EP0409065B1 - Verfahren zur Verarbeitung von photoempfindlichen Silberhalogenidmaterialien - Google Patents

Verfahren zur Verarbeitung von photoempfindlichen Silberhalogenidmaterialien Download PDF

Info

Publication number
EP0409065B1
EP0409065B1 EP19900113278 EP90113278A EP0409065B1 EP 0409065 B1 EP0409065 B1 EP 0409065B1 EP 19900113278 EP19900113278 EP 19900113278 EP 90113278 A EP90113278 A EP 90113278A EP 0409065 B1 EP0409065 B1 EP 0409065B1
Authority
EP
European Patent Office
Prior art keywords
processing
reverse osmosis
water
silver halide
bath
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
EP19900113278
Other languages
English (en)
French (fr)
Other versions
EP0409065A1 (de
Inventor
Akira Abe
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.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
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 Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0409065A1 publication Critical patent/EP0409065A1/de
Application granted granted Critical
Publication of EP0409065B1 publication Critical patent/EP0409065B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • G03C5/3956—Microseparation techniques using membranes, e.g. reverse osmosis, ion exchange, resins, active charcoal
    • 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

Definitions

  • This invention concerns a method of processing silver halide photographic materials, and in particular it concerns a method of processing silver halide photographic materials in such a way that the washing water and/or stabilizing bath is regenerated by a reverse osmosis membrane treatment.
  • silver halide color photographic materials are subjected to processes such as color development, bleach-fixing and water washing.
  • Silver halide color reversal photographic materials are subjected to black-and-white development processing prior to color development. Furthermore, black-and-white silver halide photographic materials are, after imagewise exposure, subjected to processes such as black-and-white development, fixing and water washing.
  • JP-A-60-241053 describes a method of processing in which silver halide color photographic materials are color developed, processed in a processing bath which has a fixing capacity and then subjected to a stabilizing process essentially without water washing, wherein the stabilizer solution is treated by means of a reverse osmosis membrane.
  • JP-A-62-254151 describes a method of processing silver halide color photographic materials in which, when water washing and/or stabilizing is carried out using a multi-stage counter-flow system after processing a silver halide color photographic material in a bath which has a fixing function, the overflow from the water washing tank and/or stabilizing tank is introduced into a storage tank, and the solution in the storage tank is treated with a reverse osmosis membrane.
  • the solution permeating through the reverse osmosis membrane returns to the water washing tank and/or the stabilizing tank, and the concentrated solution returns to the storage tank in order to reduce the amount of concentrated solution which is expelled from the reverse osmosis membrane treatment apparatus and to minimize replenishment of the washing water.
  • the amount of water used in the washing and/or stabilizing process can be greatly reduced when this method is used, and the processing can be accomplished without increased yellow staining even though the amount of water which is being used is reduced.
  • the reverse osmosis membrane treatment of washing water and stabilizing solution is very useful for greatly reducing amount of washing water or stabilizing solution.
  • concentration in the processed photosensitive material when the concentration in the final bath exceeds 0.0003 mol/liter.
  • silver contamination of the photosensitive material due to the formation of silver sulfide, for example also occurs because of an increased silver concentration in the final bath.
  • the methods of processing described above all involve reusing the expelled washing water or expelled stabilizing solution by means of a reverse osmosis treatment and are such that uncontaminated washing water or stabilizing solution is obtained.
  • An effective reverse osmosis membrane which produces washing water or stabilizing solution which is of high purity can be used for the reverse osmosis membrane treatment.
  • the valuable components in the washing water are recovered and returned to the bleach-fixing tank, so a reverse osmosis membrane of the type which passes virtually no solute is used.
  • Reverse osmosis membranes of this type have fine pores, so the operating pressure is high.
  • the operating pressure in the treatment apparatus described in the JP-A-58-105150 is from 40 to 50 kg/cm2
  • the operating pressure in the method of treatment described in JP-A-60-241053 where stabilizing solution is being subjected to a reverse osmosis membrane treatment is 55 kg/cm2.
  • Expelled washing water or stabilizing solution can be reused to a high degree when reverse osmosis membranes which have such fine pores are used.
  • a high degree of reuse when silver halide color photographic materials are washed, for example, in water or solution- from which all the salts, etc. have been removed, the problem of reticulation occurs depending on changes in humidity in storage after processing. This produces fine crinkly wrinkles in the surface of the emulsion film and results in a dulling of the luster. Consequently, the image quality is greatly reduced.
  • an increase in the extent of cyan dye fading is another adverse effect.
  • the object of the present invention is to provide a method of processing silver halide color photographic materials with a sufficiently high rate of water permeation in which the EDTA-Fe which is the cause of yellow staining is completely removed while a small residual NH4 salt content is maintained in the permeated water.
  • the present invention provides a method of processing silver halide photographic materials comprising processing, an imagewise-exposed silver halide photographic material in a bath which has a fixing ability and then processing the photographic material in at least one of a water washing bath and a stabilizing bath, wherein at least one of washing water and stabilizing solution, from at least one of the water washing bath and stabilizing bath, respectively, is subjected to a reverse osmosis treatment using a reverse osmosis membrane, characterized in that said reverse osmosis membrane removes NaCl in an amount of 30% to 90% when treating a 1000 ppm NaCl solution at 25° C under a feed pressure of 7 kg/cm2.
  • FIG. 1 is a diagram of the processing apparatus as used in Example 1
  • Figure 2 is a diagram of the processing apparatus as used in Example 2, both of which are described below, wherein: 1 and 21 are color development tanks (D), 2 is a bleach-fixing tank (BF); 3 and 25 are first water washing tanks (W1); 4 and 26 are second water washing tanks (W2); 5 and 27 are third water washing tanks (W3); 6 and 29 are washing water; 7, 8, 30, 31 and 38 are connecting pipes; 9, 32, and 39 are overflow streams, 10 and 33 are flow pipes for removing washing water; 11 and 34 are pumps (P); 12 and 35 are reverse osmosis membrane module; 13,14, 36 and 37 are connecting pipes; 15, 16 and 17 are valves; 22 is a bleach tank (B); 23 is a first fixing tank (F1); 24 is a second fixing tank (F2); and 28 is a stabilizing tank (S);
  • D color development tanks
  • BF bleach-fixing tank
  • 3 and 25 are first water washing tanks (W1)
  • 4 and 26
  • This method of processing is especially effective for the processing of silver halide color photographic materials where a color development process and a bleaching process are involved.
  • Reverse osmosis membranes which have various fine pore sizes have permeation characteristics which are based on the fine pores.
  • the characteristics of reverse osmosis membranes have been represented by the extent of the removal of NaCl on permeating an NaCl solution and this has come to be used as a standard. There is some correlation between the amount of NaCl removed and the state of the fine pores of a membrane.
  • the present invention uses a reverse osmosis membrane which removes NaCl in an amount of about 30% to about 90% under conditions such as those described earlier. Those membranes which remove NaCl in an amount of from about 40% to about 85% are preferred, and those which remove NaCl in an amount of from about 50% to about 80% are especially desirable. Also, those membranes which remove EDTA-Fe(III) in an amount at least 90% are preferred.
  • the solution of a final water wash tank or stabilizing tank contains not more than 0.0003 mol/l of EDTA-Fe(III), preferably not more than 0.0002 mol/l and the most preferably not more than 0.0001 mol/l.
  • a concentration of ammonium salt in permeated water is preferably from 6.7 x 10 ⁇ 4 to 3.4 x 10 ⁇ 3 mol/l.
  • These reverse osmosis membranes are composed of a porous polysulfone film as a substrate to which an aromatic polyamide film of 0.2 »m in thickness having anionic charge are intimately attached as a separating film.
  • the membranes having such a constitution as above is called as a composite film.
  • a NaCl removal of DRA-40®, DRA-80® and DRA-89® is about 45%, about 80% and about 85% respectively, when 1000 ppm of aqueous NaCl solution is fed under pressure of 7 kg/cm2.
  • these membranes are made of polymer, the membrans show superior anti-bacteria properties comparing with those made of cellulose acetate which are liable to be suffered from bacterial. In view of the foregoings, these membranes are remarkably advantageous in regenerating a waste solution in photographic processings.
  • SU-200® membrane is also made of aromatic polyamide separating film and polysulfone substrate and shows NaCl removal of about 60% which is made by the Toray Co.
  • Suitable reverse osmosis membranes include cellulose acetate membranes, ethyl cellulose/polyacrylic acid membranes, polyacrylonitrile membranes, poly(vinylene carbonate) membranes, polyether-based membranes, crosslinked aramid-based composite membranes, and crosslinked polyamide-based composite membranes.
  • the composite membrane is composed of a porous polymer substrate, with which a thin polymer film having solute separating function is integrated.
  • a porous polymer substrate with which a thin polymer film having solute separating function is integrated.
  • Preferable composite membrane according to the present invention includes those having a substrate of porous polysulfone film which is reinforced with polyester non-woven fabric, and a polymer thin film formed by plasma polymerization or interfacial polymerization, preferably with further effective crosslinking reaction.
  • Example of the thin film includes aromatic polyamide and aromatic polyimide, having 0.1 to 0.4 »m in thickness, preferably 0.15 to 0.25 »m.
  • Reverse osmosis membranes with a spiral, tubular, hollow fiber, pleated or rod type construction can be used.
  • the membrane may be a single layer membrane or a plural membrane, but plural membranes (synthetic plural membranes) are preferred from the viewpoint of durability with respect to EDTA-Fe.
  • These reverse osmosis membranes are comprised of a skin layer which dominates membrane performance characteristics such as the amount of water permeated and the removal rates, for example, and a supporting layer which supports the skin layer.
  • asymmetrical membranes in which the two are comprised of the same material and composite membranes in which they are comprised of different materials.
  • examples of asymmetrical membranes include cellulose acetate membranes
  • examples of composite membranes include synthetic composite membranes in which a skin layer is formed by coating polyethyleneimine and tolylenediisocyanate onto a supporting layer of polysulfone and those in which a skin layer is formed by polymerizing furfuryl alcohol.
  • the reverse osmosis membranes used in reverse osmosis membrane treatments carried out in the past removed NaCl in an amount of at least 95%. These membranes completely removed the solutes referred to earlier rather than allowing them to be present. Membranes which remove NaCl in an amount of at least 95% must be operated under a high pressure to obtain a practical water permeation rate.
  • the reverse osmosis membranes according to the present invention which remove NaCl in amounts of about 30% to about 90%
  • a sufficiently high water permeation rate can be achieved at a pressure of from 2 to 10 kg/cm2
  • the reverse osmosis membrane DRA-98® which removes NaCl in an amount of 98%)
  • a similar water permeation rate cannot be realized without a pressure of at least 15 kg/cm2.
  • the water permeation is preferably carried out under a pressure of from 3 to 7 kg/cm2, more preferably from 3 to 5 kg/m2 in consideration of reducing a running cost, power consumption, noises pollution, and heat generation.
  • washing water or stabilizing solution In the case where four washing tanks or stabilization tanks are present, the preferred position for the removal of washing water or stabilizing solution from the water washing process or the stabilization process for reverse osmosis treatment is from the third tank, and the permeated water which has been subjected to reverse osmosis for reuse is supplied to the fourth stage, to which fresh water or solution is also being supplied. Washing water or stabilizing solution can also be removed from any of the water washing tanks or stabilizing tanks, or from two or more of these tanks.
  • the water washing process or the stabilization process is preferable carried out in multiple stages, preferably in 3 to 5 stages, the more preferably 3 to 4 stages.
  • a solution is preferably passed through under a counter flow.
  • Various compounds may be added to the washing water or stabilizing solution in the present invention.
  • film hardening agents as typified by magnesium salts and aluminum salts, surfactants for reducing the drying load and preventing unevenness, fluorescent whiteners for improving whiteness and sulfites as preservatives may be added.
  • the compounds disclosed in, for example, L.E. West, "Water Quality Criteria", Photo. Sci. and Eng. , Volume 9, No. 6 (1965), may be added.
  • a stabilizing solution is a solution which has an image stabilizing function which cannot be achieved with water washing.
  • Such a solution contains components which fulfill an image stabilizing role in addition to the aforementioned components which can be added to the washing water.
  • it may be a solution to which formalin, bismuth salts and aqueous ammonia or ammonium salts, for example, have been added.
  • the pH of the washing water or stabilizing solution in the present invention is generally about 7, but it may be within the range from 3 to 9, depending on the carry-over from the previous bath.
  • the water washing or stabilization temperature is generally from 5°C to 40°C, and preferably from 10°C to 35°C. Heaters, temperature controllers, circulating pumps, filters, floating lids and squeegees, etc. may be used, in the water washing tanks or stabilizing tanks.
  • the processing method of the present invention is effective when applied to cases in which the concentration of aminopolycarboxylic acid ferric complex salt increases in the final water wash tank or stabilizing tank because of a reduced replenishment rate in which the rate of replenishment of the washing water or stabilizing solution is not more than 200 ml/m2.
  • the rate of replenishment is preferably from 50 to 190 ml/m2 when three water wash tanks or stabilizing tanks may be used, and is also preferably from 50 to 120 ml/m2 when four water wash tanks or stabilizing tanks may be used.
  • the development processing of the photographic materials in the present invention may be processing in which a silver image is formed (black-and-white processing) or it may involve a development process in which a colore image is formed (color development processing).
  • black-and-white processing a black-and-white negative development process is carried out first, followed by a white light exposure or treatment in a bath which contains a fogging agent, and a color development process.
  • Black-and-white development processing consists of a development process, a fixing process and a water washing process.
  • a stop process is sometimes carried out after the development process, and in cases where a stabilizing process is carried out after the fixing process, the water washing process can be omitted.
  • Development processes in which lith developers are used for the developer can also be used.
  • the known black-and-white developers generally used for the processing of black-and-white photographic materials can be used for the black-and-white developer which is used for the black-and-white processing operation, and the various additives which are generally added to a black-and-white developer can be included.
  • Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators comprised of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate, inorganic or organic restrainers such as potassium bromide or 2-methylbenzimidazole and methylbenzthiazole, water softening agents such as polyphosphate, and inhibitors for surface over-development such as trace quantities of iodide or mercapto compounds.
  • developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone
  • preservatives such as sulfites
  • accelerators comprised of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate
  • inorganic or organic restrainers such as potassium bromide or 2-methylbenzimidazole and methylbenzthiazole
  • water softening agents such as polyphosphate
  • inhibitors for surface over-development such as trace quantities of iodide
  • Color development processing is carried out with a color development process, a bleaching process, a fixing process, a water washing process and, where required, a stabilizing process, but a bleach-fixing process with a single bleach-fix bath can be used instead of processing with a process in which a bleach bath is used and a process in which a fixing bath is used.
  • Mono-bath processing in which a single developing, bleaching and fixing bath is used for color development, bleaching and fixing can also be used.
  • Pre-film hardening processes, and neutralizing processes, stop-fix processes and post-film hardening processes, for example, can be combined with these processes.
  • process prior to the stabilization process is a water washing process
  • this water washing process can be omitted and the stabilization process can be carried out directly.
  • a color developing agent is present in the color development baths which are used in the present invention.
  • the p-phenylene diamines derivatives are preferred and typical examples are indicated below, but the developing agent is not limited by these examples.
  • these p-phenylenediamine derivatives may take the form of salts, such as their sulfates, hydrochlorides, sulfites and p-toluenesulfonates.
  • the compounds indicated above have been disclosed, for example, in U.S. Patents 2,193,015, 2,552,241, 2,566,271, 2,592,364, 3,656,950 and 3,698,525.
  • the primary aromatic amine developing agents are used at concentrations of from about 0.1 gram to about 20 grams, and preferably from about 0.5 gram to about 10 grams, per liter of developer.
  • Known hydroxylamines can be present in the color development baths which are used in the present invention.
  • hydroxylamines can be used in a color development bath in the form of the free amines, they are more generally used in the form of their water soluble salts.
  • General examples of such salts include the sulfates, oxalates, chlorides, phosphates, carbonates and acetates.
  • the hydroxylamines may be substituted or unsubstituted, and the nitrogen atoms of the hydroxylamines may be substituted with alkyl groups.
  • the color development baths used in this present invention preferably have a pH of from 9 to 12, and most desirably have a pH of from 9 to 11.0.
  • caustic soda, caustic potash, sodium carbonate, potassium carbonate, sodium tertiary phosphate, potassium tertiary phosphate, potassium metaborate and borax can be used either individually or in combinations as alkalis and pH buffers.
  • various salts such as disodium or dipotassium hydrogen phosphate, potassium or sodium dihydrogen phosphate, sodium or potassium carbonate, boric acid, alkali nitrate or alkali sulfate, for example, can be used to provide a buffering capacity, for mixing purposes or for increasing the ionic strength.
  • chelating agents can be used to prevent the precipitation of calcium or magnesium in the color development bath.
  • suitable chelating agents include polyphosphates, amino-polycarboxylic acids, phosphonocarboxylic acids, amino-polysulfonic acids and 1-hydroxy-alkylidene-1,1-diphosphonic acids.
  • Optional development accelerators can be added to the color development baths, where required.
  • Suitable development accelerators include various pyridinium compounds and other cationic compounds as typified by those disclosed in U.S. Patent 2,648,604, JP-B-44-9503 and U.S. Patent 3,171,247, neutral salts such as thallium nitrate and potassium nitrate, non-ionic compounds such as the polyethyleneglycol, derivatives thereof and polythiol ethers disclosed, for example, in JP-B-44-9304 and U.S. Patents 2,533,990, 2,531,832, 2,950,970 and 2,577,127, and the thioether-based compounds disclosed in U.S. Patent 3,201,242.
  • JP-B as used herein signifies an "examined Japanese patent publication"
  • sodium sulfite, potassium sulfite, potassium bisulfite and sodium bisulfite which are generally used as preservatives, can be added.
  • Optional anti-foggants can be added, where required, to the color development bath in the present invention.
  • Alkali metal halides such as potassium bromide, sodium bromide and potassium iodide, and organic anti-foggants can be used as anti-foggants.
  • organic anti-foggants include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenztriazole, 5-nitrobenztriazole, 5-chlorobenztriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethyl-benzimidazole and hydroxyazaindolidine, mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole and 2-mercaptobenzthiazole, and mercapto-substituted aromatic compounds such as thiosalicylic acid can be used.
  • the nitrogen-containing heterocyclic compounds are especially desirable. These anti-foggants may be dissolved out of the color photosensitive material during processing and accumulated in the color development bath.
  • Iron complexes are included among the bleaching agents in the bleach baths or bleach-fix baths which can be used in the present invention.
  • the aminopolycarboxylic acid iron complexes are preferred from among the iron complexes and are added in an amount of from 0.01 to 1.0 mol/liter, and preferably in an amount of from 0.05 to 0.50 mol/liter.
  • Thiosulfate can be used as a fixing agent in the fixing baths or bleach-fixing baths.
  • Ammonium thiosulfate is especially desirable and can be added in an amount of from 0.1 to 5.0 mol/liter, and preferably in an amount of from 0.5 to 2.0 mol/liter.
  • Sulfite is generally added in the fixing or bleach-fixing bath as a preservative, but ascorbic acid, carbonyl/bisulfite adducts or carbonyl compounds can also be used for this purpose.
  • buffers, fluorescent whiteners, chelating agents and fungicides for example, can also be added, in the fixing or bleach-fixing bath where required.
  • Various compounds can be used as bleaching accelerators in the bleach baths, bleach-fix baths and/or bleach or bleach-fix pre-baths.
  • the compounds which have a mercapto group or a disulfide group disclosed in U.S. Patent 3,893,858, West German Patent 1,290,812, JP-A-53-95630 and Research Disclosure , No. 17129 (July, 1978) the thiazolidine derivatives disclosed in JP-A-50-140129, the thiourea derivatives disclosed in U.S. Patent 3,706,561, the iodide disclosed in JP-A-58-16235, the polyethyleneoxides disclosed in West German Patent 2,748,430 and the polyamine compounds disclosed in JP-B-45-8836 can be used for this purpose.
  • the photographic material to which the invention is applied may be, for example, an ordinary black-and-white silver halide photographic material (for example, a camera black-and-white sensitive material, an X-ray black-and-white sensitive material or a black-and-white sensitive material for printing purposes), an ordinary multi-layer color photosensitive material (for example, a color negative film, a color reversal film, a color positive film, a color negative film for cinematographic purposes), or a sensitive material for use with infrared light laser scanners.
  • an ordinary black-and-white silver halide photographic material for example, a camera black-and-white sensitive material, an X-ray black-and-white sensitive material or a black-and-white sensitive material for printing purposes
  • an ordinary multi-layer color photosensitive material for example, a color negative film, a color reversal film, a color positive film, a color negative film for cinematographic purposes
  • a sensitive material for use with infrared light laser scanners for example, an ordinary black-
  • Color development processing using a color development process is effective for the efficient realization of the present invention and is the preferred type of processing in the present invention.
  • the couplers preferably used in the color photosensitive materials in the present invention are described below.
  • 5-Pyrazolone-based compounds and pyrazoloazole-based compounds are preferred as magenta couplers, and those disclosed, for example, in U.S. Patents 4,310,619 and 4,351,897, European Patent 73,636, U.S. Patents 3,061,432 and 3,725,064, Research Disclosure , No. 24220 (June, 1984), JP-A-60-33552, Research Disclosure , No. 24230 (June, 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, U.S. Patents 4,500,630, 4,540,654 and 4,556,630, and WO(PCT) 88/04795 are especially desirable.
  • Phenol-based couplers and naphthol-based couplers are used as cyan couplers, and those disclosed, for example, in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, West German Laid-Open Patent 3,329,729, European Patents 121,365A and 249,453A, U.S. Patents 3,446,622, 4,333,999, 4,753,871, 4,451,559, 4,427,767, 4,690,889, 4,254,212 and 4,296,199, and JP-A-61-42658 are preferred.
  • couplers disclosed in U.S. Patent 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Laid-Open Patent 3,234,533 are preferred as couplers which release colored dyes having a suitable degree of diffusibility.
  • couplers which release photographically useful residual groups on coupling are preferred in the present invention.
  • the DIR couplers which release development inhibitors disclosed in the patents cited in section VII-F of the Research Disclosure 17643 (December, 1978), JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346 and U.S. Patent 4,248,962 are preferred.
  • couplers disclosed in British Patents 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferred as couplers which release nucleating agents or development accelerators in the form of the image during development.
  • couplers which can be used in the photosensitive materials in the present invention include the competitive couplers disclosed, for example, in U.S. Patent 4,130,427, the multi-equivalent couplers disclosed, for example, in U.S. Patents 4,283,472, 4,338,393 and 4,310,618, the DIR redox compound-releasing couplers, DIR coupler-releasing couplers, DIR coupler-releasing redox compounds or DIR redox-releasing redox compounds disclosed, for example, in JP-A-60-185950 and JP-A-62-24252, the couplers disclosed in European Patent 173,302A, which release dyes which have had their color restored after elimination, the bleach accelerator-releasing couplers disclosed, for example, in Research Disclosure No.
  • the reverse osmosis membranes used in the reverse osmosis membrane treatment in the present invention have a lower NaCl removal rate than those used conventionally, so the operating pressure can be reduced, the pump generates less heat and there is no problem with a rising solution temperature.
  • the color printing paper described below was cut to a width of 82.5 mm, exposed in an automatic printer and then processed on the basis of the processing operations indicated in Table 1 under the processing conditions described below in a processing apparatus which had water washing tanks to which a reverse osmosis membrane module was attached, as shown in Figure 1. Three days after processing, the processed color printing paper samples were assessed in regard to (1) reticulation which had occurred on storage, (2) fading of the cyan dye, and (3) adhesion between prints.
  • 1 is the color development tank (D)
  • 2 is the bleach-fix tank (BF)
  • 3 4 and 5 are the first water washing tank W1, the second water washing tank W2 and the third water washing tank W3, respectively.
  • Fresh washing water 6 is supplied to the third water washing tank (W3) 5, and washing water from this tank is fed via the connecting pipe 7 to the second water washing tank (W2) 4 of the previous stage, and ultimately via the connecting pipe 8 to the first water washing tank (W1) 3, thereby providing a multi-stage counter-flow system.
  • Washing water was taken out via the connecting pipe 10 from the second water washing tank (W2) 4 and fed by the pump (P) 11 to the reverse osmosis membrane module (RO) 12.
  • the permeated water obtained from the reverse osmosis membrane module 12 was supplied to the third water washing tank (W3) 5 via the connecting pipe 13 and the concentrate was returned to the second water washing tank (W2) 4 via the connecting pipe 14.
  • Reverse osmosis membranes for the reverse osmosis membrane module 12 were selected from among the synthetic composite membranes of the DRA series and the cellulose acetate membranes of the DRC series made by the Daicell Chemical Co., and from among the composite membranes of the SU-200 series made by the Toray Co.
  • the membranes removed NaCl in amounts as estimated using the method described below.
  • the operating conditions were as follows.
  • the reverse osmosis pressure due to the pump (P) 11 and the openings of the valves 15, 16 and 17 were adjusted in such a way as to maintain a washing water flow rate from the water washing tank (W2) 4 to the reverse osmosis membrane module (RO) 12 of 3 liters/minute and a permeated water flow rate from the reverse osmosis membrane module 12 of from 150 to 200 ml/min.
  • the actual pressure was within the range from 3 to 12 kg/cm2.
  • the tempered circulation of the automatic developing machine was run for 10 hours per day, and the reverse osmosis membrane device was operated continuously during this time.
  • Color developer, bleach-fixer and water washing water having the compositions described below were supplied to the color development tank (D) 1, the bleach-fix tank (BF) 2 and the first to the third water washing tanks (W1 - W3) 3 - 5 of this processing apparatus.
  • Chlorinated sodium isocyanurate (10 mg/l) was added to town water having a calcium content of 27 mg/l, a magnesium content of 4.2 mg/l, a pH of 7.3 and an electrical conductivity of 183 »s/cm.
  • a content of ammonium thiosulfate in permeated water in Run numbers 2, 3, 5, 6 and 7 were 0.02, 0.04, 0.23, 0.29 and 0.34 g/l, respectively.
  • the multi-layer color printing paper having the layer structure described below was prepared on a paper support which had been laminated on both sides with polyethylene.
  • the coating solution s were prepared by mixing and dissolving the emulsions, various reagents and emulsified coupler dispersions. The methods of preparation are described in detail below.
  • magenta, cyan and intermediate layer emulsions below were prepared in the same way.
  • the compounds used in each emulsion are indicated below.
  • the compound indicated below was added at the rate of 2.6 x 10 ⁇ 3 mol per mol of silver halide to the red sensitive emulsion layer.
  • Green Sensitive Emulsion A mono-disperse cubic silver chloride emulsion containing grains having an average grain size of 0.48 »m and a variation coefficient of 0.10 was prepared by preparing silver chloride grains which contained K2IrCl6 and 1,3-dimethylimidazolin-2-thione in the same manner as disclosed in JP-A-2-100049, Example 1, and then adding 4 x 10 ⁇ 4 mol/mol ⁇ Ag of sensitizing dye (S-2) and KBr. After ripening, sodium thiosulfate was added, and chemical sensitization was carried out optimally. Then adding 5 x 10 ⁇ 4 mol/mol ⁇ Ag of stabilizer (Stb-1) was added to obtain the emulsion.
  • Red Sensitive Emulsion This emulsion was prepared in the same way as the green sensitive emulsion. However, the sensitizing dye (S-3) was used in an amount of 1.5 x 10 ⁇ 4 mol/mol ⁇ Ag instead of S-2.
  • composition of each layer in the sample is indicated below.
  • the numerical value indicates the coated weight (g/m2).
  • the coated weights of silver halide emulsions are shown after calculation as silver.
  • the color printing paper prepared in the way described above was cut to a width of 82.5 mm.
  • the color negative film described below was cut to a width of 35 mm and then exposed in a camera and processed under the processing conditions described below on the basis of the processing operations indicated in Table 3 in the processing apparatus shown diagrammatically in Figure 2. Then, samples of film processed after 2 days of processing were evaluated in terms of (1) reticulation which occurred on storage and (2) fading of the cyan dye.
  • 21 is the development tank (D)
  • 22 is the bleach tank (B)
  • 23 and 24 are the first fixer tank (F1) and the second fixer tank (F2), respectively
  • 25, 26 and 27 are the first water washing tank (W1), the second water washing tank (W2) and the third water washing tank (W3), respectively
  • 28 is the stabilizing tank.
  • Fresh washing water 29 is supplied to the third water washing tank (W3) 27 and washing water from this tank is fed to the second water tank 26 via the connecting pipe 30, and subsequently via the connecting pipe 31 to the first water washing tank (W1) 25.
  • the washing water 32 expelled therefrom as an overflow is supplied to the second fixer bath (F2) 24 to provide a multi-stage counter-flow system. With the fixer baths, the fixer from the second fixer bath (F2) 24 is sent to the first fixer bath (F1) 23.
  • Washing water was taken out via the flow pipe 33 from the second water washing tank (W2) 26 and sent to the reverse osmosis membrane module (RO) 35 at a flow rate of 2 l/min by the pump (P) 11.
  • the permeated water obtained from the reverse osmosis membrane module 35 was supplied at a flow rate of 100 to 180 ml/min via the connecting pipe 36 to the third water washing tank (W3) 27, and the concentrate was returned at a flow rate of 0.9 to 1.8 l/m via the connecting pipe 37 to the second water washing tank (W2) 26.
  • the multi-layer color photosensitive material was prepared by the lamination coating of layers having the compositions indicated below on a cellulose triacetate film support having a subbing layer.
  • the numerical value corresponding to each component indicates the coated weight in units of g/m2, and in the case of the silver halides, coated weights calculated as silver are shown. However, for the sensitizing dyes, the coated weights are indicated in units of mol per mol of silver halide in the same layer.
  • gelatin hardening agent H-1 and a surfactant were added to each layer in addition to the components mentioned above.
  • the present invention uses a reverse osmosis membrane which removes NaCl in an amount of from 30 to 90%, there is no increase in the amino-polycarboxylic acid ferric complex salt concentration in the washing water or stabilizing solution and no increase in yellow staining even with a decrease in the amount of washing water and stabilizing solution used. Consequently, the amount of washing water or stabilizing solution can be significantly reduced.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Claims (11)

  1. Verfahren zur Verarbeitung von photographischen Silberhalogenidmaterialien, welches das Verarbeiten eines bildweise belichteten photographischen Silberhalogenidmaterials in einem Bad mit einem Fixiervermögen und dann das Verarbeiten des photographischen Materials in einem Waschwasserbad und/oder einem Stabilisierungsbad umfaßt, wobei das Waschwasser und/oder die Stabilisierungslösung von jeweils dem Waschwasserbad und/oder dem Stabilisierungsbad einer Umkehrosmosebehandlung unter Verwendung einer Umkehrosmosemembran unterworfen wird/ werden, dadurch gekennzeichnet, daß die Umkehrosmosemembran NaCl in einer Menge von 30% bis 90% entfernt, wenn eine NaCl-Lösung mit einer Konzentration von 1000 ppm bei 25°C und bei einem angelegten Druck von 7 kg/cm² behandelt wird.
  2. Verfahren zur Verarbeitung von photographischen Silberhalogenidmaterialien nach Anspruch 1, worin das Waschwasser und/oder die Stabilisierungslösung in dem Waschwasserbad und/oder dem Stabilisierungsbad in einer Menge von nicht mehr als 200 ml/m² ergänzt wird/werden.
  3. Verfahren zur Verarbeitung von photographischen Silberhalogenidmaterialien nach Anspruch 1, worin die Umkehrosmosemembran eine synthetische zusammengesetzte Membran ist.
  4. Verfahren zur Verarbeitung von photographischen Silberhalogenidmaterialien nach Anspruch 1, worin die verwendete Umkehrosmosemembran NaCl in einer Menge von 40% bis 85% entfernt, wenn eine NaCl-Lösung mit einer Konzentration von 1000 ppm bei 25°C und bei einem angelegten Druck von 7 kg/cm² behandelt wird.
  5. Verfahren zur Verarbeitung von photographischen Silberhalogenidmaterialien nach Anspruch 4, worin die verwendete Umkehrosmosemembran NaCl in einer Menge von 50% bis 80% entfernt, wenn eine NaCl-Lösung mit einer Konzentration von 1000 ppm bei 25°C und bei einem angelegten Druck von 7 kg/cm² behandelt wird.
  6. Verfahren zur Verarbeitung von photographischen Silberhalogenidmaterialien nach Anspruch 1, worin die Umkehrosmosemembran EDTA-Fe (III) in einer Menge von mindestens 90% entfernt.
  7. Verfahren zur Verarbeitung von photographischen Silberhalogenidmaterialien nach Anspruch 1, worin vier Waschwasserbäder vorhanden sind, und das Waschwasser, das der Umkehrosmosebehandlung unterworfen wird, vom dritten Waschwasserbad in Richtung der Materialverarbeitung entfernt wird, und das filtrierte Wasser, das der Umkehrosmosemembranbehandlung unterworfen worden ist, dem vierten Waschwasserbad in Richtung der Materialverarbeitung zugeführt wird.
  8. Verfahren zur Verarbeitung von photographischen Silberhalogenidmaterialien nach Anspruch 1, worin vier Stabilisierungsbäder vorhanden sind, und die Stabilisierungslösung, die der Umkehrosmosebehandlung unterworfen wird, vom dritten Stabilisierungsbad in Richtung der Materialverarbeitung entfernt wird, und das filtrierte Wasser, das der Umkehrosmosemembranbehandlung unterworfen worden ist, dem vierten Stabilisierungsbad in Richtung der Materialverarbeitung zugeführt wird.
  9. Verfahren zur Verarbeitung von photographischen Silberhalogenidmaterialien nach Anspruch 1, worin die Temperatur des Waschwassers und der Stabilisierungslösung 5°C bis 40°C beträgt.
  10. Verfahren zur Verarbeitung von photographischen Silberhalogenidmaterialien nach Anspruch 9, worin die Temperatur 10°C bis 35°C beträgt.
  11. Verfahren zur Verarbeitung von photographischen Silberhalogenidmaterialien nach Anspruch 1, worin das Verfahren zur Verarbeitung eine Verarbeitung eines farbphotographischen Silberhalogenidmaterials ist, welches einen Farbentwicklungsprozeß und einen Bleichprozeß umfaßt.
EP19900113278 1989-07-20 1990-07-11 Verfahren zur Verarbeitung von photoempfindlichen Silberhalogenidmaterialien Expired - Lifetime EP0409065B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP18613589 1989-07-20
JP186135/89 1989-07-20

Publications (2)

Publication Number Publication Date
EP0409065A1 EP0409065A1 (de) 1991-01-23
EP0409065B1 true EP0409065B1 (de) 1995-01-18

Family

ID=16182987

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900113278 Expired - Lifetime EP0409065B1 (de) 1989-07-20 1990-07-11 Verfahren zur Verarbeitung von photoempfindlichen Silberhalogenidmaterialien

Country Status (3)

Country Link
EP (1) EP0409065B1 (de)
JP (1) JP2715333B2 (de)
DE (1) DE69016118T2 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2676638B2 (ja) * 1989-12-28 1997-11-17 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JP3372994B2 (ja) 1993-06-11 2003-02-04 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
FR2721227B1 (fr) * 1994-06-17 1996-08-14 Kodak Pathe Procédé et dispositif pour la séparation de substance dissoutes dans les eaux de rinçage utilisées en aval d'un bain de traitement d'un film photographique.
FR2812218B1 (fr) 2000-07-28 2003-01-10 Eastman Kodak Co Procede pour ameliorer le fonctionnement d'une membrane d'un dispositif de nanofiltration
JP2003071252A (ja) * 2001-09-06 2003-03-11 Nitto Denko Corp 多段式逆浸透処理方法
CN115814605B (zh) * 2022-12-06 2024-04-12 浙江大学 一种废弃反渗透膜修复剂及修复方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4251624A (en) * 1979-02-23 1981-02-17 England Evelyn F Stabilizing colored photographic print against fading and staining
JPS58105150A (ja) * 1981-12-17 1983-06-22 Fuji Photo Film Co Ltd カラ−写真処理装置
JP2648911B2 (ja) * 1986-06-06 1997-09-03 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法及び装置
JP2648913B2 (ja) * 1986-08-22 1997-09-03 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JPS6374060A (ja) * 1986-09-18 1988-04-04 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料の処理方法

Also Published As

Publication number Publication date
JP2715333B2 (ja) 1998-02-18
DE69016118T2 (de) 1995-06-01
JPH03121448A (ja) 1991-05-23
EP0409065A1 (de) 1991-01-23
DE69016118D1 (de) 1995-03-02

Similar Documents

Publication Publication Date Title
EP0567126B1 (de) Verarbeitungszusammensetzung für ein photographisches Silberhalogenidmaterial und Verarbeitungsverfahren unter Verwendung derselben
JPH01105948A (ja) ハロゲン化銀カラー写真感光材料の処理方法
EP0412532B1 (de) Verarbeitungsverfahren für Silberhalogenid enthaltende farbphotographische Materialien
US5223379A (en) Processing compositions for silver halide color photographic materials and method for processing the same materials
EP0426062B1 (de) Verfahren zur Verarbeitung eines farbphotographischen Silberhalogenidmaterials
EP0409065B1 (de) Verfahren zur Verarbeitung von photoempfindlichen Silberhalogenidmaterialien
EP0407979B1 (de) Verfahren zur Verarbeitung von photoempfindlichen Silberhalogenidmaterialien
EP0652477A1 (de) Beschleunigung der Silberentfernung durch Thioetherverbindungen in sulfitenthaltenden Fixierlösungen
EP0569008B1 (de) Beschleunigung der Silberentfernung durch Thioetherverbindungen
US4855218A (en) Method for processing silver halide photographic lightsensitive materials
US5063142A (en) Process for processing silver halide color photographic materials
DE69032450T2 (de) Verfahren zur Verarbeitung farbphotographischer Silberhalogenidmaterial
EP0427204A1 (de) Verfahren zur Verarbeitung von farbphotographischen Silberhalogenidmaterialien
JPS5816172B2 (ja) 写真処理液中のカブリ成分の除去方法
US5221597A (en) Method for processing silver halide color photographic materials
EP0329051B1 (de) Verfahren zur Verarbeitung von farbphotographischen Silberhalogenidmaterialien
JP2640143B2 (ja) ハロゲン化銀写真感光材料の処理方法
EP0568953A2 (de) Verfahren und Zusammensetzungen zum Retuschieren von Filmbildern
JP2640152B2 (ja) 撮影用ハロゲン化銀カラー写真感光材料の処理方法
JP2849662B2 (ja) ハロゲン化銀カラー写真感光材料の処理方法
US5266448A (en) Method of processing silver halide color photographic materials
JP2630473B2 (ja) ハロゲン化銀カラー写真感光材料の処理方法
JPH0267552A (ja) 自動現像処理装置
JP2630472B2 (ja) ハロゲン化銀カラー写真感光材料の処理方法
JP3545454B2 (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): BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19910315

17Q First examination report despatched

Effective date: 19931018

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT NL

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

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19950118

Ref country code: BE

Effective date: 19950118

Ref country code: NL

Effective date: 19950118

REF Corresponds to:

Ref document number: 69016118

Country of ref document: DE

Date of ref document: 19950302

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
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
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

Ref country code: FR

Ref legal event code: TP

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

Ref country code: DE

Payment date: 20090619

Year of fee payment: 20

Ref country code: GB

Payment date: 20090708

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20100710

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 EXPIRATION OF PROTECTION

Effective date: 20100710

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

Ref country code: FR

Payment date: 20090910

Year of fee payment: 20

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 EXPIRATION OF PROTECTION

Effective date: 20100711