EP0712040B1 - Verfahren zur Verarbeitung eines photographischen, lichtempfindlichen Silberhalogenidmateriales - Google Patents

Verfahren zur Verarbeitung eines photographischen, lichtempfindlichen Silberhalogenidmateriales Download PDF

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Publication number
EP0712040B1
EP0712040B1 EP19950308047 EP95308047A EP0712040B1 EP 0712040 B1 EP0712040 B1 EP 0712040B1 EP 19950308047 EP19950308047 EP 19950308047 EP 95308047 A EP95308047 A EP 95308047A EP 0712040 B1 EP0712040 B1 EP 0712040B1
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EP
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Prior art keywords
group
fixing
solution
hydrogen atom
thiosulphate
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Expired - Lifetime
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EP19950308047
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English (en)
French (fr)
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EP0712040A3 (de
EP0712040A2 (de
Inventor
Yutaka c/o Konica Corp. Ueda
Masao c/o Konica Corp. Ishikawa
Satoru c/o Konica Corp. Kuse
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Konica Minolta Inc
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Konica Minolta Inc
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Priority claimed from JP4005095A external-priority patent/JPH08190178A/ja
Priority claimed from JP6605895A external-priority patent/JPH08262670A/ja
Priority claimed from JP7610395A external-priority patent/JPH08272061A/ja
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0712040A2 publication Critical patent/EP0712040A2/de
Publication of EP0712040A3 publication Critical patent/EP0712040A3/de
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Publication of EP0712040B1 publication Critical patent/EP0712040B1/de
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • 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
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/44—Regeneration; Replenishers
    • 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
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains

Definitions

  • the present invention relates to a method for processing a silver halide photographic light-sensitive material, particularly relates to a method for processing a silver halide photographic light-sensitive material which is effective to reduce the amount of waste liquid of photographic processing effluent.
  • C-41RA from Eastman Kodak Co., Ltd., which is the processing method most widely used in in-shop laboratories or mini-labo's, involves 4 steps, and the replenishing amounts per roll of 135 size, 24 exp. film are 23 ml for the color developing step, 5 ml for the bleaching step, 33 ml for the fixing step and 40 ml for the stabilizing step, respectively.
  • the replenishing amount for the stabilizing solution is largest in these steps. Therefore, a reduction in the replenishing amount of the stabilizing solution has been demanded.
  • a fixing agent such as thiosulfate, a component of a fixing solution
  • the fixing agent is carried into the stabilizing solution from the previous fixing bath by a processed light-sensitive material on which the fixing agent is adhered.
  • the accumulated fixing agent causes formation of a stain on the back surface of the light-sensitive material.
  • the stain appears on a printed picture from the light-sensitive material and causes a serious defect destroying the commercial value of the print.
  • the renewing ratio of the stabilizing solution is lowered by the reduction of the replenishing amount, which causes an extension of time for oxidation of the stabilizing solution by air.
  • formaldehyde is usually contained in the stabilizing solution for preventing stain formation in a unexposed area of the processed light sensitive material during storage and discoloration of color image by blocking the reactive site of an unreacted magenta coupler remaining in the light-sensitive material.
  • the formaldehyde reacts and forms an adduct with sulfite, which is carried over from the fixing solution accompanied with the thiosulfate to the stabilizing solution.
  • the effect of formaldehyde improving the stability of dye is lost and a serious problem of acceleration of sulfurizaton in the stabilizing solution occurs.
  • JP O.P.I. Japanese Patent Publication Open to Public Inspection
  • Nos. 5-119454/1993, 5-165174/1993 and 5-232656/1993 each describe a technology in which a solid processing composition containing thiosulfate is directly supplied into a solution having a fixing ability.
  • a fixing time of 90 seconds for color negative film is disclosed as an embodiment of the technology.
  • concentration of thiosulfate in a processing solution it is necessary to increase the concentration of thiosulfate in a processing solution to a certain level for attaining such rapidness of processing.
  • thiosulfate concentration is made higher, a problem often occurs when there is insufficient daily cleaning of transferring rollers arranged between the first and the second fixing tank or the fixing tank and the next tank such as a stabilizing tank or a washing tank.
  • a hydrophobic decomposition substance of thiosulfate is formed by drying and air-oxidizing of drops of the processing solution adhered on the rollers by the processed light-sensitive material.
  • the hydrophobic substance is tightly fixed on the surface of the rollers by hydrophilic bonding.
  • the hydrophobic substance tightly adhered on the surfaces of the rollers may cause an irrevocable defect such as scratches on the light-sensitive material.
  • the fixing property is raised with increasing the thiosulfate concentration until a certain value, the fixing property is lowered in reverse when the concentration exceeds the certain value.
  • the thiosulfate concentration for enabling the above-mentioned rapid processing corresponds to the above critical concentration. Accordingly, when the amount of light-sensitive material to be processed per day is small, the thiosulfate concentration in the processing solution is apt to raise by virtue of evaporation of the solution. This raising of the thiosulfate concentration causes a problem that the fixing property of the solution is degraded. Further, crystals of thiosulfate are precipitated and grown in the processing solution when such a concentrated processing solution as described above is left to stand under low temperature conditions.
  • the precipitation of thiosulfate causes blocking of circulation of the processing solution and degrades the property of the processing solution due to lowering the effective amount of thiosulfate in the processing solution.
  • a yellow water-insoluble sulfurous substance is formed in a thiosulfate-containing solid composition for fixer or bleach-fixer during the storage under such high temperature conditions.
  • the insoluble sulfurous substance adheres to a filter installed in the fixing tank or bleach-fixing tank of a processor and causes blocking of the filter.
  • the photographic properties of the processing solution are degraded due to insufficient circulation of the processing solution.
  • the precipitated sulfurous substance adheres on the surface of the processed light-sensitive material and considerably spoils the commercial value of the processed light-sensitive material.
  • the solid composition When the solid composition is in the form of granules or tablets, the formation of the sulfurous substance by decomposition of thiosulfate causes lowering in the combining force between components of the composition around the sulfurous substance in the granule or the tablet. As a result of this, the solid composition is easily powdered by vibration or friction.
  • a solution for processing a silver halide photographic light-sensitive material having a fixing ability such as a fixer or a bleach-fixer contains compound which is capable of forming a water-soluble complex salt by reaction with silver halide.
  • a thiosulfate such as potassium thiosulfate, sodium thiosulfate or ammonium thiosulfate
  • a thiocyanate such as potassium thiocyanate, sodium thiocyanate or ammonium thiocyanate, thiourea or a thioether is usually contained as the fixing agent.
  • thiosulfate, particularly ammonium thiosulfate has been frequently used as it is superior in processing properties, stability and solubility.
  • the solubility of potassium thiosulfate or sodium thiosulfate is lower than that of ammonium thiosulfate. Accordingly, the fixing agent is easily precipitated in a concentrated solution at low temperature when these thiosulfates are used instead of the ammonium salt.
  • the concentration of the solution particularly occurs in a mini-labo when the amount of light-sensitive material to be processed is small. Further, in a system with a small amount of replenishing, it is required to increase the concentration of thiosulfate to compensate for degradation in processing ability and stability of the processing solution. It has been found that the increasing in the thiosulfate concentration causes sulfur to adhere to transferring rollers exposed to air, particularly to rollers for transferring provided at a position between a processing tank and the next processing tank (inter-tank rollers).
  • the first object of the invention is to provide a method for processing a silver halide photographic light-sensitive material in which a stain formed on the back surface of the light-sensitive material is prevented when a replenishing amount of a stabilizing solution provided after a fixing solution is reduced.
  • the second object of the invention is to provide a method for processing a silver halide photographic light-sensitive material in which the storage stability of a stabilizing solution is improved and a processing can be stably performed for a prolonged period.
  • the third object of the invention is to provide a method for processing a silver halide photographic light-sensitive material in which reduction of waste liquid formed in the photographic processing can be realized, and the method fits the requirement of environment protection.
  • the fourth object of the invention is to provide a processing method in which a solid processing composition for a silver halide photographic light-sensitive material does not adhere to transferring rollers and maintains a stable fixing ability when the amount of light-sensitive material processed per day is small.
  • the fifth object of the invention is to provide processing method in which a solid processing composition for a silver halide photographic light-sensitive material maintains a good storage ability under a high temperature condition for a prolonged period.
  • the sixth object of the invention is to provide a processing method of a silver halide photographic light-sensitive material in which the ammonium ion concentration can be lowered without precipitation of fixing agent and adhering of insoluble sulfurous substances on inter-tank transferring rollers.
  • a method for processing a silver halide photographic light-sensitive material comprising the steps of fixing or bleach-fixing a silver halide photographic light-sensitive material with a fixing or bleach-fixing solution comprising a thiosulphate in an amount of from 0.6 to 4 moles per litre and at least one compound represented by formula III in an amount of from 0.02 to 5% by weight of the thiosulphate, and
  • Fig. 1 is a structural drawing showing the position in an auto processing machine of a solid processing composition supplying device.
  • Fig. 2 is a structural drawing of an example of a device for supplying a solid recessing composition, in which a rotatable cylinder, a slidable cap and a cartridge are shown.
  • Fig. 3 is a cross section of a supplying device for a powdered or granulated composition.
  • the amount of thiosulfate necessary to complete the fixing or bleach fixing reaction can be reduced by addition of a compound represented by Formula III to a solid processing composition containing thiosulfate.
  • a compound represented by Formula III By the reduction in the amount of thiosulfate, adhesion of the decomposition substance of thiosulfate on the surface of the inter-tank transferring rollers can be prevented and the fixing ability of the processing solution can be stably maintained when the amount of the light-sensitive material to be processed per day is small and the solution is concentrated.
  • the processing solution can maintain a stable fixing ability by the use of the above compound even when the concentration of thiosulfate in the processing solution is varied.
  • the inventors further found that the concentration of thiosulfate salt necessary for completing a fixing reaction can be decreased by adding at least one compound represented by Formula III into a fixing solution, and that the processing ability of a fixing solution can be maintained without raising the thiosulfate ion concentration by optimizing the ratio of the amount of ammonium thiosulfate to the amount of potassium thiosulfate and/or sodium thiosulfate.
  • the present invention has been accomplished.
  • a processing method has been known in which a mercapto heterocyclic compound is added to a processing solution.
  • the method includes, for example, a method in which the compound is added to a fixing solution such as described in Japanese Patent Publication Open for Public Inspection (JP O. P. I. No. 1-261640/1989), a method in which the compound is added to a solution of prebath for a bleaching solution such as described in JP O. P. I. No. 54-52534/1979, and a method in which the compound is added to a bleach-fixing solution such as described in British Patent No. 1,138,842.
  • JP O. P. I. No. 1-261640/1989 Japanese Patent Publication Open for Public Inspection
  • a method in which the compound is added to a solution of prebath for a bleaching solution such as described in JP O. P. I. No. 54-52534/1979
  • a method in which the compound is added to a bleach-fixing solution such as described in British Patent No. 1,138
  • the compound represented by Formula III is known as a bleach accelerating agent to be used in a bleaching process in which metallic silver is oxidized (refer JP O.P.I. 61-250646/1986).
  • a bleach accelerating agent to be used in a bleaching process in which metallic silver is oxidized
  • the compound has a fixing accelerating effect.
  • the compound accelerates the fixing process and is applied after the bleaching step, and silver ions are dissolved and removed from the light-sensitive material in this process.
  • the effect is newly discovered by the inventors as a result of trial-and-error experiments.
  • the solubility of the solid processing composition can be stably maintained and the precipitation of sulfurous substance formed from thiosulfate can be prevented by the use of a compound represented by Formula III even when the composition is stored under high temperature conditions of from 40 to 50°C for a prolonged period.
  • the solid processing composition is in the form of a granule or a tablet
  • powdering of the composition after storage under a high temperature condition can be prevented by adding at least one compound represented by Formula III to the solid processing composition.
  • Q 1 represents a group of atoms necessary to form a heterocyclic ring including one condensed with a five- or six-membered unsaturated ring, such as a thiazole ring, a thiadiazole ring, an imidazole ring, a pyrimidine ring, a triazole ring, a pyrazine ring, a triazine ring or an oxodiazole ring;
  • R 1 represents a hydrogen atom, an alkali metal atom, a group represented Formula III from which R 1 is removed or an alkyl group.
  • Q' is synonymous with Q 1 .
  • III-9, III-10, III-13, III-31 are preferably to be used to attain the object of the invention.
  • III-10 and III-13 can be cited.
  • the stabilizing soluton contains substantially no formaldehyde.
  • the stabilizing solution or a replenishing solution for the stabilizing solution also comprises at least one compound represented by Formulae (F-1) to (F-13):
  • R 11 to R 16 represent each a hydrogen atom or a monovalent organic group.
  • the monovalent organic group includes an alkyl group, an aryl group, an alkenyl group, an aralkyl group, an amino group, an alkoxyl group, a hydroxyl group, an acyl group, a sulfonyl group, an alkylthio group, an arylthio group, a heterocyclic residue, a carbamoyl group, a sulfamoyl group and an alkylamino group.
  • These monovalent groups each may have a substituent such as a hydroxyl group, an acyl group, a sulfonyl group, a halogen atom, an amino group or a carboxyl group. Among them, a hydroxyl group and a halogen atom are preferable.
  • the total number of carbon atoms included in the group represented R 11 to R 16 is preferably not more than 10.
  • the group consisting of R 11 , R 13 and R 15 , and the group consisting of R 12 , R 14 and R 16 may be the same or different, it is preferable that the groups consisting the one of these groups are hydrogen atoms.
  • the triazine compound represented by Formula (F-1) is used within the range of from 0.05 to 50 g, preferably from 0.1 to 20 g, per liter of the processing solution.
  • Examples of methylol compound represented by (F-2), (F-3) or (F-4) include the followings.
  • Each of these compounds is used within the range of from 0.05 to 20 g, preferably from 0.1 to 10 g, per liter of the processing solution.
  • an electron withdrawing group represented by V 1 or W 1 is selected from the groups having a positive ⁇ p value of Hammett (Lange's Handbook of Chemistry 12th ed. Vol, 3, C. Hansch & A. Leo, Substituents for Constants for Correlation Analysis in Chemistry and Biology (Jone Wily & Sons, New York 1979)).
  • Such group includes an acyl group such as an acetyl group, benzoyl group or monochloroacetyl group, an alkoxycarbonyl group such as an ethoxycarbonyl group or methoxycarbonyl group, an aryloxycarbonyl group such as phenoxycarbonyl group or p-chlorophenoxycarbonyl group, a carbamoyl group such as N-methycarbamoyl group, N,N-tetramethylenecarbamoyl group or N-phenylcarbamoyl group, a cyano group, an alkylsulfonyl group such as methanesulfonyl group or ethanesulfonyl group, an arylsulfonyl group such as benzenesulfonyl group or p-toluenesulfonyl group, and a sulfamoyl group such as sulfamoyl group
  • the group capable of being released by a hydrolysis reaction represented by Y 1 includes a trialkyl-substituted silyl group such as trimethylsilyl group, an acyl group such as acetyl group, monochloroacetyl group or trichloroacetyl group, a sulfate group, an aminocarbonyl group such as N,N-dimethylcarbonyl group, N-methylcarbonyl group or N-phenylcarbonyl group, and a sulfonate group such as methanesulfonate, benzenesulfonate or p-toluenesulfonate.
  • a trialkyl-substituted silyl group such as trimethylsilyl group
  • an acyl group such as acetyl group, monochloroacetyl group or trichloroacetyl group
  • a sulfate group an aminocarbonyl group such as N,N-di
  • the nitrogen-containing 5- or 6-member heterocyclic group represented by Z includes single ring compounds each having an element composition of [C 1 N 4 ], [C 2 N 3 ], [C 3 N 2 ], [C 4 N], [C 2 N 4 ], [C 3 N 3 ], [C 4 N 2 ], [C 5 N], [C 2 N 2 O], [C 3 NO], [C 3 N 2 O], [C 4 NO], [C 2 N 2 S], [C 3 NS], [C 3 N 2 S], [C 2 N 2 Se], [C 3 NSe] or [C 3 NTe], and condensed ring compounds each having an element composition of [C 3 N 2 -C 6 ], [C 4 N-C 6 ], [C 4 N-C 3 N 2 ], [C 3 N 2 -C 3 N 2 ], [C 3 N 2 S-C 6 ], [C 5 N-C 5 N], [C 5 N-C 6 ] or [C 4 N 2 -C 6 ].
  • These rings each may have a substituent, for example, an alkyl group such as methyl group, ethyl group, p-methoxyethyl group, benzyl group, carboxymethyl group or sulfopropyl group, an aryl group such as phenyl group or p-methoxyphenyl group, a hydroxyl group, an alkoxyl group such as methoxy group, ethoxy group or methoxyethoxy group, an aryloxy group such as phenoxy group or p-carboxyphenyl group, a carboxyl group, a sulfo group, an alkoxycarbonyl group such as methoxycarbonyl group or ethoxycarbonyl group, an aryloxycarbonyl group such as phenoxycarbonyl group, an amino group such as N,N-dimethyamino group, N-ethylamino group or N-phenylamino group, an acylamido group such as
  • a 5- or 6-member heterocyclic ring formed through divalent electron withdrawing groups represented by V 1 and W 1 includes those represented by the following Formula (F-5-a).
  • V 1 and W 1 each represent -CO-, -COO-, -SO-, -SO 2 - or -CS-;
  • Z 5 represents a group of non-metal atoms necessary to form a 5- or 6-member simple ring or condensed ring linking with V 1 and W 1 .
  • the 5- or 6-member simple or condensed ring formed by Z 5 may have a substituent, for example, an alkyl group such as methyl group, ethyl group, methoxyethyl group, benzyl group, carboxymethyl group or sulfopropyl group, an aryl group such as phenyl group or p-methoxyphenyl group, a hydroxyl group, an alkoxyl group such as methoxy group, ethoxy group or methoxyethoxy group, an aryloxy group such as phenoxy group or p-carboxyphenyl group, a carboxyl group, a sulfo group, an alkoxycarbonyl group such as methoxycarbonyl group or ethoxycarbonyl group, an aryloxycarbonyl group such as phenoxycarbonyl group, an amino group such as N,N-dimethyamino group, N-ethylamino group or N-phenylamino group
  • the compound represented by Formula (F-5) or (F-6) is added in an amount of from 0.01 to 20 g, preferably from 0.03 to 15 g, more preferably from 0.05 to 10 g, per liter of the processing solution.
  • the aliphatic group represented by R 31 , R 32 or R 33 includes a saturated alkyl group, i.e., a unsubstituted alkyl group such as methyl group, ethyl group or butyl group or a substituted alkyl group such as a benzyl group, carboxymethyl group, hydroxymethyl group or methoxyethyl group, a unsaturated alkyl group such as an allyl group or 2-butenyl group, and a cycloalkyl group such as cyclopentyl group or cyclohexyl group.
  • a saturated alkyl group i.e., a unsubstituted alkyl group such as methyl group, ethyl group or butyl group or a substituted alkyl group such as a benzyl group, carboxymethyl group, hydroxymethyl group or methoxyethyl group, a unsaturated alkyl group such as an allyl group or 2-buten
  • the aryl group represented by R 31 , R 32 or R 33 includes those which are substituted or unsubstituted.
  • the substituent of the aryl group is, for example, an alkyl group such as methyl group, ethyl group, methoxyethyl group, benzyl group, carboxymethyl group or sulfopropyl group, an aryl group such as phenyl group or p-methoxyphenyl group, a hydroxyl group, an alkoxyl group such as methoxy group, ethoxy group or methoxyethoxy group, an aryloxy group such as phenoxy group or p-carboxyphenyl group, a carboxyl group, a sulfo group, an alkoxycarbonyl group such as methoxycarbonyl group or ethoxycarbonyl group, an aryloxycarbonyl group such as phenoxycarbonyl group, an amino group such as N,N-dimethyamino
  • the 5- to 8-member ring formed by linking R 32 with R 33 includes those in which a part of the carbon atoms of the linking chain is replace by a hetero-atom.
  • R 33 a hydrogen atom is preferable.
  • the compound represented by Formula (F-7) is added in an amount of approximately from 0.01 to 20 g, preferably from 0.03 to 15 g, more preferably from 0.05 to 10 g, per liter of the processing solution.
  • the aliphatic hydrocarbon group represented by R 35 , R 36 and Z 3 are each, for example, a saturated alkyl group, i.e., a unsubstituted alkyl group such as methyl group, ethyl group or butyl group or a substituted alkyl group such as benzyl group, carboxymethyl group hydroxymethyl group or methoxyethyl group, a unsaturated alkyl group such as allyl group or 2-butenyl group, or a cycloalkyl group such as cyclopentyl group or cyclohexyl group.
  • a saturated alkyl group i.e., a unsubstituted alkyl group such as methyl group, ethyl group or butyl group or a substituted alkyl group such as benzyl group, carboxymethyl group hydroxymethyl group or methoxyethyl group, a unsaturated alkyl group such as allyl group or 2-buteny
  • the aryl group represented by R 36 or Z 3 may have a substituent, for example, an alkyl group such as methyl group, ethyl group, methoxyethyl group, benzyl group, carboxymethyl group or sulfopropyl group, an aryl group such as phenyl group or p-methoxyphenyl group, a hydroxyl group, an alkoxyl group such as methoxy group, ethoxy group or methoxyethoxy group, an aryloxy group such as phenoxy group or p-carboxyphenyl group, a carboxyl group, a sulfo group, an alkoxycarbonyl group such as methoxycarbonyl group or ethoxycarbonyl group, an aryloxycarbonyl group such as phenoxycarbonyl group, an amino group such as N,N-dimethylamino group, N-ethylamino group or N-phenylamino group, an acyla
  • the group capable of releasing by a hydrolysis reaction represented by V 2 , W 2 and Z 3 each are, for example, an acyl group such as acetyl group, benzoyl group, trifluoroacetyl group or monochloroacetyl group, or trialkylsilyl group such as trimethylsilyl group.
  • the ring formed by linking R 36 with Z 3 is a 5- to 8-member simple ring or condensed ring including those in which a part of the carbon atoms of the linking chain is replaced by a hetero-atom.
  • 1,2-dioxane- cyclopentane, m-dioxin, trioxane, teraoxane and benzdioxorane are examples of them.
  • the cation represented by M includes, for example, a hydrogen ion, an alkali metal ion such as an ion of lithium, sodium or potassium, an alkali earth metal ion such as an ion of magnesium or calcium, an ammonium ion, an organic ammonium ion such as an ion of triethyl ammonium, tripropyl ammonium or tetramethyl ammonium, and a pyridinium ion.
  • the aliphatic hydrocarbon group represented by R35 is preferably a lower alkyl group having 1 or 2 carbon atoms. It is further preferable that R 35 is a hydrogen atom.
  • the compound represented by Formulae (F-8) to (F-10) is added in an amount of from 0.01 to 20 g, preferably from 0.03 to 15 g, more preferably from 0.05 to 10 g, per liter of the processing solution.
  • an inorganic salt such as a hydrochloride, sulfate or nitrate, an organic salt such as a phenol salt, a double salt or complex salt with a metal salt, a hydrated salt and an intramolecular salt are described.
  • the compound represented by Formula (F-11) is added in an amount of from 0.01 to 20 g per liter of the processing solution.
  • Z 4 represents a group of atoms necessary to form a substituted or unsubstituted carbon ring or a substituted or unsubstituted heterocyclic ring.
  • the carbon ring and the heterocyclic ring may be a simple ring or a condensed ring. It is preferable that Z 4 is an aromatic hydrocarbon ring or a heterocyclic ring each having a substituent.
  • the substituent of Z 4 is an aldehyde group, a hydroxyl group, an alkyl group such as methyl group, ethyl group, methoxyethyl group, benzyl group, carboxymethyl group or sulfopropyl group, an aralkyl group, an alkoxyl group such as methoxy group, ethoxy group or methoxyethoxy group, a halogen atom, a nitro group, a sulfo group, a carbonyl group, an amino group such as N,N-dimethyamino group, N-ethylamino group or N-phenylamino group, a hydroxyalkyl group, an aryl group such as phenyl group or p-methoxyphenyl group, a cyano group, an aryloxy group such as phenoxy group or p-carboxyphenyl group, an acyloxy group, an acylamino group
  • the carbon ring represented by Z 4 is preferably a benzene ring, and the heterocyclic ring represented by Z 4 is preferably a 5-or 6-member heterocyclic ring.
  • the 5-member ring includes, for example, a ring of thiophene, pyrrole, furane, thiazole, imidazole, succinimide, triazole, and tetrazole and the 6-member ring includes, for example, a ring of pyridine, pyrimidine , triazine and thiadiazine.
  • Exemplified compounds (F-12-1) to (F-12-52) are obtained by inserting a substituent to 1- to 6-position of the above formula as mentioned in the following table.
  • the compounds represented by Formula (F-12) are easily available on the market.
  • the compound represented by Formula (F-12) is added in an amount of from 0.05 to 20 g, preferably from 0.1 to 15 g, more preferably from 0.5 to 10 g, per liter of the processing solution.
  • R 51 , R 52 , and R 53 each represent a hydrogen atom, an alkyl group which may have a substituent such as methyl group, ethyl group, methoxyethyl group, benzyl group, carboxymethyl group, suflopropyl group, hydroxyethyl group, n-propyl group, iso-propyl group, chloromethyl group or carboxyethyl group, or an aryl group such as phenyl group, p-methoxyphenyl group, m-sulfophenyl group or m-carboxyphenyl group;
  • X1 represents a heterocyclic ring which may have a substituent such as a ring of pyrrole, imidazole, piperidine, pyrazole, succinimide, triazole, tetrazole, thiadiazine, thiadiazoline, morpholine, piperadine, thiamorpholine, indole,
  • the compound represented by Formula (F-13) is added in an amount of from 0.05 to 20 g, preferably from 0.1 to 15 g, more preferably from 0.5 to 10 g, per liter of the processing solution.
  • the stabilizing solution used in the invention further comprises a compound represented by Formula (2) or (3):
  • R 54 represents an organic group
  • R 55 represents an ethylene group, a trimethylene group or a propylene group
  • m is from 4 to 50.
  • X 2 represents a hydrogen atom, -SO 3 M 1 or -PO 3 M 2 , in which M 1 and M 2 each represent a hydrogen atom, an alkali metal atom or an ammonium group.
  • R 56 represents a hydroxyl group, a lower alkyl group, an alkoxyl group,
  • R 57 , R 58 and R 59 each represent a hydrogen atom, a lower alkyl group, preferably an alkyl group having from 1 to 4 carbon atoms such as a methyl group, ethyl group or propyl group; R 57 , R 58 and R 59 may be the same or different.
  • l 1 to l 3 are each from 1 to 30;
  • p, q 1 and q 2 are each 0 or from 1 to 30.
  • X 3 and X 4 represent each an ethylene group, trimethylene group,
  • R 45 in the formula is a monovalent organic group, for example, an alkyl group having from 4 to 30, preferably from 6 to 20 carbon atoms such as a hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group or dodecyl group, or an aryl group substituted with an alkyl group having from 3 to 20 carbon atoms.
  • the preferable substituent of the aryl group is an alkyl group having from 3 to 12 carbon atoms such as a propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group or dodecyl group.
  • the above aryl group includes a phenyl group, tolyl group, xynyl group, biphenyl group and naphthyl group, and a phenyl group and tolyl group are preferable.
  • the alkyl group may be bonded at any of the ortho-, meta- and para-positions of the aryl group.
  • R 55 represents an ethylene group or a trimethylene group, both of them may have a substituent; m is from 4 to 50; X 2 represents a hydrogen atom, -SO 3 M 1 or -PO 3 M 2 , in which M 1 and M 2 represent each a hydrogen atom, an alkali metal atom such as Na, K or Li, or NH 4 .
  • These compounds represented by Formula (2) can be used in an amount of 0.1 to 40 g, preferably 0.3 to 20 g, per liter of the stabilizing solution.
  • the effect of the water-soluble siloxane compound having a polyoxyalkylene group is enhanced when the compound is used in an amount of within the range of 0.01 to 20 g per liter of the stabilizing solution.
  • the compound is particularly effective to prevent formation of precipitation and scratch marks.
  • water-soluble organic siloxane compounds are conventional ones such as those described in JP O.P.I. No. 47-18333/1972, Japanese Patent Examined Publication (JP) Nos. 55-51172/1980 and 51-37538/1976, JP O.P.I. No. 49-62128/1974 and US Patent No. 3,545,970.
  • water-soluble organic siloxane compounds are available from UCC (Union Carbide Co., Ltd.) or Sjin'etsu Kagaku Kogyo Co., Ltd.
  • the silver halide contained in a light-sensitive material to be processed may be silver chloride, silver chlorobromide, silver bromide, silver iodobromide, or silver iodide
  • the light-sensitive material is one having a relatively high silver iodide content of not less than 5 mol% such as a light-sensitive material for photo-taking.
  • the fixing or bleach-fixing solution relating the invention contains a so-called fixing agent.
  • the fixing agent there is employed a thiosulfate such as potassium thiosulfate, sodium thiosulfate or ammonium thiosulfate. It is preferable that the ratio of ammonium sulfate to all of the thiosulfates in the fixing solution is not more than 70 mole %. The above ratio of ammonium thiosulfate is more preferably not more than 50 mole %. further preferably not more 20 mole %.
  • the ratio of the total weight of the compound represented by Formula III to the weight of thiosulfate in the fixing solution is not less than 0.02% and not more than 5% by weight, preferably not less than 0.1% and not more than 2% by weight.
  • a fixing solution such as a pH buffer including various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide, alkylamines and polyethyleneoxide, may be optionally added to the fixing solution.
  • a pH buffer including various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide, alkylamines and polyethyleneoxide
  • the fixing agent is used in an amount of from 0.6 to 4 moles, more preferably from 0.9 to 3.0 moles, suitably from 1.1 to 2.0 moles, per liter of the processing solution.
  • air or oxygen may be blown into a processing bath or a replenishing tank for raising the activity of the processing solution.
  • An appropriate oxidizing agent such as hydrogen peroxide, bromic acid or persulfate may be optionally added for the same purpose.
  • the fixing solution used in the invention is preferably used within the range of pH value of from 4 to 8.
  • the fixing solution used in the invention may further comprise a sulfite or a compound capable of releasing sulfite.
  • a sulfite or a compound capable of releasing sulfite includes potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogen sulfite, potassium hydrogen sulfite, sodium hydrogen sulfite, potassium metabisulfite, sodium metabisulfite and ammonium metabisulfite.
  • formaldehyde-sodium bisulfite acetaldehyde-sodium bisulfite, propionylaldehyde-sodium bisulfite, butylaldehyde-sodium bisulfite, butylaldehyde-sodium bisulfite, succinaldehyde-sodium bisulfite, glutaraldehyde-bis-sodium bisulfite, glutaraldehyde-bis-sodium bisulfite, ⁇ -methylglutalaldehyde-bis-sodium bisulfite and maleicdialdehyde-bis-sodium bisulfite are also usable.
  • the sulfite or sulfite releasing compound is suitably in an amount of not more than 0.1 moles, preferably from 0.12 to 0.55 moles, more preferably from 0.15 to 0.50 moles, particularly preferably from 0.20 to 0.40 moles, in terms of sulfite, per liter of the fixing solution.
  • the number of tanks for the stabilizing process may be either one or more than one.
  • Replenisher for the fixer may be either in the form of a liquid or a solid. It is preferable that the replenisher is in the form of a solid from the viewpoint of providing a fixing process in which a stable fixing ability is maintained when a small amount of light-sensitive material is processed per day, and a good storage ability is kept during a prolonged storage under a high temperature condition.
  • the ratio of the total weight of at least one compound represented by Formula III to the weight of thiosulfate is not less than 0.05% and not more than 5%, more preferably not less than 0.2% and not more than 2%, in total.
  • Decomposition and moisture absorption of thiosulfate in the solid processing composition due to storage under a high temperature and high moisture condition can be prevented by making use of sodium thiosulfate and /or potassium thiosulfate, and ammonium thiosulfate as thiosulfate component of the solid processing composition and making the ratio of the sum of the weight of sodium thiosulfate and/or potassium thiosulfate not less than 2% by weight to the total weight of the thiosulfates contained in the composition.
  • the composition is in the form of a solid, it is preferable to make the sum of the weight of sodium thiosulfate and/or potassium thiosulfate not less than 2% and not more than 70%, particularly not less than 5% and not more than 20%, by weight to the total weight of the thiosulfates contained in the composition.
  • the solid processing composition used in the invention comprises a compound represented by Formula III and a thiosulfate and is useful in a fixer or bleach-fixer.
  • the solid fixer or bleach-fixer composition may further comprise a known component of a fixer composition, other than thiosulfate, such as sulfite, bisulfite, a sulfite-adduct, a mesoionic compound, thiocyanate, a chelating agent, a nonionic or anionic surfactant or a buffering agent.
  • the solid bleach-fixer composition may further comprise a known bleaching or fixing compound such as a halide, a ferric organic salt including a ferric complex of aminocarboxylic acid, an organic acid in a solid form, an antimold agent or a rust preventing agent.
  • the preventing effects on decomposition of thiosulfate and powder formation caused by friction produced after storage for a prolonged period can be enhanced by addition of a compound selected from polyethylene glycols, polyvinylpyrrolidones, polyvinyl alcohols and sugars.
  • polyethylene glycol is a compound represented by the following Formula (I):
  • A, B and D each represent -CH 2 CH 2 O-, -CH 2 CH(R)O-, -CH 2 CH 2 CH 2 O- or -CH 2 CH(R)CH 2 O-, in which R represents a substituted or unsubstituted lower alkyl group (such as a methyl group, an ethyl group and a propyl group) or a hydroxyl group; and n 1 , n 2 and n 3 are each 0 or from 1 to 500, provided, however, that the average molecular weight of these compounds is preferably within the range of from 2000 to 20000.
  • the sugar means a monosaccharide or a polysaccharide in which plural monosaccharides are glycoside-bonded together.
  • a monosaccharide is a general term for a single polyhydroxy aldehyde or polyhydroxy ketone and a wide range of derivatives thereof such as the reduced derivatives, oxidized derivatives, deoxy derivatives, amino derivatives and thio derivatives thereof.
  • Many saccharides are represented by such a formula as C n H 2n O n .
  • the above-mentioned saccharides including the compounds derived from a saccharide skeleton represented by the formula are defined generically as a monosaccharide.
  • the preferable ones include, for example, a sugar alcohol in which the aldehyde and ketone groups of sugar are each so reduced as to be primary and secondary alcohol groups, respectively, and the particularly preferable ones are, for example, hexitol having 6 carbon atoms.
  • Polysaccharides include, for example, celluloses, starches and glycogens.
  • the celluloses include, for example, derivatives of a cellulose ether of which the whole or a part of the hydroxyl group is etherified.
  • the starches include, for example, dextrin such as a variety of decomposed products produced in the course between a hydrolysis and a production of malt sugar.
  • the celluloses may also be in a form of an alkali-metal salt from the viewpoint of the solubility.
  • those preferably applicable include, for example, celluloses and dextrins and, those more preferable include dextrins.
  • B- (66) to (83) are preferably used and B- (74) to (83) are particularly preferable.
  • C-(21) to (64) are preferable and C-(21) to (48) are more preferable.
  • These saccharides may be added in an amount within the range of, preferably from 0.5% (W/W) to 30% (W/W) and, more preferably from 1.0% (W/W) to 20% (W/W) per unit weight of the solid processing composition.
  • Saccharides are widely present in nature and are readily available on the market. A variety of derivatives can also readily be synthesized by carrying out a reduction, oxidation, dehydration reaction or the like.
  • the prevention of formation of sulfurous substances and of formation of powder after storage under high temperature conditions in the solid processing composition can be further enhanced by addition of a sulfite or a pyrosulfite.
  • the sulfite and pyrosulfite include ammonium salt, sodium salt and potassium salt thereof, and sodium salt and potassium salt are preferable from the view point of the above-mentioned effects.
  • the form of the solid composition includes powder, granule and tablet. Granules and tablets are preferred and tablets are most preferred.
  • binder means a mass of fine crystals.
  • Gram means grains having a diameter of from 50 to 5,000 ⁇ m, which is preferably prepared by granulating a powder.
  • Tablet means one which is prepared by shaping a powder or granules in a required tablet form by compression. As the shaping method of the tablet, it is preferable to tablet by compression after granulating the powder or granules, because a stable processing ability can be maintained by thus prepared tablet.
  • granulating methods for preparation of a tablet a known method such as a tumbling granulation method, extrusion granulation method, compression granulation method, crushing granulation method, agitation granulation method, fluid-bed granulation method and spray granulation method can be used.
  • the average size of the granulated particles is preferably from 100 to 2,000 ⁇ m, more preferably from 200 to 1,500 ⁇ m, from the viewpoint that a nonuniformity or demixing of the composition is avoided at the time of mixing and compression of the granulated particles for tableting.
  • the granulated particles preferably have a particle size distribution in which 50% of the particles each have a particle size falling within the range of ⁇ 250 ⁇ m.
  • granulated particles may be used as the granulated composition without any treatment.
  • known compressing machines such as an oil hydraulic pressing machine, single tableting machine, rotary tableting machine and briquetting machine, can be used.
  • the tablet may be prepared by tabulating a mixture of the granulated particles prepared by the above granulating method and crystals of a raw material available on the market.
  • the solid processing composition prepared by compression can take any shape, a cylindrical shape or tablet shape is preferable from the viewpoint of producibility, handling property and dust formation on the user's side.
  • the replenishing composition for the fixer is preferably one containing a small amount of ammonium thiosulfate for improving the working environment. It is preferable that the ratio of ammonium thiosulfate to the total amount of thiosulfates in the fixing solution is not more than 70 mole %, more preferably not more than 30 mole %.
  • the ratio of the sum of the weight of compounds represented by Formula III to the weight of thiosulfate in the composition is preferabaly within the range of from 0.05% to 5% by weight, more preferably within the range of from 0.2% to 2% by weight.
  • the interval from the time at which the fixing process of a light-sensitive material is completed, to the time at which the light-sensitive material is contacted with the stabilizing solution is preferably not more than 7 seconds, more preferably not more than 5 seconds, further preferably from 1 to 3 seconds.
  • the number of stabilizing tanks may be one, but may be increased to from 2 to 10. Although the replenishing amount of the stabilizing solution can be reduced by increasing the number of stabilizing tanks, the number of stabilizing tanks is preferably from 2 to 6 from the viewpoint of the miniaturization of automatic processor.
  • the replenisher may be separately supplied at several portions, but it is preferable that the replenishing is carried out by a counter-current method (multi-steps counter-current method) in which the replenisher is supplied to a tank provided at a downstream portion with respect to the flow of the light-sensitive material and the overflow solution from the tank (including a solution flowing through a pipe when the tanks are connected by a pipe provided under the surface of the solution) is poured into a tank provided upstream of the tank.
  • the counter-current method includes a cascade method. It is further preferable that the replenisher is supplied to the last stabilizing tank among two or more stabilizing tanks and the over flow solution is poured into previous tank in sequence.
  • the replenishing amount of the stabilizing solution can be considerably reduced by approximately 900 ml or less per square meter of the light-sensitive material processed only by making use of the compound represented by Formula (1). However, it is made possible to obtain the effects of the invention by using the above-mentioned treatment with a replenishing amount of from 50 to 800 ml per square meter of the light-sensitive material.
  • the replenishing amount of the stabilizing solution is preferably from 100 to 650 ml, more preferably from 150 to 500 ml per square meter of the light-sensitive material.
  • the replenishing amount can be further reduced by introducing a processing solution pumped out from the stabilizing tank to the fixing solution in the fixing treatment process.
  • a processing was run for 20 days until the sum of the replenishing amount of stabilizing replenishing solution is 2 times the volume of the stabilizing tank in which Konica Color Negative Film Super DD100, imagewise exposed in a camera, was processed. Steps and conditions of the processing are described below: Processing steps Processing time Processing Temperature Replenishing amount Color develop. 3 min. 15 sec. 38 °C 625 ml/m 2 Bleaching 45 sec. 37°C 250 ml/m 2 Fixing 1 min. 30 sec. 37°C 900 ml/m 2 Stabilizing 60 sec. 37°C 600 ml/m 2 Drying 60 sec. 70°C -
  • the fixing step was performed by a two-tank counter-current system (45 seconds for each tank) and the stabilizing step was performed by a four-tank counter-current system (15 seconds for each tank).
  • the cross-over time for each tanks was 3 seconds respectively.
  • composition of the processing solutions used are described below: (Color developer) Sodium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 4 g Sodium bromide 1.3 g Potassium iodide 1.2 g Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino-3-methyl-N-ethyl-N-( ⁇ -hydroxyethyl)-aniline sulfate 4.8 g Potassium hydroxide 1.2 g
  • formalin is an aqueous solution of formaldehyde with a concentration of about 38%.
  • the norm of the evaluation was as follows.
  • the amount of remaining silver not more than 3 mg/dm 2 does not cause any problem in practical use.
  • the adding amount of the raw materials of the silver halide photographic light-sensitive material is described in terms of gram per square meter except where specifically mentioned.
  • the amount of the silver halide emulsion and the colloidal silver are described in terms of silver.
  • a multilayered color photographic color light-sensitive material was prepared by forming the layers each having the following compositions on a triacetyl cellulose film support in the following order from the support.
  • coating aids Su-2 and Su-3, hardener H-1 and H2 an antimolding agent DI-1, a stabilizer Stab-1, antifoggants AF-1 and AF-2 were added to each the layers.
  • the emulsion used were as follows.
  • Em-1 to Em-3 and Em-4 were each mainly composed of octahedral grains having a multilayer structure, which were prepared in accordance with JP O.P.I. Nos. 60-138538/1985 and 61-245151/1986.
  • the average values of the ratio of grain size to grain thickness were 1.0 and the width of grain size distribution (variation coefficient) were 14%, 10%, 12% and 12%, respectively.
  • Processed film was stored in dark for 10 days at 75°C and a RH of 10%, and the difference of the yellow transfer density at the unexposed area of the film was and that of the film before the storage (or yellow stain) was determined.
  • the part of replenishing device in Color Negative Film Processor CL-KP-50QA was modified as shown in Fig 1, in which a supplying device shown in Fig. 2 was used for supplying solid processing composition.
  • a columnar cartridge in which tablets were contained was set on a tablet supplying portion of the processor and imagewise exposed Konicolor Super DD400 film was processed in the processor.
  • Fig. 1 shows setting positions on KP-500Q (Autoprocessor A) at which solid processing composition supplying devices 2A, 2B, 2C and 2D to be set.
  • the above solid processing composition supplying devices 2A, 2B, 2C and 2D are each set at the upper portion of a color developing tank 1A, bleaching tank 1B, fixing tank 1C and stabilizing tank 1D, respectively, which are shown by hatching.
  • Fig. 2 is a scheme showing an embodiment of the above-mentioned solid processing composition supplying devices 2A, 2B, 2C and 2D. Beside each tank, a dissolving chamber 106 is provided, a solid processing composition 111 is supplied thereto.
  • the solid processing composition (hereinafter referred as tablet or tablet chemical) 111 is contained in a cartridge 101 which has plural divided chambers and is sealed up with a slidable cap 102.
  • the cap 102 is opened and a tablet is rolled down from the diagonally set cartridge into a cut out portion 105 of a rotatable cylinder 104.
  • Plural cut out portions 105 are alternately made on the cylinder 104 so as to prevent simultaneously rolling down of tablets each contained in different chambers of the cartridge.
  • the cylinder 104 is rotated according to the amount of processed light-sensitive material and a shutter 108 is opened at the same time so that the tablet is supplied one by into a filtering or dissolving tank 106.
  • 107 is a filter.
  • Treatment processes were as follows. Processing Time Temperature Replenishing water (ml/m 2 ) Color deve. 3'15" 38.0°C 520 Bleaching 45" 38.0°C 100 Fixing-1 45" 38.0°C Fixing-2 45" 38.0°C Shown in Table 7 Stabi.-1 20" 38.0°C Stabi.-2 20" 38.0°C Stabi.-3 20" 38.0°C 860 Drying 80" 55°C
  • the fixer and stabilizer were each counter-flowed 2 to 1, and 3 to 2 and 2 to 1, respectively.
  • aeration of the bleaching solution was performed by an air pump.
  • the solutions filled in the tanks at the start of processing were prepared by making use of replenishers and starters of processing compositions CNK-4-52 for Konica Color Negative Film.
  • the above-obtained granules (A), (B) and (C) were mixed and 2 g of sodium N-myristoylalanine was added thereto.
  • the mixture was uniformly mixed for 10 minutes by a mixer installed in a room conditioned at 25°C and a RH of 40% or less.
  • the mixture was tableted by a tableting machine, modified Tough Press Collect 1527UH manufactured by Kikusui Seisakusyo in a rate of 10 g per tablet.
  • a tablet for color developer replenisher having a diameter of 30 mm was prepared.
  • the granules prepared by the above Operations (4) to (6) were uniformly mixed by a mixer installed in a room conditioned at 25°C and a RH of 40% or less. Then the mixture of the granules was further mixed for 3 minutes after adding 6 g of sodium N-lauroylsarcosine.
  • the mixture was tableted by a tableting machine, modified Tough Press Collect 1527UH, manufactured by Kikusui Seisakusyo, in a rate of 10 g per tablet.
  • a tablet bleaching solution replenisher for color negative film having a diameter of 30 mm and a thickness of 10 mm was prepared.
  • the above obtained granules were mixed with 30 g of sodium N-lauroylsarcosine for 5 minutes in a mixing machine installed in a room conditioned at 25°C and a RH of 40% or less.
  • the mixture was tableted by a tableting machine, modified Tough Press Collect 1527UH, manufactured by Kikusui Seisakusyo, in a rate of 10 g per tablet.
  • a tablet having a diameter of 30 mm and a thickness of 10 mm was prepared.
  • mHBA m-hydroxybenzaldehyde
  • lithium hydroxide mono-hydrate 200 g of m-hydroxybenzaldehyde, hereinafter referred as mHBA, and lithium hydroxide mono-hydrate were powdered until the average size of the powdered particles was 10 ⁇ m.
  • the powder was uniformly mixed for 10 minutes in a mixing machine installed in a room conditioned at 25°C and a RH of 40% or less to prepare a powdered mixture.
  • the above powdered mixture was granulated in a flow-layer atomizing granulating machine for 7 minutes at room temperature while atomizing 3.0 ml of water, and was dried for 8 hours at 45°C.
  • the granules were further dried under a vacuum for 20 hours so that the moisture content of the granules was 0.1 to 0.3% by weight.
  • the average size and the bulk density of the granules were 300 to 600 ⁇ m and 0.8 g/cm 3 , respectively.
  • the granules were tableted by a tableting machine, modified Tough Prestcollect 1527UH, manufactured by Kikusui Seisakusyo, in a rate of 9.0 g per tablet. Thus a tablet having a diameter of 30 mm was prepared. The bulk density of the tablet was 1.7 g/cm 3 .
  • a running test of processing was performed for 3 weeks under the foregoing processing conditions and the processing compositions.
  • the processed amount of the negative film was 0.5 m 2 per day.
  • an unexposed light-sensitive material was processed and the silver amount remaining in the light-sensitive material was determined by an X-ray fluorescent method.
  • the thiosulfate concentration shown in the table is a value of thiosulfate concentration in the solution of the second fixing tank after completion of the running test, which is determined by a reversal iodine titration method.
  • the fixing ability of fixer can be maintained even when the concentration of thiosulfate is lowered by the use of a compound of Formula III. Further, the formation of scratch and adhesion of smudge on the surface of light-sensitive material, which are caused by precipitation of the crystals during storage of the processing solution at a low temperature and precipitation the substance on the surface of transfer rollers provided between the fixing tanks, can also be prevented by making use of the compound.
  • Example 1 Experiments and evaluations were performed in the same manner as in Example 1 except that the method for supplying a solid composition of fixer was changed, and the addenda to be used, the amount of supplying water and the supplying interval of the solid composition were changed also as shown in Table 8. Test results are shown in Table 8.
  • Fig. 3 shows a cross section of another supplying device for a solid processing composition, which can be used processing composition in a form of granule or powder.
  • a processing composition in a form of granule or powder is put into a hopper 71.
  • a piston 75 is moved for horizontal (right) direction, according to the amount of light-sensitive material processed, to put a prescribed amount of granules or powder of processing composition into an amount measuring hole 72.
  • the piston 75 is moved for reverse (left) direction to supply the powdered or granulated processing composition to a filter chamber through an exit hole 74.
  • the device is adjusted so as to supply 10 g of the powdered composition per time of supply.
  • Granules prepared in operation (7) in Example 1 was used as fixer replenishing granules.
  • the supplying device of Fig. 1 used in Example 1 was replaced by that shown in Fig. 3.
  • the device is adjusted so as to supply 10 g of the granulated composition per time of supply.
  • Example 2 The same tablet and supplying device as in Example 1 were used.
  • the fixing ability of fixer can be maintained by the use of the compound of Formula III even when the concentration of thiosulfate is lowered. Further, the formation of scratch and adhesion of smudge on the surface of the light-sensitive material, which are caused by the crystals precipitated during storing of the processing solution at a low temperature and the substance precipitated on the surface of the transfer roller between the fixing tanks, can also be prevented by the use of the compound.
  • Solid fixer replenishing compositions for color light-sensitive material were prepared as follows.
  • the granules were dried at 60°C for 120 minutes so that almost all of the moisture contained in the granules was removed.
  • the dried granules were classified so that the average size was 800 ⁇ m and 50% of the granules were within a deviation range of ⁇ 200 ⁇ m to ⁇ 250 ⁇ m.
  • the above obtained granules were mixed with 30 g of sodium N-lauroylsarcosine for 5 minutes in a mixing machine installed in a room conditioned at 25°C and a RH of 40% or less.
  • the mixture was tableted by a tableting machine, modified Tough Press Collect 1527UH, manufactured by Kikusui Seisakusyo, in a rate of 10 g per tablet.
  • a tablet having a diameter of 30 mm and a thickness of 10 mm was prepared.
  • the above granulated processing composition stored for one month at 50°C and a HR of 50% was taken out from the bag and sieved to remove particles each having a diameter of not more than 149 ⁇ m and remaining granules were weighed.
  • the remaining granules were enclosed again in a polyethylene bag and shaken by a vibration testing machine BF-UA manufactured by TDEX Co. with a shaking condition in which the sample was shaked for 5 minutes while varying the shaking cycles 5 to 67 Hz and the shaking was repeated for 24 times, 120 minutes in total. After the shaking test, the granules were sieved again for removing particles of not more than 194 ⁇ m and remained granules were weighed.
  • the degree of powder formation during the storage in the granulated composition was evaluated by the following equation.
  • the followings are evaluation ranks of the appearance of the solution in which the solid processing composition after stored at the high temperature was dissolved, and the powder formation degree in the solid processing composition after stored at the high temperature.
  • a solid bleach-fixer composition for color paper was prepared as follows.
  • the granules obtained by operations (12) and (13) were mixed by a mixing machine in a room conditioned at 25° C and a RH of 40%. Thus granulated bleach-fixing composition was prepared.
  • the above-prepared granulated bleach-fixing composition was mixed with 30 g of sodium N-lauroylsarcosine for 5 minutes by a mixer in a room conditioned at 25°C and a HR of not more than 45%.
  • the mixture was tableted by a tableting machine, modified Tough Press Collect 1527UH, manufactured by Kikusui Seisakusyo, in a rate of 10 g per tablet.
  • a tablet having a diameter of 30 mm and a thickness of 10 mm was prepared.
  • Example 11 Experiments and evaluations were carried out in the same manner as in Example 1 except that the supplying amount of water, the supplying interval of solid composition and the weight ratio of the addenda to thiosulfate were changed as shown in Table 11. Thus obtained test results are shown in Table 11.
  • the fixing ability of fixer can be maintained by making use of the compound of Formula III and adjusting the ratio of the weight of the compound to the weight of thiosulfate in the composition to the preferable rage, even when the concentration of thiosulfate is lowered. Further, the formation of scratch and adhesion of smudge on the surface of the light-sensitive material, which are caused by the crystals precipitated out during storage of the processing solution at a low temperature and the substance precipitated on the surface of the transfer roller between the fixing tanks, can also be prevented by making use of the compound of Formula III and adjusting the ratio of the weight of the compound to the weight of thiosulfate in the composition.
  • Example 2 Experiments and evaluations were carried out in the same manner as in Example 1 except that the supplying amount of water, the supplying interval of solid composition and the weight ratio of the addenda to thiosulfate were changed as shown in Table 12, further the tableted fixing replenisher compositions used in Example 1 were each replaced with those which has been left to stand for 2 weeks at 50°C and a RH of 80% in a high-density polyethylene bag.
  • the fixing ability of fixer can be maintained by making use of the compound of Formula III and adjusting the ratio of the weight of the compound to the weight of thiosulfate in the composition to the preferable range, even when the concentration of thiosulfate is lowered. Further, the formation of scratch and adhesion of smudge on the surface of the light-sensitive material, which are caused by the crystals precipitated during storage of the processing solution at a low temperature and the substance precipitated on the surface of the transfer roller between the fixing tanks, can also be prevented by making use of the compound of Formula III and adjusting the ratio of the weight of the compound to the weight of thiosulfate in the composition.
  • Konica Color Super DD Film exposed by an ordinary method was processed for 3 weeks in a rate of 10 rolls per day with the following starting solution and replenisher by a color negative film processor L-KP-50QA having the following processing steps, and is evaluated (Color developer starting solution)
  • Sodium carbonate 30 g
  • Sodium hydrogencarbonaate 2.5 g
  • Potassium sulfite 3.0 g
  • Sodium bromide 1.2
  • Potassium iodide 0.6 mg Hydroxylamine sulfate 2.5 g
  • Sodium chloride 0.6 g 4-amino-3-methyl-N-ethyl-N-( ⁇ -hydroxyethyl)-aniline sulfate 4.6 g
  • Diethylenetriaminepentaacetic acid 3.0 g
  • Potassium hydroxide 1.2 g Make to 1 liter with water and adjust pH value to 10.0 using potassium hydroxide or 20% sulfuric acid.
  • the fixer was flowed to Fixing-2 to Fixing-1, and the stabilizer was flowed to Stabilizing-3 to Stabilizing-2, and Stabilizing-2 to Stabilizing-1 each by a counter-current method.
  • a part of the fixer was sampled after the running of processing and is stored at 0° C.
  • Example 7 Experiments was carried out in the same manner as in Example 7 except that the mole ratio of ammonium salt was fixed at 10 mole % and the whole concentration of thiosulfate in the fixer replenisher and the kind of compound of the invention were changed as shown in Table 14. Processing and evaluation were carried out in the same manner in Example 7.
  • the compound of Formula III is effective when the ratio of the using amount by weight of the compound to the weight of thiosulfates is within the range of from 0.05 to 5.0.
  • a modified color Negative Film Processor CL-KP-50QA (produced by Konica Corporation) shown in Fig. 1 was used, and replenishing was carried out by making use of a solid processing composition supplying device as shown in Fig. 2. Pillar-shaped packages each including tablets were set on the tablet supplying portions of the processor, and Konica Color Super DD100 Film imagewise exposed was process in a rate of 20 rolls per day.
  • the fixer and stabilizer were each counter-flowed 2 to 1, and 3 to 2 and 2 to 1, respectively.
  • the above-obtained granules (1) to (3) were mixed and 2 g of sodium N-myristoylalanine was added thereto.
  • the mixture was uniformly mixed for 10 minutes by a mixer installed in a room conditioned at 25°C and a RH of 40% or less.
  • the mixture was tableted by a tableting machine, modified Tough Prestcollect 1527UH manufactured by Kikusui Seisakusyo in a rate of 10 g per tablet.
  • a tablet for color developer replenisher having a diameter of 30 mm was prepared.
  • the granules prepared by the above Operations (4) to (6) were uniformly mixed by a mixer installed in a room conditioned at 25°C and a RH of 40% or less. Then the mixture of the granules was further mixed for 3 minutes after adding 6 g of sodium N-lauroylsarcosine.
  • the mixture was tableted by a tableting machine, modified Tough Press Collect 1527UH, manufactured by Kikusui Seisakusyo, in a rate of 10 g per tablet.
  • a tablet bleaching solution replenisher for color negative film having a diameter of 30 mm and a thickness of 10 mm was prepared.
  • the above obtained granules were mixed with 30 g of sodium N-lauroylsarcosine for 5 minutes in a mixing machine installed in a room conditioned at 25°C and a RH of 40% or less.
  • the mixture was tableted by a tableting machine, modified Tough Press Collect 1527UH, manufactured by Kikusui Seisakusyo, in a rate of 10 g per tablet.
  • a tablet having a diameter of 30 mm and a thickness of 10 mm was prepared.
  • replenisher tables were supplied to the processing tanks at the following interval.
  • Supplying interval of replenishing tablet Developer replenisher tablet 1 tablet per 8.3 rolles of color negative film (24EX)
  • a processing method for silver halide photographic lightsensitive material which is suited for environmental protection can be provided by the present invention, in which the replenishing amount of a stabilizing solution can be reduced without stain formation on the back surface of film and sulfurization of the stabilizing solution, and a stable processing during a prolonged period can be realized.
  • the fixing ability of a fixer can be maintained even when the concentration of thiosulfate is lowered and adhesion of insoluble substance on a transferring rollers can be prevented by making use of the method of the invention.

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  • General Chemical & Material Sciences (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (13)

  1. Verfahren zur Behandlung eines lichtempfindlichen photographischen Silberhalogenidaufzeichnungsmaterials, umfassend die Stufen:
    Fixieren oder Bleichfixieren eines lichtempfindlichen photographischen Silberhalogenidaufzeichnungsmaterials mit einer Fixier- oder Bleichfixierlösung, die ein Thiosulfat in einer Menge von 0,6-4 mol/l und mindestens eine Verbindung der Formel III in einer Menge von 0,02-5 Gew.-%, bezogen auf das Thiosulfat, umfasst, und
    anschließendes Stabilisieren des lichtempfindlichen Aufzeichnungsmaterials mit einer Stabilisierungslösung, die mindestens eine Verbindung der Formel F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12 oder F-13 in einer Menge von 0,05-50 g/l für die Verbindung der Formel F-1, 0,05-20 g/l für die Verbindungen der Formeln F-2 bis F-4, 0,01-20 g/l für die Verbindungen F-5 bis F-11 und 0,05-20 g/l für die Verbindungen der Formeln F-12 oder F-13 umfasst:
    Figure 01670001
    worin Q1 eine zur Bildung eines stickstoffhaltigen heterocyclischen Rings einschließlich eines Rings mit einem ankondensierten 5- oder 6gliedrigen gesättigten oder ungesättigten Ring notwendige Gruppe von Atomen ist; R1 ein Wasserstoffatom oder ein Alkalimetallatom oder
    Figure 01680001
    oder eine Alkylgruppe bedeutet; und Q' synonym mit Q1 ist;
    Figure 01680002
    worin R11 bis R16 jeweils für ein Wasserstoffatom oder eine einwertige organische Gruppe stehen;
    Figure 01680003
    Figure 01680004
    Figure 01690001
    worin R21 bis R23 jeweils für ein Wasserstoffatom oder eine Methylolgruppe stehen;
    Figure 01690002
    Figure 01690003
    worin bedeuten:
    V1 und W1 jeweils eine elektronenabziehende Gruppe, wobei V1 und W1 zusammen mit dem Stickstoffatom unter
    Bildung eines 5- oder 6gliedrigen stickstoffhaltigen heterocyclischen Rings verbunden sein können;
    Y1 ein Wasserstoffatom oder eine Gruppe mit der Fähigkeit, durch eine Hydrolysereaktion freigesetzt zu werden;
    Z eine Gruppe von Atomen, die zur Bildung eines einzelnen oder kondensierten stickstoffhaltigen heterocyclischen Rings zusammen mit dem Stickstoffatom notwendig ist;
    Figure 01690004
    worin bedeuten:
    R31 ein Wasserstoffatom oder eine aliphatische Gruppe;
    R32 und R33 jeweils eine aliphatische Gruppe oder eine
    Arylgruppe, wobei R32 und R33 zusammen mit Z1 und
    Z2 unter Bildung eines Rings verbunden sein können;
    Z1 und Z2 jeweils ein Sauerstoffatom, ein Schwefelatom oder -N(R34)-, wobei Z1 und Z2 nicht beide gleichzeitig Sauerstoffatome oder -N(R34)-Gruppen sind;
    R34 ein Wasserstoffatom, eine Hydroxylgruppe, eine aliphatische Gruppe oder eine Arylgruppe;
    Figure 01700001
    Figure 01700002
    Figure 01700003
    worin bedeuten:
    R35 ein Wasserstoffatom oder eine aliphatische Kohlenwasserstoffgruppe;
    V2 eine Gruppe mit der Fähigkeit, durch eine Hydrolysereaktion freigesetzt zu werden;
    M ein Kation;
    W2 und Y2 jeweils ein Wasserstoffatom oder eine Gruppe mit der Fähigkeit, durch eine Hydrolysereaktion freigesetzt zu werden;
    n 1 bis 10;
    Z3 ein Wasserstoffatom, eine aliphatische Kohlenwasserstoffgruppe, eine Arylgruppe oder eine Gruppe mit der Fähigkeit, durch eine Hydrolysereaktion freigesetzt zu werden;
    R36 eine aliphatische Kohlenwasserstoffgruppe oder eine Arylgruppe;
    wobei Z3 unter Bildung eines Rings mit R36 verbunden sen kann;
    Figure 01710001
    worin A1 bis A4 jeweils für ein Wasserstoffatom, eine Alkylgruppe, eine Alkenylgruppe oder eine Pyridylgruppe stehen und l 0 oder 1 bedeutet;
    Figure 01710002
    worin Z4 eine Gruppe von Atomen bedeutet, die zur Bildung eines Kohlenwasserstoffrings oder eines heterocyclischen Rings notwendig ist; X für eine Aldehydgruppe,
    Figure 01710003
    mit R41 und R42 jeweils gleich einer Niedrigalkylgruppe steht und n 1 bis 4 beträgt;
    Figure 01720001
    worin R51 bis R53 jeweils für ein Wasserstoffatom, eine Alkylgruppe oder eine Arylgruppe stehen und X1 für eine stickstoffhaltige heterocyclische Gruppe steht.
  2. Das Verfahren nach Anspruch 1, wobei mindestens ein Teil der Stabilisierungslösung der Fixier- oder Bleichfixierlösung zugesetzt wird.
  3. Das Verfahren nach Anspruch 1 oder 2, wobei die Stabilisierungslösung in einer Menge von im wesentlichen nicht mehr als 900 ml/m2 des behandelten lichtempfindlichen Aufzeichnungsmaterials ergänzt wird.
  4. Das Verfahren nach einem der vorhergehenden Ansprüche, wobei das Verhältnis von Ammoniumthiosulfat zu allen Thiosulfaten in der Fixierlösung nicht mehr als 70 Mol-% beträgt.
  5. Das Verfahren nach einem der vorhergehenden Ansprüche, wobei die Fixier- oder Bleichfixierlösung aus einer festen Behandlungszusammensetzung hergestellt wird.
  6. Das Verfahren nach Anspruch 5, wobei die feste Behandlungszusammensetzung Kaliumthiosulfat und/oder Natriumthiosulfat und Ammoniumthiosulfat umfasst und das Verhältnis des Gesamtgewichts von Kaliumthiosulfat und/oder Natriumthiosulfat zum Gesamtgewicht der Thiosulfate in der festen Behandlungszusammensetzung 2-70 Gew.-% beträgt.
  7. Das Verfahren nach Anspruch 5 oder 6, wobei die feste Behandlungszusammensetzung in der Form eines Granulats oder einer Tablette vorliegt.
  8. Das Verfahren nach einem der Ansprüche 5 bis 7, wobei die feste Behandlungszusammensetzung in der Form einer Tablette vorliegt.
  9. Das Verfahren nach einem der Ansprüche 5 bis 8, wobei das Verhältnis des Gesamtgewichts der Verbindungen der Formel III zum Gewicht von Thiosulfat in der festen Behandlungszusammensetzung 0,05-5 Gew.-% beträgt.
  10. Das Verfahren nach einem der vorhergehenden Ansprüche, wobei die Fixierlösung mittels einer Ergänzungszusammensetzung, die ein Thiosulfat und eine Verbindung der Formel III umfasst, ergänzt wird und nicht mehr als 70 Mol-% des Thiosulfats aus Ammoniumthiosulfat bestehen.
  11. Das Verfahren nach Anspruch 10, wobei das Verhältnis des Gesamtgewichts der Verbindungen der Formel III zum Gewicht von Thiosulfat in der Ergänzungszusammensetzung 0,05-5 Gew.-% beträgt.
  12. Das Verfahren nach einem der vorhergehenden Ansprüche, wobei die Silberhalogenidemulsion nicht weniger als 5 Mol-% Silberiodid umfasst.
  13. Das Verfahren nach einem der vorhergehenden Ansprüche, wobei die Stabilisierungslösung eine Verbindung der Formel F-3, F-4, F-6 oder F-12 umfasst.
EP19950308047 1994-11-11 1995-11-10 Verfahren zur Verarbeitung eines photographischen, lichtempfindlichen Silberhalogenidmateriales Expired - Lifetime EP0712040B1 (de)

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JP277983/94 1994-11-11
JP27798394 1994-11-11
JP27798394 1994-11-11
JP4005095A JPH08190178A (ja) 1994-11-11 1995-02-28 ハロゲン化銀写真感光材料用固体処理剤
JP40050/95 1995-02-28
JP4005095 1995-02-28
JP66058/95 1995-03-24
JP6605895 1995-03-24
JP6605895A JPH08262670A (ja) 1995-03-24 1995-03-24 ハロゲン化銀写真感光材料処理用補充組成物及びハロゲン化銀写真感光材料用固体処理剤
JP7610395 1995-03-31
JP7610395A JPH08272061A (ja) 1995-03-31 1995-03-31 ハロゲン化銀写真感光材料の処理方法
JP76103/95 1995-03-31

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US6001545A (en) * 1998-12-30 1999-12-14 Eastman Kodak Company Photographic fixing composition and method of rapid photographic processing
US6007972A (en) * 1999-02-16 1999-12-28 Eastman Kodak Company Photographic fixing composition containing an oxadiazolethione and method of rapid photographic processing
US6087077A (en) * 1999-02-16 2000-07-11 Eastman Kodak Company Photographic fixing composition containing a 1,3-thiazolidine-2-thione and method of rapid photographic processing
US6013424A (en) * 1999-02-16 2000-01-11 Eastman Kodak Company Photographic fixing composition containing aminoalkyltriazole and method of rapid photographic processing

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JP2709463B2 (ja) * 1988-02-15 1998-02-04 コニカ株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JP2739322B2 (ja) * 1988-04-13 1998-04-15 コニカ株式会社 ハロゲン化銀カラー写真感光材料の処理方法
EP0476434A3 (en) * 1990-09-05 1992-05-06 Konica Corporation Method for processing silver halide color photographic light sensitive materials
JPH04124662A (ja) * 1990-09-14 1992-04-24 Konica Corp ハロゲン化銀カラー写真感光材料の処理方法
DE69225419T2 (de) * 1991-02-19 1998-09-03 Fuji Photo Film Co Ltd Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials und photographische Fixierzusammensetzung
JP2909668B2 (ja) * 1991-09-05 1999-06-23 コニカ株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JP3038418B2 (ja) * 1991-12-13 2000-05-08 コニカ株式会社 ハロゲン化銀写真感光材料用固形処理剤
GB9222048D0 (en) * 1992-10-21 1992-12-02 Ilford Ltd Fixing baths
US5480768A (en) * 1993-02-17 1996-01-02 Konica Corporation Method for processing exposed silver halide photographic light-sensitive material using a solid processing composition replenisher

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