EP1074886A1 - Verfahren zur Verarbeitung eines farbphotographischen Silberhalogenidmaterials und eine Verarbeitungslösung für ein photographisches lichtempfindliches Silberhalogenidmaterial - Google Patents

Verfahren zur Verarbeitung eines farbphotographischen Silberhalogenidmaterials und eine Verarbeitungslösung für ein photographisches lichtempfindliches Silberhalogenidmaterial Download PDF

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EP1074886A1
EP1074886A1 EP00116702A EP00116702A EP1074886A1 EP 1074886 A1 EP1074886 A1 EP 1074886A1 EP 00116702 A EP00116702 A EP 00116702A EP 00116702 A EP00116702 A EP 00116702A EP 1074886 A1 EP1074886 A1 EP 1074886A1
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Prior art keywords
group
processing
carbon atoms
solution
formula
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French (fr)
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Hideo c/o Fuji Photo Film Co. Ltd. Miyazaki
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Fujifilm Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421—Additives other than bleaching or fixing agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • the present invention relates to a method for processing a silver halide color photographic material which has been imagewise exposed to light (hereinafter merely referred to as "light-sensitive material") with a processing composition having a fixing ability. More particularly, the present invention relates to a processing composition for improving liquid stability and photographic properties and a processing method using the processing composition.
  • a light-sensitive material which has been subjected to exposure and development is processed with a bleaching solution or fixing solution.
  • a fixing agent to be incorporated in the fixing solution there has conventionally been well-known a thiosulfate.
  • a thiosulfate has been widely used in combination with sulfites which are used as preservatives therefor and auxiliaries such as aminopolycarboxylic acid and organic phosphonic acid described in JP-A-2-139548 (The term "JP-A" as used herein means an "unexamined published Japanese patent application") and JP-A-6-130567.
  • a processing solution having a fixing ability is liable to deterioration or affects the color forming property of dyes when its pH value is lowered. Therefore, the processing solution having a fixing ability is preferably used around pH 7. However, when the processing solution has a pH value within this range, it reacts with calcium or magnesium ion contained in water used to prepare the solution or eluate from the light-sensitive material to produce precipitates or sludge or color the light-sensitive material or accelerate the change of photographic properties with time after processing. Thus, various problems cannot necessarily be solved satisfactorily, leaving much to be desired. It is further disadvantageous in that the precision in reading magnetically recorded data from a light-sensitive material having a magnetic recording layer as described in International Patent WO90/04205 is remarkably deteriorated.
  • a processing solution having a fixing ability e.g., fixing solution, blixing solution
  • the present invention lies in a method for processing a silver halide color photographic material comprising color development, desilvering, rinsing and/or processing with a stabilizer, wherein the desilvering is effected with (a) a processing solution with a bleaching ability containing at least one ferric complex salt (III) of a compound represented by formula (I) and having a pH value of from 3 to 7 and (b) a processing solution with a fixing ability containing at least complex-forming agent selected from the group consisting of a compound represented by formula (II), EDTA and an organic phosphonic acid and having a pH value of from 6.1 to 8.0.
  • R 1 represents a hydrogen atom, aliphatic hydrocarbon group, aryl group or heterocyclic group
  • L 1 and L 2 each represent an alkylene group
  • M 1 and M 2 each represent a hydrogen atom or cation
  • R 21 , R 22 , R 23 and R 24 each represent a hydrogen atom, aliphatic hydrocarbon group, aryl group, heterocyclic group, hydroxyl group or carboxyl group
  • t and u each represent an integer of 0 or 1
  • W represents a divalent connecting group containing carbon atoms
  • M 21 , M 22 , M 23 and M 24 each represent a hydrogen atom or cation.
  • the inhibition of stain (particularly cyan stain) on the image thus formed the improvement of stability of the image thus processed (particularly magenta) with time and the minimization of so-called failure of color restoration (phenomenon involving failure in exhibition of desired color (forming) density due to a trouble in which the production of a dye stops at an intermediate step during development process, making it impossible to produce a desired dye completely) can be remarkably accomplished, making it possible to obtain an excellent color image having a minimized change with time and hence achieve the foregoing objects.
  • the processing solution with a fixing ability to be used in desilvering contains a compound represented by formula (A) in addition to the at least one complex-forming agent selected from the group consisting of the compound represented by formula (II), EDTA and an organic phosphonic acid
  • the foregoing objects of the present invention can be further accomplished.
  • the minimization of failure of color restoration can be remarkably accomplished.
  • Q represents a nonmetallic atom group required to form a heterocyclic group
  • p represents an integer of 0 or 1
  • M a represents a hydrogen atom or cation.
  • the processing solution with a fixing ability for a silver halide photographic material containing at least one complex-forming agent selected from the group consisting of the compound represented by formula (II), EDTA and an organic phosphonic acid and a compound represented by formula (A) and having a pH value of from 6.1 to 8.0 is according to the present invention.
  • This processing solution is preferably a processing solution having a fixing ability for a color light-sensitive material.
  • a preferred embodiment of the processing solution according to the present invention is a fixing solution for color light-sensitive material.
  • Examples of the complex-forming agent belonging to any of the foregoing compound represented by formula (II), EDTA (ethylenediamine-N,N,N',N'-tetraacetic acid) and the organic phosphonic acid include those included in the formulae of compound to be added to fixing solution disclosed in JP-A-1-206342, JP-A-2-139548, JP-A-4-313752, and JP-A-6-67370.
  • these disclosed techniques are all intended to accelerate desilvering by a processing solution having a fixing ability or prevent the processing solution from becoming turbid. Accordingly, there are no suggestions on the effect of the present invention of improving the stability of magenta dye or minimizing failure of color restoration.
  • the present invention exerts its effect by incorporating the compound represented by formula (I) in the processing solution having a bleaching ability. None of the above described patents has reference to the compound represented by formula (I). There is found no knowledge that such a compound is incorporated in a processing solution having a bleaching ability.
  • Pyridine-2,6-dicarboxylic acid which is one of the compounds represented by formula (A) is incorporated in the fixing solution disclosed in JP-A-51-7930.
  • the above described patent is intended to prevent cyan stain caused by iron chloride bleaching solution and thus differs from the present invention in purpose, process and composition of processing solution. Similarly, there is found no knowledge of the scope of the present invention.
  • the light-sensitive material is processed with a color developer, desilvered, and then rinsed and/or processed with a stabilizer.
  • the light-sensitive material is essentially subjected to bleaching with a processing solution having a bleaching ability, and then subjected to fixing with a processing solution having a fixing ability.
  • Bleaching and fixing may be separately effected.
  • bleaching and fixing may be simultaneously effected with a blixing solution having both a bleaching ability and a fixing ability (blixing).
  • blixing fixing ability
  • processing solution having a fixing ability means a processing solution containing a fixing agent among the processing solutions to be used in the desilvering step, particularly fixing solution and blixing solution.
  • processing solution having a bleaching ability means a processing solution containing a bleaching agent among the processing solutions to be used in the desilvering step, particularly bleaching solution and blixing solution.
  • a rinsing step may be provided between these processing steps.
  • the effect of the present invention can be exerted particularly with the foregoing steps 1, 5 and 7.
  • the processing solution having a bleaching ability to be used in the processing method of the present invention will be described hereinafter.
  • an inorganic oxidizing agent such as red prussiate, ferric chloride, bichromate, persulfate, bromate and hydrogen peroxide, and organic acid ferric complex salt (III).
  • the processing solution having a bleaching ability to be used in the present invention may contain these bleaching agents but essentially contains a compound represented by formula (I): wherein R 1 represents a hydrogen atom, aliphatic hydrocarbon group, aryl group or heterocyclic group; L 1 and L 2 each represent an alkylene group; and M 1 and M 2 each represent a hydrogen atom or cation.
  • R 1 represents a hydrogen atom, aliphatic hydrocarbon group, aryl group or heterocyclic group
  • L 1 and L 2 each represent an alkylene group
  • M 1 and M 2 each represent a hydrogen atom or cation.
  • the aliphatic hydrocarbon group represented by R 1 is a straight-chain, branched or cyclic alkyl group (preferably having from 1 to 12 carbon atoms, more preferably from 1 to 10 carbon atoms, most preferably from 1 to 8 carbon atoms), alkenyl group (preferably having from 2 to 12 carbon atoms, more preferably from 2 to 10 carbon atoms, most preferably from 2 to 7 carbon atoms) or alkinyl group (preferably having from 2 to 12 carbon atoms, more preferably from 2 to 10 carbon atoms, most preferably from 2 to 7 carbon atoms) which may have substituents.
  • substituents include aryl group preferably having from 6 to 12 carbon atoms, more preferably from 6 to 10 carbon atoms, particularly preferably from 6 to 8 carbon atoms such as phenyl and p-methylphenyl, alkoxy group preferably having from 1 to 8 carbon atoms, more preferably from 1 to 6 carbon atoms, particularly preferably from 1 to 4 carbon atoms such as methoxy and ethoxy, aryloxy group preferably having from 6 to 12 carbon atoms, more preferably from 6 to 10 carbon atoms, particularly preferably from 6 to 8 carbon atoms such as phenyloxy, acyl group preferably having from 1 to 12 carbon atoms, more preferably from 2 to 10 carbon atoms, particularly preferably from 2 to 8 carbon atoms such as acetyl, alkoxycarbonyl group preferably having from 2 to 12 carbon atoms, more preferably from 2 to 10 carbon atoms, particularly preferably from 2 to 8 carbon atoms such as methoxycarbony
  • substituents on the aliphatic hydrocarbon group represented by R 1 include alkoxy group, carboxyl group, hydroxyl group, and sulfo group. Preferred among these substituents are carboxyl group and hydroxyl group.
  • the aliphatic hydrocarbon group represented by R 1 is preferably an alkyl group, more preferably a chain alkyl group, most preferably methyl, ethyl, carboxymethyl, 1-carboxyethyl, 2-carboxyethyl, 1,2-dicarboxyethyl, 1-carboxy-2-hydroxyethyl, 2-carboxy-2-hydroxyethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-sulfoethyl, 1-carboxypropyl, 1-carboxybutyl, 1,3-dicarboxypropyl, 1-carboxy-2-(4-imidazolyl)ethyl, 1-carboxy-2-phenylethyl, 1-carboxy-3-methylthiopropyl, 2-carbamoyl-1-carboxyethyl or 4-imidazolylmethyl, particularly preferably methyl, carboxymethyl, 1-carboxyethyl, 2-carboxyethyl, 1,
  • the aryl group represented by R 1 is preferably a C 6-20 monocyclic or bicyclic aryl group (e.g., phenyl, naphthyl), more preferably a C 6-15 phenyl group, most preferably a C 6-10 phenyl group.
  • the aryl group represented by R 1 may have substituents.
  • substituents include those exemplified as the aliphatic hydrocarbon group represented by R 1 , alkyl group preferably having from 1 to 8 carbon atoms, more preferably from 1 to 6 carbon atoms, particularly preferably from 1 to 4 carbon atoms such as methyl and ethyl, alkenyl group preferably having from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms, particularly preferably from 2 to 4 carbon atoms such as vinyl and allyl, and alkinyl group preferably having from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms, particularly preferably from 2 to 4 carbon atoms such as propargyl.
  • substituents on the aryl group represented by R 1 include alkyl group, alkoxyl group, hydroxyl group, and sulfo group. Preferred among these substituents are alkyl group, carboxyl group, and hydroxyl group.
  • aryl group represented by R 1 examples include 2-carboxyphenyl, and 2-carboxymethoxyphenyl.
  • the heterocyclic group represented by R 1 is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of N, O and S atoms.
  • the heterocyclic group may be monocyclic or may form a condensed ring with other rings.
  • the heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, more preferably a 5- or 6-membered aromatic heterocyclic group containing nitrogen atoms, most preferably a 5- or 6-membered heterocyclic group containing one or two nitrogen atoms.
  • heterocyclic group examples include pyrrolidinyl, piperidinyl, piperadinyl, imidazolyl, pyrazolyl, pyridyl, and quinolyl. Preferred among these heterocyclic groups are imidazolyl and pyridyl.
  • the heterocyclic group represented by R 1 may have substituents.
  • substituents include those exemplified as the aliphatic hydrocarbon group represented by R 1 , alkyl group preferably having from 1 to 8 carbon atoms, more preferably from 1 to 6 carbon atoms, particularly preferably from 1 to 4 carbon atoms such as methyl and ethyl, alkenyl group preferably having from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms, particularly preferably from 2 to 4 carbon atoms such as vinyl and allyl, and alkinyl group preferably having from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms, particularly preferably from 2 to 4 carbon atoms such as propargyl.
  • substituents on the heterocyclic group represented by R 1 include alkyl group, alkoxyl group, hydroxyl group, and sulfo group. Preferred among these substituents are alkyl group, carboxyl group, and hydroxyl group.
  • the alkylene groups represented by L 1 and L 2 may be the same or different and may be chain-like, branched or cyclic. These alkylene groups may have substituents. Examples of these substituents include those exemplified as the aliphatic hydrocarbon group represented by R 1 , alkenyl group preferably having from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms, particularly preferably from 2 to 4 carbon atoms such as vinyl and allyl, and alkinyl group preferably having from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms, particularly preferably from 2 to 4 carbon atoms such as propargyl.
  • substituents on the alkylene groups represented by L 1 and L 2 include aryl group, alkoxyl group, hydzoxyl group, carboxyl group, and sulfo group. Preferred among these substituents are aryl group, carboxyl group, and hydroxyl group.
  • the alkylene groups represented by L 1 and L 2 are each preferably an alkylene group having an alkylene moiety having from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms, most preferably a substituted or unsubstituted methylene or ethylene.
  • alkylene group examples include methylene, ethylene, trimethylene, methymethylene, ethylmethylene, n-propylmethylene, n-butylmethylene, 1,2-cyclohexylene, 1-carboxymethylene, carboxymethylmethylene, carboxyethylmethylene, hydroxymethylmethylene, 2-hydroxyethylmethylene, carbamoylmethylmethylene, phenylmethylene, benzylmethylene, 4-imidazolylmethylmethylene, and 2-methylthioethylmethylene.
  • alkylene groups Preferred among these alkylene groups are methylene, ethylene, methymethylene, ethylmethylene, n-propylmethylene, n-butylmethylene, 1-carboxymethylene, carboxymethylmethylene, carboxyethylmethylene, hydroxymethylmethylene, benzylmethylene, 4-imidazolylmethylmethylene, and 2-methylthioethylmethylene.
  • Particularly preferred among these alkylene groups are methylene, ethylene, methymethylene, ethylmethylene, n-propylmethylene, n-butylmethylene, 1-carboxymethylene, carboxymethylmethylene, hydroxymethylmethylene, and benzylmethylene.
  • the cations represented by M 1 and M 2 each are an organic or inorganic cation.
  • Examples of these cations include alkali metal ions (e.g., Li + , Na + , K + , Cs + ), alkaline earth metal ions (e.g.
  • Mg + , Ca + ) ammonium ions (e.g., ammonium ion, trimethylammonium ion, triethylammonium, tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, 1,2-ethanediammonium ion), pyridinium ion, imidazolium ion, and phosphonium ions (e.g., tetrabutylphosphonium ion).
  • M 1 and M 2 are preferably alkali metal ions or ammonium ions, more preferably Na + , K + or NH 4 + .
  • L 1 and M 1 have the same meaning as defined in formula (I).
  • the preferred range of L 1 and M 1 are also the same as in formula (I).
  • M a1 and M a2 have the same meaning as M 2 in formula (I).
  • L 1 be a substituted or unsubstituted methylene or ethylene and M 1 , M a1 and M a2 be any of hydrogen atom, alkali metal and ammonium. It is most preferable that L 1 be a substituted or unsubstituted methylene and M 1 , M a1 and M a2 be any of hydrogen atom, alkali metal and ammonium. It is particularly preferable that L 1 be a substituted or unsubstituted methylene having from 1 to 10 carbon atoms in total, including substituents, and M 1 , M a1 and M a2 be any of hydrogen atom, Na + , K + and NH 4 + .
  • the compound represented by formula (I) has asymmetric carbon atoms in its molecule, at least one asymmetric carbon atom is preferably in S-form. When there are two or more asymmetric carbon atoms, it is preferred that the asymmetric carbon moiety have more S-forms.
  • the processing method of the present invention use the compound represented by formula (I).
  • the symbol (S) indicates that the marked asymmetric carbon moiety is in S-form.
  • the unmarked compounds each are a mixture of R-form and S-form.
  • the foregoing compounds may have a cation substituted for hydrogen atom in the carboxyl group.
  • the cation has the same meaning as M 1 or M 2 in formula (I).
  • the compound group having as a partial structure an aspartic acid or glutamic acid structure such as Compounds I-15 and I-54 can be synthesized by subjecting aspartic acid or glutamic acid and an acrylic acid derivative or acrylonitrile derivative to addition reaction.
  • an acrylic acid derivative or acrylonitrile derivative it is necessary that N-(2-cyanoalkyl)-amino acid produced by the addition reaction be subjected to hydrolysis.
  • the aspartic acids and glutamic acids to be used as starting materials are not specifically limited. Those industrially available can be used. These aspartic acids and glutamic acids may be in the form of metal salt such as alkali metal salt (e.g., Li salt, Na salt, K salt, Rb salt, Cs salt), alkaline earth metal salt (e.g., Ca salt, Mg salt, Ba salt) and transition metal salt (e.g., Zn salt), tertiary ammonium salt such as triethylammonium salt, quaternary ammonium salt such as tetrabutylammonium salt or pyridinium salt. It goes without saying that these aspartic acids and glutamic acids may be in the form of free acid. These acids may also be in the form of solid, slurry or aqueous solution.
  • metal salt such as alkali metal salt (e.g., Li salt, Na salt, K salt, Rb salt, Cs salt), alkaline earth metal salt (e.g.
  • the asymmetric carbon moiety may be in S-form, R-form or mixture thereof, preferably S-form.
  • ferric complex (III) of compound represented by formula (I) may be added in the form of ferric complex (III) previously obtained.
  • a compound represented by formula (I) and a ferric salt (III) e.g., ferric nitrate (III), ferric chloride
  • ferric salt (III) e.g., ferric nitrate (III), ferric chloride
  • the compound represented by formula (I) may be used in slight excess of the amount required for complex-forming of ferric ion (III) (e.g., 0.5 mols, 1 mol, 2 mols per mol of ferric ion (III)). It is usually preferred that the excess be from 0.01 to 15 mol-%.
  • the organic acid ferric complex salt(III) to be incorporated in the processing solution having a bleaching ability of the invention may be used in the form of metal salt or ammonium salt.
  • the alkali metal salt include lithium salt, sodium salt, and potassium salt.
  • the ammonium salt include ammonium salt, and tetraethylammonium salt.
  • the ammonium ion concentration of the processing solution having a bleaching ability is preferably from 0 to 2.0 mol/l, particularly preferably from 0 to 1.0 mol/l.
  • bleaching agents may be used in combination with the ferric complex (III) of compound represented by formula (I).
  • bleaching agents described in JP-A-4-121739, lower right column, page 4 - lower left column, page 5, including ferric complex salt (III) of organic acid such as ethylenediamine-N,N,N',N'-tetraacetic acid, diethylenetriaminepentaacetic acid, trans-1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid, N-methyliminodiacetic acid, N-(hydroxyethyl)iminodiacetic acid and glycoletherdiaminetetraacetic acid and ferric complex salt (III) of 1,3-propanediamine-N,N,N',N'-tetraacetic acid, carbamoyl-based bleaching agents described in European Patent Publication No.
  • ferric complex salt (III) of N-(1-carboxy-2-phenyethyl)aspartic acid bleaching agents described in European Patent Publication No. 591934, including ferric complex salt (III) of N-(1-carboxyethyl)iminodiacetic acid, bleaching agents described in European Patent Publication No. 501479, bleaching agents described in European Patent Publication No. 461670, bleaching agents described in European Patent Publication No. 430000, and ferric complex salt (III) of aminopolycarboxylic acid described in JP-A-3-144446.
  • the ferric complex salt (III) of compound represented by formula (I) preferably accounts for 10% or more of all the bleaching agents. All the bleaching agents may be constituted by the ferric complex salt (III) of compound represented by formula (I). Preferably, the ferric complex salt (III) of compound represented by formula (I) accounts for 10% to 100% of all the bleaching agents and the ferric complex salt (III) of aminopolycarboxylic acid other than the compound represented by formula (I) accounts for 90% or less of all the bleaching agents. More preferably, the ferric complex salt (III) of compound represented by formula (I) accounts for 30% to 100%, most preferably 50% to 100% of all the bleaching agents.
  • the concentration of the ferric complex salt (III) of compound represented by formula (I) in the processing solution having a bleaching ability is preferably from 0.003 to 3.00 mols/l, more preferably from 0.02 to 2.00 mols/l, most preferably 0.05 to 1.00 mols/l, particularly preferably from 0.08 to 0.5 mols/l.
  • the total concentration of ferric complex salt (III) is preferably from 0.005 to 0.030 mols/l.
  • the bleaching solution preferably comprises a pH buffer incorporated therein.
  • the pH buffer include organic acids with little odor such as glycolic acid, succinic acid, maleic acid, malonic acid and glutaric acid. Particularly preferred among these pH buffers are glycolic acid, malonic acid, and succinic acid.
  • the concentration of pH buffer is preferably from 0 to 3 mols/l, particularly preferably from 0.2 to 1.5 mols/l.
  • the pH value of the processing solution having a bleaching ability of the present invention is preferably from 3.0 to 7.0.
  • the pH value of the bleaching solution is preferably from 3.5 to 5.0 in particular.
  • the pH value of the blixing solution is preferably from 4.0 to 6.5 in particular.
  • the organic acid as mentioned above be added as a buffer.
  • Preferred examples of the alkali agent to be used to adjust pH include aqueous ammonia, potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate.
  • the foregoing alkali agent and a well-known acid inorganic acid, organic acid
  • a well-known acid inorganic acid, organic acid
  • the processing with the processing solution having a bleaching ability of the invention is preferably effected immediately after color development. In the case of reversal process, it is normally effected via processing with adjusting bath (or bleach accelerating bath). Such an adjusting bath may contain an image stabilizer described later.
  • the solution having a bleaching ability may comprise re-halogenating agents, pH buffers, well-known additives, aminopolycarboxylic acids and organic phosphonic acids described in JP-A-3-144446, page (12), incorporated therein besides bleaching agent.
  • Preferred examples of the re-halogenating agent employable herein include sodium bromide, potassium bromide, ammonium bromide, and potassium chloride.
  • the content of the re-halogenating agent is preferably from 0.1 to 1.5 mols, more preferably from 0.1 to 1.0 mols, particularly preferably from 0.1 to 0.8 mols per l of processing solution having a bleaching ability.
  • the solution having a bleaching ability if it is a blixing solution, doesn't need to comprise a re-halogenating agent incorporated therein.
  • the solution having a bleaching ability preferably comprises a nitric acid compound such as ammonium nitrate and sodium nitrate incorporated therein.
  • the concentration of nitric acid compound per l of the solution having a bleaching ability is preferably from 0 to 0.3 mols, more preferably from 0 to 0.2 mols.
  • a nitric acid compound such as ammonium nitrate and sodium nitrate is added to prevent the corrosion of stainless steel.
  • a nitric acid compound such as ammonium nitrate and sodium nitrate is added to prevent the corrosion of stainless steel.
  • corrosion can hardly take place, and desilvering can be fairly effected.
  • the solution having a bleaching ability if it is a blixing solution, doesn't need to comprise a re-halogenating agent incorporated therein.
  • the replenishment rate of the solution having a bleaching ability is preferably from 30 to 600 ml, more preferably from 50 to 400 ml per m 2 of light-sensitive material.
  • the processing time with the bleaching solution is preferably 7 minutes or less, particularly preferably from 10 seconds to 5 minutes, most preferably from 15 seconds to 3 minutes.
  • the processing solution having a fixing ability will be further described hereinafter.
  • the processing solution having a fixing ability to be used in the present invention comprises as an essential component a complex-forming agent selected from the group consisting of a compound represented by formula (II), EDTA and phosphonic acids incorporated therein.
  • R 21 , R 22 , R 23 and R 24 have the same meaning as those represented by R 1 in formula (I).
  • the preferred range of R 21 , R 22 , R 23 and R 24 are also the same as in formula (I).
  • R 21 , R 22 , R 23 and R 24 are each preferably a hydrogen atom or hydroxyl group, more preferably hydrogen atom.
  • the suffixes t and u each represent an integer of 0 or 1, preferably 1.
  • the divalent connecting group represented by W is preferably represented by formula (W): -(W 1 - D)v - (W 2 )w-
  • W 1 and W 2 may be the same or different and each represent a C 2-8 straight-chain or branched alkylene group such as ethylene, propylene and trimethylene, C 5-10 cycloalkylene group such as 1,2-cyclohexylene, C 6-10 arylene group such as o-phenylene, C 7-10 aralkylene group such as o-xylenyl, divalent nitrogen-containing heterocyclic group or carbonyl group.
  • the divalent nitrogen-containing heterocyclic group is preferably a 5- or 6-membered heterocyclic group having nitrogen atoms as heteroatoms, more preferably a heterocyclic group having cycles connected to each other via adjacent carbon atoms such as imidazolyl group.
  • D represents -O-, -S- or -N(Rw)-.
  • Rw represents a hydrogen atom or a C 1-8 alkyl group (e.g., methyl) or C 6-10 aryl group (e.g., phenyl) which may be substituted by carboxyl group, phosphono group, hydroxyl group or sulfo group.
  • W 1 and W 2 each are preferably a C 2-4 alkylene group.
  • the suffix v represents an integer of from 0 to 3. When v is 2 or 3, the plurality of (W 1 - D)'s may be the same or different.
  • the suffix v is preferably 0 to 2, more preferably 0 or 1, particularly preferably 0.
  • the suffix w represents an integer of from 1 to 3. When w is 2 or 3, the plurality of W 2 's may be the same or different.
  • the suffix w is preferably 1 or 2.
  • W Preferred among the groups represented by W are ethylene, propylene, trimethylene, and 2,2-dimethyltrimethylene. Particularly preferred among these groups are ethylene, and trimethylene.
  • M 21 , M 22 , M 23 and M 24 each represent a hydrogen or cation, and has the same meaning as in as defined in M 1 and M 2 in formula (I).
  • R 22 and R 24 each are a hydrogen atom and t and u each are 1.
  • Particularly preferred among these compounds are those wherein R 21 , R 22 , R 23 and R 24 each are a hydrogen atom and t and u each are 1.
  • R 21 , R 22 , R 23 and R 24 each are a hydrogen atom, t and u each are 1
  • W is ethylene and M 21 , M 22 , M 23 and M 24 each are selected from the group consisting of hydrogen atom, Na + , K + and NH 4 + and those wherein R 21 , R 22 , R 23 and R 24 each are a hydrogen atom, t and u each are 1, W is trimethylene and M 21 , M 22, M 23 and M 24 each are selected from the group consisting of hydrogen atom, Na + , K + and NH 4 + .
  • the compound represented by formula (II) has asymmetric carbon atoms in its molecule, at least one asymmetric carbon atom is preferably in S-form. When there are two or more asymmetric carbon atoms, it is preferred that the asymmetric carbon moiety have more S-forms.
  • the symbol (S) indicates that the marked asymmetric carbon moiety is in S-form.
  • the unmarked compounds each are a mixture of R-form and S-form.
  • Preferred among the foregoing exemplified compounds are Compounds II-1, II-2, II-6, II-15 and II-16. Particularly preferred among these compounds are Compounds II-15 and II-16.
  • the foregoing compounds may have a cation substituted for hydrogen atom in the carboxyl group.
  • the cation has the same meaning as in M 1 or M 2 in formula (I).
  • the compounds represented by formula (II), EDTA or phosphonic acids of the present invention each may be used singly or in combination of two or more thereof.
  • compounds represented by formula (II), EDTA and phosphonic acids may be used in combination with each other.
  • the compound represented by formula (II) may be used in the form of alkali metal salt or ammonium salt.
  • alkali metal salt include lithium salt, sodium salt, and potassium salt.
  • ammonium salt include ammonium salt, and tetraethylammonium salt.
  • the ammonium ion concentration of the processing solution having a bleaching ability is preferably from 0 to 2.0 mol/l, particularly preferably from 0.2 to 1.0 mol/l.
  • the concentration of the compound represented by formula (II) is preferably from 0.001 to 1.00 mols/l, more preferably from 0.005 to 0.9 mols/l, most preferably from 0.01 to 0.8 mols/l.
  • organic phosphonic acid to be used herein there may be used any organic phosphonic acid such as alkylphosphonic acid, phosphonocarboxylic acid and aminopolyphosphonic acid. Particularly preferred among these organic phosphonic acids are alkylphosphonic acid and aminopolyphosphonic acid.
  • organic phosphonic acids employable herein will be given below in formula.
  • B-A 1 -Z-A 2 -C wherein A 1 to A 6 each represent a C 1-3 substituted or unsubstituted alkylene group; Z represents a C 1-3 alkylene group, cyclohexane group, phenylene group, -R-O-R, -ROROR-, or >N-A 7 (in which R is a C 1-3 alkylene group, and A 7 is a hydrogen atom, C 1-3 hydrocarbon group, lower aliphatic carboxylic acid group or lower alcohol group); B, C, D, E, F and G each represent -OH, -COOM or -PO 3 M 2 (in which M is a hydrogen atom, alkali metal atom or ammonium group), with the proviso that at least one of B, C, D, E, F and G is -PO 3 M 2 ; and L has the same meaning as Z in formula (PI).
  • R 1 represents -COOM or -PO(OM) 2
  • R 2 represents a hydrogen atom, C 1-4 alkyl group, -(CH 2 ) n or COOM
  • R 3 represents a hydrogen atom or -COOM
  • M represents a hydrogen atom, alkali metal atom or ammonium group
  • m represents an integer of 0 or 1
  • n' represents an integer of from 1 to 4
  • q represents an integer of 0 or 1, with the proviso that when m is 0, R 1 is -PO(OM) 2 .
  • R 4 N(CH 2 PO 3 M 2 ) 2 wherein R 4 represents a C 1-6 substituted or unsubstituted alkyl group, C 6-12 substituted or unsubstituted aryl group, aralkyl group or nitrogen-containing 6-membered ring (Examples of substituents on these groups include -OH, -OR 5 (in which R 5 is a C 1-4 alkyl group), -PO 3 M 2 , -CH 2 PO 3 M 2 , -N(CH 2 PO 3 M 2 ) 2 , -COOM 2 , and -N(CH 2 COOM 2 )); and M represents a hydrogen atom, alkali metal atom or ammonium group.
  • R 6 and R 7 each are a hydrogen atom, C 1-4 alkyl group, -COOH, NJ 2 (in which J is H, OH, C 1-3 alkyl group or -C 2 H 4 OH);
  • R 8 represents a hydrogen atom, C 1-3 alkyl group, -OH or -NL 2 (in which L is H, OH, -CH 2 , -C 2 H 5 , -C 2 H 4 OH or -PO 3 M 2 );
  • X, Y and Z each represent a hydrogen atom, -OH, -COOM or PO 3 M 2 ;
  • M represents a hydrogen atom, alkali metal atom or ammonium group;
  • n represents an integer of 0 or 1; and
  • m represents an integer of 0 or 1.
  • R 9 and R 10 each represent a hydrogen atom, alkali metal atom, ammonium group, C 1-12 substituted or unsubstituted alkyl group, alkenyl group or cyclic alkyl group.
  • R 11 represents a C 1-12 substituted or unsubstituted alkyl group, C 1-12 substituted or unsubstituted alkoxy group, C 1-12 substituted or unsubstituted monoalkylamino group, C 2-12 substituted or unsubstituted dialkylamino group, amino group, C 6-24 substituted or unsubstituted aryloxy group, C 6-24 substituted or unsubstituted arylamino group or amyloxy group; and Q 1 to Q 2 each represent -OH, C 1-24 substituted or unsubstituted alkoxy group, C 7-24 substituted or unsubstituted aralkyloxy group or allyloxy group, -OM 2 (in which M 2 is a cationic group
  • R 12 and R 13 each represent a hydrogen atom, C 1-6 alkyl group or imine (which may be substituted by a C 1-6 alkyl group or CH 2 CH 2 COONa); M represents a hydrogen atom, alkali metal atom or ammonium group; and n represents an integer of from 2 to 16.
  • R 14 to R 16 each represent a hydrogen atom or alkyl group which may have as a substituent -OH, -OC n'' H2 n''+1 (in which n'' is an integer of from 1 to 4), -PO 3 M 2 , -CH 2 PO 3 M (in which M is a hydrogen atom, alkali metal atom or ammonium group), -NR 2 (in which R is a C 1-6 alkyl group) or -N(CH 2 PO 3 M 2 ) 2 .
  • Preferred among these compounds are P-19, P-25, P-26, P-30, P-31, P-34, P-41, P-44, P-56, P-57, P-59 and P-68. Particularly preferred among these compounds are P-25, P-57 and P-68.
  • the compound of the present invention represented by any of formulae (PI) to (PIX) is preferably incorporated in an amount of from 0.001 to 0.5 mols, more preferably from 0.005 to 0.4 mols, most preferably from 0.01 to 0.3 mols per 1 of processing solution having a fixing ability.
  • the compound represented by any of formulae (PI) to (PIX) be incorporated in the processing solution having a bleaching ability in an amount similar to that defined in the processing solution having a fixing ability.
  • the compounds represented by formulae (PI) to (PIX) may be used singly or in combination of two or more thereof.
  • the compounds represented by formulae (PI) to (PIX) may be used in combination with the compound represented by formula (II).
  • the heterocyclic residue formed by Q is a 3- to 10-membered saturated or unsaturated heterocyclic residue containing at least one of N, O and S atoms which may be monocyclic or may form a condensed ring with other rings.
  • the heterocyclic residue is preferably a 5- or 6-membered aromatic heterocyclic residue, more preferably a 5- or 6-membered aromatic heterocyclic residue containing nitrogen atoms, most preferably a 5- or 6-membered aromatic heterocyclic residue containing one or two nitrogen atoms.
  • heterocyclic residue examples include 2-pyrrolidinyl, 3-pyrrolidinyl, 2-piperidinyl, 3-piperidyl, 3-piperidyl, 4-piperidyl, 2-piperazinyl, 2-morpholinyl, 3-morpholinyl, 2-chenyl, 2-furyl, 3-furyl, 2-pyrrolyl, 3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 3-pyrazolyl, 4-pyrazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 3-pyridazinyl, 4-pyridazinyl, 3-(1,2,4-triazolyl), 4-(1,2,3-triazolyl), 2-(1,3,5-triazinyl), 3-(1,2,4-triazinyl), 5-(1,2,4-triazinyl), 6-(1,2,4-triazinyl), 2-indolyl, 3-indolyl, 4-indi
  • heterocyclic residues are 2-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 3-pyrazolyl, 2-pyridyl, 2-pyrazinyl, 3-pyridazinyl, 3-(1,2,4-triazolyl), 4-(1,2,3-triazolyl), 2-(1,3,5-triazinyl), 3-(1,2,4-triazinyl) , 5-(1,2,4-triazinyl), 6-(1,2,4-triazinyl), 2-indolyl, 3-indazolyl, 7-indazolyl, 2-prinyl, 6-prinyl, 8-prinyl, 2-(1,3,4-thiadiazolyl), 2-(1,3,4-oxadiazolyl), 2-quinolyl, 8-quinolyl, 1-phthaladinyl, 2-quinoxalinyl, 5-quinoxalinyl, 2-quinazolinyl, 4-quinazolinyl, 8-quinazolinyl, 1-phthal
  • heterocyclic residues More desirable among these heterocyclic residues are 2-imidazolyl, 4-imidazolyl, 3-pyrazolyl, 2-pyridyl, 2-pyrazinyl, 2-indolyl, 3-indazolyl, 7-indazolyl, 2-(1,3,4-thiadiazolyl), 2-(1,3,4-oxadiazolyl), 2-quinolyl, 8-quinolyl, 2-thiazolyl, 4-thiazolyl, 2-oxazolyl, and 4-oxazolyl.
  • 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 2-quinolyl, and 8-quinolyl Particularly preferred among these heterocyclic residues are 2-imidazolyl, 4-imidazolyl, 2-pyridyl, and 2-quinolyl. Further, particularly most preferred among these heterocyclic residues is 2-pyridyl.
  • the foregoing heterocyclic residue may have substituents besides (CH 2 ) p CO 2 Ma.
  • substituents include alkyl group preferably having from 1 to 12 carbon atoms, more preferably from 1 to 6 carbon atoms, particularly preferably from 1 to 3 carbon atoms such as methyl and ethyl, aralkyl group preferably having from 7 to 20 carbon atoms, more preferably from 7 to 15 carbon atoms, particularly preferably from 7 to 11 carbon atoms such as phenylmethyl and phenylethyl, alkenyl group preferably having from 2 to 12 carbon atoms, more preferably from 2 to 6 carbon atoms, particularly preferably from 2 to 4 carbon atoms such as allyl, alkinyl group preferably having from 2 to 12 carbon atoms, more preferably from 2 to 6 carbon atoms, particularly preferably from 2 to 4 carbon atoms such as propargyl, aryl group preferably having from 6 to 20 carbon atoms, more preferably from 6 to
  • substituents may be further substituted. When there are two or more of these substituents, they may be the same or different.
  • Preferred among the foregoing substituents are alkyl group, amino group, alkoxy group, carboxyl group, hydroxyl group, halogen atom, cyano group, nitro group, and mercapto group. More preferable among these substituents are alkyl group, amino group, alkoxy group, carboxyl group, hydroxyl group, and halogen atom. Most preferable among these substituents are amino group, carboxyl group, and hydroxyl group. Further, particularly preferable among these substituents is carboxyl group.
  • the suffix p represents an integer of 0 or 1, preferably 0.
  • the cation represented by Ma is an organic or inorganic cation.
  • the organic or inorganic cation include alkali metal ion such as Li + , Na + , K + and Cs + , alkaline earth metal ion such as Ca 2+ and Mg 2+ , ammonium ion such as ammonium ion and tetraethylammonium ion, pyridinium ion, and phosphonium ion such as tetrabutylphosphonium ion and tetraphenylphosphonium ion.
  • the foregoing compounds may be used in the form of ammonium salt or alkali metal salt.
  • Preferred among these exemplified compounds are (A-6), (A-7), (A-8), (A-13), (A-14), (A-20), (A-22), (A-29), and (A-49). Particularly preferred among these compounds is (A-7).
  • the compound of the present invention represented by formula (A) is preferably incorporated in an amount of from 0.001 to 0.3 mols, more preferably from 0.005 to 0.2 mols, particularly preferably from 0.01 to 0.15 mols per l of processing solution having a fixing ability.
  • the compound represented by formula (A) is preferably incorporated also in the processing solution having a bleaching ability in an amount similar to that defined in the processing solution having a fixing ability.
  • the compounds represented by formula (A) may be used singly or in combination of two or more thereof.
  • the processing solution having a fixing ability may comprise as a preservative a sulfite (e.g., sodium sulfite, potassium sulfite, ammonium sulfite), hydroxylamine, hydrazine, bisulfite adduct of aldehyde compound (e.g., sodium acetaldehydebisulfite, particularly preferably compound described in JP-A-3-158848) or sulfinic acid compound described in JP-A-1-231051.
  • the processing solution having a fixing ability may comprise various fluorescent brightening agents, antifoaming agents, surface active agents and organic solvents such as polyvinylpyrrolidone and methanol incorporated therein.
  • the processing solution having a fixing ability may comprise various chelating agents such as aminopolycarboxylic acid and organic phosphonic acid incorporated therein besides the compound of the present invention for the purpose of stabilizing the processing solution.
  • Preferred examples of the chelating agent to be incorporated include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N,N,N',N'-tetrakis(methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetraacetic acid, diethylenetriaminepentaacetic acid, trans-1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid, and 1,2-propylenediaminetetraacetic acid.
  • the present invention can exert its effect when the processing solution having a fixing ability has a pH value of from 6.1 to 8.0.
  • the pH value of the processing solution having a fixing ability falls outside the above defined range, the stability of the processing solution is deteriorated, giving generation of turbidity.
  • the pH value of the processing solution having a fixing ability is preferably from 6.4 to 7.7.
  • the compounds represented by formulae (I) and (II) described in JP-A-6-301169 are preferably incorporated in the processing solution having a fixing ability singly or in combination to enhance the fixing rate and preservability. It is also preferred from the standpoint of enhancement of preservability that p-toluenesulfionic acid salt or sulfinic acid described in JP-A-1-224762 be incorporated in the processing solution having a fixing ability.
  • the processing solution having a fixing ability preferably comprises a buffer incorporated therein to keep the pH value of the solution constant.
  • the buffer include monobasic acids such as acetic acid and glycolic acid, polybasic acids such as succinic acid, malonic acid, maleic acid and citric acid, phosphate, imidazoles such as imdazole, 1-methyl-imidazole, 2-methyl-imidazole and 1-ethyl-imidazole, triethanolamine, N-allylmorpholine, and N-benzoylpiperadine.
  • the replenishment rate of the processing solution having a fixing ability of the present invention is from 50 to 1,000 ml, preferably from 100 to 600 ml per m 2 of light-sensitive material.
  • the processing time with the processing solution having a fixing ability is 7 minutes or less, more preferably from 10 seconds to 6 minutes, most preferably from 15 seconds to 5 minutes.
  • the replenisher for the processing solution having a bleaching ability and the processing solution having a fixing ability may be in the form of liquid or solid (powder, granule, pellet).
  • a polyethyleneglycol-based surface active agent is preferably used to act as a binder as well.
  • the solidification of the photographic processing agent can be accomplished by any proper method such as method which comprises mixing a concentrated solution or finely divided or powdery photographic processing agent with a water-soluble binder, and then molding the mixture and method which comprises spraying a water-soluble binder onto the surface of a temporarily molded photographic processing agent to form a coat layer as disclosed in JP-A-4-29136, JP-A-4-85535, JP-A-4-85536, JP-A-4-88533, JP-A-4-85534, and JP-A-4-172341.
  • the production of the pelletized processing agent can be accomplished by any conventional method as disclosed in JP-A-51-61837, JP-A-54-155038, JP-A-52-88025, and British Patent 1,213,808.
  • the production of the granular processing agent can be accomplished by any conventional method as disclosed in JP-A-2-109042, JP-A-2-109043, JP-A-3-39735, and JP-A-3-39739.
  • the production of the powdery processing agent can be accomplished by any conventional method as disclosed in JP-A-54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861.
  • the replenisher for the processing solution having a bleaching ability and the processing solution having a fixing ability is in liquid form, it is preferably used as a one-pack or two-pack solution, particularly preferably one-pack solution.
  • the specific gravity of the replenisher agent is preferably from 1.0 to 5 times, particularly preferably from 1.5 to 3 times that of the replenisher.
  • the total desilvering time is preferably as short as possible so far no failure of desilvering can occur. In practice, it is preferably from 1 to 12 minutes, more preferably from 1 to 8 minutes.
  • the processing temperature is from 25°C to 50°C, preferably from 35°C to 45°C. In this preferred temperature range, the desilvering rate can be enhanced, and the occurrence of stain after processing can be effectively inhibited.
  • the processing solution having a bleaching ability of the present invention be subjected to aeration during processing to keep the photographic properties extremely stable.
  • the aeration can be accomplished by any method well-known in the art such as air blowing method, air absorption method using an ejector and method described in Eastman Kodak's bulletin Z-121 (Using Process C-41), 3rd edition, 1982, pp. BL-1 to BL-2.
  • the prebath for the processing solution having a bleaching ability may comprise various bleaching accelerators incorporated therein.
  • these bleaching accelerators to be incorporated in the prebath include compounds having mercapto or disulfide group described in US Patent 3,893,858, German Patent 1,290,821, British Patent 1,138,842, JP-A-53-95630, and Research Disclosure No.
  • the processing solution having a bleaching ability or fixing ability preferably comprises as a cation an ammonium ion incorporated therein to enhance the desilvering properties.
  • ammonium ion is preferably minimized or eliminated for the purpose of lessening environmental pollution.
  • the bleaching or fixing step is preferably provided with various silver recovering apparatus on an in-line or off-line basis to recover silver.
  • various silver recovering apparatus on an in-line basis makes it possible to effect processing with a lowered silver concentration in the processing solution, resulting in the reduction of replenishment rate.
  • silver is preferably recovered an off-line basis so that the residue can be re-used as a replenisher.
  • the blixing step or fixing step can be composed of a plurality of processing tanks.
  • the various tanks are preferably cascade-connected to form a multi-stage countercurrent system. Taking into account the balance with the size of the developing machine, a two-tank cascade structure is normally efficient.
  • the ratio of processing time at the pre-stage tank to that at the subsequent tank is preferably from 0.5 : 1 to 1 : 0.5, particularly preferably from 0.8 : 1 to 1 : 0.8.
  • agitation is preferably intensified as much as possible.
  • Specific examples of method for intensifying agitation include a method which comprises allowing a jet of processing solution to impact with the emulsion surface of the light-sensitive material as described in JP-A-62-183460 and JP-A-3-33847, line 6, upper right column - line 2, lower left column, page 8, a method which comprises enhancing the agitating effect using a rotary means as described in JP-A-62-183461, a method which comprises effecting jet agitation as described in JP-A-1-309059, a method which comprises allowing the light-sensitive material to move in contact with a wiper blade provided in the processing solution on the emulsion surface thereof so that turbulence can occur on the emulsion surface to enhance the agitation effect, and a method which comprises raising the total circulation of the processing solution.
  • Such an agitation intensifying method is useful all for the bleaching solution, blixing solution and fixing solution.
  • the automatic developing machine to be used for the light-sensitive material of the present invention preferably has a light-sensitive material conveying means as described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259.
  • a light-sensitive material conveying means as described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259.
  • the use of such a conveying means makes it possible to remarkably reduce the amount of processing solution to be carried over from one bath to a subsequent bath and hence exert a high effect of inhibiting the deterioration of the properties of the processing solution.
  • Such an effect is particularly useful for the reduction of the processing time and the amount of the replenisher to be supplied at the various steps.
  • the overflow of the processing solution having a bleaching ability of the present invention after processing can be recovered, and then provided with necessary components to modify the composition thereof for re-use.
  • Such a use is normally called regeneration.
  • regeneration is preferably effected.
  • the electrolytic regeneration can be carried out with a cathode and an anode put in the same bleaching bath or with an anode bath and a cathode bath separately provided with a separating membrane interposed therebetween.
  • the bleaching solution and developer and/or fixing solution can be simultaneously regenerated using a separating membrane.
  • the regeneration of the fixing solution and blixing solution can be accomplished by the electrolytic reduction of accumulated silver ions. Further, the removal of accumulated halogen ions through an anion exchange resin is desirable from the standpoint of maintenance of fixing properties.
  • the processing solution having a bleaching ability of the present invention is preferably received in a sealed vessel having an oxygen permeability of 1 cc/m 2 .day.atm or more during storage.
  • the bleaching solution of the present invention preferably comprises at least one of isothiazolones such as 1,2-benzoisothiazoline-3-one and 2-methyl-1,2-benzoisothiazoline-3-one or derivatives thereof incorporated therein.
  • the amount of such a compound to be incorporated is preferably from 0.001 to 1 g, more preferably from 0.01 to 0.5 g, particularly preferably from 0.02 to 0.2 g per l of bleaching solution.
  • Such a compound may be incorporated in the form of salt. Two or more of these compounds may be used in combination.
  • the replenisher for the processing solution having a bleaching ability comprises various components incorporated therein in an amount basically calculated by the following equation.
  • the concentration in the mother liquor can be kept constant.
  • the color developer will be further described hereinafter.
  • the color developer may comprise a compound described in JP-A-4-121739, line 1, upper right column, page 9 - line 4, lower left column, page 11, incorporated therein.
  • the color developing agent to be used in quick processing there may be preferably used 2-methyl-4-[N-ethyl-N-(2-hydroxyethyl) amino]aniline, 2-methyl-4-[N-ethyl-N-(3-hydroxypropyl) amino]aniline, 2-methyl-4-[N-ethyl-N-(4-hydroxybutyl) amino] aniline or 2-methyl-4-[N-ethyl-N-( ⁇ -methylsulfoamideethyl) amino]aniline.
  • These compounds may be used in the form of salt such as sulfate, hydrochloride and p-toluenesulfonate.
  • the color developer preferably comprises such a color developing agent incorporated therein in an amount of from 0.01 to 0.20 mols/l, particularly preferably from 0.012 to 0.12 mols/l, most preferably from 0.15 to 0.08 mols/l.
  • the color developer replenisher preferably comprises such a color developing agent incorporated therein in an amount of from 1.1 to 1.4 times the above defined value.
  • the color developer normally comprises a pH buffer such as carbonate, borate and phosphate of alkali metal and a development inhibitor or fog inhibitor such as chloride, bromide, iodide, benzimidazole, benzothiazole and mercapto compound incorporated therein.
  • a pH buffer such as carbonate, borate and phosphate of alkali metal
  • a development inhibitor or fog inhibitor such as chloride, bromide, iodide, benzimidazole, benzothiazole and mercapto compound incorporated therein.
  • the color developer may comprise various preservatives such as hydroxylamine, diethylhydroxylamine, hydroxylamine represented by formula (I) described in JP-A-3-144446, including N,N-bis(2-sulfonateethyl)hydroxylamine, sulfite and hydrazine (e.g., N,N-biscarboxylmethylhydrazine), phenyl semicarbazide, triethanolamine and catecholsulfonic acid, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salt and amine, dye-forming couplers, competing couplers, auxiliary development agents such as 1-phenyl-3-pyrazolidone, tackifiers, various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, e.g., ethylenediaminete
  • the processing temperature of the color developer in the present invention is from 20°C to 55°C, preferably from 30°C to 55°C.
  • the processing time of the color developer in the present invention is from 20 seconds to 10 minutes, preferably from 30 seconds to 8 minutes, more preferably from 1 to 6 minutes, particularly preferably from 1 minutes and 10 seconds to 3 minutes and 30 seconds, if a light-sensitive material for photography is processed.
  • the processing time of the color developer in the present invention is from 10 seconds to 1 minute and 20 seconds, preferably from 10 seconds to 60 seconds, more preferably from 10 seconds to 40 seconds, if a light-sensitive material for printing is processed.
  • black-and-white developer to be used herein may comprise well-known black-and-white developing agents such as dihydroxybenzene (e.g., hydroquinone, hydroquinone monosulfonate), 3-pyrazolidone (e.g., 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone) and aminophenol (e.g., N-methyl-p-aminophenol) incorporated therein, singly or in combination.
  • dihydroxybenzene e.g., hydroquinone, hydroquinone monosulfonate
  • 3-pyrazolidone e.g., 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone
  • aminophenol e.g., N-methyl-p-aminophenol
  • the foregoing color developer normally has a pH value of from 9 to 12.7.
  • the foregoing black-and-white developer has a pH value-of from 9 to 11.5.
  • the replenishment rate of these developers is 3 l or less per m 2 of the light-sensitive material, though depending on the kind of the color light-sensitive material to be processed. By reducing the bromide ion concentration in the replenisher, the replenishment rate can be reduced to 500 ml or less.
  • the contact area of the processing bath with air is preferably reduced to inhibit the evaporation and air oxidation of the processing solution.
  • the contents described in JP-A-4-125558, line 6, lower right column, page 12 - line 16, lower right column, page 13, can be preferably applied.
  • the stabilizing solution comprise an azolylmethylamine as described in European Patent Publication Nos. 504609 and 519190 or N-methylolazole as described in JP-A-4-362943 incorporated therein instead of formaldehyde, the magenta coupler be rendered two-equivalent and a surface active agent solution free of image stabilizer such as formaldehyde be used.
  • the final step bath be free of image stabilizer.
  • the processing solution has various ionic components such as calcium ion, magnesium ion, sodium ion and potassium ion coming from water used to prepare the replenisher or eluted from the light-sensitive material.
  • the sodium ion concentration in the final bath at the rinsing step or stabilizing step is preferably from 0 to 50 mg/l, particularly preferably from 0 to 20 mg/l.
  • the replenishment rate at the rinsing step and stabilizing step is preferably from 80 to 1,000 ml, more preferably from 100 to 500 ml, most preferably from 150 to 300 ml per m 2 of light-sensitive material from the standpoint of both assurance of rinsing and stabilizing functions and reduction of waste water for environmental protection.
  • a well-known antifungel agent such as thiabendazole, 1,2-benzoisothiazoline-3-one and 5-chloro-2-methylisothiazoline- 3-one
  • an antibiotic such as gentamicin or water deionized with an ion-exchange resin is preferably used to prevent the proliferation of bacteria or fungi. It is more effective to use deionized water, antibacterial agent and antibiotic in combination.
  • the processing solution in the rinsing solution or stabilizer tank is preferably subjected to reverse osmosis membrane treatment as described in JP-A-3-46652, JP-A-3-53246, JP-A-3-121448 and JP-A-3-126030 to reduce the replenishment rate.
  • the reverse osmosis membrane to be used herein is preferably a low pressure reverse osmosis membrane.
  • the evaporation loss of processing solution be made up for as disclosed in Hatsumei Kyokai Kokai Giho (Japan Institute of Invention and Innovation's Kokai Giho) No. 94-4992.
  • the evaporation loss of processing solution is preferably corrected using the data of temperature and humidity around the developing machine according to Equation-1 on page 2.
  • Water to be used to correct the evaporation loss of processing solution is preferably taken from the rinsing water replenisher tank. In this case, as the rinsing water replenisher there is preferably used deionized water.
  • processing agents automatic developing machine and method for correcting evaporation loss which can be preferably used to implicate the present invention are described in the above described Kokai Giho, line 11, right column, page 5 - final line, right column, page 7.
  • the silver halide color photographic material which can be preferably subjected to processing according to the invention will be further described hereinafter.
  • the silver halide color photographic material to which the present invention can be preferably applied may be in the form of color negative film or color reversal film comprising a silver bromoiodide emulsion coat layer, more preferably color negative film, particularly preferably one having a magnetic recording layer provided on a support.
  • the magnetic recording layer which can be preferably processed according to the present invention will be further described hereinafter.
  • the magnetic recording layer is formed by applying an aqueous or organic solvent-based coating solution having magnetic particles dispersed in a binder to a support.
  • ferromagnetic iron oxide such as ⁇ -Fe 2 O 3 , Co-coated ⁇ -Fe 2 O 3 , Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy or hexagonal Ba ferrite, Sr ferrite, Pb ferrite or Ca ferrite.
  • Particularly preferred among these magnetic materials is Co-coated ferromagnetic iron oxide such as Co-coated ⁇ -Fe 2 O 3 .
  • the shape of the magnetic material particles may be any of acicular, ellipsoidal, spherical, cubic and tabular form.
  • the specific surface area of the magnetic particles is preferably 20 m 2 /g or more, particularly preferably 30 m 2 /g or more as determined by S BET .
  • the saturated magnetization ( ⁇ s) of the ferromagnetic particle is preferably from 3.0 x 10 4 to 3.0 x 10 5 A/m, particularly preferably from 4.0 x 10 4 to 2.5 x 10 5 A/m.
  • the ferromagnetic particles may be subjected to surface treatment with silica and/or alumina or an organic material.
  • the magnetic material particles may be treated with a silane coupling agent or titanium coupling agent on the surface thereof as described in JP-A-6-161032.
  • magnetic particles coated with an inorganic or organic material on the surface thereof as described in JP-A-4-259911 and JP-A-5-81652 may be used.
  • binder for magnetic particles examples include thermoplastic resin, thermosetting resin, radiation-curing resin, reactive resin, acid-decomposable, alkali-decomposable or biodegradable polymer, natural polymer (cellulose derivative, saccharide derivative, etc.), and mixture thereof as disclosed in JP-A-4-219569.
  • the foregoing resins exhibit a glass transition temperature Tg of from - 40°C to 300°C and a weight-average molecular weight of from 2,000 to 1,000,000.
  • resins include vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate and cellulose tripropionate, acrylic resin, and polyvinyl acetal resin.
  • the binder may be cured with an epoxy-based, aziridine-based or isocyanate-based crosslinking agent.
  • isocyanate-based crosslinking include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate, products of the reaction of these diisocyanates with polyalcohols (e.g., product of reaction of 3 mols of tolylene diisocyanate with 1 mol of trimethylol propane), and polyisocyanates produced by the condensation of these isocyanates. These examples are described in, e.g., JP-A-6-59357.
  • the thickness of the magnetic recording layer is from 0.1 ⁇ m to 10 ⁇ m, preferably 0.2 ⁇ m to 5 ⁇ m, more preferably from 0.3 ⁇ m to 3 ⁇ m.
  • the weight ratio of magnetic particles to binder is preferably from 0.5 : 100 to 60 : 100, more preferably from 1 : 100 to 30 : 100.
  • the applied amount of magnetic particles is from 0.005 to 3 g/m 2 , preferably from 0.01 to 2 g/m 2 , more preferably from 0.02 to 0.5 g/m 2 .
  • the magnetic recording layer may be provided all over the back surface of the photographic support or in stripe by coating or printing.
  • the coating of the magnetic recording layer can be accomplished by means of air doctor, blade, air knife, squeeze rollers, immersion bath, reverse rolls, transfer rolls, gravure coater, kiss-roll coater, cast coater, spray coater, dip coater, bar coater, extruder or the like.
  • the coating solution described in JP-A-5-341436 is preferably used.
  • the magnetic recording layer may be capable of improving lubricity, adjusting curling, inhibiting electrification and adhesion and abrading head in combination.
  • the magnetic recording layer may be provided with other functional layers so that these functions can be added to the magnetic recording layer.
  • the magnetic particle preferably acts as an abrasive comprising nonspherical inorganic particles at least one of which has a Mohs' hardness of 5 or more.
  • the composition of the nonspherical inorganic particles comprises a fine powder of oxide such as aluminum oxide, chromium oxide, silicon dioxide and titanium dioxide, carbide such as silicon carbide and titanium carbide or diamond.
  • Such an abrasive may be treated with a silane coupling agent or titanium coupling agent on the surface thereof.
  • These particles may be incorporated in the magnetic recording layer or may be applied to the magnetic recording layer as an overcoat (e.g., protective layer, lubricant layer).
  • an overcoat e.g., protective layer, lubricant layer.
  • the binder to be used herein there may be used one previously mentioned, preferably the same binder as used for the magnetic recording layer.
  • the details of light-sensitive material comprising such a magnetic recording layer reference can be made to US Patents 5,336,589, 5,250,404, 5,229,259 and 5,215,874, and EP 466,130.
  • the processing method according to the present invention using a fixing solution containing a compound represented by formula (P) or formula (A) is further advantageous in that the deterioration of precision in reading magnetically recorded data is minimized.
  • the light-sensitive material to be processed according to the present invention is preferably a light-sensitive material for photography.
  • the support for the light-sensitive material is preferably a polyester.
  • Kokai Giho No. 94-6023 Japanese Institute of Invention and Innovation; March 15, 1994.
  • the polyester to be used herein can be formed by a diol and an aromatic dicarboxylic acid as essential components.
  • aromatic dicarboxylic acid employable herein include 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, and phthalic acid.
  • Examples of the diol employable herein include diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, and bisphenol.
  • polystyrene resin examples include homopolymers such as polyethylene terephthalate, polyethylene naphthalate and polycyclohexane dimethanol terephthalate.
  • a particularly preferred polymer is a polyester containing 2,6-naphthalenedicarboxylic acid in an amount of from 50 mol-% to 100 mol-%. Particularly preferred among these polyesters are polyethylene, and 2,6-naphthalate.
  • the average molecular weight of the polyester is from about 5,000 to 200,000.
  • the polyester of the invention has Tg of 50°C or higher, preferably 90°C or higher.
  • the polyester support is preferably subjected to heat treatment at a temperature of from not lower than 40°C to lower than Tg, more preferably from Tg - 20°C to lower than Tg to render itself little curlable.
  • the heat treatment may be effected at a constant temperature or lowering temperature within the above defined range.
  • the heat treatment time is from 0.1 to 1,500 hours, preferably from 0.5 to 200 hours.
  • the support may be subjected to heat treatment in the form of roll or while being conveyed in the form of web.
  • the surface of the support may be roughened (e.g., by applying a conductive inorganic fine particle such as SnO 2 and Sb 2 O 5 ) to improve the surface conditions thereof.
  • the support is preferably knurled at the end thereof so that it is slightly thicker at the end thereof than at other areas to prevent the cut edge of the core from affecting the other areas.
  • the heat treatment may be effected at any steps after the preparation of support, after surface treatment, after the coating of back layer (e.g., antistatic agent, sliding agent) or after the application of undercoating, preferably after the application of antistatic agent.
  • the foregoing polyester may comprise an ultraviolet absorber incorporated therein.
  • the foregoing polyester may comprise a dye or pigment commercially available for polyester such as Diaresin (produced by Mitsubishi Chemical Corporation) and Kayaset (produced by NIPPON KAYAKU CO.,LTD.) incorporated therein.
  • the undercoating layer may consist of a single layer or two or more layers.
  • the binder for undercoating layer include copolymers obtained by polymerizing monomers selected from the group consisting of vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid and maleic anhydride as starting materials, polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin.
  • the light-sensitive material to be used in the present invention preferably comprises an antistatic agent such as carboxylic acid, carboxylate, high molecular compound containing sulfonic acid, cationic high molecular compound and ionic surface active agent incorporated therein.
  • an antistatic agent such as carboxylic acid, carboxylate, high molecular compound containing sulfonic acid, cationic high molecular compound and ionic surface active agent incorporated therein.
  • the most desirable antistatic agent is a particulate crystalline metal oxide comprising at least one selected from the group consisting of ZnO, TiO 2 , SnO 2 , Al 2 O 3 , In 2 O 3 , SiO 2 , MgO, BaO, MoO 3 and V 2 O 5 having a volume resistivity of 10 7 ⁇ cm or less, preferably 10 5 ⁇ cm or less, and a particle size of from 0.001 to 1.0 ⁇ m or a particulate composite oxide thereof (e.g., Sb, P, B, In, S, Si, C). Further, a sol metal oxide or particulate composite oxide thereof is mostly preferred.
  • the content of such an antistatic agent in the light-sensitive material is preferably from 5 to 500 mg/m 2 , particularly preferably from 10 to 350 mg/m 2 .
  • the ratio of amount of electrically-conductive crystalline oxide or composite oxide thereof to binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.
  • the light-sensitive material has preferably sliding property.
  • the sliding agent-containing layer is preferably provided on both of the light-sensitive layer surface and the back surface thereof.
  • Examples of the sliding agent employable herein include polyorganosiloxane, higher aliphatic acid amide, higher aliphatic acid metal salt, and ester of higher aliphatic acid with higher alcohol.
  • Examples of the polyorganosiloxane employable herein include polydimethyl siloxane, polydiethyl siloxane, polystyryl methyl siloxane, and polymethyl phenyl siloxane.
  • the layer in which the sliding agent is incorporated is preferably the outermost layer of the emulsion layer or the back layer. Particularly preferred among these sliding agents are polydimethyl siloxane and ester having long-chain alkyl group.
  • the light-sensitive material of the invention preferably comprises a matting agent incorporated therein.
  • the matting agent may be incorporated in either the emulsion surface or the back surface. In practice, however, the matting agent is preferably incorporated in the outermost layer on the emulsion layer side.
  • the matting agent may be either soluble or insoluble in the processing solution.
  • the two types of matting agents are used in combination.
  • the particle diameter of the matting agent is preferably from 0.8 to 10 ⁇ m. The distribution of particle diameters is preferably narrow. It is preferred that 90% or more of all the particles fall within the range of from 0.9 to 1.1 times the average particle diameter.
  • a fine particle having a size of not more than 0.8 ⁇ m is preferably added at the same time.
  • the light-sensitive material to be used herein there is preferably used one described in JP-A-4-125558, line 1, upper left column, page 14 - line 11, lower left column, page 18.
  • the silver halide emulsion there is preferably used a silver bromoiodide emulsion having an average silver iodide content of from 3 to 20 mol-%.
  • the silver halide grains are preferably in the form of tabular grain having an aspect ratio of 5 or more or double structure grain having halogen composition differing between inside and outside.
  • the silver halide grains are also preferably in a layered structure which is distinct between inside and outside.
  • the aspect ratio of the silver halide grains is preferably from 5 to 20, more preferably from 6 to 12.
  • the light-sensitive material to be used in the present invention preferably has a layer containing light-insensitive silver halide grains having an average grain diameter of from 0.02 to 0.2 ⁇ m.
  • the particulate silver halide is preferably silver bromide having an iodide content of from 0.5 to 10 mol-%.
  • the light-sensitive material of the present invention may comprise various dye-forming couplers incorporated therein.
  • the following couplers are particularly preferred.
  • Couplers in which a color-forming dye has a proper diffusibility include those described in US Patent 4,366,237, GB Patent 2,125,570, EP 96,873B, and DE 3,234,533.
  • a commercially available 135 type film format (corresponding international Standard: ISO 1007) color negative film was subjected to exposure, development and evaluation of properties of processing solution and light-sensitive material according to the present invention as mentioned below.
  • Color developer Running (g) solution Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.2 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.2 Sodium sulfite 4.0 4.8 Potassium carbonate 30.0 39.0 Potassium bromide 1.4 0.3 Potassium iodide 1.5 mg - Hydroxylamine sulfate 2.4 3.3 Disodium-N,N-bis(sulfonateethyl) hydroxylamine 2.0 2.8 4-(N-ethyl-N- ⁇ -hydroxyethylamino)-2-methylaniline sulfate 4.5 6.0 Water to make 1,000 ml 1,000 ml PH 10.05 10.15 Bleaching solution Running solution Replenisher Compound I-54 0.17 mols 0.25 mols Ferric nitrate (III) nonahydrate 65.0 g 100.0 g Ammonium bromide 80.0 g 12
  • the light-sensitive materials thus processed were each then evaluated for stain, image preservability, color density and liquid stability in accordance with the following methods.
  • the light-sensitive material specimens thus developed were each then measured for density by an apparatus and method according to the international standard ISO5 group. From the characteristic curve thus obtained was read Dmin (density at unexposed area) measured with red light (R light), i.e., Dmin (R).
  • Dmax density at the highest density area measured with green light (G light), i.e., Dmax(G).
  • G light green light
  • Dmax(G) change of density of magenta dye at the highest density area
  • Dmax density at the highest density area measured with red light (R light), i.e., Dmax(R).
  • a liquid specimen was prepared by adding ferric (III) ion, calcium ion and magnesium ion to the same processing solution as the running fixing solution used in the foregoing development process in an amount of 2,000 ppm, 400 ppm and 150 ppm, respectively. The liquid specimen was then allowed to stand at a temperature of 40°C for 4 weeks. The liquid specimen was then observed for occurrence of precipitation.
  • the examples of the invention using a bleaching solution comprising a ferric complex salt (III) of compound represented by formula (I) incorporated therein and a fixing solution with a pH value of 6.4 comprising a complex-forming agent selected from the group consisting of compound represented by formula (II), EDTA and phosphonic acid incorporated therein are superior to the comparative examples (Test Nos. 9 and 10) using a fixing solution with the same pH value comprising a complex-forming agent other than compound represented by formula (II), EDTA and phosphonic acid incorporated therein in all the evaluations.
  • the examples of the invention exhibit an improved stability of magenta dye with time and show minimized cyan stain.
  • Test Nos. 14 to 21 show that even if a phosphonic acid compound is used, when the pH value of the fixing solution is higher than the range of the present invention, the red light density is insufficiently color-formed, the stability of magenta dye image is deteriorated and the fixing solution is slightly instabilized. On the other hand, even if the pH value of the fixing solution is lower than the range of the present invention, the magenta dye becomes unstable, and the fixing solution is observed turbid. On the contrary, when the pH value of the fixing solution falls within the range of the present invention, the results are excellent all in the various properties. Also, the specimens comprising a phosphonic acid compound of the present invention incorporated therein exhibit a high cyan density over various pH ranges.
  • Example 2 The same procedure as in Example 1 was carried out except that the composition of the bleaching solution, fixing solution and stabilizing solution were changed to the following ones. Cyan stain, change of magenta dye with time, color density and stability of fixing solution were then determined in the same manner as in Example 1. The results are shown in Table 2.
  • Table 2 shows that as compared with the comparative example using ferric complex salt (III) of 1,3-PDTA as a general-purpose bleaching agent (Test No. 1), the examples of the present invention using a bleaching solution and a fixing solution each comprising a compound represented by formula (I) or a compound represented by formula (II) or a phosphonic acid incorporated therein (Test Nos. 102, 104 to 107, 109) show less cyan stain, an improved stability of magenta dye and an enhanced stability of fixing solution.
  • Test Nos. 111 to 117 which are according to the present invention, with Test No.
  • Test Nos. 111 to 117 provide comparison of examples of the present invention. As can be seen in the results of these tests, when a compound of formula (I) or phosphonic acid and a compound of formula (A) are incorporated in the fixing solution in combination, there can be recognized a further enhancement in color density.
  • the incorporation of a compound of formula (I) of the present invention in a processing solution having a bleaching ability and a compound of formula (II), EDTA or phosphonic acid in a processing solution having a fixing ability makes it possible to improve the occurrence to cyan stain, the stability of magenta dye and the stability of processing solution.
  • the processing solution having a fixing ability comprises a compound of formula (II), EDTA or phosphonic acid and a compound represented by formula (A) incorporated therein in combination
  • failure of cyan color restoration can be minimized, and color density can be enhanced.
  • the sulfurization of fixing solution can be prevented, enhancing stability with time.
  • the processing method of the present invention involving desilvering with a processing solution having a bleaching ability comprising a compound of formula (I) incorporated therein and a processing solution having a fixing ability comprising a complex-forming agent selected from the group consisting of compound represented by formula (II), EDTA and phosphonic acid, preferably further a compound of formula (A), incorporated therein
  • the stability of the processing solution having a fixing ability can be improved, and the image thus obtained can be remarkably rendered insusceptible to stain such as cyan stain.
  • the use of the fixing solution comprising a compound of formula (A) incorporated therein makes it possible to minimize failure of cyan color restoration and hence enhance color density.

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EP00116702A 1999-08-03 2000-08-02 Verfahren zur Verarbeitung eines farbphotographischen Silberhalogenidmaterials und eine Verarbeitungslösung für ein photographisches lichtempfindliches Silberhalogenidmaterial Withdrawn EP1074886A1 (de)

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JP22024899 1999-08-03
JP2000222587A JP2001109116A (ja) 1999-08-03 2000-07-24 ハロゲン化銀カラー写真感光材料の処理方法及びハロゲン化銀写真感光材料用の処理液
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57185435A (en) * 1981-05-11 1982-11-15 Konishiroku Photo Ind Co Ltd Treatment of silver halide color photographic material
US4444873A (en) * 1981-12-29 1984-04-24 Fuji Photo Film Co., Ltd. Color photographic processing
EP0412532A1 (de) * 1989-08-11 1991-02-13 Fuji Photo Film Co., Ltd. Verarbeitungsverfahren für Silberhalogenid enthaltende farbphotographische Materialien
EP0427204A1 (de) * 1989-11-07 1991-05-15 Fuji Photo Film Co., Ltd. Verfahren zur Verarbeitung von farbphotographischen Silberhalogenidmaterialien
EP0657777A2 (de) * 1993-12-07 1995-06-14 Fuji Photo Film Co., Ltd. Verfahren zur Verarbeitung eines farbphotographischen Silberhalogenidmaterials
EP0663613A2 (de) * 1993-12-29 1995-07-19 Eastman Kodak Company Fixierzusätze zum Gebrauch in Kombination mit Eisenkomplexzusammensetzungen um Eisenabsetzungen zu verhindern
EP0789275A1 (de) * 1995-08-23 1997-08-13 Fuji Photo Film Co., Ltd. Verfahren zur Verarbeitung lichtempfindliches Silberhalogenidfarbmaterials
US5856074A (en) * 1996-10-24 1999-01-05 Agfa-Gevaert Ag Fixing bath
DE19957346A1 (de) * 1998-12-18 2000-06-21 Eastman Kodak Co Fotografisches Entwicklungsverfahren unter Verwendung eines auf biologischem Wege abbaubaren Bleichmittels mit anschließender Fixierung

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57185435A (en) * 1981-05-11 1982-11-15 Konishiroku Photo Ind Co Ltd Treatment of silver halide color photographic material
US4444873A (en) * 1981-12-29 1984-04-24 Fuji Photo Film Co., Ltd. Color photographic processing
EP0412532A1 (de) * 1989-08-11 1991-02-13 Fuji Photo Film Co., Ltd. Verarbeitungsverfahren für Silberhalogenid enthaltende farbphotographische Materialien
EP0427204A1 (de) * 1989-11-07 1991-05-15 Fuji Photo Film Co., Ltd. Verfahren zur Verarbeitung von farbphotographischen Silberhalogenidmaterialien
EP0657777A2 (de) * 1993-12-07 1995-06-14 Fuji Photo Film Co., Ltd. Verfahren zur Verarbeitung eines farbphotographischen Silberhalogenidmaterials
EP0663613A2 (de) * 1993-12-29 1995-07-19 Eastman Kodak Company Fixierzusätze zum Gebrauch in Kombination mit Eisenkomplexzusammensetzungen um Eisenabsetzungen zu verhindern
EP0789275A1 (de) * 1995-08-23 1997-08-13 Fuji Photo Film Co., Ltd. Verfahren zur Verarbeitung lichtempfindliches Silberhalogenidfarbmaterials
US5856074A (en) * 1996-10-24 1999-01-05 Agfa-Gevaert Ag Fixing bath
DE19957346A1 (de) * 1998-12-18 2000-06-21 Eastman Kodak Co Fotografisches Entwicklungsverfahren unter Verwendung eines auf biologischem Wege abbaubaren Bleichmittels mit anschließender Fixierung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 007, no. 032 (P - 174) 8 February 1983 (1983-02-08) *

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