EP0534086B1 - Bleichlösung für farbfotografisches Verfahren - Google Patents

Bleichlösung für farbfotografisches Verfahren Download PDF

Info

Publication number
EP0534086B1
EP0534086B1 EP19920112723 EP92112723A EP0534086B1 EP 0534086 B1 EP0534086 B1 EP 0534086B1 EP 19920112723 EP19920112723 EP 19920112723 EP 92112723 A EP92112723 A EP 92112723A EP 0534086 B1 EP0534086 B1 EP 0534086B1
Authority
EP
European Patent Office
Prior art keywords
solution
group
mole
processing
atom
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19920112723
Other languages
English (en)
French (fr)
Other versions
EP0534086A1 (de
Inventor
Satoru Kuse
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0534086A1 publication Critical patent/EP0534086A1/de
Application granted granted Critical
Publication of EP0534086B1 publication Critical patent/EP0534086B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/40—Chemically transforming developed images
    • G03C5/44—Bleaching; Bleach-fixing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • This invention relates to a processing solution having bleachability for a light-sensitive silver halide color photographic material, more specifically to a processing solution having bleachability for a light-sensitive silver halide color photographic material, which has excellent biodegradability, less bleaching fog and also excellent desilvering property.
  • a light-sensitive silver halide color photographic material is processed by a color developing solution, a bleaching solution, a fixing solution, a bleach-fixing solution and a stabilizing solution.
  • a bleaching agent for bleaching silver is added to a bleaching solution and a bleach-fixing solution.
  • a bleaching agent used most generally for processing a color paper and a color negative film is a ferric complex salt of ethylenediaminetetraacetic acid.
  • a ferric complex salt of ethylenediaminetetraacetic acid has poor biodegradability, and if it is flown out to rivers or soil, it will be accumulated without degradation or floated for a long time, which is undesirable from the standpoint of protection of environments of the earth.
  • a bleaching agent which has been used recently, there may be mentioned, for example, a ferric salt of 1,3-propanediaminetetraacetic acid (PDTA ⁇ Fe) disclosed in Japanese Provisional Patent Publications No. 103041/1990, No. 103040/1990 and No. 250651/1988.
  • This PDTA ⁇ Fe is a compound having excellent silver bleachability, rapid processing suitability and also excellent biodegradability, but it has problems in practical use. That is, when bleaching processing is carried out immediately after color development, bleaching fog is caused.
  • a technique of lowering pH by using acetic acid but this technique involves a problem of odor.
  • Another problem of the PDTA ⁇ Fe is that thiosulfate which is a fixing agent is decomposed and sulfurized because of strong oxidation power of the PDTA ⁇ Fe when processing is carried out by a fixing solution successively after a bleaching solution using the PDTA ⁇ Fe or when the PDTA ⁇ Fe is used as a bleaching agent of a bleach-fixing solution.
  • EP-A-0 430 000 discloses a well biodegradable bleaching solution having sufficient bleaching activity which comprises
  • EP-A-0 468 325 which has to be considered as a prior art reference under Article 54(3) and (4) EPC discloses a well biodegradable bleaching solution having sufficient bleaching activity, which comprises (1) a ferric complex at least 20 mole-% of the chelating agent of which is represented by the following formula (I) (HOOC-CH 2 ) 2 -N-CH 2 -CH 2 -COOH wherein said bleaching solution has a pH of (x) in a range of 6,0 > x > 4,5.
  • EP-A-0 199 604 discloses a processing method of a light-sensitive silver halide color photographic material comprising processing a light-sensitive silver halide color photographic material with a bleach-fixing solution after color developing, and successively with a stabilizing solution substituted for water washing, said bleach-fixing solution contains as main components an organic acid ferric complex salt with which a molecular weight of a free acid being not more than 280, a thiosulfate and a sulfite, and a processing time by said stabilizing solution substituted for water washing is 2 minutes or shorter.
  • DE-A-39 19 551 discloses a bleaching solution for processing color photographic silver halide materials which comprises
  • EP-A-0 329 088 discloses a processing method for silver halide color photographic material and a bleaching solution used in the processing. Sufficient desilvering in a short time and prevention of bleaching fogging can be obtained by the process. The process is applicable for silver-rich high-sensitivity color light-sensitive material.
  • the bleaching solution comprises a of a ferric complex salts of compounds represented by the following Formula A or B in an amount of at least 0,01 mol per liter of the bleaching solution and a buffer agent capable of adjusting pH value to 3 to 7; and pH value of the bleaching solution is held within the range of from 3 to 7; wherein A 1 through A 4 are each -CH 2 OH, -COOM, or -PO 3 M 1 M 2 ; M, M 1 and M 2 are each a hydrogen atom, a sodium atom, a potassium atom or an ammonium group; X is a substituted or unsubstituted alkylene group having three to six carbon atoms; B 1 and B 2 are a substituted or unsubstituted alkylene group having two to five carbon atoms; n is an integer of 1 to 8.
  • a first object of the present invention is to provide a processing solution having bleachability for a light-sensitive silver halide color photographic material, which does not cause bleaching fog and also enables rapid processing.
  • a second object of the present invention is to provide a processing solution having bleachability for a light-sensitive silver halide color photographic material, which has excellent biodegradability and environmental suitability.
  • a third object of the present invention is to provide a processing solution having bleachability for a light-sensitive silver halide color photographic material, which enables stable processing without causing sulfurization.
  • a fourth object of the present invention is to provide a processing solution having bleachability for a light-sensitive silver halide color photographic material, which prevents yellow stain at an edge portion of a light-sensitive material.
  • a 1 , A 2 , A 3 and A 4 may be the same or different, and each represent hydrogen atom, hydroxyl group, -COOM, -PO 3 M 2 , -CH 2 OH or a lower alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, isopropyl group and n-propyl group). However, at least one of A 1 , A 2 , A 3 and A 4 is -COOM or -PO 3 M 2 .
  • M, M 1 and M 2 each represent hydrogen atom, ammonium group, sodium atom, potassium atom, lithium atom or an organic ammonium group (e.g. trimethylammonium group and triethanolammonium group), provided that nitrilodiacetic-monopropionic acid is excluded.
  • preferred specific examples of the compound represented by the formula (I) are shown.
  • the processing solution having bleachability means specifically a bleaching solution, a bleach-fixing solution and a bleach-fixing solution for one bath development.
  • the amount of a ferric complex salt of the compound represented by the above formula (I) to be contained is preferably in the range of 0.1 to 2.0 mole, more preferably in the range of 0.15 to 1.5 mole per liter of the bleaching solution or bleach-fixing solution.
  • the bleaching solution or bleach-fixing solution may contain ferric complex salts of the following compounds other than a ferric complex salt of the compound represented by the above formula (I) as a bleaching agent.
  • an effect on rapid processing can be exhibited by incorporating at least one of imidazole or a derivative thereof disclosed in Japanese Provisional Patent Publication No. 295258/1989 or compounds represented by the formulae (I) to (IX) and exemplary compounds thereof disclosed in the same patent publication into the bleaching solution, bleach-fixing solution and fixing aolution.
  • exemplary compounds disclosed on pp. 51 to 115 of Japanese Provisional Patent Publication No. 123459/1987, exemplary compounds disclosed on pp. 22 to 25 of Japanese Provisional Patent Publication No. 17445/1988, and compounds disclosed in Japanese Provisional Patent Publications No. 95630/1978 and No. 28426/1978 may be also used.
  • the bleaching solution or bleach-fixing solution is preferably used at a temperature of 20 to 50 °C, desirably 25 to 45 °C.
  • the pH of the bleaching solution is preferably 6.0 or less, more preferably 1.0 to 5.5.
  • the pH of the bleach-fixing solution is preferably 5.0 to 9.0, more preferably 6.0 to 8.5.
  • the pH of the bleaching solution or bleach-fixing solution is a pH of a processing tank at the time of processing a light-sensitive silver halide material, which is clearly distinguished from a pH of a replenishing solution.
  • a halide such as ammonium bromide, potassium bromide and sodium bromide, and various fluorescent brighteners, defoaming agents or surfactants may be contained.
  • the replenishing amount of the bleaching solution or bleach-fixing solution is preferably 500 ml or less, more preferably 20 ml to 400 ml, most preferably 40 ml to 350 ml per 1 m 2 of a light-sensitive silver halide color photographic material.
  • a replenished amount is smaller, the effect of the present invention becomes remarkable.
  • air or oxygen may be blown into a processing bath or a tank for storing a processing replenishing solution if desired, or a suitable oxidizer, for example, hydrogen peroxide, hydrobromide and persulfate may be added.
  • a suitable oxidizer for example, hydrogen peroxide, hydrobromide and persulfate may be added.
  • thiocyanate and thiosulfate are preferably used as a fixing agent to be used in the fixing solution or bleach-fixing solution according to the present invention.
  • the amount of thiocyanate to be contained is preferably at least 0.1 mole/liter, and when a color negative film is processed, the amount is more preferably 0.5 mole/liter or more, particularly preferably 0.1 mole/liter or more.
  • the amount of the thiosulfate to be contained is preferably at least 0.2 mole/liter, and when a color negative film is processed, the amount is more preferably 0.5 mole/liter or more.
  • the object of the present invention can be accomplished more effectively by using thiocyanate and thiosulfate in combination.
  • a pH buffer comprising various salts may be contained alone or in combination of two or more.
  • a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride and ammonium bromide is desirably contained.
  • compounds which have been generally added to a fixing solution or bleach-fixing solution such as alkylamines and polyethylene oxides may be suitably added.
  • silver may be recovered by a known method.
  • a compound represented by the following formula (FA) and exemplary compounds thereof disclosed on p. 56 of Japanese Provisional Patent Publication No. 295258/1989 are preferably added not only for exhibiting the effect of the present invention more favorably, but also for exhibiting another effect that extremely less sludge is generated in a processing solution having fixing ability when a small quantity of light-sensitive materials are processed for a long time.
  • R' and R" each represent hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a nitrogen-containing heterocyclic ring; and n' represents 2 or 3.
  • the compounds represented by the formula (FA) disclosed in Japanese Provisional Patent Publication No. 295258/1989 can be synthesized by a common method as disclosed in U.S. Patents No. 3,335,161 and No. 3,260,718. These compounds represented by the above formula (FA) may be used alone or in combination of two or more.
  • each processing time is preferably 3 minutes 30 seconds or shorter, more preferably 10 seconds to 2 minutes 20 seconds, particularly preferably in the range of 20 seconds to 1 minute 20 seconds.
  • the processing time with the bleach-fixing solution is preferably 4 minutes or shorter, more preferably in the range of 10 seconds to 2 minutes 20 seconds.
  • the ratio of ammonium ion to whole cation in the processing solution having bleachability of the present invention is 50 mole % or less, the effect of the present invention can be exhibited more favorably.
  • Said ratio is more preferably 30 mole % or less, most preferably 10 mole % or less.
  • the nitrate according to the present invention includes specifically sodium nitrate, ammonium nitrate, potassium nitrate and lithium nitrate.
  • an alkylene group e.g. methylene group, ethylene group, trimethylene group and tetramethylene group
  • an alkenylene group e.g. ethenylene group
  • an alkynylene group e.g. ethylnylene group
  • a cycloalkylene group e.g. 1,4-cyclohexanediyl
  • an arylene group e.g. o-phenylene group and p-phenylene group
  • an alkanetriyl group e.g. 1,2,3-propanetriyl group
  • an allenetriyl group e.g. 1,2,4-benzenetriyl group
  • the n-valent group represented by A described above includes those having a substituent(s) (e.g. hydroxy group, an alkyl group and a halogen atom) such as 1,2-dihydroxyethylene, hydroxyethylene, 2-hydroxy-1,2,3-propanetriyl, methyl-p-phenylene, 1-hydroxy-2-chloroethylene, chloromethylene and chloroethenylene.
  • a substituent(s) e.g. hydroxy group, an alkyl group and a halogen atom
  • the compound represented by the formula (II) is preferably contained in an amount of 0.05 to 2.0 mole, more preferably 0.2 to 1.0 mole per liter of the processing solution having bleachability.
  • a buffer such as acetic acid may be used in combination within the range which does not impair the effect of the present invention. In the embodiment of the present invention, it is preferred that acetic acid is used in combination.
  • the problem caused by using acetic acid described above relates closely to the amount of acetic acid and pH. Even if the pH is in the range of the present invention, when the amount of acetic acid used is 0.6 mole/liter or less, preferably 0.5 mole/liter or less, the above problem is permissible. Further, in the points of buffering property and cost, acetic acid is advantageously used in combination.
  • a high boiling point solvent DNP
  • a yellow coupler Y-1
  • 100 g of a dye image stabilizer ST-1
  • 6.67 g of a dye image stabilizer ST-2
  • 0.67 g of an additive HQ-1
  • the solution was emulsified and dispersed in 220 ml of a 10 % gelatin aqueous solution containing 7 ml of a 20 % surfactant (SU-1) by using a ultrasonic homogenizer to prepare a yellow coupler dispersion.
  • the dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.
  • Second layer to seventh layer coating solutions were prepared in the same manner as the above first layer coating solution.
  • the pAg was controlled by the method disclosed in Japanese Provisional Patent Publication No. 45437/1984, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.
  • Solution A Sodium chloride 3.42 g Potassium bromide 0.03 g made up to 200 ml with addition of water.
  • Solution B Silver nitrate 10 g made up to 200 ml with addition of water.
  • Solution C Sodium chloride 102.7 g Potassium bromide 1.0 g made up to 600 ml with addition of water.
  • Solution D Silver nitrate 300 g made up to 600 ml with addition of water.
  • EMP-1 was chemically ripened at 50 °C for 90 minutes by using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-A).
  • Sodium thiosulfate 0.8 mg/mole of AgX Chloroauric acid 0.5 mg/mole of AgX Stabilizer (STAB-1) 6 x 10 -4 mole/mole of AgX Sensitizing dye (BS-1) 4 x 10 -4 mole/mole of AgX Sensitizing dye (BS-2) 1 x 10 -4 mole/mole of AgX
  • EMP-2 was chemically ripened by using the following compounds at 55 °C for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-B) Sodium thiosulfate 1.5 mg/mole of AgX Chloroauric acid 1.0 mg/mole of AgX Stabilizer (STAB-1) 6 x 10 -4 mole/mole of AgX Sensitizing dye (GS-1) 4 x 10 -4 mole/mole of AgX
  • EMP-3 was chemically ripened by using the following compounds at 60 °C for 90 minutes to obtain a red-sensitive silver halide emulsion (Em-C) Sodium thiosulfate 1.8 mg/mole of AgX Chloroauric acid 2.0 mg/mole of AgX Stabilizer (STAB-1) 6 x 10 -4 mole/mole of AgX Sensitizing dye (RS-1) 4 x 10 -4 mole/mole of AgX
  • Processing step Processing temperature Processing time Amount replenished (1) Color developing 35.0 ⁇ 0.3 °C 45 sec 162 ml/m 2 (2) Bleach-fixing 35.0 ⁇ 0.5 °C 45 sec 100 ml/m 2 (3) Stabilizing (3 tank cascade) 30 to 34 °C 90 sec 248 ml/m 2 (4) Drying 60 to 80 °C 30 sec Color developing solution Triethanolamine 10 g Diethylene glycol 6 g N,N-Diethylhydroxylamine 3.6 g Hydrazinodiacetic acid 5.0 g Potassium bromide 20 mg Potassium chloride 3.5 g Diethylenetriaminepentaacetic acid 5 g Potassium sulfite 0.3 g Color developing agent (3-methyl-4-amino-N-ethyl-N-( ⁇ -methanesulfonamidoethyl)aniline sul
  • Bleach-fixing solution Water 600 ml Ferric organic acid complex salt (shown in Table 2) 0.15 mole Thiosulfate 0.6 mole Sulfite 0.15 mole 1,3-Propanediaminetetraacetic acid 2 g adjusted to pH 7.0 by suitably using aqueous ammonia, potassium hydroxide or acetic acid, and made up to 1 liter in total.
  • ammonium salts and potassium salts of the above additives were used suitably for controlling the ratio (mole %) of ammonium ion in the bleach-fixing solution.
  • each concentration of the respective additives was increased by 1.25 times and each pH was made 5.8.
  • Stabilizing solution and replenishing solution Orthophenylphenol 0.1 g Uvitex MST (trade name) (produced by Ciba Geigy AG) 1.0 g ZnSO 4 ⁇ 7H 2 O 0.1 g Ammonium sulfite (40 % solution) 5.0 ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60 % solution) 3.0 g Ethylenediaminetetraacetic acid 1.5 g adjusted to pH 7.8 with aqueous ammonia or sulfuric acid, and made up to 1 liter with water.
  • the running processing was carried out by charging an automatic processor with the above color developing tank solution, bleach-fixing tank solution and stabilizing tank solution, and processing the above light-sensitive color photographic material while replenishing the above color developing replenishing solution, bleach-fixing replenishing solution and stabilizing replenishing solution through metering pumps at intervals of 3 minutes.
  • the running processing was carried out continuously until the amount of the bleach-fixing replenishing solution replenished to the bleach-fixing tank solution became a 3-fold volume of that of the bleach-fixing tank solution.
  • “1R” means that the bleach-fixing replenishing solution is replenished in an amount of a bleach-fixing tank volume.
  • EDTA ⁇ Fe represents a ferric complex salt of ethylenediaminetetraacetic acid
  • PDTA ⁇ Fe a ferric complex salt of 1,3-propylenediaminetetraacetic acid
  • DTPA ⁇ Fe a ferric complex salt of diethylenetriaminepentaacetic acid
  • NTA ⁇ Fe a ferric complex salt of nitrilotriacetic acid
  • (I-1) ⁇ Fe a ferric complex salt of Exemplary compound (1-I)
  • I-2) ⁇ Fe a ferric complex salt of Exemplary compound (I-2) and “(I-3) ⁇ Fe” a ferric complex salt of Exemplary compound (I-3), respectively.
  • amounts added to a light-sensitive silver halide photographic material are represented by gram per 1 m 2 of a light-sensitive material unless otherwise indicated. Further, silver halide and colloidal silver are represented by calculating them on silver.
  • a light-sensitive silver iodobromide color photographic material (color film) was prepared as described below.
  • First layer Antihalation layer Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Colored cyan coupler (CC-1) 0.02 g High boiling point solvent (Oil-1) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g
  • Second layer Intermediate layer Gelatin 1.3 g
  • Third layer Low sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (average grain size: 0.3 ⁇ m) 0.4 g Silver iodobromide emulsion (average grain size: 0.4 ⁇ m) 0.3 g Sensitizing dye (S-1) 3.0 x 10 -4 (mole/mole of silver) Sensitizing dye (S-2) 3.2 x 10 -4 (mol
  • the silver iodobromide emulsion used in the tenth layer was prepared as described below.
  • the silver iodobromide emulsion was prepared by the double jet method by using a monodispersed silver iodobromide grain having an average grain size of 0.33 ⁇ m (silver iodide content: 2 mole %) as a seed crystal.
  • the pAg and pH were controlled by using a potassium bromide aqueous solution and a 56 % acetic acid aqueous solution. After formation of grains, the grains were subjected to washing processing according to a conventional flocculation method. Then, the grains were added to gelatin and redispersed, and the pH and pAg were adjusted to 5.8 and 8.06, respectively, at 40 °C.
  • the emulsion obtained was a monodispersed emulsion containing an octahedral silver iodobromide grain having an average grain size of 0.80 ⁇ m, a variation coefficient of a grain size distribution of 12.4 % and a silver iodide content of 9.0 mole %.
  • G-1 Ossein gelatin 100.0 g 10 % by weight methanol solution of Compound-1 25.0 ml 28 %
  • Acetic acid aqueous solution 660.0 ml made up to 5000.0 ml with water.
  • (H-1) Ossein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g made up to 1030.5 ml with water.
  • (S-1) Silver nitrate 309.2 g 28 % Aqueous ammonia Equivalent amount made up to 1030.5 ml with water.
  • (H-2) Ossein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g made up to 3776.8 ml with water.
  • (S-2) Silver nitrate 1133.0 g 28 % Aqueous ammonia Equivalent amount made up to 3776.8 ml with water.
  • m and n each represent a natural number up to 30, which may be the same or different.
  • the above respective emulsions having different average grain sizes and silver iodide contents were prepared by changing an average grain size of a seed crystal, temperature, pAg, pH, flow rate, addition time and halide composition.
  • Either of them was a core/shell type monodispersed emulsion having a variation coefficient of a grain size distrubiton of 20 % or less.
  • the respective emulsions were applied to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and a sensitizing dye, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added.
  • the above light-sensitive silver iodobromide color photographic material was prepared so as to have an average silver iodide content of 8 mole %.
  • the light-sensitive material thus prepared was subjected to wedge exposure according to a conventional method, and then running procesing according to the following processing steps.
  • the running processing was cairred out continuously until the amount of the bleach-fixing replenishing solution became a 2-fold volume of a bleach-fixing tank volume (2R).
  • Processing step Processing time Processing temperature Amount replenished (per 135 size 24 EX1) (1) Color developing 3 min 15 sec 38 °C 20 ml (2) Bleach-fixing 3 min 15 sec 38 °C 30 ml (3) Stabilizing (3 tank cascade) 1 min 38 °C 40 ml (4) Drying 1 min 40 to 80 °C Color developing solution Potassium carbonate 30.0 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N-( ⁇ -hydroxylethyl)-aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g made up to 1 liter with addition of water, and adjusted to pH 10.00 with potassium hydroxide or 20 % sulfuric acid.
  • Bleach-fixing tank solution Water 600 ml Ferric organic acid complex salt (shown in Table 3) 0.4 mole Thiosulfate 2.0 mole Sulfite 0.15 mole 1,3-Propanediaminetetraacetic acid 2 g adjusted to pH 7.0 with aqueous ammonia or acetic acid, and made up to 1 liter in total.
  • ammonium salts and potassium salts of the above additives were used suitably for controlling the ratio (mole %) of ammonium ion in the bleach-fixing solution.
  • each concentration of the respective additives was increased by 1.07 times, and each pH was made 6.0.
  • (I-4) ⁇ Fe represents a ferric complex salt of Exemplary compound (I-4), and "(I-5) ⁇ Fe” a ferric complex salt of Exemplary compound (I-5).
  • ammonium salts and potassium salts of the above additives were used suitably for controlling the ratio (mole %) of ammonium ion in the bleaching solution.
  • magenta transmission density (green light density) at an unexposed portion of the film sample was measured, and at the same time, the residual silver quantity at an exposed portion was measured by a fluorescent X ray method.
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • HEDTA N-hydroxyethylethylene-diaminetriacetic acid
  • I-1 ethylenediaminetetraacetic acid
  • I-2 diethylenetriaminepentaacetic acid
  • HEDTA N-hydroxyethylethylene-diaminetriacetic acid
  • biodegradabilities were determined according to the 301C modified MITI Test (I) of OECD Chemical Product Test Guideline (adopted on May 12, 1981).
  • the biodegradability of the ferric complex salt of the chelating agent of the present invention was extremely good while the ferric complex salts of EDTA, DTPA and HEDTA were not hardly degraded, and therefore the chelating agent of the present invention is extremely preferred from the standpoint of protection of environments of the earth.
  • Example 5 Experiments were carried out in the same manner as in Example 3 except for adding nitrate (sodium nitrate) to the bleaching solutions used in Experiments No. 3 to No. 29 in Example 3 as shown in Table 5. The results are shown in Table 5.
  • nitrate sodium nitrate
  • Residual silver quantity (mg/100 cm 2 ) Magenta transmission density at unexposed portion 5-1 0 0.3 0.56 5-2 5 0.2 0.56 5-3 10 0.2 0.55 5-4 20 0.1 0.55 5-5 40 0 0.55 5-6 100 0.2 0.55
  • a processing solution having bleachability for a light-sensitive silver halide color photographic material which does not cause bleaching fog, enables rapid processing, has excellent biodegradability and environmental suitability, enables stable processing without causing sulfurization, and prevents yellow stain at an edge portion of a light-sensitive material.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (9)

  1. Behandlungsbad mit Bleichfähigkeit für lichtempfindliches farbphotographisches Silberhalogenid-Aufzeichnungsmaterial, umfassend mindestens ein Eisen(III)-komplexsalz einer Verbindung der folgenden Formel I:
    Figure 00720001
    worin bedeuten:
    A1, A2, A3 und A4, die gleich oder verschieden sein können, jeweils ein Wasserstoffatom, eine Hydroxylgruppe, -COOM, -PO3M2, -CH2OH oder eine Niedrigalkylgruppe mit 1 bis 4 Kohlenstoffatom(en), wobei mindestens einer der Reste A1, A2, A3 und A4 für -COOM oder -PO3M2 steht, und
    M, M1 und M2 jeweils ein Wasserstoffatom, eine Ammoniumgruppe, ein Natriumatom, ein Kaliumatom, ein Lithiumatom oder eine organische Ammoniumgruppe, ausgenommen Nitrilodiessig-mono-propionsäure,
    wobei das Verhältnis Ammoniumion/sämtliche Kationen im Behandlungsbad 50 Mol-% oder weniger beträgt.
  2. Bad nach Anspruch 1, wobei A1, A2, A3 und A4 jeweils für ein Wasserstoffatom, eine Hydroxylgruppe, -COOM, -PO3M2, -CH2OH, eine Methylgruppe, eine Ethylgruppe, eine Isopropylgruppe oder eine n-Propylgruppe stehen und M, M1 und M2 jeweils ein Wasserstoffatom, eine Ammoniumgruppe, ein Natriumatom, ein Kaliumatom, ein Lithiumatom, eine Trimethylammoniumgruppe oder eine Triethanolammoniumgruppe bedeuten.
  3. Bad nach Anspruch 1, wobei die Verbindung der Formel (I) aus einer Verbindung, die aus der Gruppe:
    Figure 00730001
    Figure 00730002
    Figure 00730003
    Figure 00730004
    Figure 00730005
    Figure 00740001
    Figure 00740002
    Figure 00740003
    und
    Figure 00740004
    ausgewählt ist, besteht
  4. Bad nach Anspruch 1, wobei die Verbindung der Formel (I) aus mindestens einer aus der Gruppe:
    Figure 00740005
    Figure 00740006
    Figure 00750001
    und
    Figure 00750002
    ausgewählten Verbindung besteht.
  5. Bad nach Anspruch 1, bei dem es sich um ein Bleichbad, ein Bleich/Fixierbad oder ein Bleich/Fixierbad zur Einbadentwicklung handelt.
  6. Bad nach Anspruch 1, in welchem das Eisen(III)komplexsalz in einer Menge von 0,1 - 2,0 mol/l enthalten ist.
  7. Bad nach Anspruch 1, enthaltend Salpetersäure oder ein Nitrat.
  8. Bad nach Anspruch 1, enthaltend eine Verbindung der folgenden Formel (II): A-(COOM1)n worin bedeuten:
    n eine ganze Zahl von 2 bis 5;
    A eine Einfachbindung oder eine n-wertige organische Gruppe und
    M1 ein Wasserstoffatom, ein Alkalimetallatom oder eine Ammoniumgruppe, wobei die n Reste M1 gleich oder verschieden sein können.
  9. Bad nach Anspruch 1, enthaltend HOOCCH=CHCOOH.
EP19920112723 1991-07-26 1992-07-24 Bleichlösung für farbfotografisches Verfahren Expired - Lifetime EP0534086B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP187164/91 1991-07-26
JP18716491 1991-07-26

Publications (2)

Publication Number Publication Date
EP0534086A1 EP0534086A1 (de) 1993-03-31
EP0534086B1 true EP0534086B1 (de) 1998-03-25

Family

ID=16201242

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920112723 Expired - Lifetime EP0534086B1 (de) 1991-07-26 1992-07-24 Bleichlösung für farbfotografisches Verfahren

Country Status (2)

Country Link
EP (1) EP0534086B1 (de)
DE (1) DE69224867T2 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3084119B2 (ja) * 1992-02-25 2000-09-04 コニカ株式会社 ハロゲン化銀写真感光材料の処理方法
JP3464540B2 (ja) * 1993-09-28 2003-11-10 イーストマン コダック カンパニー 三成分系第二鉄錯塩含有漂白一定着組成物
DE4337846A1 (de) * 1993-11-05 1995-05-11 Agfa Gevaert Ag Bleichmittel
US5521056A (en) * 1995-01-10 1996-05-28 Eastman Kodak Company Photographic peracid bleaching composition and processing method using ternary iron carboxylate complexes as catalysts in peracid bleaching solutions
US5582958A (en) * 1995-01-10 1996-12-10 Eastman Kodak Company Photographic bleaching composition and processing method using ternary iron carboxylate complexes as bleaching agents
JPH08314089A (ja) * 1995-05-12 1996-11-29 Fuji Photo Film Co Ltd 写真用金属キレート化合物、処理組成物及び処理方法
US5693456A (en) * 1996-02-01 1997-12-02 Eastman Kodak Company Photographic bleaching compositions and method of photographic processing using mixture of ferric complexes
GB2305510B (en) * 1995-09-18 1999-06-02 Eastman Kodak Co Improved photographic bleaching compositions and method of photographic processing using mixture of ferric complexes
US6520694B1 (en) 2002-01-18 2003-02-18 Eastman Kodak Company System and method for processing photographic film images

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU590557B2 (en) * 1985-04-25 1989-11-09 Konishiroku Photo Industry Co., Ltd. Processing method of light-sensitive silver halide color photographic material
EP0270217B1 (de) * 1986-10-08 1993-08-04 Konica Corporation Bleichfixierlösung mit einer guten Behandlungswirkung und Verfahren zur Behandlung eines lichtempfindlichen Materials, das diese verwendet
DE68927983T2 (de) * 1988-02-15 1997-10-09 Konishiroku Photo Ind Verfahren zur Verarbeitung und Bleichlösung für farbphotographische lichtempfindliche Silberhalogenidmaterialien
DE3919551A1 (de) * 1989-06-15 1990-12-20 Agfa Gevaert Ag Bleichbad
DE3939755A1 (de) * 1989-12-01 1991-06-06 Agfa Gevaert Ag Bleichbad
EP0468325B1 (de) * 1990-07-27 1995-11-22 Agfa-Gevaert AG Bleichbad

Also Published As

Publication number Publication date
DE69224867D1 (de) 1998-04-30
DE69224867T2 (de) 1998-09-17
EP0534086A1 (de) 1993-03-31

Similar Documents

Publication Publication Date Title
EP0532003B1 (de) Bleichfixier-Lösung für farbphotographisches, lichtempfindliches Silberhalogenidmaterial
US5635341A (en) Bleach or bleach-fixer and method for processing silver halide color photographic light-sensitive materials by use thereof
EP0534086B1 (de) Bleichlösung für farbfotografisches Verfahren
JP3208686B2 (ja) ハロゲン化銀写真用処理剤組成物及び処理方法
JP3116194B2 (ja) ハロゲン化銀写真感光材料用処理液
EP0466372B1 (de) Verfahren zur Verarbeitung farbphotographischer lichtempfindlicher Silberhalogenidmaterialien
US5260185A (en) Concentrated color developer composition for silver halide photographic light-sensitive materials
JPH07120894A (ja) 写真用処理組成物及び処理方法
JP3041739B2 (ja) ハロゲン化銀カラー写真感光材料用の漂白能を有する処理液
US5707787A (en) Processing solution for silver halide photographic light-sensitive materials
JP2949879B2 (ja) ハロゲン化銀カラー写真感光材料の処理方法
JP3049329B2 (ja) ハロゲン化銀写真感光材料用処理液
JP3086982B2 (ja) ハロゲン化銀カラー写真感光材料用の漂白能を有する処理液
WO2005111718A1 (en) Method for reducing sensitizing dye stain
JP3078149B2 (ja) ハロゲン化銀カラー写真感光材料の処理方法
JP3065775B2 (ja) ハロゲン化銀カラー写真感光材料の処理方法
JPH06175299A (ja) 写真用処理組成物及び処理方法
JPH06214352A (ja) 写真用処理組成物及び処理方法
EP0598216B1 (de) Verarbeitungsverfahren für farbphotographisches Silberhalogenidmaterial
CA1327905C (en) Method of processing silver halide color photographic material and photographic color developing composition
JP3172899B2 (ja) ハロゲン化銀写真感光材料用処理液及び漂白能を有する処理液
JP3855538B2 (ja) ハロゲン化銀写真感光材料用処理液及び印刷用ハロゲン化銀写真感光材料用減力液
JP3491233B2 (ja) ハロゲン化銀写真用処理剤組成物及び処理方法
JP3491232B2 (ja) ハロゲン化銀写真用処理剤組成物及び処理方法
JP2894642B2 (ja) ハロゲン化銀カラー写真感光材料の処理方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB NL

17P Request for examination filed

Effective date: 19930716

17Q First examination report despatched

Effective date: 19960718

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RBV Designated contracting states (corrected)

Designated state(s): DE GB

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE GB

REF Corresponds to:

Ref document number: 69224867

Country of ref document: DE

Date of ref document: 19980430

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20010718

Year of fee payment: 10

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020724

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20020724

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20040806

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060201