Verarbeiten eines farbphotographischen Silberhalogenidmaterials, welches das Verarbeiten eines bildmäßig belichteten farbphotographischen Silberhalogenidmaterials mit einer Verarbeitungslösung umfaßt, die mindestens einen Bestandteil, ausgewählt aus Fe(III), Mn(III), Co(III), Rh(II), Rh(III), Au(II), Au(III) und Ce(lV)-Chelatverbindungen von einer Verbindung, die durch die Formel (I) dargestellt ist, enthält
    Figure 01900001
    worin X1, X2 und X3 jeweils ein Wasserstoffatom, -L-COOM oder
    Figure 01900002
    darstellen;
    Z eine Kohlenstoff-Atomgruppe darstellt, die zum Bilden einer Arylgruppe erforderlich ist; R1 ein Wasserstoffatom oder eine Substituentengruppe darstellt; R2 eine Alkylgruppe, eine Alkoxygruppe, eine Acylaminogruppe, eine Alkylsulfonylaminogruppe, eine Arylsulfonylaminogruppe, eine Ureidogruppe, eine Alkoxycarbonylaminogruppe, eine Aryloxycarbonylaminogruppe, eine Sulfamoylgruppe, eine Carbamoylgruppe, eine Alkylthiogruppe, eine Alkylsulfonylgruppe, eine Arylsulfonylgruppe, eine Alkylsulfinylgruppe, eine Arylsulfinylgruppe, eine Hydroxygruppe, ein Halogenatom, eine Cyanogruppe, -SO3M1, -COOM1, eine -PO3M1M2-Gruppe, eine Acylgruppe, eine Alkoxycarbonylgruppe, eine Acyloxygruppe, eine Nitrogruppe oder eine Hydroxamsäuregruppe darstellt; n 0 oder eine ganze Zahl von 1 bis 7 darstellt; L eine Alkylengruppe darstellt; M, M1 und M2 jeweils ein Wasserstoffatom oder ein Kation darstellen; und W eine zweiwertige Verbindungsgruppe darstellt, die eine Alkylengruppe und/oder eine Arylengruppe enthält,
    dadurch gekennzeichnet, daß mindestens einer der Reste X1, X2 und X3
    Figure 01910001
    darstellt.
  5. Verfahren zum Verarbeiten eines farbphotographischen Silberhalogenidmaterials nach Anspruch 4, worin der durch R1 dargestellte Substituent (i) eine Alkylgruppe, eine Aralkylgruppe, eine Alkenylgruppe, eine Alkinylgruppe, eine Alkoxygruppe, eine Arylgruppe, eine Aminogruppe, eine Acylaminogruppe, eine Alkylsulfonylaminogruppe, eine Arylsulfonylaminogruppe, eine Ureidogruppe, eine Alkoxycarbonylaminogruppe, eine Aryloxycarbonylaminogruppe, eine Aryloxygruppe, eine Sulfamoylgruppe, eine Carbamoylgruppe, -SM3, eine Alkylthiogruppe, eine Arylthiogruppe, eine Alkylsulfonylgruppe, eine Arylsulfonylgruppe, eine Alkylsulfinylgruppe, eine Arylsulfinylgruppe, eine Hydroxygruppe, ein Halogenatom, eine Cyanogruppe, -SO3M3, -COOM3, -PO3M3M4, eine Aryloxycarbonylgruppe, eine Acylgruppe, eine Alkoxycarbonylgruppe, eine Acyloxygruppe, eine Nitrogruppe oder eine Hydroxamsäuregruppe bedeutet, worin M3 und M4 jeweils ein Wasserstoffatom oder ein Kation darstellen.
  6. Verarbeitungsverfahren für ein farbphotographisches Silberhalogenidmaterial nach Anspruch 4, worin die durch W dargestellte zweiwertige Gruppe eine Gruppe ist, die durch die Formel (W) dargestellt ist; -(W1-D)m-W2- worin W1 und W2, welche gleich oder verschieden sein können, jeweils eine geradkettige oder verzweigte Alkylengruppe, eine Cycloalkylengruppe, eine Arylengruppe oder eine Aralkylengruppe darstellen, und D -O-, -S-, -N(Rw)- oder eine zweiwertige stickstoffhaltige heterocyclische Gruppe darstellen, Rw ein Wasserstoffatom, eine Alkylgruppe oder eine Arylgruppe darstellt, jede Gruppe mit -COOM2, -PO3M3M4, -OH oder -SO3M5 substituiert sein kann (worin M2, M3, M4 und M5 jeweils die gleiche Bedeutung wie M in Formel (I) aufweisen) und m eine ganze Zahl von 0 bis 3 darstellt und wenn m 2 oder 3 ist, die (W1-D)-Reste gleich oder verschieden sein können.
  7. Verfahren zum Verarbeiten eines farbphotographischen Silberhalogenidmaterials nach Anspruch 4, worin R1 ein Wasserstoffatom oder -COOM3 darstellt.
  8. Verfahren zum Verarbeiten eines farbphotographischen Silberhalogenidmaterials nach Anspruch 4, worin R2 eine Hydroxygruppe, -SO3M1, -COOM1 oder eine Nitrogruppe darstellt.
  9. Verfahren zum Verarbeiten eines farbphotographischen Silberhalogenidmaterials nach Anspruch 6, worin W1 und W2 jeweils eine Alkylengruppe mit 2 bis 4 Kohlenstoffatomen darstellen.
  10. Verfahren zum Verarbeiten eines farbphotographischen Silberhalogenidmaterials nach Anspruch 9, worin m 0 bedeutet.
  11. Verfahren zum Verarbeiten eines farbphotographischen Silberhalogenidmaterials nach Anspruch 4, worin L eine Methylengruppe oder eine Ethylengruppe darstellt.
  12. Verfahren zum Verarbeiten eines farbphotographischen Silberhalogenidmaterials nach Anspruch 4, worin Z eine Kohlenstoff-Atomgruppe darstellt, die zum Bilden einer Phenylgruppe erforderlich ist.
  13. Verfahren zum Verarbeiten eines farbphotographischen Silberhalogenidmaterials nach Anspruch 4, worin die durch Formel (I) dargestellte Verbindung eine Verbindung ist, die durch Formel (II) oder (III) dargestellt ist;
    Figure 01920001
    worin X11 ein Wasserstoffatom, -L13-COOM13 oder
    Figure 01930001
    darstellt; Z11 und Z11' jeweils die gleiche Bedeutung wie Z in Formel (I) aufweisen; R11 und R11' jeweils die gleiche Bedeutung wie R1 in Formel (I) aufweisen; R12 und R12' jeweils die gleiche Bedeutung wie R2 in Formel (I) aufweisen, n1 und n1' jeweils die gleiche Bedeutung wie n in Formel (I) aufweisen; W1 die gleiche Bedeutung wie W in Formel (I) aufweist; L11, L12 und L13 jeweils die gleiche Bedeutung wie L in Formel (I) aufweisen; und M11, M12 und M13 jeweils die gleiche Bedeutung wie M in Formel (I) aufweisen;
    Figure 01930002
    worin Z21 und Z21' jeweils die gleiche Bedeutung wie Z in Formel (I) aufweisen; R21 und R21' jeweils die gleiche Bedeutung wie R1 in Formel (I) aufweisen; R22 und R22' die gleiche Bedeutung wie R2 in Formel (I) aufweisen, n2 und n2' jeweils die gleiche Bedeutung wie n in Formel (I) aufweisen; W2 die gleiche Bedeutung wie W in Formel (I) aufweist; L21 und L22 jeweils die gleiche Bedeutung wie L in Formel (I) aufweisen; und M21 und M22 jeweils die gleiche Bedeutung wie M in Formel (I) aufweisen.
  14. Verarbeitungsverfahren für ein farbphotographisches Silberhalogenidmaterial nach Anspruch 4, worin die chelatbildende Verbindung in einer Menge von 1mMol bis 1 Mol/l der Verarbeitungslösung eingearbeitet ist.
  15. Verarbeitungsverfahren für ein farbphotographisches Silberhalogenidmaterial nach Anspruch 4, worin die Verarbeitungslösung eine Bleichlösung oder Bleichfixierlösung ist und die Chelatverbindung darin als Bleichmittel eingearbeitet ist.
  16. Verfahren zum Verarbeiten eines farbphotographischen Silberhalogenidmaterials nach Anspruch 13, worin R11 -COOM33 bedeutet und X11 -L13COOM13 bedeutet und M33 die gleiche Bedeutung wie M in Formel (I) aufweist.
EP19920115176 1991-09-05 1992-09-04 Photographische Verarbeitungszusammensetzung und Verarbeitungsverfahren Expired - Lifetime EP0530828B1 (de)

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JP252775/91 1991-09-05
JP3252745A JP3042640B2 (ja) 1991-09-05 1991-09-05 ポリアリーレンスルフィドオリゴマーの分離方法
JP3252775A JP2889999B2 (ja) 1991-09-05 1991-09-05 写真用処理組成物及び処理方法
JP252745/91 1991-09-05

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