EP0514868A1 - Procédé de traitement d'un matériau photographique à l'halogénure d'argent et procédé de recyclage d'une solution photographique - Google Patents

Procédé de traitement d'un matériau photographique à l'halogénure d'argent et procédé de recyclage d'une solution photographique Download PDF

Info

Publication number
EP0514868A1
EP0514868A1 EP92108520A EP92108520A EP0514868A1 EP 0514868 A1 EP0514868 A1 EP 0514868A1 EP 92108520 A EP92108520 A EP 92108520A EP 92108520 A EP92108520 A EP 92108520A EP 0514868 A1 EP0514868 A1 EP 0514868A1
Authority
EP
European Patent Office
Prior art keywords
solution
silver
processing
mol
compound
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.)
Withdrawn
Application number
EP92108520A
Other languages
German (de)
English (en)
Inventor
Naoki Konica Corporation Takabayashi
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 EP0514868A1 publication Critical patent/EP0514868A1/fr
Withdrawn legal-status Critical Current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
    • G03C5/395—Regeneration of photographic processing agents other than developers; Replenishers therefor
    • G03C5/3952—Chemical, mechanical or thermal methods, e.g. oxidation, precipitation, centrifugation

Definitions

  • the present invention relates to a method for processing a silver halide light-sensitive material and a method for recycling a processing solution. More particularly, the present invention relates to a method for processing a silver halide light-sensitive material and a method for recycling a processing solution, which not only enable the recovery of silver from a processing solution but also prevent yellow stains even when the recycling is repeated many times.
  • Japanese Patent O.P.I. Publication No. 14849/1980 discloses a technique to utilize the so-called electrolytic method which comprises electrodialysis to recover silver and recycling processing solutions.
  • Japanese Patent O.P.I. Publication No. 69626/1981 discloses a method, in which an electrolyzer is partitioned into a cathode chamber and an anode chamber by a membrane of ion exchange resin, in order that the recovery of silver and the recycling of fixing solutions are carried out in the cathode chamber and the recycling of bleaching solutions is performed in the anode chamber.
  • the ion exchange resin membrane used as a diaphragm cannot last long and has to be replaced at least once a year, which needs an intricate replacing work and a high replacing cost owing to the expensiveness of ion exchange resin membranes.
  • the above electrolytic method requires additional processes such as analysis of composition of a processing solution and replenishment of shortages, because a processing solution after silver recovery differs in composition from that before silver recovery.
  • Japanese Patent Examined Publication No. 24822/1977 discloses a method for precipitating metal silver by reducing silver ions with dithionic acid at a pH of 8.5 to 10. This technique, however, cannot be practiced within doors because of an unpleasant odor generated. Moreover, the use of a fixing solution recycled by this method is liable to cause yellow stains.
  • the object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material and a method for recycling a processing solution, which can recycling simply and effectively a waste solution of a processing solution for silver halide photographic light-sensitive materials, and has no adverse effect on the photographic properties of a light-sensitive material when a recycled solution is reused as a processing solution or as a replenisher thereof.
  • the present inventors have made a close study to achieve the above object and found that a precipitating treatment, or a recycling treatment with a precipitant, can decrease the formation of stains and the fading of cyan dyes even when a light-sensitive material is processed even with a repeatedly recycled, fixing-capable processing solution.
  • the method for recycling a processing solution according to the invention is characterized in that a waste liquid of a silver halide light-sensitive material processing solution is reclaimed by removing silver compounds through a precipitating treatment, and that the reclaimed solution is then reused as a portion or all of the above processing solution or replenisher.
  • the method for processing a silver halide light-sensitive material according to the invention is characterized in that a waste liquid of a processing solution having a fixing capability is subjected to a precipitating treatment to remove silver compounds, and that the processing solution after the precipitating treatment is then reused as a portion or all of the above replenisher.
  • a compound of which the solubility product with silver ion is not more than 10 ⁇ 9 be used in the precipitating treatment, that a reducing agent be used in the precipitating treatment, that said reducing agent be selected from boron hydride salts, aluminium hydride salts and hydrosulfite salts, and that the surface tension of the above processing solution having a fixing capability be not more than 60 dyn/cm.
  • a silver halide light-sensitive material processing solution recovered for reuse may be any of a color developing solution, a bleaching solution, a fixing-capable processing solution, a stabilizing solution, a rinsing solution and a prewashing solution.
  • processing solutions bleach-fixing solution and fixing solution containing silver compounds in large amounts are preferred.
  • the reclaimed solution after silver removal may be used as a processing solution again, or as a replenisher in continuous processing.
  • the solution When the reclaimed solution is used as a replenisher, the solution may be used without any further adjustment, or shortages of chemicals estimated in advance may be added thereto as reactivators, or shortages of chemicals may be first confirmed by analyzing the component of the solution according to a usual method and then replenished thereto. In each case, the pH is adjusted as occasion demands.
  • the precipitating treatment according to the invention is carried out in the presence of a compound of which the solubility product with silver ion is not more than 10 ⁇ 9, preferably not more than 10 ⁇ 10, and more preferably not more than 10 ⁇ 11.
  • solubility product with silver ion is not more than 10 ⁇ 9
  • tetrazaindene derivatives 6-aminopurine derivatives
  • sulfur compounds are particularly preferred.
  • the solubility product used in the invention has the same meaning as the general meaning described in Kagaku Daijiten (Chemical Encyclopedia), 14th reduced-size edition, vol. 9, p. 399, Kyoritsu Shuppan, September 15, 1972, and shows a product of the concentration (gram ion/liter) of the compound and that of silver ion at 25°C when a sparingly water-soluble silver salt is formed between silver ions and the compound.
  • Usable tetrazaindene derivatives include those which are used as a stabilizer for silver halide photographic emulsion, and those represented by the following Formula I are particularly effective.
  • useful ones are those denoted by A-1 to A-8 from the 1st line on the 12th page to the 7th line on the 13th page of Japanese Patent O.P.I. Publication No. 252656/1991.
  • These compounds can be synthesized by a conventional method.
  • ones having a hydroxyl group at the 4-position are preferred, and ones having a hydroxyl group at the 4-position and an alkyl or aryl group at the 6-position are particularly preferred.
  • the above 6-aminopyrine derivative includes ones known as a stabilizer for photographic silver halide emulsions, and ones represented by the following Formula II are preferred.
  • tetrazaindene derivatives and 6-aminopyrine derivatives are used in an amount of preferably 0.5 to 500 g, especially 1.0 to 400 g per liter of processing solution.
  • the sulfur compounds effectively used in the invention include sulfides, polysulfides, thiourea compounds and other sulfur compounds.
  • Examples of the sulfide include alkali metal sulfides such as potassium sulfide, sodium sulfide and ammonium sulfide.
  • Examples of the polysulfide include those compounds which are described in Kogyo Kagaku Zasshi, vol. 63, No. 3, pp. 482-485 (1960). The addition amount of these sulfides or polysulfides is not particularly limited. But these compounds are used at a concentration not less than 1.0 time, preferably not less than 1.5 times, and especially not less than 2.0 times the concentration of silver ion contained in a waste processing solution.
  • Usable thiourea compounds are those represented by the following Formula III.
  • Typical examples thereof are, for example, dithiocarbamic acid compounds, polythiols, methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, allyl mercaptan, benzyl mercaptan, thioglycol, thiolactic acid and ⁇ -thiolpropionic acid.
  • ALM-648 a water-soluble heavy metal ion fixative made by Nippon Soda Co.
  • Oritol S made by Oriental Giken Kogyo Co.
  • a flocculant be used together with the above compound of which solubility product with silver ion is not more than 10 ⁇ 9, and it is particularly preferable that such a flocculant be a high-molecular flocculant.
  • High-molecular flocculants fall into the anionic type, the cationic type and the nonionic type.
  • Ones usable in the invention are described from the 1st line on the 21th page to the 8th line on the 22nd page of Japanese Patent O.P.I. Publication No. 252656/1991.
  • a flocculation aid such as kaolin, bentonite, acid clay, fly ash, sodium silicate, soda ash, slaked lime or wood powder.
  • a precipitate appears after the addition of the compound of which solubility product with silver ion is not more than 10 ⁇ 9, or after the addition of a flocculent under the necessity. Then, the precipitate is separated from a processing solution to recover the solution for recycling. There are the following three modes for recycling.
  • a filtering means there can be employed any of filtration using a filter medium (sand, filter paper, filter cloth, sintered glass or sintered metal), ultrafiltration (including use of flat membranes or hollow fiber membranes), reverse osmosis, and an activated carbon treatment.
  • a filter medium sand, filter paper, filter cloth, sintered glass or sintered metal
  • ultrafiltration including use of flat membranes or hollow fiber membranes
  • reverse osmosis and an activated carbon treatment.
  • a method which combines centrifugation and filtration can also be used.
  • dehydration of sludge may be performed by use of a conventional dehydration means, such as a precoat filter, instead of centrifugation.
  • reducing agents suitable for the invention there may be employed any reducing agent as long as it has a potential more negative than -0.50 V as a standard oxidation reduction potential.
  • the preferred reducing agent is one having a potential more negative than -10 V.
  • Preferable examples thereof include boron hydride salts (salts of BH4 ⁇ ), aluminium hydride salts (salts of AlH4 ⁇ ), hydrosulfite salts (salts of S2O82 ⁇ ) and Rongalite.
  • These compounds are used in amount of preferably 0.5 to 500 g and especially 1.0 to 400 g per liter of a processing solution.
  • the surface tension of the above fixing-capable processing solution is preferably not more than 60 dyn/cm, especially 8 to 55 dyn/cm. With a surface tension set as above, stains can be effectively prevented.
  • the surface tension can be measured by a general method described, for example, in K. Kitahara, S. Hayano and I. Hara, Method for Analyzing and Testing Surface Active Agents, Kodansha Co., March 1, 1982. In the invention, values of the surface tension measured at 20°C by such a general method are used.
  • One method for making the surface tension of a processing solution less than 60 dyn/cm at 20°C is to use a water-soluble surfactant.
  • Usable surfactants include those which are described, for example, in Japanese Patent O.P.I. Publication Nos. 40824/1981, 116031/1981, 130744/1981, 199346/1983, 17551/1984, 126533/1984, 50148/1986, 154153/1989, 316743/1989 and Japanese Patent Application No. 341357/1989.
  • the fixing-capable processing solution contain the optical whitening agent described paragraph Nos. 0038 to 0042 of Japanese Patent Application No. 59466/1991.
  • the fixing-capable processing solution is not particularly limited except the above composition and may contain additives similar to those used in the bleach-fixing solution or the fixing solution described in Japanese Patent Application No. 51226/1990.
  • the bleaching solution, the color developing solution and the stabilizing solution may be analogous to those described in Japanese Patent Application No. 51226/1990, or may be similar to the bleaching solution, the color developing solution and the stabilizing solution described in Japanese Patent O.P.I. Publication No. 48548/1988.
  • the invention can be applied to a light-sensitive material to be processed by the so-called coupler-in-emulsion process as well as a light-sensitive material to be processed by the so-called coupler-in-developer process, and can be applied to any of color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TVs and color reversal paper.
  • a multilayered color light-sensitive material was prepared by forming the layers shown below on the titanium-oxide-containing side of a paper support coated with polyethylene on one side and with titanium-oxide-containing polyethylene on the other side.
  • the coating solutions were prepared as follows:
  • a mixture of 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), 6.67 g of dye image stabilizer (ST-2), 0.67 g of additive (HQ-1) and 6.67 g of high boiling solvent (DNP) was dissolved in 60 ml of ethyl acetate.
  • the solution was dispersed with a supersonic homogenizer in 220 ml of 10% gelatin solution containing 7 ml of 20% surfactant (SU-1) solution to prepare a yellow coupler dispersion.
  • the dispersion was then mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions, so that the 1st coating solution was obtained.
  • the 2nd to the 7th coating solutions were prepared in a similar manner as in the above.
  • hardener (H-1) was added to the 2nd and 4th layer and hardener (H-2) to the 7th layer.
  • Surfactants (SU-1) and (SU-2) were employed as coating aids to adjust the surface tension.
  • the layer configuration of the color light-sensitive material was as follows:
  • the control of the pAg was carried out by the method disclosed in Japanese Patent O.P.I. Publication No. 45437/1984, and that of the pH was made by use of sulfuric acid or an aqueous solution of sodium hydroxide.
  • Solution A Sodium chloride 3.42 g Sodium bromide 0.03 g Water was added to make 200 ml Solution B
  • Silver nitrate 10 g Water was added to make 200 ml Solution
  • the emulsion, EMP-1, prepared as above was comprised of monodispersed cubical grains having an average grain size of 0.85 ⁇ m, a grain size distribution variation coefficient ( ⁇ /r) of 0.07 and a silver chloride content of 99.5 mol%.
  • EMP-1 was chemically sensitized at 50°C for 90 minutes using the following chemicals to obtain a blue-sensitive silver halide emulsion, Em-B.
  • Sodium thiosulfate 0.8 mg/mol Ag X Chloroauric acid 0.5 mg/mol Ag X Stabilizer (STAB-1) 6 ⁇ 10-4 mol/mol Ag X Sensitizing dye (BS-1) 4 ⁇ 10-4 mol/mol Ag X Sensitizing dye (BS-2) 1 ⁇ 10-4 mol/mol Ag X
  • EM-2 An monodispersed cubical silver halide emulsion, EM-2, was prepared in the same procedure as in EMP-1, except that the addition time of solutions A and B and that of solutions C and D were changed.
  • EM-2 was comprised of grains having an average grain size of 0.43 ⁇ m, a grain size distribution variation coefficient ( ⁇ /r) of 0.08 and a silver chloride content of 99.5 mol%.
  • EMP-2 was chemically sensitized at 55°C for 120 minutes using the following chemicals to obtain a green-sensitive silver halide emulsion, Em-G.
  • Sodium thiosulfate 1.5 mg/mol Ag X
  • Chloroauric acid 1.0 mg/mol Ag X Stabilizer (STAB-1) 6 ⁇ 10-4 mol/mol Ag X Sensitizing dye (GS-1) 4 ⁇ 10-4 mol/mol Ag X
  • EM-3 An monodispersed cubical silver halide emulsion, EM-3, was prepared in the same procedure as in EMP-1, except that the addition time of solutions A and B and that of solutions C and D were changed.
  • EM-3 was comprised of grains having an average grain size of 0.50 ⁇ m, a grain size distribution variation coefficient ( ⁇ /r) of 0.08 and a silver chloride content of 99.5 mol%.
  • EMP-3 was chemically sensitized at 60°C for 90 minutes using the following chemicals to obtain a red-sensitive silver halide emulsion, Em-R.
  • Sodium thiosulfate 1.8 mg/mol Ag X
  • Chloroauric acid 2.0 mg/mol Ag X Stabilizer (STAB-1) 6 ⁇ 10 ⁇ 4 mol/mol Ag X Sensitizing dye (BS-1) 4 ⁇ 10 ⁇ 4 mol/mol Ag X
  • the light-sensitive material samples prepared as above were exposed according to a usual manner and processed by use of the following processes and processing solutions, then the waste processing solutions were reclaimed and recycled as described later.
  • the pH is adjusted to 5.4 with aqueous ammonia or glacial acetic acid, and water is added to make 1 liter.
  • Optical whitening agent (Uvitex made by Ciba Geigy) 1.0 g ZnSO4 ⁇ 7H2O 0.15 g Ammonium sulfite (40% solution) 5.0 ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60% solution) 2.5 g Ethylenediaminetetracetic acid 1.5 g
  • the pH is adjusted to 7.8 with aqueous ammonia or sulfuric acid, and water is added to make 1 liter.
  • processing was continuously run: firstly, an automatic processor was filled with the above color developer tank solution, bleach-fixer tank solution and stabilizer tank solution, and then the above color paper was continuously processed, during which the above color developer replenisher, bleach-fixer replenisher and stabilizer replenisher were fed thereto at 3-minute intervals through a volume measuring pump.
  • the amount replenished to the color developing tank was 100 ml per square meter of the color paper, that replenished to the bleach-fixing tank was 80 ml per square meter, and that replenished to the stabilizing tank was 250 ml per square meter.
  • This continuous processing was run at a rate of 0.05 R per day till the amount of the color developer replenisher fed to the color developing tank reached three times the volume of the color developer tank solution.
  • 1R means that the amount of the color developer replenisher fed reaches the capacity of the color developing tank.
  • the yellow stain was determined by measuring the blue light reflection density of the unexposed portion of the processed light-sensitive material using a PDA-65 made by Konica Corp.
  • ⁇ D R indicating fading of the cyan dye
  • the following silver halide color photographic light-sensitive material was prepared.
  • a triacethylcellulose film support was subbed on one side, then the other side (backside) was coated with the following layers in sequence.
  • Backside 1st layer Alumina sol AS-100 aluminium oxide made by Nissan Chemical Co.
  • Backside 2nd layer Diacethylcellulose 100 mg Stearic acid 10 mg Silica fine particles (average size: 0.2 ⁇ m) 50 mg
  • a-1 multilayered color photographic light-sensitive material
  • 1st layer antihalation layer (HC) Black colloidal silver 0.15 g UV absorbent (UV-1) 0.22 g Colored cyan coupler (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g High boiling solvent (Oil-2) 0.20 g Gelatin 1.6 g 2nd layer: intermediate layer (IL-1) Gelatin 1.3 g 3rd layer: low-speed red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (average grain size: 0.3 ⁇ m) 0.6 g Silver iodobromide emulsion (average grain size: 0.4 ⁇ m) 0.3 g Sensitizing dye (S-1) 3.2 ⁇ 10 ⁇ 4 (mol/Ag mol) Sensitizing dye (S-2) 3.2 ⁇ 10 ⁇ 4 (mol/Ag mol)
  • the above color light-sensitive material further contains compounds Su-1 and Su-2, viscosity regulator, hardeners H-1 and H-2, stabilizer ST-1, antifoggants AF-1 and AF-2 (weight average molecular weights were 10,000 and 1,100,000, respectively), dyes AI-1 and AI-2, and compound DI-1 (9.4 mg/m2).
  • the silver iodobromide emulsion used in the 10th layer was prepared by the double jet method, using monodispersed silver iodobromide grains with an average grain size of 0.33 ⁇ m and a silver iodide content of 2 mol% as seed grains.
  • the pAg and pH were controlled by use of a potassium bromide aqueous solution and a 56% acetic acid aqueous solution. After grains were formed, these were desalted by a conventional flocculation method, then dispersed again with the addition of gelatin, and the emulsion obtained was adjusted to pH 5.8 and pAg 8.06 at 40°C.
  • This emulsion was comprised of monodispersed octahedral silver iodobromide grains having an average grain size of 0.80 ⁇ m, a grain size distribution extent of 12.4%, and a silver iodide content of 8.5 mol.
  • Solution G-1 Ossein gelatin 100.0 g 10% Methanol solution of compound-1 25.0 ml 28% Aqueous ammonia 440.0 ml 56% Acetic acid aqueous solution 660.0 ml Water is added to make 5000.0 ml Solution H-1 Ossein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Water is added to make 1030.5 ml Solution S-1 Silver nitrate 309.2 g 28% Aqueous ammonia equivalent Water is added to make 1030.5 ml Solution H-2 Ossein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Water is added to make 3776.8 ml Solution S-2 Silver nitrate 1133.0 g 28% Aqueous ammonia equivalent Water is added to make 3776.8 ml
  • Average molecular weight The other emulsions different in average grain size and silver iodide content were prepared likewise by varying the average grain size of seed grains, temperature, pAg, pH, flow, addition time and halide composition.
  • any of those emulsions was a monodispersed emulsion comprised of core/shell type grains having a grain size distribution extent less than 20%.
  • Each emulsion was subjected to chemical ripening under optimum conditions in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and then sensitizing dyes, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added thereto.
  • the light-sensitive materials prepared as above, Gold 100 made by Eastman Kodak Co. and Super-HR-II100 made by Fuji Photo Film Co. were processed at a ratio of 2:1:2 using the following processes and processing solutions. The processing was continued for 1 month at a daily processing amount of 20 rolls (24 exposures) of film.
  • Processing conditions Process Processing time Processing temp Amount (ml/m2) replenished* Color developing 3 min 15 sec 38°C 570 Bleaching 45 sec 38°C 155 Fixing 1 min 45 sec 38°C 500 Stabilizing** 1 min 30 sec 38°C 775 Drying 1 min 40 to 70°C - Notes * The amount replenished is shown by values per m2 of light-sensitive material ** Stabilizing was performed in a 3-tank countercurrent system, in which the replenisher was fed to the final tank and the overflow was allowed to flow into the preceding tank.
  • Ammonium ferric 1,3-diaminopropanetetracetate 0.35 mol Disodium ethylenediaminetetracetate 2 g Ammonium bromide 150 g Glacial acetic acid 38 ml Ammonium nitrate 40 g Ammonium 1,3-diaminopropanetetracetate 2.0 g
  • Ammonium ferric 1,3-diaminopropanetetracetate 0.40 mol Disodium ethylenediaminetetracetate 2 g Ammonium bromide 170 g Ammonium 1,3-diaminopropanetetracetate 2.0 g Ammonium nitrate 50 g Glacial acetic acid 61 ml
  • Water is added to make 1 liter, and the pH is adjusted to 7.0 with potassium hydroxide or 50 % sulfuric acid.
  • Example 1 Each sample was subjected to continuous processing in the same manner as in Example 1. Then, the fixing solution was processed and evaluated in the same manner as in Example 1. In the evaluation, the blue light density at the unexposed portion was determined by subtracting the mask density. The evaluation results were much the same as those obtained in Example 1.
  • Example 2 The same procedure as in Example 1 was repeated, except that 1 g/l of an optical whitening agent was contained in the bleach-fixing solution to evaluate the effect of preventing yellow stains.
  • optical whitening agent the following E-4, E-24, E-34, E-35, E-36 and E-44 were used.
  • Example 2 The procedure of Example 2 was repeated, except that the ammonium thiosulfate in the fixing solution was replaced by sodium thiosulfate of the same molar concentration, and that the ammonium thiocyanate was also replaced by potassium thiocyanate of the same molar concentration.
  • Table 2 Compound added (1 ⁇ 10 ⁇ 1 mol/l) Surface tension (dyn/cm) Transmitted blue light density at unexposed portion after subtracting mask density NaVO3 (solubility product: 5 ⁇ 10 ⁇ 7) 65 0.11 60 0.09 55 0.04 40 0.02 30 0.02 Sodium dithiocarbamate (solubility product: ca.
  • Emulsion A so obtained was comprised of monodispersed cubical grains having an average grain size of 0.3 ⁇ m.
  • Emulsion A was subjected to chemical sensitization under optimum conditions using sodium thiosulfate. After stopping the chemical sensitization by adding the following inhibitor SB-1, the emulsion was subjected to spectral sensitization under optimum conditions using the following sensitizing dyes A and B.
  • a light-sensitive material sample was prepared by simultaneously coating the following emulsion layer and protective layer on a 200- ⁇ m thick paper support laminated with polyethylene on both sides.
  • Process Temperature Time Amount replenished Developing 33°C 45 sec 200 ml/m2 Fixing 31°C 45 sec 200 ml/m2 Stabilizing 31°C 1st tank 30 sec* 250 ml/m2 2nd tank 30 sec 3rd tank 30 sec Drying 50 to 70°C 70 sec - *
  • Process Temperature Time Amount replenished Developing 33°C 45 sec 200 ml/m2 Fixing 31°C 45 sec 200 ml/m2 Stabilizing 31°C 1st tank 30 sec* 250 ml/m2 2nd tank 30 sec 3rd tank 30 sec Drying 50 to 70°C 70 sec - *
  • a 3-tank countercurrent system was used by feeding a replenisher to the 3rd tank.
  • Water is added to make 1 liter, and the pH is adjusted to 10.2 with acetic acid and caustic soda.
  • Water is added to make 1 liter, and the pH is adjusted to 10.5 with acetic acid and caustic soda.
  • Water is added to make 1 liter, and the pH is adjusted to 5.0 with sulfuric acid and aqueous ammonia.
  • Water is added to make 1 liter, and the pH is adjusted to 8.0 with sulfuric acid and aqueous ammonia.
  • Example 3 After completion of the continuous processing, the fixing solution was recycled as in Example 1, and the formation of yellow stains was observed. The results are shown in Table 3 As apparent from Table 3, the results were much the same as in Example 1 and the formation of yellow stains was limited to a small extent.
  • Table 3 Compound added (1x10 ⁇ 1 mol/l) Surface tension dyn/cm Yellow stain Remarks Silver recovery of (Experiment 1) 50 0.05 Comparison NaVO3 (solubility product: 5 ⁇ 10 ⁇ 7) 65 0.03 Invention 60 0.02 55 0.01 40 0.01 30 0.01 Sodium dithiocarbamate (solubility product: ca.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP92108520A 1991-05-24 1992-05-20 Procédé de traitement d'un matériau photographique à l'halogénure d'argent et procédé de recyclage d'une solution photographique Withdrawn EP0514868A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP149791/91 1991-05-24
JP14979191A JPH04347852A (ja) 1991-05-24 1991-05-24 ハロゲン化銀写真感光材料の処理方法及び処理液の再生使用方法

Publications (1)

Publication Number Publication Date
EP0514868A1 true EP0514868A1 (fr) 1992-11-25

Family

ID=15482798

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92108520A Withdrawn EP0514868A1 (fr) 1991-05-24 1992-05-20 Procédé de traitement d'un matériau photographique à l'halogénure d'argent et procédé de recyclage d'une solution photographique

Country Status (2)

Country Link
EP (1) EP0514868A1 (fr)
JP (1) JPH04347852A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0717314A1 (fr) * 1994-12-17 1996-06-19 Kodak Limited Dispositif et méthode pour le blanchiment de matériaux photographiques en utilisant le peroxyde
EP0863138A1 (fr) * 1997-03-05 1998-09-09 Eastman Kodak Company Procédé de récupération de mercapto-s-triazine à partir d'un précipite avec de l'argent
US5884116A (en) * 1996-06-07 1999-03-16 Eastman Kodak Company Photographic processing apparatus

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2041128A1 (de) * 1970-08-19 1972-02-24 Agfa Gevaert Ag Verfahren zur kontinuierlichen Entsilberung von Bleichfixierbaedern und Fixierbaedern
FR2189776A1 (en) * 1972-06-21 1974-01-25 Ilford Ltd Regeneration of bleach-fix solns - using mercapto-/seleno-tri-/tetra-azole cpd, for easily filtered silver complex
US3832453A (en) * 1971-11-23 1974-08-27 Eastman Kodak Co Recovery of silver from photographic processing solutions
DD204169A1 (de) * 1981-12-02 1983-11-16 Galgon Hans Ulrich Verfahren zur regenerierung von fixierbaedern
JPS6150141A (ja) * 1984-08-19 1986-03-12 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
JPS61223737A (ja) * 1985-03-28 1986-10-04 Konishiroku Photo Ind Co Ltd 写真処理液の脱銀方法及び写真処理機

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2041128A1 (de) * 1970-08-19 1972-02-24 Agfa Gevaert Ag Verfahren zur kontinuierlichen Entsilberung von Bleichfixierbaedern und Fixierbaedern
US3832453A (en) * 1971-11-23 1974-08-27 Eastman Kodak Co Recovery of silver from photographic processing solutions
FR2189776A1 (en) * 1972-06-21 1974-01-25 Ilford Ltd Regeneration of bleach-fix solns - using mercapto-/seleno-tri-/tetra-azole cpd, for easily filtered silver complex
DD204169A1 (de) * 1981-12-02 1983-11-16 Galgon Hans Ulrich Verfahren zur regenerierung von fixierbaedern
JPS6150141A (ja) * 1984-08-19 1986-03-12 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
JPS61223737A (ja) * 1985-03-28 1986-10-04 Konishiroku Photo Ind Co Ltd 写真処理液の脱銀方法及び写真処理機

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
FERNSEH UND KINO TECHNIK. vol. 38, no. 9, September 1984, BERLIN DE pages 369 - 376; GERHARD BERGFRIED: 'Neue Recycling-Verfahren in der Filmentwicklung' *
JOURNAL OF APPLIED PHOTOGRAPHIC ENGINEERING. vol. 5, no. 3, 1979, SPRINGFIELD US pages 144 - 147; M.M.COOK ET AL: 'Use of sodium borohydride to control heavy metal discharge in the photographic industry' *
PATENT ABSTRACTS OF JAPAN vol. 10, no. 210 (P-479)(2266) 23 July 1986 & JP-A-61 050 141 ( KONISHIROKU PHOTO-INDUSTRY CO. LTD. ) 12 March 1986 *
PATENT ABSTRACTS OF JAPAN vol. 11, no. 58 (P-550)(2505) 21 February 1987 & JP-A-61 223 737 ( KONISHIROKU PHOTO-INDUSTRY CO. LTD. ) 4 October 1986 *
SMPTE JOURNAL. vol. 85, April 1976, US pages 206 - 216; ROBERT L. LAPERLE: 'The removal of metals from photographic effluent by sodium sulfide precipitation' *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0717314A1 (fr) * 1994-12-17 1996-06-19 Kodak Limited Dispositif et méthode pour le blanchiment de matériaux photographiques en utilisant le peroxyde
US5578428A (en) * 1994-12-17 1996-11-26 Eastman Kodak Company Process and apparatus for the peroxide bleaching of photographic materials
US5884116A (en) * 1996-06-07 1999-03-16 Eastman Kodak Company Photographic processing apparatus
EP0863138A1 (fr) * 1997-03-05 1998-09-09 Eastman Kodak Company Procédé de récupération de mercapto-s-triazine à partir d'un précipite avec de l'argent

Also Published As

Publication number Publication date
JPH04347852A (ja) 1992-12-03

Similar Documents

Publication Publication Date Title
EP0329088B1 (fr) Procédé de traitement et solution de blanchiment pour des matériaux photographiques couleur à l'halogénure d'argent sensible à la lumière
EP0186169B1 (fr) Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent sensible à la lumière
DE3739025C2 (de) Verfahren zur kontinuierlichen Behandlung eines photographischen Farbumkehrmaterials
EP0189191A2 (fr) Méthode de traitement d'un matériau photosensible couleur à l'halogénure d'argent
US5055382A (en) Bleach-fix regeneration kit and use thereof in photographic processing
EP0514868A1 (fr) Procédé de traitement d'un matériau photographique à l'halogénure d'argent et procédé de recyclage d'une solution photographique
US5736308A (en) Color photographic silver halide material
EP0466372B1 (fr) Procédé de traitement des matériaux photosensibles pour la photographie en couleur
EP0466510A1 (fr) Solution de traitement et procédé de traitement d'un matériau à l'halogénure d'argent pour la photographie en couleur
EP0727702A2 (fr) Elément photographique comportant une couche d'amélioration de la couleur située entre une couche d'émulsion et une couche contenant un composé suceptible de capturer un développateur oxydé
DE69130625T2 (de) Verarbeitungsverfahren für farbphotographisches Silberhalogenidmaterial
US6682880B2 (en) Method for preparing kit part for bleach-fixing solution and kit for bleaching solution for use in silver halide color photographic material and method for processing silver halide color photographic material
JP2867050B2 (ja) ハロゲン化銀カラー写真感光材料の処理方法
JPH03252656A (ja) 写真処理廃液からの銀回収方法
JPH03192351A (ja) ハロゲン化銀カラー写真感光材料の処理方法
JPH0233142A (ja) ハロゲン化銀カラー写真感光材料の処理方法
US20050244762A1 (en) Method for reducing sensitizing dye stain
US5866308A (en) Production of a color photographic image
JP2673699B2 (ja) ハロゲン化銀写真感光材料の処理方法及び装置並びに通電装置
EP0758763A1 (fr) Procédé de traitement de matériaux photographiques à l'halogénure d'argent
EP0465076A1 (fr) Procédé de traitement des matériaux photographiques à l'halogénure d'argent
JPH0219844A (ja) ハロゲン化銀カラー写真感光材料の処理方法
EP0617324A1 (fr) Méthode de traitement de matériaux photographiques à base d'halogénure d'argent
JPH0876331A (ja) ハロゲン化銀写真感光材料用処理剤組成物および処理方法
JPH04194931A (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

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19930526