EP0458131A1 - Photographische Verarbeitungszusammensetzung und diese verwendendes Verarbeitungsverfahren - Google Patents

Photographische Verarbeitungszusammensetzung und diese verwendendes Verarbeitungsverfahren Download PDF

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Publication number
EP0458131A1
EP0458131A1 EP91107440A EP91107440A EP0458131A1 EP 0458131 A1 EP0458131 A1 EP 0458131A1 EP 91107440 A EP91107440 A EP 91107440A EP 91107440 A EP91107440 A EP 91107440A EP 0458131 A1 EP0458131 A1 EP 0458131A1
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EP
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Prior art keywords
processing composition
processing
group
solution
photographic
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Application number
EP91107440A
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English (en)
French (fr)
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EP0458131B1 (de
Inventor
Hisashi Okada
Shigeru Nakamura
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP12858890A external-priority patent/JPH0422948A/ja
Priority claimed from JP17502690A external-priority patent/JP2654714B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Priority to EP96103402A priority Critical patent/EP0720049B1/de
Publication of EP0458131A1 publication Critical patent/EP0458131A1/de
Application granted granted Critical
Publication of EP0458131B1 publication Critical patent/EP0458131B1/de
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/268—Processing baths not provided for elsewhere, e.g. pre-treatment, stop, intermediate or rinse baths
    • 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
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers
    • 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
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers
    • G03C5/3053—Tensio-active agents or sequestering agents, e.g. water-softening or wetting 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
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • 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 processing composition for processing silver halide photographic materials, and more particularly to a photographic processing composition containing a novel bleaching agent for use in the bleaching step after color development or a photographic processing composition containing a novel chelating agent for sequestering metal ions which are harmful to photographic processing.
  • the present invention also relates to a method for processing silver halide photographic materials using these compositions.
  • imagewise exposed silver halide black-and-white photographic materials are processed by processing steps such as black-and-white development, fixing, rinse, etc.
  • imagewise exposed silver halide color photographic materials (hereinafter referred to as color photographic materials) are processed by processing steps such as color development, desilverization, rinse, stabilization, etc.
  • imagewise exposed silver halide reversal color photographic materials are processed by processing steps such as black-and-white development and reversal development followed by color development, desilverization, rinse, stabilization, etc.
  • the color development step exposed silver halide grains are reduced by color developing agents to form silver and at the same time, the thus formed oxidant of the color developing agent reacts with a coupler to form a dye image.
  • auxiliary steps such as a rinse step, a stabilization step, a hardening step and a stop step are carried out to retain the photographic and physical qualities of the dye image.
  • Photographic processing is conducted by various laboratores ranging from large-scale laboratories provided with large-size automatic processors to more recent photo shops (called mini-laboratories) using small-size automatic processors in the shop.
  • mini-laboratories small-size automatic processors in the shop.
  • metal ions such as calcium, magnesium and iron contained in water, or metal ions such as calcium dissolved out from photographic materials, are incorporated into the processing solutions. Such metal ions have an adverse effect on processing performance.
  • the solution may have turbidity due to the formation of bacteria therein and cause the stain of film.
  • a transition metal type ion such as iron ion
  • the preservability of film after processing is deteriorated since the ion remains in the film.
  • chelating agents for sequestering the metal ions.
  • the chelating agents conventionally used include amino polycarboxylic acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc.) as described in JP-B-48-30496 (the term “JP-B” as used herein means an "examined Japanese patent publication") and JP-B-44-30232, organic phosphonic acids as 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, phosphonocarboxylic acids as 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
  • the iron(III) complex salt of ethylenediaminetetraacetic acid conventionally used has a fundamental disadvantage in that the oxidizing power thereof is low.
  • Bleaching accelerators e.g., mercapto compounds described in U.S. Patent 1,138,842
  • rapid bleaching cannot be achieved.
  • Red prussiate, iron chloride, bromates, etc. are known as bleaching agents capable of achieving rapid bleaching.
  • red prussiate cannot be widely used due to environmental concerns.
  • Iron chloride is inconvenient to handle, because it corrodes metals. Bromate solutions are unstable.
  • Iron(III) complex salt of 1,3-diaminopropanetetraacetic acid has been proposed as a bleaching agent meeting the above requirements in recent years.
  • this bleaching agent causes bleach fog.
  • the addition of buffering agents to the bleaching agent has been proposed as a method for reducing the bleach fog (see, JP-A-1-213657).
  • the problem is not be sufficiently solved by this method.
  • high-activity developing solutions are used which result in a much greater degree of bleach fog.
  • a first object of the present invention is to provide a photographic processing composition which does not form a precipitate or sludge even when metal ions are contained therein.
  • a second object of the present invention is to provide a stable processing composition which does not reduce the effectiveness of the active components in the processing solutions and does not form a component having an adverse effect on photographic characteristics even when metal ions are contained therein.
  • a third object of the present invention is to provide a processing composition which enhances preservability of the image without the increase of stain despite the presence of metal ions left behind in the processed photographic material, which metal ions are contained in the processing composition, and to provide a processing method using the processing composition.
  • a fourth object of the present invention is to provide a processing composition which is easy to handle and is free from the problem of environmental pollution caused by waste liquor and to provide a processing method using the same.
  • a fifth object of the present invention is to provide a processing composition which is excellent in desilverization performance and has a bleaching ability, and to provide a processing method using the same.
  • a sixth object of the present invention is to provide a processing composition which substantially does not cause bleach fog and has a bleaching ability, and to provide a processing method using the same.
  • a seventh object of the present invention is to provide a processing composition which does not stain a processed photographic material upon storage and which has a bleaching ability, and to provide a processing method using the same.
  • An eighth object of the present invention is to provide a processing composition which can stably retain the above-described performance even when continuous processing is conducted, and to provide a processing method using the same.
  • a processing composition for use in processing a color photographic material comprising a metal chelate compound formed from a compound represented by formula (I) and a metal salt selected from the group consisting of the salts of Fe(III), Mn(III), Co(III), Rh(II), Rh(III), Au(III), Au(II) and Ce(IV), and a processing method using the same: wherein R, R, and R 2 each represents a hydrogen atom, an alkyl group or an aryl group; and L, represents an alkylene group or an arylene group.
  • R, R, and R 2 independently represent a hydrogen atom, an alkyl group which may be substituted or an aryl group which may be substituted.
  • the alkyl group represented by R, R, and R 2 may be a straight-chain, branched or cyclic alkyl group with an alkyl group having 1 to 10 carbon atoms being preferred.
  • examples of the straight-chain alkyl group include a methyl group and an ethyl group
  • examples of the branched alkyl group include a tert-butyl group
  • examples of the cyclic alkyl group include a cyclohexyl group. More preferred examples of the alkyl group are methyl group and ethyl group.
  • the aryl group represented by R, R 1 and R 2 preferably has 6 to 10 carbon atoms. Phenyl group is more preferred.
  • the alkyl group and the aryl group represented by R, R and R 2 may be substituted.
  • substituent groups include an alkyl group having preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (e.g., methyl, ethyl, i-propyl), an aralkyl group having preferably 7 to 11 carbon atoms (e.g., phenylmethyl), an alkenyl group having preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms (e.g., allyl), an alkynyl group having preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, an alkoxy group having preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (e.g., methoxy, ethoxy), an aryl group having preferably 6 to 10 carbon atoms (e.g., phenyl), a substituted amino group (e.g., wherein
  • R, R 1 and R 2 or all of R, R 1 and R 2 may be combined together to form a ring such as pyrrolidine, imidazoline, piperidine, piperazine and morpholine.
  • L 1 represents an alkylene group having preferably 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms or an arylene group having preferably 6 to 10 carbon atoms, and is preferably methylene group or ethylene group or a group having a benzene ring.
  • the alkylene group and the arylene group may be substituted.
  • substituent groups for L 1 include those described above in the definition of the substituent groups for R, R, and R 2 .
  • R 1 has the same meaning as R 1 in formula (I)
  • substituent groups for the alkyl group and the aryl group include a carboxyl group, a group of (wherein R 3 is as defined above), a hydroxyl group, an alkyl group, an aryl group, a sulfo group and a phosphono group and more preferred examples thereof include a carboxyl group, an alkyl group and R 31 and R 32 have the same meaning as R in formula (I);
  • L 2 , L 3 , L 4 , L 5 and L 6 each represent an alkylene group having preferably 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, which may be substituted or an arylene group having preferably 6 to 10 carbon atoms, more preferably a benzene ring- containing group, which may be substituted (examples of substituent groups include those described above in the definition of the substituent groups
  • R 11 preferably represents a hydrogen atom or an alkyl group which may be substituted, and particularly an alkyl group which may be substituted.
  • D preferably represents a 5- or 6-membered divalent heterocyclic group containing N as a hetero atom.
  • the hydrocarbon represented by A preferably has 1 to 10 carbon atoms. More preferably, the hydrocarbon is an alkyl group having 1 to 6, particularly 1 to 3 carbon atoms. These divalent bonding groups may have one or more substituent groups. Examples of the substituent groups include those already described above in the definition of the substituent groups for the alkyl group and the aryl group represented by R, R 1 and R 2 .
  • Examples of D include the following groups.
  • Examples of W include the following groups.
  • W include the following groups.
  • the total carbon number of the compounds represented by formula (I) of the present invention is preferably 40 or less, more preferably 30 or less.
  • Useful examples of the compounds represented by formula (I) include, but are not limited to, the following compounds.
  • the compounds of the present invention can be synthesized by methods described in Chelate Chemistry (5), page 318 (1975) edited by Keihei Ueno (published by Nankodo) or Inorganic Chemistry, Vol. 27, 474 (1988).
  • the amounts of the compounds of formula (I) to be added to a processing composition varies depending on the type and application of the processing composition to be used, but is generally used in the range of from 10 mg to 50 g per liter of the processing composition.
  • the compound represented by formula (I) when the compound represented by formula (I) is added to a black-and-white developing solution or a color developing solution, the compound is used in the range of preferably 0.5 to 10 g, particularly preferably 0.5 to 5 g per liter of the processing composition.
  • a bleaching solution e.g., comprising hydrogen peroxide, persulfate, bromate, etc.
  • the compound is used in the range of preferably 0.1 to 20 g, particularly preferably 0.1 to 5 g per liter of the bleaching solution.
  • the compound represented by formula (I) When the compound represented by formula (I) is added to a fixing solution or bleach-fixing solution, the compound is used in the range of preferably 1 to 40 g, particularly preferably 1 to 20 g per liter of the solution. When the compound represented by formula (I) is added to a stabilizing bath, the compound is used in the range of preferably 50 mg to 1 g, particularly preferably 50 to 300 mg, per liter of the bath.
  • the compounds represented by formula (I) may be used either alone or in a combination of two or more of these compounds.
  • the compounds represented by formula (I) can generally be applied to all processing compositions for use in processing silver halide light-sensitive materials.
  • processing compositions include, but are limited to, general-purpose black-and-white developing solutions, infectious developing solutions for lith films, color developing solutions, bleaching solutions, fixing solutions, bleach-fixing solutions, compensating developers, stop-solutions, hardening solutions, washing solutions, stabilizing solutions, rinsing solutions, fogging solutions and toners.
  • the compound represented by formula (I) forms a metal complex (a metal chelate compound) with a metal salt selected from the group consisting of the salts of Fe(III), Mn(III), Co(III), Rh(II) , Rh(III), Au(II), Au-(III) and Ce(IV), and it has excellent characteristics as the bleaching agent for silver halide color photographic materials.
  • a processing composition containing a metal chelate compound of the present invention the bleaching of developed silver is accomplished very rapidly by treating a silver halide color photographic material with the processing composition containing the metal chelate compound of the present invention after the imagewise exposed silver halide color photographic material is subjected to color development.
  • No bleach fog results which is in sharp contrast the bleach fog resulting from the use of conventional bleaching agents for rapid bleaching.
  • the effect is striking, particularly when rapid color development is carried out in a short time of 3 minutes or less followed by the treatment with the processing composition containing the metal chelate compound of the present invention.
  • image preservability after processing is good, and the processing composition of the present invention is preferred from the viewpoint of handling.
  • the metal salt which forms the metal chelate compound of the present invention is selected from the group consisting of the salts of Fe(III), Mn(III), Co(III), Rh(II), Rh(III), Au(II), Au(III) and Ce(IV).
  • the salts of Fe(III), Mn(III) and Ce(IV) are preferred with a salt of Fe(III) being particularly preferred.
  • Halogen ions e.g., Cl - , Br-, I-
  • nitrate ion and sulfate ion are preferably used as counter ions to the metal salts.
  • the metal chelate compound of the present invention may be isolated as a metal chelate compound for use in the processing composition.
  • metal chelate compound of the present invention examples include, but are not limited to, the following compounds.
  • a complex of a metal salt and the compound of formula (I) is preferred.
  • the compound of formula (I) and the above-described metal salt such as ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate or ferric phosphate are reacted with each other in a solution and may be used as such.
  • the compound of formula (I) is used in a molar ratio of the compound to the metal ion of at least 1.0. A higher ratio is preferable when the stability of the metal chelate compound is low. The ratio is generally in the range of 1 to 30.
  • a small amount of the metal chelate compound may be incorporated in the fixing solution or an intermediate bath between color development and the desilverization step.
  • the compound of the present invention functions effectively as a bleaching agent in the bleaching solution or the bleach-fixing solution.
  • the compound When 0.05 to 1 mol of the metal chelate compound of the present invention per liter of the processing solution is incorporated in the processing solution having a bleaching ability, the compound functions effectively as a bleaching agent as described above.
  • An amount of the metal chelate compound in the range of 0.1 to 0.5 mol per liter of the processing solution is more preferred.
  • the metal chelate compound of the present invention When used as a bleaching agent in a processing solution having a bleaching ability, the compound of the present invention may be used together with other conventional bleaching agents, as long as the effect of the present invention is obtained.
  • conventional bleaching agents include Fe(III), Co(III) or Mn(III) chelate type bleaching agents of compounds described below, persulfates (e.g., peroxodisulfate), hydrogen peroxide and bromates.
  • Examples of the compounds which form the above-described conventional chelate bleaching agents include, but are not limited to, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, diammonium ethylenediaminetetraacetate, tetra(trimethylammonium) ethylenediaminetetraacetate, tetrapotassium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, trisodium ethylenediaminetetraacetate, diethylenetriaminepentaacetic acid, pentasodium diethylenetriaminepentaacetate, ethylenediamine-N-( ⁇ -oxyethyl)-N,N',N'-triacetic acid, trisodium ethylenediamine-N-( ⁇ -oxyethyl)-N,N',N'-triacetate, triammonium ethylenediamine-N-(,6-oxyethyl)
  • the processing solution having a bleaching ability contains a halide such as a chloride, bromide or iodide as a re-halogenating agent for accelerating the oxidation of silver in addition to the metal chelate compound functioning as a bleaching agent.
  • a halide such as a chloride, bromide or iodide
  • an organic ligand which forms a sparingly soluble silver salt may be added in place of the halide.
  • the halide is added in the form of an alkali metal salt or ammonium salt or a salt of guanidine or an amine. Examples of the halide include sodium bromide, ammonium bromide, potassium chloride and guanidine hydrochloride. Ammonium bromide is preferable.
  • the re-halogenating agent is used in an amount of generally from 0 to 2.0 mol/t, preferably 0.01 to 2.0 mol/t, more preferably 0.1 to 1.5 mol/t, still more preferably 0.3 to 1.0 moll in the bleaching solution.
  • the bleach-fixing solution containing the metal chelate compound of the present invention contains a fixing agent (described hereinafter) and optionally the re-halogenating agent in addition to the metal chelate compound.
  • a fixing agent described hereinafter
  • the re-halogenating agent is used in the bleach-fixing solution, the re-halogenating agent is used in an amount of from 0.001 to 2.0 molli, preferably from 0.01 to 1.0 mol/l.
  • the bleaching solution or the bleach-fixing solution may optionally contain a bleaching accelerator, a corrosion inhibitor for preventing the processing bath tank from being corroded, a buffering agent for maintaining the desired pH of the solution, a fluorescent brightener, anti-foaming agent, etc.
  • bleaching accelerator examples include compounds having mercapto group or disulfide group as described in U.S. Patent 3,893,858, German Patent 1,290,812, U.S. Patent 1,138,842, JP-A-53-95630 and Research Disclosure No. 17129 (1978); thiazolidine derivatives as described in JP-A-50-140129; thiourea derivatives as described in U.S. Patent 3,706,561; polyethylene oxides as described in German Patent 2,748,430; polyamine compounds as described in JP-B-45-8836; and imidazole compounds as described in JP-A-49-40493.
  • the mercapto compounds described in U.S. Patent 1,138,842 are preferable.
  • the corrosion inhibitor include nitrates such as ammonium nitrate and potassium nitrate.
  • the corrosion inhibitor is used in an amount of from 0.01 to 2.0 moUR, preferably 0.05 to 0.5 mol/l.
  • the pH of the bleaching solution or the bleach-fixing solution is in the range of from 2.0 to 8.0, preferably 3.0 to 7.5.
  • the pH of the solution is not higher than 6.0, and preferably not higher than 5.5 to inhibit bleach fog.
  • the pH is less than 2.0, the metal chelate compound of the present invention is unstable. Therefore, pH is preferably in the range of from 2.0 to 5.5.
  • the pH is preferably in the range of from 3 to 7 to prevent cyan dye from being converted to leuco dye.
  • the pH buffering agent is not particularly limited as long as the buffering agent is substantially not oxidized by the bleaching agent and provides buffer action in the pH range described above.
  • useful buffering agents include organic acids such as acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid and ureidopropionic acid and organic bases such as pyridine, dimethylpyrazole, 2-methyl-o-oxazoline and aminoacetonitrile.
  • Organic acids having a pKa of 2.0 to 5.5 are preferred in the present invention.
  • Acetic acid and glycolic acid are particularly preferred.
  • the buffering agent is used in an amount of from 0 to 3.0 moi/t, preferably 0.5 to 2.0 mol/t.
  • the buffering agent may be used either alone or in a combination of two or more buffering agents.
  • the above-described acids may be used together with an alkali agent (e.g., ammonia water, KOH, NaOH, imidazole, monoethanolamine, diethanolamine) to adjust the pH of the processing solution having a bleaching ability to a value within the range described above.
  • an alkali agent e.g., ammonia water, KOH, NaOH, imidazole, monoethanolamine, diethanolamine
  • ammonia water is preferred.
  • the processing solution having a bleaching ability is aerated to oxidize the iron(II) complex salt formed therein, whereby the bleaching agent is reproducable and photographic performance is stable.
  • the bleaching or bleach-fixing step can be carried out at a temperature of from 30 to 50° C, preferably from 35 to 45 C.
  • the time of the bleaching step and/or the bleach-fixing step is generally 10 seconds to 5 minutes, preferably 10 to 60 seconds in the case of a photographic material for photographing.
  • the time is generally from 5 to 70 seconds, preferably from 5 to 60 seconds, more preferably from 5 to 30 seconds in the case of a print photographic material. Good results can be obtained under these preferred processing conditions under which processing is rapid and staining is not increased.
  • the fixing solution and the bleach-fixing solution of the present invention can contain a conventional fixing agents.
  • the fixing agent include thiosulfates, thiocyanates, thioethers, amines, mercapto compounds, thiones, thioureas and iodides. More specifically, examples of the fixing agent include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, potassium thiocyanate, dihydroxyethyl thioether, 3,6-dithia-1,8-octanediol and imidazole.
  • thiosulfates particularly ammonium thiosulfate are preferred when rapid fixing is desired. More rapid fixing can be conducted by using two or more fixing agents in combination. For example, it is preferred that ammonium thiosulfate is used in combination with ammonium thiocyanate, imidazole, thiourea, thioether, etc. In this case, the second fixing agent is used in an amount of preferably 0.01 to 100 mol% based on the amount of ammonium thiosulfate.
  • the fixing agent is used in an amount of from 0.1 to 3.0 mol, preferably 0.5 to 2.0 mol per liter of the fixing solution or the bleach-fixing solution.
  • the pH of the fixing solution varies depending on the type of fixing agent, but is generally in the range of from 3.0 to 9.0. Particularly, when thiosulfates are used, a pH of from 6.5 to 8.0 is preferred to obtain stable fixing performance.
  • Preservatives can be added to the fixing solution and/or the bleach-fixing solution to enhance the stability of the solution with time.
  • the fixing solution or the bleach-fixing solution contains thiosulfates, sulfites and/or bisulfite adducts of hydroxylamine, hydrazine and aldehydes (e.g., bisulfite adduct of acetaldehyde, particularly preferably bisulfite adducts of aromatic aldehydes described in JP-A-1-298935) are effective as preservatives.
  • the sulfinic acid compounds described in JP-A-62-143048 are also preferred.
  • a buffering agent is preferably added to the fixing solution and/or the bleach-fixing solution to keep the pH of the solution constant.
  • the buffering agent include phosphates, imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole and 1-ethyl-imidazole, triethanolamine, N-allylmorpholine and N-benzoylpiperazine.
  • a chelating agent is added to the fixing agent, iron ion carried over from the bleaching solution is sequestered to thereby improve the stability of the solution.
  • Preferred examples of such a chelating agent include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N,N,N',N'- tetramethylenephosphonic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid and 1,2-propanediaminetetraacetic acid.
  • the fixing step is conducted at a temperature of from 30 to 50° C, preferably 35 to 45 . C.
  • the time of the fixing step is from 35 seconds to 2 minutes, preferably from 40 to 100 seconds in the case of a photographic material for photographing.
  • the time is from 10 to 70 seconds, preferably from 10 to 30 seconds in the case of a print photographic material.
  • the desilverization step of the present invention is carried out by a combination of a bleaching step and/or a bleach-fixing step. Typical examples of such combinations include the following.
  • the processing combinations (1), (2), (3) and. (4) are preferred with (1), (2) or (3) being more preferred.
  • the processing combination (5) is preferred.
  • the present invention can be applied to the desilverization treatment by means of a stop bath, rinse bath, etc. after color development.
  • stirring is vigorously carried out as much as possible in the desilverization steps such as the bleaching, bleach-fixing and fixing steps to enhance the effect of the present invention.
  • Examples of methods for vigorously stirring include a method wherein a jet stream of the processing solution is directed to the emulsion surface of the light-sensitive material as described in JP-A-62-183460 and JP-A-62-183461; a method wherein a stirring effect is improved by using a rotating means as described in JP-A-62-183461; a method wherein the light-sensitive material is transferred while a wire blade provided in the solution is brought into contact with the emulsion surface to cause a turbulent flow on the emulsion surface, whereby stirring is improved; and a method wherein the circulating flow rate of the entire processing solution is increased.
  • Such methods for improving stirring can be effectively applied to any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the transport of the bleaching agent and the fixing agent into the emulsion layer is expedited by vigorous stirring, and as a result, the desilverization rate is increased.
  • the above-described vigorous stirring means are more effective when a bleaching accelerator is used.
  • the bleaching accelerating effect is greatly increased by this technique, and the problem of a fixation inhibiting action is solved.
  • the above-described vigorous stirring can be preferably applied to the color developing solution, the rinsing solution and the stabilizing solution.
  • the color developing solution of the present invention can contain conventional aromatic primary amine color developing agents.
  • Preferred developing agents are p-phenylenediamine derivatives. Typical examples thereof include, but are not limited to, the following compounds.
  • D-5, D-6 and D-12 are preferable.
  • these p-phenylenediamine derivatives are used in the form of a salt such as a sulfate, hydrochloride, sulfite or p-toluenesulfonate.
  • the aromatic primary amine color developing agent is used in an amount of preferably from 0.005 to 0.1 mol, more preferably from 0.01 to 0.06 mol per liter of the color developing solution.
  • the color developing solution may contain a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite and potassium metabisulfite and carbonyl sulfite adducts as a preservative.
  • a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite and potassium metabisulfite and carbonyl sulfite adducts as a preservative.
  • the hydroxyl amines e.g., those described in JP-A-63-5341 and JP-A-63-106655, preferably the compounds having a sulfo group or a carboxyl group
  • hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, phenols described in JP-A-63-44657 and JP-A-63-58443, a-hydroxyketones and a-aminoketones described in JP-A-63-44656 and/or various saccharide described in JP-A-63-36244 are directly added to the aromatic primary amine color developing agent.
  • Examples of other preservatives which may be contained in the developing solution of the present invention include various metals as described in JP-A-57-44148 and JP-A-57-53749, salicylic acids as described in JP-A-59-180588, alkanolamines as described in JP-A-54-3582, polyethyleneimines as described in JP-A-56-94349 and aromatic polyhydroxy compounds as described in U.S. Patent 3,746,544. Among them, aromatic polyhydroxy compounds are preferable.
  • the preservative is used in an amount of from 0.005 to 0.2 mol, preferably from 0.01 to 0.05 mol per liter of the developing solution.
  • the pH of the color developing solution of the present invention is in the range of from 9 to 12, preferably from 9.5 to 11.5.
  • the color developing solution may contain other compounds conventionally employed in a color developing solution.
  • a buffering agent is preferably used in the color developing solution of the present invention to maintain the pH in the range described above.
  • useful buffering agents include, but are not limited to, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium tertiary phosphate, potassium tertiary phosphate, disodium hydrogenphosphate, dipotassium hydrogenphosphate, 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) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
  • the buffering agent is preferably used in an amount of from at least 0.1 mol, particularly preferably 0.1 to 0.4 mol per liter of the color developing solution.
  • various chelating agents can be added to the color developing solution in such an amount that the chelating agents do not diminish the affect of the present invention, or otherwise interfere with the compounds of the present invention.
  • Organic acid compounds are preferred as chelating agents.
  • examples thereof include aminopolycarboxylic acids, organic phosphonic acids and phosphonocarboxylic acids. More specifically, examples of these acids include, but are not limited to, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'- tetramethylenephosphonic acid, trans-cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine-o-hydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and N,N'-bis(2-hydroxybenzyl)ethylenediamine
  • chelating agents may be used either alone or in a combination of two or more of the chelating agents.
  • the chelating agent is used in an amount sufficient to sequester metal ions in the color developing solution.
  • the chelating agent is used in an amount of from 0.001 to 0.05 mol/t, preferably from 0.003 to 0.02 mol/t.
  • the color developing solution of the present invention may contain a development accelerator.
  • Examples of the development accelerator 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; p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554; quaternary ammonium salts described in JP-A-50- 1 37726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429; amine compounds described in U.S.
  • a 1-phenyl-3-pyrazolidone as an auxiliary developing agent is added to conduct rapid development.
  • Examples thereof include the following compounds.
  • auxiliary developing agent is used in an amount of from 0.0005 to 0.03 mol, preferably from 0.001 to 0.01 mol per liter of the color developing solution.
  • the color developing solution of the present invention may contain an anti-fogging agent.
  • the anti-fogging agent include alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic anti-fogging agents.
  • organic anti-fogging agents include nitrogen-containing heterocyclic compounds such as benztriazole, 6-nitrobenzimidazole, 5-nitroisoin- dazole, 5-methylbenztriazole, 5-nitrobenztriazole, 5-chlorobenztriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.
  • the color developing solution of the present invention may contain a fluorescent brightener.
  • Preferred examples of the fluorescent brightener include 4,4'-diamino-2,2'-disulfostilbene compounds.
  • the compound is used in an amount of from 0 to 5 g/t, preferably from 0.1 to 4 g/L
  • various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids and aromatic carboxylic acids may be added to the color developer solution.
  • the processing temperature using the color developing solution of the present invention is in the range of from 20 to 55 C, preferably 33 to 55 C.
  • the processing time is from 20 seconds to 5 minutes, preferably from 30 seconds to 3 minutes and 20 seconds, more preferably from 1 to 2 minutes and 30 seconds in the case of a color photographic material for photographing.
  • the time is from 10 to 80 seconds, preferably from 20 to 60 seconds in the case of a print photographic material.
  • Black-and-white developing solutions which are first used in reversal color processing and contain a compound of the present invention and black-and-white developing solutions which are used for processing black-and-white silver halide photographic materials which contain a compound of the present invention can contain various additives conventionally used in such developing solutions.
  • Typical examples of the additives include developing agents such as 1-phenyl-3-pyrazolidone, Metol and hydroquinone, preservatives such as sulfites, accelerators comprising alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate, inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole, hard water softeners such as polyphosphates and development restrainers comprising a very small amount of an iodide or a mercapto compound.
  • developing agents such as 1-phenyl-3-pyrazolidone, Metol and hydroquinone
  • preservatives such as sulfites
  • accelerators comprising alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate
  • inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole
  • hard water softeners such as polyphosphates
  • development restrainers comprising a very small amount of an
  • the effect of the present invention can also be obtained by adding a compound of formula (I) of the present invention to a rinsing water or stabilizing solution.
  • the processing method of the present invention comprises basically the aforesaid color development step and the subsequent desilverization step.
  • a rinsing step and/or a stabilization step subsequent to these steps is preferably carried out.
  • Rinsing water for use in the rinsing step may contain various surfactants to prevent unevenness caused by water droplets during the drying step of the photographic material after processing.
  • useful surfactants include polyethylene glycol type nonionic surfactants, polyhydric alcohol type nonionic surfactants, alkylbenzenesulfonate type anionic surfactants, higher alcohol sulfuric ester salt type anionic surfactants, alkylnaphthalenesulfonate type anionic surfactants, quaternary ammonium salt type cationic surfactants, amine salt type cationic surfactants, amino acid type ampholytic surfactants and betaine type ampholytic surfactants.
  • nonionic surfactants When ionic surfactants are used, there is a possibility that the surfactant becomes bonded to various ions introduced by processing to form precipitates. Accordingly, the use of nonionic surfactants is preferable. Particularly, alkylphenol ethylene oxide adducts are preferred. Octylphenol, nonylphenol, dodecylphenol and dinonylphenol are particularly preferred as the alkylphenol. The addition of ethylene oxide is preferably 8 to 14 moles. Further, silicone surfactants having a high anti-foaming effect are preferably used.
  • the rinsing water may contain various anti-bacterial agents and antifungal agents to prevent bacteria from proliferating or to prevent mold from being grown on the processed photographic material.
  • useful anti-bacterial agents and antifungal agents include the thiazolylbenzimidazole compounds described in JP-A-57-157244 and JP-A-58-105145, the isothiazolone compounds described in JP-A-54-27424 and JP-A-57-8542, chlorophenol compounds such as trichlorophenol, bromophenol compounds, organotin compounds, organozinc compounds, thiocyanic acid or isothiocyanic acid compounds, acid amide compounds, diazine compounds, triazine compounds, thiourea compounds, benztriazole alkylguanidine compounds, quaternary ammonium salts such as benzammonium chloride, antibiotics such as penicillin and the general-purpose antifungal agents described in J. Antibact. Antifung. Agents, Vol. 1, No. 5,
  • JP-A-48-83820 can be used.
  • Chelating agents can be added to the rinsing water in such an amount that they do not interfere with the effect of the compound of formula (I) of the present invention.
  • Preferred examples of the chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid and hydrolyzates of maleic anhydride polymers described in European Patent 345172A1.
  • aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid
  • organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid
  • hydrolyzates of maleic anhydride polymers described in European Patent 345172A1.
  • the same preservatives contained in the fixing solution and the bleach-fixing solution are also preferably contained in the rinsing water.
  • a processing solution used to stabilize a dye image is used as a stabilizing solution in the stabilization step.
  • the stabilizing solution include a solution containing an organic acid, solutions having a buffer ability at a pH of 3 to 6 and solutions containing aldehydes (e.g., formalin, glutaraldehyde).
  • the stabilizing solution may also contain any of compounds which can be added to the rinsing water.
  • ammonium compounds such as ammonium chloride and ammonium sulfite, compounds of metals such as Bi and Al, fluorescent brighteners, various dye stabilizers such as N-methylol compounds and stabilizing method using the same as described in JP-A-2-153350, JP-A-2-153348 and U.S. Patent 4,859,574, hardening agents and alkanolamines described in U.S. Patent 4,786,583 may be used.
  • Multi-stage countercurrent systems are preferred in the rinsing step and the stabilization step.
  • the number of stages is preferably 2 to 4.
  • Replenishment rate per unit area is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount carried over from the prebath.
  • Tap water can be used as the water in the rinsing step and the stabilization step.
  • Ion-exchanged (deionized) water is preferably used having a Ca and Mg concentration each of 5 mg/t or less by treating water with an ion exchange resin, and water which is sterilized by a halogen or ultraviolet sterilization lamp is also preferably used.
  • Tap water may be used to compensate for water lost by evaporation.
  • deionized water or sterilized water which is preferably used in the rinsing step and the stabilization step is preferable.
  • an appropriate amount of water or replenisher is fed to the bleaching solution and the bleach-fixing solution as well as other the processing solutions to correct concentration caused by evaporation.
  • Overflow from the rinsing step and the stabilization step can be directed to a bath having a fixing ability which is a prebath, whereby the amount of waste solution is reduced.
  • each processing solution of the present invention is preferably enhanced as much as possible.
  • methods for enhancing stirring include a method wherein a jet stream of the processing solution is directed to the emulsion surface of the photographic material as described in JP-A-62-183460; a method wherein a stirring effect is improved by using a rotating means as described in JP-A-62-18346; a method wherein the photographic material is transferred while the emulsion surface is brought into contact with a wire blade or squeeze roller provided in the solution to provide turbulent flow on the emulsion surface, whereby a stirring effect is improved; and a method wherein the circulating flow rate of the entire processing solution is increased.
  • the processing method of the present invention is preferably carried out using an automatic processor.
  • Conveying methods for an automatic processor are described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. It is desirable that cross-over time between processing baths in the automatic processor is short to carry out rapid processing with the processing composition of the present invention.
  • An automatic processor wherein cross-over time is not longer than 10 seconds is described in JP-A-1-319038.
  • the replenisher is preferably added in an amount depending on the amount of the photographic material processed to supplement the consumed ingredients in the processing solution and to inhibit the accumulation of undesirable components in the processing solution.
  • the undesirable components are generally dissolved out from the photographic material.
  • Each processing step may comprise two or more processing bath tanks. In this case, a countercurrent system wherein the replenisher is allowed to flow from the rear bath into the prebath is preferred. A cascade having 2 to 4 stages is preferred for the rinsing step and the stabilization step in particular.
  • the amount of the replenisher is preferably reduced, so long as a change in the composition of each processing solution does not lower photographic performance or cause staining.
  • the amount of replenisher of the color developing solution is from 100 to 1500 ml, preferably from 100 to 1000 ml per m 2 of the photographic material in the case of a color photographic material for photographing.
  • the amount of the replenisher is from 20 to 500 ml, preferably from 20 to 220 ml, more preferably from 30 to 200 ml, most preferably from 30 to 160 ml in the case of a color print material.
  • the amount of the replenisher of the bleaching solution is from 10 to 500 ml, preferably from 10 to 160 ml per m 2 of the photographic material in the case of a photographic material for photographing.
  • the amount of the replenisher is from 20 to 300 ml, preferably from 50 to 150 ml in the case of a print material.
  • the amount of the replenisher of the bleach-fixing solution is from 100 to 3000 ml, preferably from 200 to 1300 ml per m 2 of a photographic material for photographing.
  • the amount of the replenisher is from 20 to 300 ml, preferably from 50 to 200 ml in the case of a photographic print material.
  • the replenishment of the bleach-fixing solution may be made by a single solution, or by dividing the solution into a bleaching composition and a fixing composition. If desired, the replenisher of the bleach-fixing solution may be provided by mixing overflow from the bleaching bath and/or the fixing bath.
  • the amount of the replenisher of the fixing solution is from 300 to 3000 ml, preferably, from 300 to 1000 ml per m 2 of the photographic material in the case of a photographic material for photographing.
  • the amount of the replenisher is from 20 to 300 ml, preferably from 50 to 200 ml in the case of a photographic print material.
  • the replenishment rate of rinsing water or the stabilizing solution per unit area is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount carried over from the prebath.
  • the amount of the replenisher is further reduced by combining various regeneration methods.
  • Regeneration may be carried out while the processing solution is circulated in the automatic processor.
  • regeneration may be carried out in such a manner that after the processing solution used is removed from the processing tank, the solution is subjected to an appropriate regeneration treatment and the regenerated solution as a replenisher is again returned to the processing tank.
  • the developing solution can be regenerated by an ion exchange treatment with an anion exchange resin, the removal of accumulated materials with electrodialysis treatment and/or the addition of a regenerant.
  • the regeneration ratio is preferably at least 50%, more preferably at least 70%.
  • anion exchange resins can be used, but an ion exchanger having high selectivity described in JP-A-63-11005 is preferred.
  • the metal chelate bleaching agent in the bleaching solution and/or the bleach-fixing solution is brought into a reduced state with the bleaching treatment.
  • bleaching performance is lowered.
  • the dye of the dye image can be converted to a leuco dye to result in a lowering of the image density.
  • it is desirable that the bleaching solution and/or the bleach-fixing solution is continuously subjected to a regeneration treatment in during processing.
  • air can be blown into the bleaching solution and/or the bleach-fixing solution by means of an air pump to re-oxidize, i.e., aerate the metal chelate in the reduced state with oxygen.
  • the bleaching solution and/or the bleach-fixing solution can be regenerated by adding an oxidizing agent such as hydrogen peroxide, persulfate or bromate.
  • the regeneration of the fixing solution and the bleach-fixing solution can be achieved by electrolytically reducing accumulated silver ion. It is also preferred for retaining fixing performance that accumulated halogen ion be removed using an anion exchange resin.
  • Ion exchange or ultrafiltration can be used to reduce the amount of rinsing water. Ultrafiltration is particularly preferred.
  • photographic materials which can be processed with the processing composition of the present invention include general-purpose black-and-white silver halide photographic materials (e.g., black-and-white photographic materials for photographing, X-ray black and white photographic materials, black-and-white photographic materials for printing), general-purpose multi-layer silver halide color photographic materials (e.g., color negative film, reversal color films, color positive films, movie color negative films, color photographic paper, reversal color photographic paper, direct positive color photographic paper), infrared light-sensitive photographic materials for laser scanner and diffusion transfer photographic materials (e.g., silver diffusion transfer photographic materials, color diffusion transfer photographic materials).
  • general-purpose black-and-white silver halide photographic materials e.g., black-and-white photographic materials for photographing, X-ray black and white photographic materials, black-and-white photographic materials for printing
  • general-purpose multi-layer silver halide color photographic materials e.g., color negative film, reversal color films, color positive films, movie color negative films, color photographic paper
  • the photographic materials for processing in accordance with the present invention may have various layer structures (e.g., red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers, undercoat layer, antihalation layer, filter layer, interlayer, surface protective layer) on one side or both sides of the support according to the intended purpose.
  • layer structures e.g., red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers, undercoat layer, antihalation layer, filter layer, interlayer, surface protective layer
  • the arrangement of the layers is not particularly limited.
  • the support for the photographic material for processing in accordance with the present invention there are no particular limitations with regard to the support for the photographic material for processing in accordance with the present invention; coating methods; the types of silver halide (e.g., silver iodobromide, silver iodochlorobromide, silver bromide, silver chlorobromide, silver chloride) used in the silver halide emulsion layers and the surface protective layer, the shape of the grains (e.g., cube, tabular form, sphere), grain size, coefficient of variation, crystal structure (e.g., core/shell structure, polyphase structure, uniform phase structure), method for preparing the grains (e.g., single jet process, double jet process), binders (e.g., gelatin), hardening agents, anti-fogging agents, metal doping agents, solvents for silver halide, thickeners, emulsion precipitants, dimensional stabilizers, adhesion inhibitors, stabilizers, stain inhibitors, dye image stabilizers
  • the photographic material suited for the processing in accordance with the present invention may comprise a support having thereon at least one silver halide emulsion layer comprising a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer.
  • a typical example of the photographic material is a silver halide photographic material comprising a support having thereon a light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity and different light sensitivity.
  • a light-sensitive layer is a unit light-sensitive layer having a color sensitivity to any one of blue light, green light and red light.
  • the unit light-sensitive layer is generally arranged in the order of a red-sensitive layer, a green-sensitive layer and then a blue-sensitive layer on the support.
  • this arrangement may be in the reverse order to that described above according to the intended purpose.
  • the arrangement may be such that a layer having a different color sensitivity is interposed between layers having the same color sensitivity.
  • a light-insensitive layer such as an interlayer may be provided between the silver halide light-sensitive layers or as the uppermost layer and the lowermost layer.
  • the interlayer may contain a coupler and DIR compound as described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037 and JP-A-61-20038 and may further contain conventional color mixing inhibitors, ultraviolet light absorbers and anti-staining agents.
  • a plurality of silver halide emulsion layers which constitute each unit light-sensitive layer preferably have a two layer structure consisting of a high-snsitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent 1,121,470 and U.K. Patent 923,045.
  • the emulsion layers are arranged such that light sensitivity decreases in order toward the support.
  • a light-insensitive layer may be provided between the silver halide emulsion layers.
  • a low-sensitivity emulsion layer may be provided farther from the support than the high-sensitivity emulsion layer, and a high-sensitivity emulsion layer may be provided nearer the support as described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543.
  • a low-sensitivity blue-sensitive layer (BL)/high-sensitivity blue-sensitive layer (BH)/high-sensitivity green-sensitive layer (GH)/low-sensitivity green-sensitive layer (GL)/high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer can be provided in this order from the side which is farthest away from the support.
  • the layers can be arranged in order of BH/BUGUGH/RH/RL or BH/BUGH/GURURH.
  • a blue-sensitive layer/GH/RH/GURL can be arranged in this order from the side which is farthest away from the support as described in JP-B-55-34932.
  • a blue-sensitive layer/GURUGH/RH in this order can be arranged from the side which is farthest away from the support as described in JP-A-56-25738 and JP-A-62-63936.
  • a three layer structure can be used comprising three layers having different light sensitivity.
  • the light sensitivity is decreased in order toward the support.
  • the upped layer is a silver halide emulsion layer having the highest light sensitivity
  • the intermediate layer is a silver halide emulsion layer having a lower light sensitivity than that of the upper layer
  • the lower layer is a silver halide emulsion layer having a lower light sensitivity than that of the intermediate layer as described in JP-B-49-15495.
  • medium-sensitivity emulsion layer/high- sensitivity emulsion layer/low-sensitivity emulsion layer in this order may be arranged in the same color sensitivity layer from the side which is farther away from the support as described in JP-A-59-202464.
  • the dry thickness of the entire constituent layers of the color photographic material for processing in accordance with the present invention is 20.0 nm or less excluding the support and the undercoat and back layer of the support. More preferably, the dry thickness is 18.0 u.m or less.
  • the formation of bleach fog caused by the remaining color developing agent in the photographic material and stain formed during the storage of the image after processing are inhibited.
  • the layer thickness is desirably reduced to the extent that the performance of the photographic material is not deteriorated.
  • the lower limit of the dry thickness of the entire constituent layers of the photographic material is 12.0 I.1.m excluding the support and the undercoat layer of the support.
  • the lower limit of the entire dry thickness of a constituent layer provided between the undercoat layer of the support and the light-sensitive layer nearest the support is 1.0 ⁇ m.
  • the reduction of the layer thickness may be accomplished by any of the light-sensitive layer and the light-insensitive layer.
  • the layer thickness of a multi-layer color photographic material for processing in accordance with the present invention is measured in the following manner.
  • the photographic material to be measured is stored at 25 C and 50% RH for 7 days after the preparation thereof.
  • the overall thickness of the photographic material is first measured.
  • the coated layers on the support are removed and the thickness of the residue is again measured. A difference therebetween is the thickness of the entire coated layers excluding the support of the photographic material.
  • the measurement of the thickness is made, for example, by using a layer thickness measuring device (Anritsu Electric Co., Ltd., K-402B Stand.) using a contact type piezoelectric transducing element.
  • the coated layers on the support can be removed by using an aqueous solution of sodium hypochlorite.
  • a photograph of the cross section of the photograph is taken (preferably at least 3,000X magnification) using a scanning type electron micrograph.
  • the overall thickness of the layers on the support and the thickness of each layer are measured and compared with the measured value (the absolute value of actual measurement) of the overall thickness measured by using the above layer thickness measuring device, whereby the thickness of each layer is calculated.
  • the swelling ratio (equilibrium swelling layer thickness in H 2 0 at 25° C - overall dry layer thickness at 25 C and 55% RH)/overall dry layer thickness at 25°C and 55% RH x 100] of the photographic material for processing in accordance with the present invention is preferably 50 to 200%, more preferably 70 to 150%.
  • image quality e.g., desilverization degree
  • layer physical properties such as layer strength are adversely affected.
  • the swelling rate T, 12 of the photographic material of the present invention is preferably 15 seconds or shorter wherein the swelling rate T i 1 2 is defined by the time which has elapsed until the layer thickness reaches 1/2 of the saturated swelling layer thickness, 90% of the maximum swelling layer thickness in color developing solution (30 C, 3 minutes and 15 sec) being referred to as the saturated swelling layer thickness. More preferably, T 1 ⁇ 2 is 9 seconds or less.
  • the silver halide to be contained in the photographic emulsion layers of the color photographic material for processing in accordance with the present invention may have any silver halide composition. Namely, any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride and silver iodochlorobromide can be used.
  • color photographic materials for photographing and reversal color photographic materials e.g., color negative films, reversal films, reversal color paper
  • silver iodobromide, silver iodochloride or silver iodochlorobromide is preferred, each having a silver iodide content of 0.1 to 30 mol%.
  • direct positive color photographic materials silver bromide or silver chlorobromide is preferred.
  • photographic materials for paper silver chloride or silver chlorobromide is preferred.
  • Silver halide grains in the photographic emulsions may have a regular crystal form such as a cube, octahedron or tetradecahedron, an irregular crystal form such as a sphere or tabular form, a crystal form having defect such as twin plane or a composite form thereof.
  • silver halide grains may range from fine grains having a grain size of not larger than about 0.2 um to large-size grains having a grain size of about 10 u.m in terms of the diameter of a sphere having an area equal to the projected area of the grain. Any of a polydisperse emulsion and monodisperse emulsion can be used.
  • Photographic silver halide emulsions for use in a photographic material for processing in accordance with the present invention can be prepared, for example, by the methods described in Research Disclosure (RD), No. 17643 (December, 1978), pp. 22-23; ibid. No. 307105 (November, 1989), pp. 863-865, "I. Emulsion Preparation and Types"; ibid. No. 18716 (November, 1979) page 648; P. Glafkides, Chimie et Physique Photographique (Paul Montel, 1967), G.F. Duffin, Photographic Emulsion Chemistry (Focal Press, 1966) and V.L. Zelikman et al., Making and Coating Photographic Emulsion (Focal Press, 1964).
  • Tabular grains having an aspect ratio of not lower than about 5 can be used in the photographic material for processing in accordance with the present invention
  • the tabular grains can be easily prepared by methods described in Gutoff, Photographic Science and Engineering, Vol. 14, pp. 248-257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and U.K. Patent 2,112,157.
  • the crystal structure may be uniform or constitute a phase structure where the interior of the grain is different in halogen composition from the surface layer thereof.
  • Silver halide grains having different compositions may be joined by epitaxial growth. Grains may be joined to a compound such as silver rhodanine or lead oxide other than a silver halide.
  • mixtures of grains having various crystal forms may be used.
  • the silver halide emulsions are usually subjected to physical ripening, chemical ripening and spectral sensitization and used. Additives used in these stages are described in Research Disclosure No. 17643, ibid. No. 18716 and ibid. No. 307105 and indicated in the following Table.
  • color couplers can be used in the photographic material for processing in accordance with the present invention.
  • Useful examples of the color couplers are described in the patent specifications cited in the aforesaid RD No. 17643, VII-C N G and ibid. No. 307105, VII-C ⁇ G and JP-A-62-215272.
  • yellow couplers include those described in U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752 and 4,248,961, JP-B-58-10739, U.K. Patents 1,425,020 and 1,476,760, U.S. Patents 3,973,968, 4,314,023 and 4,511,649 and European Patent 249,473A.
  • magenta couplers include 5-pyrazolone compounds and pyrazoloazole compounds.
  • the present invention is particularly effective in solving the problem of bleach fog and stain caused by pyrazoloazole couplers.
  • cyan couplers examples include phenol couplers and naphthol couplers.
  • Preferred examples of colored couplers for correcting unnecessary absorption of developed dyes include those described in Research Disclosure (RD) No. 17643, item VII-G, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258 and U.K. Patent 1,146,368. It is preferred to use couplers for correcting unnecessary absorption of developed dyes by fluorescent dyes released during coupling as described in U.S. Patent 4,774,181 and couplers having, as an eliminable group, a dye precursor group which reacts with a developing agent to form a dye as described in U.S. Patent 4,777,120.
  • Couplers which provide a developed dye having a proper diffusibility include those described in U.S. Patent 4,366,237, U.K. Patent 2,125,570, European Patent 96,570 and West German Patent Application (OLS) No. 3,234,533.
  • Typical examples of dye forming polymer couplers include those described in U.S. Patents 3,451,820, 4,080,211, 4,367,282, 4,409,320 and 4,576,910 and U.K. Patent 2,102,179.
  • Couplers which release a photographically useful residue upon coupling are preferably used in a photographic material for processing in accordance with the present invention.
  • DIR couplers which release a development restrainer include those described in the patent specifications cited in Research Disclosure (RD) No. 17643, item VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, U.S. Patents 4,248,962 and 4,782,012.
  • couplers which imagewise release a nucleating agent or a development accelerator include those described in U.K. Patents 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840.
  • RD Research Disclosure
  • the couplers for use in a photographic material for processing in accordance with the present invention can be introduced into the photographic material by various conventional dispersion methods.
  • high-boiling solvents which are used for oil-in-water dispersion methods are described in U.S. Patent 2,322,027, etc.
  • Useful examples of high-boiling organic solvents which have a boiling point of not lower than 175°C under atmospheric pressure and are used in the oil-in-water dispersion methods include phthalic esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl)-phthalate, etc.); phosphoric esters and phosphonic esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricycl
  • Organic solvents having a boiling point of not lower than about 30 C, preferably not lower than 50 C, but not higher than about 160 C can be used as co-solvents.
  • Typical examples of the co-solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- ethoxyethyl acetate and dimethylformamide.
  • the couplers are impregnated with loadable latex polymer (e.g., described in U.S. Patent 4,203,716) in the presence or absence of the above noted high-boiling organic solvent or dissolved in a water-insoluble, organic solvent-soluble polymer to be dispersed in an aqueous solution of a hydrophilic colloid.
  • loadable latex polymer e.g., described in U.S. Patent 4,203,712
  • the homopolymers or copolymers described in WO(PCT) 88/00723 are used.
  • Acrylamide polymers are particularly preferred for stabilization of the dye image.
  • the photographic material for processing in accordance with the present invention may contain a developing agent.
  • a developing agent which can be contained in the photographic material are described in RD No. 17643 (Developing Agents of page 29). Hydroquinones and pyrazolidones are particularly preferred.
  • An undercoated cellulose triacetate film support was coated with the following layers having the following compositions to prepare a multi-layer color photographic material s sample 101.
  • Each layer had the following composition. Numerals represent coating weight (g/m 2 ). The amounts of silver halide emulsions and colloidal silver are coating weights (g/m 2 ) in terms of silver. The amounts of sensitizing dyes are represented by moles per one mole of silver halide in the same layer.
  • Second Red-Sensitive Emulsion Layer Second Red-Sensitive Emulsion Layer
  • Second Blue-Sensitive Emulsion Layer Second Blue-Sensitive Emulsion Layer
  • the thus prepared sample was cut to form pieces having a width of 35 mm, exposed to white light (color temperature of light source: 4800 K) through a wedge and processed in the following processing steps by using a processing machine for motion picture film (FP-350, manufactured by Fuji Photo Film Co., Ltd.).
  • the sample selected for evaluation of performance was only processed until after the accumulated replenishment of the color developing solution reached three times the tank capacity of the mother solution.
  • the bleaching solution was aerated at a rate of 200 ml/min through a pipe having many pores of 0.2 mm ⁇ provided at the bottom of the bleaching solution tank. Processing was carried out while carrying out the aeration under the above conditions.
  • the amount of the developing solution carried into the bleaching step and the amount of the fixing solution carried into the rinsing step were 2.5 ml and 2.0 ml, respectively, each amount being per 35 mm wide by 1 m long strip of the photographic material .
  • Cross-over time was 5 seconds from both color development to bleaching and from bleaching to fixing. The time was included in the processing time of the previous step.
  • Each processing solution had the following composition.
  • chelate compound refers to organic acids capable of forming iron(III) ammonium salts of organic acids used as bleaching agents.
  • the mother solution and replenisher had the same composition.
  • the mother solution and the replenisher were the same.
  • Tap water was passed through a mixed bed column packed with an H type strongly acidic cation exchange resin (Amberlite IR-120B, a product of Rohm & Haas Co.) and an OH type strongly acidic anion exchange resin (Amberlite IRA-400) to reduce the concentration of each of calcium ion and magnesium ion to not more than 3 mg/L Subsequently, sodium dichloroisocyanurate (20 mg/l) and sodium sulfate (150 mg/1) were added thereto. The pH of the solution was in the range of 6.5 to 7.5.
  • H type strongly acidic cation exchange resin Amberlite IR-120B, a product of Rohm & Haas Co.
  • Amberlite IRA-400 OH type strongly acidic anion exchange resin
  • the mother solution and replenisher had the same composition.
  • Processing was carried out in the same manner as described above except that the following processing solution was used as a standard bleaching solution which caused no bleach fog.
  • the bleaching time was 390 seconds
  • the processing temperature was 38°C
  • the replenishment rate was 25 ml per 35 mm wide by 1 m long strip of the sample.
  • the density of the processed sample obtained by using the above standard bleaching solution was measured in the same manner as described above, and the D min value was also read from the characteristic curve.
  • the Dmin value obtained by using the above standard bleaching solution is referred to as the standard.
  • a difference ADmin between the samples was determined from the Dmin values obtained from the standard.
  • the Dmin value obtained by using the standard bleaching solution was 0.60.
  • AD (Dmin after storage) - (Dmin before storage)
  • the compounds of the present invention reduce the amount of residual silver in comparison with the comparative compounds and at the same time, the compounds of the present invention have an excellent effect of improving properties with regard to bleach fog and stain upon storage of dye image after processing.
  • the sample 311 described in JP-A-2-28637 (a silver iodobromide type multilayer color photographic material for photography) was processed in the following steps.
  • the rinse step was a countercurrent system of from (2) to (1). All overflow of the bleaching solution was introduced into the bleach-fixing bath.
  • the amount of fixing solution carried into the rinsing step in the above processing was 2 ml per 35 mm wide by 1 mm long strip of the photographic material.
  • the mother solution and replenisher had the same composition.
  • the density of the processed sample was measured, and the Dmin value measured with green light was read from the characteristic curve.
  • Example 1-1 The sample 311 described in JP-A-2-28637 was processed with the standard bleaching solution used in Example 1-1. In the same manner as in Example 1-1, bleach fog ADmin value was calculated on the basis of the Dmin value obtained on the standard bleaching solution. The Dmin value obtained by using the standard bleaching solution was 0.57. The results are shown in Table 1-2.
  • Example 1-1 The above processed sample was tested under the same conditions as in Example 1-1 to determine the increase in stain upon storage of the image after processing. Evaluation of stain was carried out. The results are shown in Table 1-2.
  • the comparative compounds, A, B, C and D are the same compounds as those used in Example 1-1. It is clearly seen from the results of Table I-2 that the compounds of the present invention reduce the amount of residual silver and have an excellent effect of improving properties with regard to bleach fog and stain upon storage of the dye image after processing in comparison with the comparative compounds.
  • Both sides of a paper support were laminated with polyethylene.
  • the surface of the polyethylene-laminated paper support was treated with corona discharge and coated with a gelatin undercoat layer containing sodium dodecylbenzenesulfonate and then with the following photographic constituent layers to prepare a multi-layer color photographic paper having the following layer structure.
  • Coating solutions were prepared in the following manner.
  • a silver chlorobromide emulsion A (cubic, a 3:7 (by silver molar ratio) mixture of a larger-size emulsion A having an average grain size of 0.88 u.m and a smaller-size emulsion A having an average grain size of 0.70 nm, a coefficient of variation in grain size distribution: 0.08 and 0.10, respectively, 0.3 mol% of silver bromide being localized on a part of the surface of the grain in each emulsion) was prepared.
  • the following blue-sensitive sensitizing dyes A and B were added to the emulsion in such an amount that 2.Ox10- 4 mol of each of the dyes A and B was added to the larger-size emulsion A and 2.5x10 -4 mol of each of the dyes A and B was added to the smaller-size emulsion A, each amount being per mol of silver.
  • the chemical ripening of the emulsion was carried out by adding a sulfur sensitizing agent and a gold sensitizing agent.
  • the above emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved.
  • a coating solution for the first layer was prepared to provide the following composition.
  • Coating solutions for the second layer through the seventh layer were prepared in the same manner as the coating solution for the first layer.
  • Sodium salt of 1-oxy-3,5-dichloro-s-triazine was used as the hardening agent for gelatin in each layer.
  • Cpd-10 and Cpd-11 were added to each layer in an amount of 25.0 mg/m 2 and 50.0 mg/m 2 in total, respectively.
  • the following spectral sensitizing dyes were used in the silver chlorobromide emulsion for the following light-sensitive emulsion layers.
  • the following dyes (parenthesized numerals being coating weights) were added to the emulsion layers to prevent irradiation.
  • Each layer had the following composition. Numerals represent coating weight (g/m 2 ). The amounts of silver halide emulsions are represented by coating weight in terms of silver.
  • Polyethylene on the first layer contains white pigment (Ti0 2 ) and bluish dye (ultramarine)]
  • Second Layer Color Mixing Inhibiting Layer
  • UV-1) Ultraviolet Light Absorbent 4:2:4 mixture (by weight)
  • Each processing solution had the following composition.
  • the above-described photographic material was processed by the following processing steps.
  • Example 1-1 The same photographic material as that of Example 1-1 was exposed to white light (color temperature of 4800° K) through a wedge and processed in the following processing steps.
  • Processing was carried out until the accumulated replenishment rate reached twice the tank capacity of the mother solution. At this point, the processing was evaluated.
  • the processing was evaluated by measurement of the amount of residual silver in the maximum developed color density part, the measurement of bleach fog and the measurement of the increase in stain under dark moist heat storage conditions as in Example 1-1. The results are shown in Table 1-4.
  • the bleaching solutions containing the compounds of the present invention as bleaching agents provide superior desilverization, prevention of bleach fog and stain after processing as compared to the comparative bleaching solution.
  • the amounts of silver halide and colloidal silver are represented by coating weight in g/m 2 in terms of silver.
  • the amounts of couplers, additives and gelatin are represented by coating weight in g/m 2.
  • the amounts of sensitizing dyes are represented by moles per one mole of silver halide in the same layer.
  • Second Red-Sensitive Emulsion Layer Second Red-Sensitive Emulsion Layer
  • Second Blue-Sensitive Emulsion Layer Second Blue-Sensitive Emulsion Layer
  • the photographic material thus prepared was exposed through an optical wedge and processed in the following steps.
  • the rack of the automatic processor was replaced with a shortened rack such shorter processing times could be selected.
  • the time of each of the bleaching, bleach-fixing and fixing was 50 seconds.
  • the time of each of the bleaching and bleach-fixing was shortened to 20 seconds, and the time of fixing was shortened to 30 seconds.
  • Rinse was a countercurrent system of from (2) to (1), and all of the overflow of the rinsing water was introduced into the fixing bath.
  • Replenishment to the bleach-fixing bath was carried out in the following manner.
  • the upper part of the bleaching tank in the automatic processor was connected with the bottom of the bleach-fixing tank by means of a pipe, and the upper part of the fixing tank was connected with the bottom of the bleach-fixing tank by means of a pipe such that all of the overflow produced by the supply of replenisher to the bleaching tank and the fixing tank was allowed to flow into the bleach-fixing bath.
  • the amount of the developing solution carried into the bleaching step, the amount of the bleaching solution carried into the fixing step and the amount of the fixing solution carried into the rinsing step were 2.5 ml, 2.0 ml and 2.0 ml, respectively, each amount being per 35 mm wide by 1 mm long strip of the photographic material.
  • Cross-over time was 5 seconds in each case. The cross-over time was included in the processing time of the previous step.
  • the processing was started by using the following mother solution having the following composition. While the wash processing step was replenished with a replenisher in an amount corresponding to the processed amount of the photographic material, the processing was continuously carried out until the accumulated replenishment rate reached three times the tank capacity.
  • Each processing solution had the following composition.
  • Tap water was passed through a mixed bed column packed with H type strongly acidic cation exchange resin (Amberlite IR-120B, a product of Rohm & Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA-400) to reduce the concentration of each of calcium ion and magnesium ion to not higher than 3 mg/t. Subsequently, sodium dichloroisocyanurate (20 mg/l) and sodium sulfate (150 mg/l) were added thereto. The pH of the solution was in the range of 6.7 to 7.5.
  • the processed sample was tested under the same conditions as those of Example 1-1 to evaluate an increase in stain during the storage of image. The results are shown in Table 1-5.
  • the sample was uniformly exposed to provide a gray density of 2.0, and the exposed sample was processed in the same manner as described above.
  • the amount of silver remaining in the sample was determined by X-ray fluorometry. The results are shown in Table 1-5.
  • the photographic material was uniformly exposed to provide a gray density of 2.2, and the exposed material was processed in the following manner to determine the amount of residual silver after processing.
  • the amount of residual silver of the sample was determined by X-ray fluorometry.
  • the sample was subjected to gradation exposure through a wedge and processed in the same manner as described above to examine an increase in stain upon storage after processing.
  • the processed sample was stored at 80 C and 70% RH for one week, and an increase in stain before and after storage was evaluated.
  • the processing was carried out in the following steps by using the above-described processing solutions.
  • the processing was started by introducing each tank solution into each processing tank and continuously carried out while adding each replenisher in an amount corresponding to the amount of sample processed in each tank.
  • the bleaching agents of the present invention are superior in properties with regard to desilverization as well as stain upon storage after processing as compared to the bleaching agents of the Comparative Examples.
  • the effect of the present invention is particularly remarkable wherein the bleach-fixing time is shortened. Namely, even when the bleach-fixing time is reduced by 1/2 or less, the amount of residual silver is small and staining upon storage is superior before and after running.
  • Comparative Example 2 wherein comparative compound B is used, there is little residual silver when processing is carried out immediately after the preparation of the processing solution, but the desilverization property is greatly reduced and precipitates are formed as the running proceeds.
  • Fuji color SUPER HG400 (the manufacturer's serial number 311130) and Fuji color REALA (the manufacturer's serial number 861016) were processed by processing Nos. 201 to 211 of Example 1-2, similar effects to those of Example 1-2 were obtained.
  • compositions having a bleaching ability according to the present invention when used, rapid processing is achieved with the formation of bleach fog, staining substantially does not form upon storage after processing, and a high degree of desilverization is achieved.
  • Example 3 The same photographic material as that of Example 1-3 was prepared, and the following processing solutions were prepared. Each processing solution had the following composition.
  • sample 1101 The above developing solution is referred to as sample 1101.
  • Samples 1102 to 1112 were prepared by adding the compounds of formula (I) of the present invention and comparative compounds in the amounts indicated in Table 11-1 below.
  • the above-described photographic material was subjected to gradation exposure through three-color separation filter for sensitometry by using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd.). Exposure time was 0.1 second and exposure was conducted to provide an exposure amount of 250 CMS.
  • processing was carried out in the following steps by using the fresh solutions (the above color developing solutions immediately after the preparation thereof) and the stored solutions (the color developing solutions which were stored for a given period of time after preparation).
  • the sample was processed with each of the fresh color developing solution (the fresh solution) and the stored color developing solution (the stored solution).
  • the minimum density (Dmin) of the yellow and the sensitivity of the magenta (logarithmic value log E of an exposure amount giving a density of 0.5) images were measured.
  • the increase (ADmin) in the minimum density of the yellow image and the change (AS) in the sensitivity of magenta image were measured.
  • the residual amount of the developing agent in the stored solution was determined by means of high speed liquid chromatography to determine whether a precipitate was formed in the developing solution with the passage of time. The results are shown in Table 11-1.
  • the developing agent With regard to the residual amount of the developing agent, the developing agent remains unchanged in an amount sufficient to exhibit effective performance when the compounds of formula (I) of the present invention is used.
  • the compounds of formula (I) of the present invention provide stable developing solutions without the formation of a precipitate.
  • B indicates the formation of a precipitates (a multiple number of B's indicates the formation of a larger amount of precipitate).
  • An undercoated cellulose triacetate film support was coated with the following layers having the following compositions to prepare a multi-layer color photographic material as a sample.
  • Each layer had the following composition. Numerals represent coating weight (g/m 2 ). The amounts of silver halide and colloidal silver are represented by coating weight (g/m 2 ) in terms of silver. The amounts of sensitizing dyes are represented by moles per one mole of silver halide in the same layer.
  • Second Red-Sensitive Emulsion Layer Second Red-Sensitive Emulsion Layer
  • Second Blue-Sensitive Emulsion Layer Second Blue-Sensitive Emulsion Layer
  • Tap water was passed through a mixed bed column packed with H type strongly acidic cation exchange resin (Amberlite IR-120B, a product of Rohm & Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA-400) to reduce the concentration of each of calcium ion and magnesium ion to not higher than 3 mg/L Subsequently, sodium dichloroisocyanurate (20 mg/l) and sodium sulfate (150 mg/l) were added thereto. The pH of the solution was in the range of 6.5 to 7.5.
  • H type strongly acidic cation exchange resin Amberlite IR-120B, a product of Rohm & Haas Co.
  • Amberlite IRA-400 OH type strongly basic anion exchange resin
  • the sample prepared above was cut to from pieces of 33 mm in width and exposed to white light (color temperature of light source: 4800° K) through a wedge.
  • the exposed sample was processed in the following steps by using the color developing solutions (samples 1201 to 1207) immediately after the preparation thereof and the color developing solutions (samples 1201 to 1207) which had been stored for a given period of time.
  • a lowering in density (ADmax) of the G (green) density resulting from the use of the stored developing solution was determined on the basis of the maximum density obtained when the sample was processed with the fresh color developing solution (fresh solution).
  • the residue ratios of the developing agents and hydroxylamine after storage were determined by analysis. Furthermore, the color developing solutions were visually examined for the formation of precipitates upon storage. The results are shown in Table 11-2.
  • Each of compounds 7, 8, 9 and 12 of formula (I) of the present invention in an amount of 3 g/l was added to the fixing solution of Example II-2. Furthermore, ferric ion in an amount corresponding to the amount of ferric ion carried over from the bleaching solution of the prebath was added thereto to prepare sample solutions 1301 to 1304. These sample solutions were stored in a beaker having an opening ratio of 0.1 cm -1 at 38°C for 30 days, and the turbidity of the solutions was observed. The solution not containing a compound of formula (I) became greatly turbid. The fixing solutions containing a compound of formula (I) of the present invention remained clear and did not form a precipitate.
  • Example 11-2 The stabilizing solution of Example 11-2 was used as such for the purpose of comparison. Each of compounds 7, 8, 9 and 12 in an amount of 100 ml/l was added thereto to prepare sample solutions 1401 to 1405. Processing was carried out in the same manner as in Example 11-2 by using these stabilizing solutions and the fresh solutions of Example 11-2. After processing, films were stored under wet heat conditions at 45 C and 70% RH for one week. An increase in stain of the magenta image (ADmin) was determined before and after storage.
  • ADmin magenta image
  • Example 11-2 To examine bleaching performance, the same photographic material as that of Example 11-2 was used.
  • the color developing solution used was the sample solution 1201 of Example II-2 and the fixing solution, the stabilizing solution and the rinsing solution were the same as those used in Example II-2.
  • sample solutions 1501 to 1505 fresh solution
  • sample solutions stored solutions
  • the amount of residual silver in the maximum density part was analyzed by X-ray fluorometry.
  • the amount of residual hydrogen peroxide was analyzed.
  • Example 2 of JP-A-2-90151 The sample 201 of Example 2 of JP-A-2-90151, the photographic material 9 of Example 3 of JP-A-2-93641 and the photographic material of Example 11-1 were used, and evaluation was made in the same manner as in Example 11-2. A similar effect was obtained.
  • Example 1 of JP-A-2-58041 was used, and disodium ethylenediaminetetraacetate in the developing solution (A) thereof was replaced with an equal amount of compound 8 to prepare a developing solution (B).
  • the developing solution was stored at 40 C for 4 days and then subjected to running processing. It was found that precipitation was reduced.
  • the processing compositions of the present invention have the following excellent effects.

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US5733342A (en) * 1993-04-22 1998-03-31 Basf Aktiengesellschaft Hydroxamic acids and hydroxamic acid ethers, and the use thereof as complexing agents
WO1994024096A1 (de) * 1993-04-22 1994-10-27 Basf Aktiengesellschaft Hydroxamsäuren und hydroxamsäureether sowie ihre verwendung als komplexbildner
US8329946B2 (en) 1996-03-26 2012-12-11 President And Fellows Of Harvard College Histone deacetylases, and uses related thereto
US8426592B2 (en) 1996-03-26 2013-04-23 President And Fellows Of Harvard College Histone deacetylases, and uses related thereto
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US8362084B2 (en) 1996-03-26 2013-01-29 President And Fellows Of Harvard College Histone deacetylases, and uses related thereto
US8329945B2 (en) 1996-03-26 2012-12-11 President And Fellows Of Harvard College Histone deacetylases, and uses related thereto
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US10172905B1 (en) 2005-03-22 2019-01-08 President And Fellows Of Harvard College Treatment of protein degradation disorders
US9572854B2 (en) 2005-03-22 2017-02-21 President And Fellows Of Harvard College Treatment of protein degradation disorders
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US9540317B2 (en) 2009-08-11 2017-01-10 President And Fellows Of Harvard College Class- and isoform-specific HDAC inhibitors and uses thereof
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EP0720049A3 (de) 1997-02-26
DE69131509T2 (de) 1999-11-25
DE69127130D1 (de) 1997-09-11
EP0720049B1 (de) 1999-08-04
DE69131509D1 (de) 1999-09-09
DE69127130T2 (de) 1997-12-11
EP0720049A2 (de) 1996-07-03
EP0458131B1 (de) 1997-08-06

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