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
  • 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
  • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings
• • 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
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/407—Development processes or agents therefor

Definitions

• the present invention relates to a processing composition for silver halide photographic material and a processing method with such a processing composition.
• a silver halide black-and-white photographic material which has been exposed to light is then subjected to processing, including black-and-white development, fixing and rinsing.
• a silver halide color photographic material (hereinafter referred to as "color photographic material) which has been exposed to light is then subjected to processing including color development, desilvering, rinsing and stabilization.
• a silver halide color reversal photographic material which has been exposed to light black-and-white development and reversal processing followed by color development, desilvering, rinsing and stabilization.
• the developed silver grains produced at the color development procedure are oxidized (bleached) with an oxidizing bleaching agent to silver salts which are than removed from the photographic layer (fixing) together with unused silver halide grains by a fixing agent which forms soluble silver grains.
• Bleach and fixing may be separately conducted as bleach procedure and fixing procedure or simultaneously conducted as blix procedure.
• auxiliary procedures may be added to the foregoing basic processing procedures.
• auxiliary procedures include rinsing, stabilizing, film hardening and stop procedures.
• Various metallic ions can get mixed in the processing solution through various processes.
• calcium, magnesium or sometimes iron ions may get mixed in the processing solution via water used in the preparation of the processing solution.
• calcium contained in gelatin incorporated in the photographic material may get mixed in the processing solution.
• an iron chelate contained in the blix solution can get mixed in the prebath, i.e., development bath.
• metallic ions can get mixed in the subsequent bath.
• the calcium and magnesium ions which have got mixed in the developer react with a carbonate used as a buffer to produce precipitates or sludges that cause troubles such as clogging of the filter in the circulation system in the automatic developing machine and processing stain on the film.
• the contamination of the developer with a salt of a transition metal ion such as iron ion causes decomposition of a paraphenylenediamine color developing agent, a black-and-white developing agent such as hydroquinone and monole or a preservative such as hydroxylamine and sulfite that results in a remarkable deterioration of photographic properties.
• a stabilizing solution prepared from hard water containing a large amount of calcium and/or magnesium ions bacteria proliferate with these ions as nutrition sources, causing liquid turbidity that gives stain on the film. Further, when the stabilizing solution is contaminated with transition metal ions, some of these ions are left in the film, causing a deterioration of the preservability of the processed film.
• a chelating agent for hiding metallic ions examples include aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid) as disclosed in JP-B-48-30496 and JP-B-44-30232 (The term “JP-B” as used herein means an "examined Japanese patent publication”), organic phosphonic acids as disclosed in JP-A-56-97347 (The term “JP-A” as used herein means an "unexamined published Japanese patent application"), JP-A-56-39359, and West German Patent 2,227,639, phosphonocarboxylic acids as disclosed in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, JP-A-55-126241, and JP-A-55-65956, and compounds as disclosed in JP-A-
• aminopolycarboxylic acids e.g., ethylenediaminetetra
• ethylenediaminetetraacetic acid exhibits a great capacity of hiding calcium ions.
• this compound accelerates the decomposition of a developing agent or developing agent preservative in the presence of iron ions, causing a deterioration of photographic properties such as image density drop and fog increase.
• alkylidenediphosphonic acid doesn't exert any such bad effects even in the presence of iron ions.
• this compound produces solid matters in a processing solution prepared from hard water containing much calcium ions, causing troubles in the automatic developing machine.
• a photographic processing composition for silver halide photographic material comprising at least one of compounds represented by the following general formula (I) or salts thereof: wherein R1 represents a carboxyl, aliphatic or aromatic group; R2 and R3 each represents a carboxyl, phosphono, sulfo or hydroxyl group; L1, L2, L3 and L4 each represents an alkylene group; X represents a hydrogen atom, aliphatic group or aromatic group; M represents a hydrogen atom or cation; and m and n each represents an integer 0 to 3.
• the foregoing objects of the present invention are also accomplished by a processing method using such a processing composition.
• the aromatic group having preferably 6 to 20, more preferably 6 to 12 carbon atoms, represented by R1 or X is a monocyclic or bicyclic aromatic hydrocarbon group which may contain substituents, preferably phenyl or naphthyl group which may contain substituents, more preferably phenyl group which may contain substituents.
• substituents include alkyl group having preferably 1 to 10, more preferably 1 to 4 carbon atoms (e.g., methyl, ethyl, iso-propyl), aralkyl group having preferably 7 to 13 carbon atoms (e.g., phenylmethyl), alkenyl group having preferably 2 to 10 carbon atoms (e.g., allyl), alkoxy group (having preferably 1 to 10, more preferably 1 to 3 carbon atoms (e.g., methoxy, ethoxy), aryl group having preferably 6 to 13 carbon atoms (e.g., phenyl, p-methylphenyl), acylamino group having 1 to 13, more preferably 2 to 5 carbon atoms (e.g., acetylamino), sulfonylamino group having preferably 1 to 13, more preferably 1 to 5 carbon atoms (e.g., methanesulfonylamino), ureide group having
• substituents are alkyl group, alkoxy group, sulfinyl group, hydroxyl group, halogen atom, cyano group, sulfo group, carboxyl group, phosphono group, acyl group, and nitro group. Particularly preferred among these substituents are alkoxy group, hydroxyl group, and carboxyl group.
• the aliphatic group having preferably 1 to 20, more preferably 1 to 5 carbon atoms, represented by R1 or X may be straight-chain, branched or cyclic, preferably straight-chain or branched.
• Examples of the aliphatic group include alkyl group, alkenyl group, and alkinyl group. Preferred among these aliphatic groups is alkyl group.
• the aliphatic group may be substituted by substituents. As such substituents there may be used those described with reference to the aromatic group represented by R1 or X. Preferred among these substituents are hydroxyl group, sulfo group, carboxyl group, and phosphono group. Particularly preferred among these substituents are hydroxyl group, and carboxyl group.
• R1 is preferably a carboxyl group or aromatic group, more preferably carboxyl group.
• X is preferably an aliphatic group or hydrogen atom, more preferably hydrogen atom.
• R2 and R3 each represents a carboxyl, phosphono, sulfo or hydroxyl group. Preferred among these groups are carboxyl group and hydroxyl group. Most preferred among these groups is carboxyl group.
• the alkylene group represented by L1, L2, L3 or L4 may be straight-chain, branched or cyclic, preferably straight-chain.
• the alkylene group preferably has 1 to 6 carbon atoms.
• the alkylene group may be substituted by substituents.
• substituents there may be used those described with reference to the aromatic group represented by R1 or X.
• Preferred among these substituents are alkoxy group, sulfo group, hydroxyl group, carboxyl group, and phosphono group. Further preferred among these substituents is carboxyl group.
• Specific examples of L1 to L4 include the following groups: Particularly preferred among these groups are methylene group and ethylene group.
• Examples of the cation represented by M include alkaline metal (e.g., lithium, potassium, sodium), ammonium (e.g., ammonium, tetraethylammonium), and pyridinium.
• alkaline metal e.g., lithium, potassium, sodium
• ammonium e.g., ammonium, tetraethylammonium
• pyridinium examples of the cation represented by M include alkaline metal (e.g., lithium, potassium, sodium), ammonium (e.g., ammonium, tetraethylammonium), and pyridinium.
• the general formula (I) is preferably represented by the general formula (II) or (III): wherein L 2a and L 3a have the same meaning as L2 end L3 in the general formula (I), respectively; R 2a and R 3a have the same meaning as R2 and R3 in the general formula (I), respectively; M 1a and M 2a each has the same meaning as M in the general formula (I); and m a represents an integer 0 to 5, preferably 0, 1 or 2, more preferably 1 or 2.
• L 2b and L 3b have the some meaning as L2 and L3 in the general formula (I), respectively; R 2b and R 3b have the same meaning as R2 and R3 in the general formula (I), respectively; M 1b and M 2b each has the same meaning as M in the general formula (I); m b represents an integer 0 to 3, preferably 0, 1 or 2, more preferably 0 or 1; X b represents a substituent.
• substituent X b there may be used one of the substituents described with reference to the aromatic group represented by R1 or X in the general formula (I). Preferred among these substituents are hydroxyl group and alkoxy group.
• the suffix k represents an integer 0 to 5, preferably 0.
• the compound represented by the general formula (I) may be in the form of ammonium salt (e.g., ammonium salt, tetraethylammonium salt) or alkaline metal salt (e.g., lithium salt, potassium salt, sodium salt).
• ammonium salt e.g., ammonium salt, tetraethylammonium salt
• alkaline metal salt e.g., lithium salt, potassium salt, sodium salt
• the compound of the present invention can be synthesized by synthesis methods as disclosed in "Bulletin of the Chemical Society of Japan", vol. 42, pp. 2835-2840, 1969, (Aspartic-N,N-diacetic acid), "Inorganic Chemistry", 34 (1974), West German Patent 3,739,610, and JP-A-63-267751 or analogous synthesis methods.
• a solution of 18.0 g (0.450 mol) of sodium hydroxide in 50 ml of water was added dropwise to the aqueous solution. During this process, the pH value of the system was kept to 9 to 11. After the completion of the dropwise addition, the system was further heated for 1 hour to complete the reaction. After cooled, the material was adjusted with concentrated sulfuric acid to pH 2. The material was then distilled off under reduced pressure until the volume thereof was halved. The resulting salt was recovered by filtration. The filtrate was distilled off under reduced pressure to remove the solvent. The resulting salt was recovered by filtration. To the salt thus recovered was added a small amount of acetone. The material was then allowed to stand in a refrigerator for 2 weeks.
• the system was further heated for 1 hour to complete the reaction.
• the material was adjusted with concentrated sulfuric acid to pH 2.
• the material was then distilled off under reduced pressure until the volume thereof was halved.
• the resulting salt was recovered by filtration.
• the filtrate was distilled off under reduced pressure to remove the solvent.
• the resulting salt was recovered by filtration.
• To the salt thus recovered was added a small amount of acetone.
• the material was then allowed to stand in a refrigerator for 1 month.
• the resulting white powder was recovered by filtration, and then recrystallized from a 1 : 1 mixture of acetone and water.
• the compound of the present invention can be applied to all processing compositions for processing silver halide black-and-white photographic materials or silver halide color photographic materials.
• the compound of the present invention can be applied to general black-and-white developer, lith film infectious developer, fixing solution, washing water, etc.
• the compound of the present invention can be applied to color developer, bleaching solution, fixing solution, blix solution, adjustor, stop solution, film hardener, washing water, stabilizing solution, rinsing solution, fogging solution, toner, etc.
• the present invention is not limited to these applications.
• the amount of the compound of the present invention to be incorporated in the system depends on the processing composition to be added and is normally in the range of 10 mg to 50 g per l of processing composition.
• the amount of the compound of the present invention is preferably in the range of 0.5 to 10 g, particularly 0.5 to 5 g per l of processing solution.
• the amount of the compound of the present invention is preferably in the range of 0.1 to 20 g, particularly 0.1 to 5 g per l of bleaching solution.
• the amount of the compound of the present invention is preferably in the range of 1 to 40 g, particularly 1 to 20 g per l of processing solution.
• the amount of the compound of the present invention is preferably in the range of 50 mg to 1 g, particularly 50 to 300 mg per l of stabilizing solution.
• Preferred examples of chelating agents to be used in combination with the compound of the present invention include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, glycoletherdiaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, carbamoylmethyliminodiacetic acid, hydroxyethyliminodiacetic acid and ethylenediamine-N-( ⁇ -hydroxyethyl)-N,N',N'-triacetic acid, organic phosphonio acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid and ethylenediamine-N,N
• the black-and-white developer preferably comprises a hydroquinone developing agent such as hydroquinone, bromohydroquinone, methylhydroquinone and 2,5-dichlorohydroquinone as a developing agent.
• a hydroquinone developing agent such as hydroquinone, bromohydroquinone, methylhydroquinone and 2,5-dichlorohydroquinone
• a p-aminophenolic developing agent such as N-methyl-p-aminophenol or 3-pyrazolidone developing agent such as 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone.
• a sulfite compound such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde sodium bisulfite.
• the pH value of the black-and-white developer is preferably in the range of 9 to 13.
• Examples of an alkaline agent to be used for the adjustment of pH value include sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
• the developer may further comprise a pH buffer such as boric acid, borax, silicate, tribasic sodium phosphate and tribasic potassium phosphate.
• the developer may comprise a development inhibitor such as potassium bromide and potassium iodide, an organic solvent such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol, and a fog inhibitor such as indazole compound, benzimidazole compound and benztriazole compound.
• the developer may comprise a development accelerator as disclosed in Research Disclosure No. 17643, vol. 176, Chapter XXI, December 1978.
• the developer may comprise an amine compound as disclosed in U.S. Patent 4,269,929, JP-A-61-267759, and Japanese Patent Application No. 1-29418.
• the developer may further comprise a color toner, a surface active agent, a film hardener, etc. as necessary.
• the developer may comprise a silver stain inhibitor as disclosed in JP-A-56-24347.
• the developer may further comprise an amino compound such as alkanolamine as disclosed in European Patent 136582, British Patent 958678, U.S. Patent 3,232,761, and JP-A-56-106244 for the purpose of enhancing contrast.
• the black-and-white fixing solution is an aqueous solution having a pH value of 4.2 to 7.0 containing a thiosulfate as a fixing agent.
• a thiosulfate examples include sodium thiosulfate and ammonium thiosulfate.
• a mesoionic compound as disclosed in JP-A-57-150842 may be preferably used.
• the fixing solution may contain a film hardener (e.g., water-soluble aluminum salt), tartaric acid, citric acid, gluconic acid, derivative thereof, a preservative (e.g., sulfite, bisulfite), a pH buffer (e.g., acetic acid, boric acid), and a pH adjustor (e.g., sulfuric acid).
• a film hardener e.g., water-soluble aluminum salt
• tartaric acid citric acid, gluconic acid, derivative thereof
• a preservative e.g., sulfite, bisulfite
• a pH buffer e.g., acetic acid, boric acid
• a pH adjustor e.g., sulfuric acid
• the color developer is an alkaline aqueous solution having a pH value of 9 to 12 containing an aromatic primary amine color developing agent as a main component.
• an aromatic primary amine color developing agent there may be used an aminophenolic compound, preferably p-phenylenediamine compound.
• Typical examples of such a p-phenylenediamine compound include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl- ⁇ -methoxyethylaniline, and sulfates, hydrochlorides and p-toluenesulfonates thereof.
• the color developer normally contains a carbonate of alkaline metal (e.g., potassium carbonate), a pH buffer such as borate and phosphate, and a development inhibitor or fog inhibitor such as chloride (e.g., potassium chloride), bromide (e.g., potassium bromide), iodide (e.g., potassium iodide), benzimidazole, benzotriazole, benzothiazole and mercapto compound.
• alkaline metal e.g., potassium carbonate
• a pH buffer such as borate and phosphate
• a development inhibitor or fog inhibitor such as chloride (e.g., potassium chloride), bromide (e.g., potassium bromide), iodide (e.g., potassium iodide), benzimidazole, benzotriazole, benzothiazole and mercapto compound.
• the color developer may contain various preservatives such as hydroxylamine (e.g., hydroxylamine, diethylhydroxylamine, bis-(sulfonateethyl)hydroxylamine) and sulfite (e.g., sodium sulfite, sodium bisulfite), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salt and amine, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, nucleating agents such as sodium boron hydride and hydrazine compound, thickening agents, fluorescent brightening agents such as 4,4'-diamino-2,2'-disulfostilbene compound, various surface active agents such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid, etc.
• hydroxylamine e
• bleaching agent to be incorporated in the bleaching solution or blix solution examples include compounds of polyvalent metals such as ferric iron(III), peracids, quinones, and iron salts.
• Typical examples of the bleaching agents include iron chloride, ferricyanides, bichromates, organic complex salts of ferric iron(III) (e.g., complex salts of metal with aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and 1,3-diaminopropanetetraacetic acid), and persulfates.
• the bleaching solution or blix solution containing a ferric complex of aminopolycarboxylic acid is used in the pH range of 3.5 to 8.
• the bleaching solution or blix solution may comprise any known additive such as rehalogenating agent (e.g., ammonium bromide, sodium bromide, potassium bromide, ammonium chloride), pH buffer (e.g., ammonium nitrate) and metal corrosion inhibitor (e.g., ammonium sulfate) incorporated therein.
• rehalogenating agent e.g., ammonium bromide, sodium bromide, potassium bromide, ammonium chloride
• pH buffer e.g., ammonium nitrate
• metal corrosion inhibitor e.g., ammonium sulfate
• the bleaching solution or blix solution may comprise an organic acid for the purpose of inhibiting bleach stain.
• a particularly preferred organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5.5. Specific examples of such a compound include acetic acid, glycolic acid, and propionic acid.
• Examples of the fixing agent to be incorporated in the fixing solution or blix solution for color photographic light-sensitive materials include thiosulfate, thiocyanate, thioether compound, thiourea, mesoionic compound, and iodide (used in a large amount).
• a thiosulfate is normally used.
• ammonium thiosulfate can be most widely used.
• Such a thiosulfate may be preferably used in combination with thiocyanate, thioether compound, thiourea, etc.
• the fixing solution or blix solution may contain a sulfite, a bisulfite, a carbonyl-bisulfurous acid adduct, a preservative such as sulfinic compound as disclosed in European Patent 294769A, various fluorescent brightening agents, an antifoaming agent, a surface active agent, polyvinylpyrrolidone, methanol, a buffer such as imidazole, a bleach accelerator such as mercapto- or disulfide-containing compound as disclosed in U.S. Patent 3,893,858, West German Patent 1,290,812, and JP-A-53-95630, etc.
• the washing water or stabilizing solution may contain an inorganic phosphoric acid, isothiazolone compound, thiabendazole, chlorine germicide such as chlorinated sodium isocyanurate, metallic salt such as magnesium salt, aluminum salt and bismuth salt, surface active agent, film hardener, etc. Further, the washing water and/or stabilizing solution may contain various bactericides or mildewproofing agents for the purpose of inhibiting the generation of fur or the proliferation of mildew in the photographic light-sensitive material after processing.
• bactericides or mildewproofing agents examples include thiazolylbenzimidazole compounds as disclosed in JP-A-57-157244 and JP-A-58-105145, isothiazolone compounds as disclosed in JP-A-54-27424 and JP-A-57-8542, chlorophenolic compounds represented by trichlorophenol, bromophenolic compounds, organic tin compounds, organic zinc compounds, thiocyanic compounds, isothiocyanic compounds, acid amide compounds, diazine compounds, triazine compounds, thiourea compounds, benzotriazolealkylguanidine compounds, quaternary ammonium salts represented by benzalconium chloride, antibiotics represented by peniciline, and general-purpose anti-fungas agents as disclosed in "Journal Antibacteria And Antifungas Agents", vol. 11, No. 5, pp. 207-223, 1983. Two or more of these bactericides and mildewproofing agents can be used in combination. Further
• a dye stabilizer to be incorporated in the stabilizing solution there may be normally used formaldehyde. From the standpoint of safety in the working atmosphere, N-methylolazole, hexamethylenetetramine, formaldehyde-bisulfurous acid adduct, dimethylolurea, azolylmethylamine derivatives, etc. may be preferably used. These dye stabilizers are further described in JP-A-2-153348, and JP-A-4-270344.
• the stabilizing solution may further contain a pH adjusting buffer such as boric acid and sodium hydroxide, a sulfurization inhibitor such as alkanolamine, a fluorescent brightening agent, etc.
• photographic materials which can be processed with the processing composition according to the present invention include ordinary black-and-white silver halide photographic materials (e.g., black-and-white photographic material for picture taking, X-ray black-and-white photographic material, black-and-white photographic material for printing), ordinary multi-layer silver halide color photographic materials (e.g., color negative film, color reversal film, color positive film, color negative film for motion picture, color photographic paper, reversal color photographic paper, direct positive color photographic material), infrared-sensitive photographic materials for laser scanner, and diffusion transfer photographic materials (e.g., silver diffusion transfer photographic material, color diffusion transfer photographic material).
• black-and-white silver halide photographic materials e.g., black-and-white photographic material for picture taking, X-ray black-and-white photographic material, black-and-white photographic material for printing
• ordinary multi-layer silver halide color photographic materials e.g., color negative film, color reversal film, color positive film, color negative film for motion picture, color photographic paper
• the photographic material according to the present invention may have various layer configurations (e.g., silver halide emulsion layers sensitive to red, green and blue, respectively, undercoating layer, antihalation layer, filter layer, interlayer, surface protective layer) on one or both, sides thereof depending on the purpose.
• layer configurations e.g., silver halide emulsion layers sensitive to red, green and blue, respectively, undercoating layer, antihalation layer, filter layer, interlayer, surface protective layer
• the support for the photographic material of the present invention, the coating method, the kind of silver halide grains to be coated on the silver halide emulsion layer, surface protective layer, etc. e.g., silver bromoiodie, silver bromochloroiodide, silver bromide, silver bromochloride, silver chloride), the crystal form thereof (e.g., cube, tabular, sphere), the size thereof, the size flutuation coefficient, the crystalline structure thereof (e.g., core/shell structure, polyphase structure, uniform phase structure), the preparation method thereof (e.g., single jet process, double jet process), the binder to be incorporated therein (e.g., gelatin), the film hardener to be incorporated therein, the fog inhibitor to be incorporated therein, the metal doping agent to be incorporated therein , the silver halide solvent to be incorporated therein, the thickening agent to be incorporated therein, the emulsion precipitant to be incorporated therein, the dimensional stabiliser to
• the processing solution containing the compound of the present invention exhibits minimized oxidation or decomposition of components of the processing solution due to metallic ions, maintains desired properties for a prolonged period of time, and shows no precipitation even due to the accumulation of metallic ions. Accordingly, the processing solution according to the present invention causes no troubles such as film stain and clogging in the filter in the automatic developing machine. Further, the compound of the present invention is biodegradable and thus contributes to environmental protection.
• Diethylenetriaminepentaacetic acid 1.0 g Chelate compound (set forth in Table 1) 0.01 mol Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 g 4-(N-ethyl-N- ⁇ -hydroxyethylamino)-2-methylaniline sulfate 4.5 g Water to make 1,000 ml pH 10.05
• ferric chloride as ferric ion in an amount of 5 ppm and calcium nitrate as calcium ion in an amount of 150 ppm to prepare Specimens 101 to 113.
• These specimens were each packed into a hard vinyl chloride container having a length of 10 cm, a width of 25 cm and a depth of 30 cm in an amount of 5 l.
• the solution in the container was continuously circulated at a rate of 3 l per minute by means of a pump while being kept to a temperature of 38°C for 30 days for ageing test.
• the liquid surface was covered by a floating cover by 200 cm2 and left open to the air by 50 cm2.
• a multi-layer color photographic material specimen 101 described in Example 1 of JP-A-4-274236 was cut into strips having a width of 35 mm, and then wedgewise exposed to light with 5CMS at a color temperature of 4,800°K.
• the photographic sensitive material specimen was then processed with the color developer specimens 101 to 113 which had been just prepared (fresh solution) or the same color developer specimens which had been aged in accordance with the following procedures: Processing step Processing time Processing temperature (°C) Color development 3 min. 15 sec. 37.8 Bleach 50 sec. 38.0 Fixing 1 min. 40 sec. 38.0 Rinse (1) 30 sec. 38.0 Rinse (2) 20 sec. 38.0 Stabilization 20 sec. 38.0
• Tap water was passed through a mixed bed column filled with an H type strongly acidic cation exchange resin (Amberlite IR-120B produced by Rohm & Haas) and an OH type anion exchange resin (Amberlite IR-400) so that the calcium and magnesium ion concentrations were each reduced to 3 mg/l or less.
• H type strongly acidic cation exchange resin Amberlite IR-120B produced by Rohm & Haas
• Amberlite IR-400 OH type anion exchange resin
• the specimen which had been processed with the fresh solution exhibits B density of 2.5 when measured with blue light
• the specimen which had been processed with the aged solution was measured for B density by means of a Type X Light 310 photographic densitometer to determine a difference ⁇ D B from that of the fresh solution. Further, the percent residue of developing agent and hydroxylamine after ageing were determined by analysis. Moreover, the color developers which had been aged were visually examined for the presence of precipitate. The results are set forth in Table 1.
• Table 1 shows that the use of conventional chelating agents leaves much to be desired in the prevention of precipitate and the maintenance of solution stability while the use of the compound of the present invention provides great effects.
• Example 1 To the fixing solution of Example 1 were added the present compounds 1, 2, 3, 4, 7, 13, 21, 22, 30 and 31, respectively, in an amount of 3 g/l, and ferric ions corresponding to those brought over from the prebath bleaching solution to prepare Specimens 201 to 210. These specimens were aged at a temperature of 38°C with an opening value of 0.1 cm ⁇ 1 for 30 days, and then observed for turbidity. The specimens free of compound of the present invention showed a remarkable turbidity after ageing while the specimens comprising the compound of the present invention incorporated therein all stayed transparent, showing no precipitation.
• the stabilizing solution of Example 1 was used as Comparative Specimen 301.
• the multi-layer color photographic light-sensitive material specimen 101 was then processed with the fresh form of the color developer as used for Specimen 101 in Example 1.
• the multi-layer color photographic light-sensitive material specimen 101 which had been thus processed was then aged at a temperature of 45°C and a relative humidity of 70% for 1 week.
• the magenta stain increase ( ⁇ Dmin) from before ageing to after ageing was then determined.
• Table 2 shows that the use of the stabilizing solution of the present invention containing the compound of the present invention inhibits the stain increase and improves the image preservability.
• the foregoing color developer was used Specimen 401. To the same color developer were added the compounds of the present invention and comparative compounds in amounts set forth in Table 3, respectively, to prepare Specimens 402 to 408. To these color developers were then added ferric ion in an amount of 5 ppm and calcium ion in an amount of 150 ppm, respectively. These color developers were then aged in a beaker with an opening value of 0.10 cm ⁇ 1 at a temperature of 38°C for 20 days.
• Specimen 103 described in JP-A-4-145433 was subjected to gradation exposure through a three-color separation filter for sensitometry. The exposure was effected in such a manner that an exposure of 250CMS reached for 0.1 second.
• the photographic light-sensitive material thus exposed was then processed with the foregoing color developer which had been just prepared (fresh solution) and the same color developer which had been aged (aged solution) in accordance with the following procedures: Processing step Temperature (°C) Time (sec.) Color development 38 45 Blix 35 25 Rinse 1 35 20 Rinse 2 35 20 Rinse 3 35 20 Drying 80 60
• Ion-exchanged water (calcium and magnesium concentrations: 3 ppm or less each)
• Dmin minimum yellow density
• magenta sensitivity log E of exposure which gives a density of 0.5
• Table 3 shows that the use of the compound of the present invention provides small ⁇ Dmin and ⁇ S values, showing reduced flutuations of photographic properties. Further, the use of the compound of the present invention provides a great improvement in the inhibition of precipitation as compared to the comparative compounds. In particular, the comparative compounds which exert a great effect of inhibiting precipitation exhibit a poor preservability of developing agent while the comparative compounds which cause little decomposition of developing agent leave much to be desired in the inhibition of precipitation. On the contrary, the compound of the present invention provides a stable developer free from precipitation.
• a color developer (A) was prepared having the composition as mentioned below. Further, a color developer (B) was prepared by replacing disodium ethylenediaminetetraacetate in the color developer (A) by Exemplary Compound 3 in the equimolecular amount. The two color developers were aged at a temperature of 40°C for 4 days. Specimen B-6 of an example in JP-A-3-174148 was then subjected to running processing with the color developers, respectively. As a result, the color developer (B) showed some improvement in the inhibition of precipitation. The percent residue of hydroquinone and potassium sulfite in the developer and the pH value of the developer after ageing were determined. As a result, it was found that the use of the compound of the present invention provides minimum loss of hydroquinone and potassium sulfite by air oxidation and hence a reduced rise of pH.
• the compounds of the present invention and a comparative compound were subjected to a biodegradability test in accordance with an amended SCAS method defined in PECD chemical test guide line. The results are set forth in Table 4.
• Table 4 shows that the compound of the present invention exhibits an excellent biodegradability.

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• 1992
  • 1992-10-05 JP JP4265963A patent/JP2819487B2/ja not_active Expired - Fee Related
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