EP0435352B1 - Verfahren zur Verarbeitung farbphotographischer Silberhalogenidmaterialien - Google Patents

Verfahren zur Verarbeitung farbphotographischer Silberhalogenidmaterialien Download PDF

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Publication number
EP0435352B1
EP0435352B1 EP90125786A EP90125786A EP0435352B1 EP 0435352 B1 EP0435352 B1 EP 0435352B1 EP 90125786 A EP90125786 A EP 90125786A EP 90125786 A EP90125786 A EP 90125786A EP 0435352 B1 EP0435352 B1 EP 0435352B1
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EP
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Prior art keywords
processing
layer
silver halide
bath
complex salt
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French (fr)
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EP0435352A1 (de
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Akira C/O Fuji Photo Film Co. Ltd. Abe
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • This invention concerns a method of processing silver halide color photographic photosensitive materials, mare particularly, it concerns an improved method of processing silver halide color photographic photosensitive materials for camera use, with which excellent images are obtained, even when the processing time after processing in a bath which has a bleaching function before reaching the drying process is shortened and the replenishment rates of the water washing water and/or stabilizer are reduced.
  • Shortening of the processing time is based on improving the service for producing prints while the customer waits without the need for the customer to make two visits to the store.
  • color papers In connection with the shortening of processing times, research has been carried out on processing of silver halide color photographic photosensitive materials for color print purposes (referred to hereinafter as "color papers"). For example, the wet processing time prior to the drying operation has been shortened in practice to about 3 minutes for color papers in which silver chloride is used and which have been developed most recently.
  • color negative films the processing of silver halide color photographic photosensitive materials for camera purposes (referred to hereinafter as “color negative films”) takes a long time, a period of about 20 minutes, or of about 10 minutes in the case of especially rapid processing.
  • the coated silver weight and the developed silver weight are both high in high speed color negative films and a long period of time is required for the bleaching process.
  • a ferric complex salt of ethylenediamine tetraacetic acid has been widely used in the past as a bleaching agent.
  • the bleaching rate is slow because of its weak oxidizing power and various bleaching accelerators have had to be used in combination. Even so, the amount of the processing time which has been shortened is still inadequate.
  • bleach baths have been developed using bleaching agents which have a stronger bleaching power and a higher bleaching rate, such as ferric complex salts of 1,3-diaminopropane tetraacetic acid and cyclohexanediamine tetraacetic acid for example.
  • bleaching agents which have a stronger bleaching power and a higher bleaching rate
  • ferric complex salts of 1,3-diaminopropane tetraacetic acid and cyclohexanediamine tetraacetic acid for example.
  • magenta staining arises on storage under conditions of high temperature and high humidity after rapid processing using these bleaches.
  • magenta staining is a serious problem when the replenishment rate of the water washing or stabilization processes is reduced where bleaching agents which have a high bleaching rate such as 1,3-diaminopropane tetraacetic acid ferric complex salt and cyclohexanediamine tetraacetic acid ferric complex salt are used and there are difficulties in practice.
  • bleaching agents which have a high bleaching rate such as 1,3-diaminopropane tetraacetic acid ferric complex salt and cyclohexanediamine tetraacetic acid ferric complex salt are used and there are difficulties in practice.
  • EP-A-0 410 388 discloses a method for the processing of a silver halide photographic material which comprises the steps of developing a silver halide photographic material which has been previously exposed to light, processing the developed silver halide photographic material with a bath which contains a thiosulfate and which has a fixing ability, and subsequently subjecting the developed silver halide photographic material to washing and/or stabilizing in a multi-stage counter current process which includes a reverse osmosis membrane and washing solution and/or stabilizing solution.
  • organic complex salts of iron (III) with aminopolycarboxylic acid are mentioned.
  • EP-A-0 409 065 describes a method of processing silver halide photographic materials comprising processing the imagewise-exposed materials in a bath which has a fixing ability and then in at least one of a water bath and a stabilizing bath, wherein at least one of the washing water and stabilizing solutions is subjected to a reverse osmosis treatment using a reversed osmosis membrane which removes NaCl.
  • a color negative film is processed with a bleaching solution containing 1,3-diaminopropane tetraacetic acid ferric ammonium salt dihydrate and a washing solution which is used in a multi-stage counter-flow system using a reverse osmosis membrane.
  • EP-A-0 410 388 and EP-A-0 409 065 are prior art documents in the sense of Art. 54(3) EPC and do not refer to silver halide color photographic photosensitive materials for camera use as specified according to the present invention.
  • EP-A-0 329 052 discloses a method for forming color photographic images comprising the steps of imagewise exposing to light a silver halide color photographic light-sensitive material, developing said light-sensitive material with a color developer, bleaching, immediately after said step of developing, said light-sensitive material with a bleaching solution, and treating, after said step of bleaching, said light-sensitive material with a solution having fixing capability, wherein said light-sensitive material comprises a support and hydrophilic colloid layers including a silver halide emulsion layer provided on a side of said support, and a total dry thickness of said hydrophilic colloid layers is not more than 17 ⁇ m, and said bleaching solution contains a ferric complex salt of a compound represented by the following formula A in an amount of within the range of from 0.002 mole to 0.4 mole per liter of said bleaching solution; wherein A 1 through A 4 are each a -CH 2 OH group, a -COOM group, or a -PO 3 M 1 M 2 group,
  • the inventors discovered that the above-described problems could be resolved more effectively by including at least one compound selected from the group consisting of 1,3-diaminopropane tetraacetic acid ferric complex salt, 1,4-diaminobutane tetraacetic acid ferric complex salt, 1,5-diaminopentane tetraacetic acid ferric complex salt, trans-cyclohexanediamine tetraacetic acid ferric complex salt, glycol ether diamine tetraacetic acid ferric complex salt and diethylenetriamine pentaacetic acid ferric complex salt in the bath which has a bleaching function.
  • FIG. 1 is a schematic drawing of the processing apparatus used in Comparative Example 1 in which a reverse osmosis membrane treatment apparatus is in the water washing process in accordance with the present invention.
  • FIG. 2 is a schematic drawing of the processing apparatus used in Example 1 in which a reverse osmosis membrane treatment apparatus is in the stabilization process.
  • FIG. 3 is a schematic drawing in which a reverse osmosis membrane treatment apparatus is in the water washing process when processing is carried out with a combination of two-tank counter-flow water washing and single tank stabilization.
  • Figure 4 is a schematic drawing in which a reverse osmosis membrane treatment apparatus is established in a four tank counter-flow stabilization process.
  • the imagewise exposed photosensitive material is color developed and then processed in a bath which has a bleaching function.
  • the bath which has a bleaching function which is used in the present invention is either a bleach bath or a bleach-fix bath which also has a fixing function.
  • the bath which has a bleaching function contains an aminopolycarboxylic acid ferric complex salt of which the molecular weight of the aminopolycarboxylic acid is at least 300 but not more than 450 as a bleaching agent, and this may take the form of a salt such as an ammonium, sodium or potassium salt for example.
  • aminopolycarboxylic acids of which the molecular weight is at least 300 but not more than 450.
  • 1,3-Diaminopropane tetraacetic acid 306.3
  • 1,4-Diaminobutane tetraacetic acid 320.3
  • 1,5-Diaminopentane tetraacetic acid 334.3
  • Trans-cyclohexanediamine tetraacetic acid 346.4
  • the preferred bleaching agents in the present invention have a high bleaching rate when used in bleach baths and bleach-fix baths and those which have a molecular weight of at least 300 and not more than 400 are preferred in view of the excellent storage properties obtained when they are used in combination with a reverse osmosis membrane treatment, and the use of 1,3-diaminopropane tetraacetic acid, 1,4-diaminobutane tetraacetic acid, 1,5-diaminopentane tetraacetic acid, trans-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid and diethylenetriamine pentaacetic acid is preferred.
  • 1,3-diaminopropane tetraacetic acid is especially preferred, while trans-cyclohexanediamine tetraacetic acid and diethylenetriamine pentaacetic acid are both especially preferred when a bleach-fix bath is being used.
  • the amount of these bleaching agents used in a bleach bath is preferably from 0.1 mol/liter to 1 mol/liter. However, the use of from preferably 0.2 to 0.5 mol/liter, and most preferably of from 0.25 to 0.4 mol/liter, provides a high bleaching rate and there is little concern about precipitation out of solution.
  • the amount of these bleaching agents used in a bleach-fix bath is preferably from 0.05 mol/liter to 0.5 mol/liter, the use of from 0.1 to 0.4 mol/liter is more preferred, and the use of from 0.15 to 0.3 mol/liter is especially desirable, since the bleaching rate and fixing rate are high and there is little concern about precipitation.
  • aminopolycarboxylic acid ferric complex salts can be used in combination as bleaching agents in the present invention within the range where the effect of the present invention can be still be achieved.
  • Examples of aminopolycarboxylic acids of these bleaching agents and their molecular weights are indicated below. Ethylenediamine tetraacetic acid 292.3 Methylimino diacetic acid 147.1 Iminodiacetic acid 133.1 Nitrilo tri-acetic acid 191.1 Triethylenetetramine hexaacetic acid 494.5
  • the bath pH is preferably from 2 to 7 where the bath which has a bleaching function is a bleach bath. Moreover, a pH in the range from 3 to 6.5 is preferred, and a pH in the range from 3.2 to 5.5 is especially preferred, to increase the bleaching rate and minimizing bleach fogging.
  • the pH is preferably from 4 to 8 where the bath which has a bleaching function is a bleach-fix bath.
  • a pH of from 4.5 to 7.0 is preferred, and a pH of from 5.0 to 6.5 is especially preferred, as a pH range in which the bleaching rate is high, the extent of bleach fogging is minimized and the fixer which is also present is stable.
  • the processing time after processing in the bath which has a bleaching function (bleach bath or bleach-fix bath) which contains a bleaching agent in accordance with the present invention until reaching the drying process is shortened to 6 minutes or less there is a pronounced increase in magenta staining as described earlier and this cannot be used in practice.
  • the effect of preventing the occurrence of magenta staining of the present invention in this way is especially pronounced where the above-described treatment time is not more than 5 minutes, and it is even more pronounced when the above-described processing time is not more than 4 minutes. The effect is even more marked when the above-described processing time is not more than 3 minutes.
  • the processing time after processing in the bath which has a bleaching function until reaching the drying process may comprise, for example, bleach ⁇ fix (1 minute 30 seconds) ⁇ water wash (50 seconds) ⁇ stabilization (20 seconds).
  • magenta staining there is a pronounced increase in magenta staining of the type described earlier when the replenishment rate is reduced in the water washing and/or stabilization process.
  • the replenishment rate is reduced to 800ml or less per square meter of photosensitive material there is a pronounced increase in magenta staining and this cannot be used in practice.
  • the reverse osmosis membrane which can be used in the water washing and/or stabilization process in the present invention may be a high pressure reverse osmosis membrane or a medium pressure reverse osmosis membrane, but a low pressure reverse osmosis membrane is preferred. More specifically, a reverse osmosis membrane providing a removal factor for NaCl in liquid which permeates the membrane on subjecting an aqueous solution containing 2000 ppm of NaCl to a reverse osmosis treatment under conditions of a temperature of 25°C, and a pressure of 5 kg/cm 2 , is from 30% to 90% is preferred. When such a loose reverse osmosis membrane is used, the amount of liquid which permeates is high even at low pressure and it is also possible to prevent magenta staining effectively.
  • These reverse osmosis membranes may comprise a skin layer which controls the membrane performance such as the amount of water permeating the membrane and the removal factor, for example, and a support layer which supports the above described layer.
  • the membrane may be an asymmetric membrane in which these are both made of the same material or a composite membrane in which they are both made of different materials.
  • Cellulose acetate membranes and polyamide membranes are examples of asymmetric membranes
  • composite membranes include synthetic composite membranes in which synthetic materials are used, such as those in which a skin layer is formed by coating polyethyleneimine and tolylenediisocyanate onto a support layer comprising a polysulfone and those in which a skin layer is formed by the polymerization of furfuryl alcohol.
  • synthetic composite membranes include DRA-40, DRA-80 and DRA-89 made by Daicel Chemical Industries and SU-200, SU-210 and SU-220 made by Toray.
  • the feed pressure of the liquid to be treated which is supplied to the reverse osmosis membrane is preferably from 2 to 20 kg/cm 2 , more preferably from 3 to 15 kg/cm 2 , even more preferably from 3 to 10 kg/cm 2 and most desirably from 3 to 6 kg/cm 2 .
  • reverse osmosis membrane treatment apparatus is used in the water washing process and/or stabilizing process, and the construction is described with reference to Figures 1 to 4.
  • Figure 1 is a schematic drawing of the processing apparatus used in Comparative Example 1 in which reverse osmosis membrane treatment apparatus in accordance with the present invention is placed in the water washing process.
  • 1 is the color development tank (D)
  • 2 is the bleach tank (B)
  • 3 is the fixer tank (F)
  • 4a, 4b and 4c are respectively the first water washing tank (W 1 ), the second water washing tank (W 2 ) and the third water washing tank (W 3 )
  • 5 is the stabilizing tank (S).
  • Fresh washing water for replenishment is supplied to the third water washing tank 4c by pipe 6 and washing water from this tank is sent to the second water washing tank 4b which is an earlier stage by means of the counter-flow pipe 7a and washing water is sent to the fist water washing tank 4a via the sequential counter-flow pipe work 7b.
  • the overflow from this tank is removed from the system as effluent via the overflow pipe 8 to form a three stage counter-flow water washing system.
  • the single stabilization tank 5 is included after the third water washing tank 4c.
  • Washing water is removed from the second water washing tank 4b by means of liquid feed pipe 9 and sent by liquid feed pump 10 to the pressure resistant apparatus 11 which houses the reverse osmosis membrane.
  • the liquid which permeates and passes through the reverse osmosis membrane is supplied to the third water washing tank 4c by the permeating liquid pipe 12 and the concentrated liquid which does not pass through the reverse osmosis membrane is returned to the second water washing tank 4b by concentrated liquid pipe 13.
  • FIG. 2 is a schematic drawing of the processing apparatus used in Example 1 in which a reverse osmosis membrane treatment apparatus in accordance with the present invention is placed in the stabilization process.
  • 1 is the color development tank (D)
  • 14 is the bleach-fix tank (BF)
  • 5a, 5b and 5c are respectively the first stabilization tank (S 1 ), the second stabilization tank (S 2 ) and the third stabilization tank (S 3 ).
  • Fresh stabilizer for replenishment purposes is supplied to the third stabilization tank 5c by means of pipe 15, and stabilizer from the same tank is sent to the second stabilization tank 5b which is the previous stage by means of the counter-flow pipe 7a, and to the first stabilization tank 5a via the sequential counter-flow pipe 7b.
  • the overflow from here is removed from the system as effluent via overflow pipe 8 to provide a three stage counter-flow stabilization system.
  • Stabilizer is removed from the second stabilization tank 5b by means of liquid feed pipe 9 and sent to the pressure resistant apparatus 11 which houses the reverse osmosis membrane by means of liquid feed pump 10.
  • the permeating liquid which permeates and passes through the reverse osmosis membrane is supplied to the third stabilization tank 5c by permeated liquid pipe 12 and the concentrated liquid which has not passed through the reverse osmosis membrane is returned to the second stabilization tank 5b by concentrated liquid pump 13.
  • FIG. 3 is a schematic diagram of an apparatus in which reverse osmosis membrane treatment apparatus in accordance with the present invention is used in the water washing process in a processing system which includes a two stage counter-flow water washing process and a single tank stabilization process.
  • water washing water is removed from the first water washing tank 4a by liquid feed pipe 9 and fed to the pressure resistant apparatus 11 which houses the reverse osmosis membrane by means of liquid feed pump 10.
  • the liquid which permeates and passes through the reverse osmosis membrane is supplied to the second water washing tank 4b by means of permeated liquid pipe 12 and the concentrated liquid which has not passed through the reverse osmosis membrane is returned to the first water washing tank 4a by concentrated liquid pipe 13.
  • FIG. 4 is a schematic drawing of a reverse osmosis membrane treatment apparatus in accordance with the present invention in a four stage counter-flow stabilization process.
  • stabilizer is removed from the third stabilization tank 5c by means of liquid feed pipe 9 and sent to pressure resistant apparatus 11 which houses the reverse osmosis membrane by liquid feed pump 10.
  • the liquid which permeates and passes through the reverse osmosis membrane is supplied to the fourth stabilization tank 5d by means of permeated liquid pipe 12 and the concentrated liquid which has not passed through the reverse osmosis membrane is returned to third stabilization tank 5c by the concentrated liquid pipe 13.
  • the color development tank, the bleach tank and the bleach-fix tank are not shown in Figures 3 and 4 but, needless to say, they are established in the same way as indicated in Figures 1 and 2 described above.
  • the color photographic photosensitive material can be developed and processed using conventional methods as disclosed in Research Disclosure (RD) No. 17643, pages 28 - 29 and in ibid, No. 18716 in the left to right hand columns of page 615.
  • RD Research Disclosure
  • the color developers used in the development processing of the photosensitive material are preferably aqueous alkaline solutions which contain a primary aromatic amine based color developing agent as the principal component.
  • Aminophenol based compounds are also useful as color developing agents, but the use of p-phenylenediamine based compounds is preferred.
  • Typical examples include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl- ⁇ -methoxyethylaniline, and the sulfate, hydrochloride and p-toluenesulfonate salts of these compounds.
  • 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate is especially preferred. Two or more of these compounds can be used conjointly, depending on the intended purpose.
  • the color developer generally contains pH buffers such as alkali metal carbonates, borates or phosphates, and development inhibitors or anti-foggants such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds.
  • pH buffers such as alkali metal carbonates, borates or phosphates
  • development inhibitors or anti-foggants such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds.
  • the color developer may also contain, as required, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine and catecholsulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts and amines, dye forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, thickeners and various chelating agents exemplified by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids.
  • various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides
  • Typical examples of these compounds include ethylenediamine tetraacetic acid, nitrilo triacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediamine-di(o-hydroxyphenylacetic acid) and the salts thereof.
  • black and white developing agents including dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, and aminophenols such as p-aminophenol, for example, can be used individually, or in combination, in the black and white developer.
  • the pH of these color developers and black and white developers is generally from 9 to 12.
  • the replenishment rate for these developers depends on the color photographic photosensitive material which is being processed but, in general, it is 3 liters or less per square meter of photosensitive material and it can be 500 ml or less by reducing the bromide ion concentration in the replenisher. Where the replenishment rate is low it is preferred that evaporation and aerial oxidation of the liquid should be prevented by minimizing the area of contact with the air in the processing tank.
  • Open Factor Processing bath and Air Contact Area (cm 2 ) Processing Bath Volume (cm 3 )
  • the open factor is preferably less than 0.1, and more preferably from 0.001 to 0.05.
  • the method involving the use of a shielding material such as a floating lid for example, on the surface of the photographic processing bath in the processing tank, the method involving the use of a movable lid as disclosed in JP-A-1-82033 and the method involving slit development processing disclosed in JP-A-63-216050 can be used to reduce the open factor.
  • Reduction in the open factor is preferably applied not only to color development and black-and-white development processes but also to all subsequent processes, such as the bleaching, bleach-fixing, fixing, water washing and stabilizing processes.
  • the replenishment rate can be reduced by using by suppressing the accumulation of bromide ion in the development bath.
  • the color development processing time is between 2 and 5 minutes, but shorter processing times can be achieved by increasing the pH and the temperature or by using a higher concentration of the color developing agent.
  • the photosensitive material is generally processed in a bath which has a bleaching function after color development.
  • the bleaching process may be carried out at the same time as a fixing process (in a bleach-fix process) or it may be carried out as a separate process.
  • a bleach-fix process can be carried out after a bleaching process in order to speed up processing.
  • the processing can be carried out in two connected bleach-fix baths, a fixing process can be carried out before a bleach-fixing process or a bleaching process can be carried out after a bleach-fix process, as required.
  • bleaching agents in accordance with the present invention are used for the bleaching agent.
  • Bleaching accelerators can be used, as required, in the bleach baths, bleach-fix baths or bleach or bleach-fix pre-baths.
  • Specific examples of useful bleach accelerators are the compounds which have a mercapto group or a disulfide group disclosed, for example, in U.S.
  • Patent 3,893,858 West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, and Research Disclosure No.
  • Patent 3,706,561 the iodides disclosed in West German Patent 1,127,715 and JP-A-58-16235; the polyoxyethylene compounds disclosed in West German Patents 966,410 and 2,748,430; the polyamine compounds disclosed in JP-B-45-8836; the other compounds disclosed in JP-A-49-42434, JP-A-49-40943, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940; and the bromide ion.
  • Re-halogenating agents such as bromides (for example potassium bromide, sodium bromide, ammonium bromide) or chlorides (for example potassium chloride, sodium chloride, ammonium chloride) can also be present in the bleach or bleach-fixer, and the use of ammonium bromide is preferred.
  • the re-halogenating agent concentration is preferably from 0.1 to 5 mol/liter, and most preferably from 0.5 to 3 mol/liter.
  • ammonium nitrate as a metal corrosion inhibitor is also preferred.
  • the bleach or bleach fixer can contain organic acids to prevent the occurrence of bleach staining.
  • the most preferred organic acids are compounds which have an acid dissociation constant (pKa) of from 2 to 5, and preferred examples include acetic acid, hydroxyacetic acid, lactic acid, propionic acid, tartaric acid, and citric acid. Acetic acid and hydroxyacetic acid are especially preferred.
  • the amount of these organic acids is from 0.1 to 3 mol/liters, preferably from 0.5 to 2 mol/liter, and most preferably from 0.8 to 1.5 mol/liter.
  • Thiosulfate, thiocyanate, thioether based compounds, thioureas and large amounts of iodide can be used, for example, as the fixing agent which is used in the fixer or bleach-fixer, but thiosulfate is generally used. Ammonium thiosulfate in particular can be used in the widest range of applications. Furthermore, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea etc. is also preferred. Sulfite, bisulfite, carbonyl/bisulfite addition compounds or the sulfinic acid compounds disclosed in European Patent 294,769A are preferred as preservatives for fixers and bleach-fixers.
  • the total de-silvering process time is preferably as short as possible as long as insufficient de-silvering does not occur.
  • the preferred de-silvering time is from 1 to 3 minutes, and most preferably the de-silvering time is from 1 to 2 minutes.
  • the processing temperature is from 25°C to 50°C, and preferably from 35°C to 45°C. The desilvering rate is improved and staining after processing is effectively prevented within the preferred temperature range.
  • the de-silvering baths are preferably agitated as strongly as possible during the de-silvering process.
  • methods of achieving strong agitation include methods in which a processing liquid is jetted against the emulsion surface of the photosensitive material as disclosed in JP-A-62-183460 and JP-A-62-183461, methods in which the agitation effect is increased using a rotary device as disclosed in JP-A-62-183461, methods in which the photosensitive material is moved with a wiper blade which is established in the bath in contact with the emulsion surface and the agitation effect is increased by the generation of turbulence at the emulsion surface, and methods in which the circulating flow rate of the processing bath as a whole is increased.
  • These means of increasing agitation are effective for bleaches, bleach-fixers and fixers.
  • Automatic processors used for processing photosensitive materials preferably have photosensitive material transporting devices as disclosed in JP-A-60-191257, JP-A-60-191258 or JP-A-60-191259.
  • a transporting device such as that disclosed in JP-A-60-191257, the carry over of processing bath from one bath to the next is greatly reduced and this is very effective for preventing deterioration in processing bath performance.
  • These effects are especially useful for shortening the processing time in each process and for reducing the replenishment rate of each processing bath.
  • the silver halide color photographic photosensitive materials of this invention are generally subjected to a water washing process and/or stabilizing process after the desilvering process.
  • the amount of wash water used in the washing process can be fixed within a wide range, depending on the application and the nature (depending on materials such as couplers which are used, for example) of the photosensitive material, the wash water temperature, the number of water washing tanks (the number of water washing stages) and the replenishment system, i.e. whether a counter-flow or a sequential flow system is used, and various other conditions.
  • the relationship between the amount of water used and the number of washing tanks in a multi-stage counter-flow system can be obtained using the method outlined on pages 248 - 253 of the Journal of the Society of Motion Picture and Television Engineers , Volume 64 ( May 1955).
  • the amount of wash water used can be greatly reduced by using the multi-stage counter-flow system described in the literature above, but bacteria proliferate due to the increased residence time of the water in the tanks and problems arise with suspended matter which is produced and attaches to the photosensitive material.
  • the method in which the calcium ion and magnesium ion concentrations are reduced, as disclosed in JP-A-62-288838, is very effective as a means of overcoming this problem in the method of processing color photosensitive materials of the present invention.
  • the isothiazolone compounds and thiabendazoles disclosed in JP-A-57-8542 the chlorine based disinfectants such as chlorinated sodium isocyanurate, and benzotriazole, for example, and the disinfectants disclosed in Horiguchi, The Chemistry of Biocides and Fungicides , in Killing Microorganisms, Biocidal and Fungicidal Techniques published by the Health and Hygiene Technology Society, and in A Dictionary of Biocides and Fungicides published by the Japanese Biocide and Fungicide Society, can also be used in this connection.
  • the pH of the washing water when processing photosensitive materials in accordance with the present invention is, for example, from 4 to 9, and preferably from 5 to 8.
  • the washing water temperature can vary depending on the nature and application of the photosensitive material but, in general, a temperature within the range from 15°C to 45°C, and preferably within the range from 25°C to 40°C, is generally used.
  • the photosensitive materials of the invention can be processed directly in a stabilizing bath instead of being subjected to a water wash as described above.
  • the known methods disclosed in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used for a stabilization process of this type.
  • a stabilization process is carried out following the above-described water washing process, and the stabilizing baths which contain dye stabilizing agents and surfactants which are used as final baths with color photosensitive materials for camera use are an example of such a process.
  • Aldehydes such as formaldehyde and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde/bisulfite addition compounds can be used, for example, as dye stabilizing agents.
  • nonionic surfactants are preferred for the surfactant, and alkyl phenyl ether based compounds and silicon based compounds are especially preferred.
  • Various chelating agents and fungicides can also be added to these stabilizing baths.
  • the overflow which accompanies replenishment of the above described water washing or stabilizing baths can be reused in other processes, such as the de-silvering process for example.
  • Concentration correction with the addition of water is desirable in cases where the above described processing baths become concentrated due to evaporation when processing in an automatic processor, for example.
  • Color developing agents can be incorporated into the silver halide color photosensitive material of the present invention to simplify and speed up processing.
  • the incorporation of various color developing agent precursors is preferred.
  • the indoaniline based compounds disclosed in U.S. Patent 3,342,597, the Shiff's base type compounds disclosed in U.S. Patent 3,342,599, Research Disclosure No. 14850 and ibid. , No. 15159, the aldol compounds disclosed in Research Disclosure No. 13924, the metal complex salts disclosed in U.S. Patent 3,719,492 and the urethane based compounds disclosed in JP-A-53-135628 can be used for this purpose.
  • Various 1-phenyl-3-pyrazolidones may be incorporated, as required, into the silver halide color photosensitive materials of the present invention to accelerate color development.
  • Typical compounds are disclosed, for example, in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.
  • the various processing baths employed in the present invention are used at a temperature of from 10°C to 50°C.
  • the standard temperature is generally from 33°C to 38°C, but accelerated processing and shorter processing times can be achieved at higher temperatures while, on the other hand, increased picture quality and better processing bath stability can be achieved at lower temperatures.
  • processing using hydrogen peroxide intensification or cobalt intensification as disclosed in West German Patent 2,226,770 or U.S. Patent 3,674,499 can be carried out in order to economize on silver in the photosensitive material.
  • the color photographic photosensitive materials for camera use according to the present invention preferably comprise, on support, at least one blue sensitive silver halide emulsion layer, at least one green sensitive silver halide emulsion layer and at least one red sensitive silver halide emulsion layer, but no particular limitation is imposed upon the number of or order of these silver halide emulsion layers and the non-photosensitive layers present.
  • silver halide photographic photosensitive materials have, on a support, at least one photosensitive layer comprising a plurality of silver halide layers which have essentially the same color sensitivity but different photographic speeds, the photosensitive layer being a photosensitive layer unit which is color sensitive to blue light, green light or red light.
  • the arrangement of the unit photosensitive layers generally involves the positioning of the layers in the order, from the support side, of red sensitive layer, green sensitive layer, and blue sensitive layer.
  • this order may be varied, as required, and the layers may be arranged such that a layer which has a different color sensitivity is sandwiched between layers which have the same color sensitivity.
  • non-photosensitive layers such as intermediate layers, may be positioned between the silver halide photosensitive layers, and as uppermost and lowermost layers.
  • the intermediate layers may contain couplers and DIR compounds such as those disclosed in the specifications of JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037 and JP-A-61-20038, and they may also contain anti-color mixing compounds, ultraviolet absorbers and anti-staining agents generally used.
  • the plurality of silver halide emulsion layers each photosensitive layer unit is preferably a double layer structure comprising a high speed emulsion layer and a low speed emulsion layer as disclosed in West German Patent 1,121,470 or British Patent 923,045.
  • a high speed emulsion layer and a low speed emulsion layer as disclosed in West German Patent 1,121,470 or British Patent 923,045.
  • nonphotosensitive layers may be established between each of the silver halide emulsion layers.
  • the low speed layers may positioned on the side furthest away from the support and the high speed layers may be positioned on the side closest to the support as disclosed, for example, in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543.
  • the arrangement may be, from the side furthest from the support, low speed blue sensitive layer (BL)/high speed blue sensitive layer (BH)/high speed green sensitive layer (GH)/low speed green sensitive layer (GL)/high speed red sensitive layer (RH)/low speed red sensitive layer (RL), or BH/BL/GL/GH/RH/RL, or BH/BL/GH/GL/RL/RH.
  • BL low speed blue sensitive layer
  • BH high speed blue sensitive layer
  • GH high speed green sensitive layer
  • GL low speed green sensitive layer
  • RH high speed red sensitive layer
  • RL low speed red sensitive layer
  • the layers can be arranged in the order, from the side furthest from the support, of blue sensitive layer/GH/RH/GL/RL as disclosed in JP-B-55-34932. Furthermore, the layers can also be arranged in the order, from the side farthest from the support, of blue sensitive layer/GL/RL/GH/RH, as disclosed in the specifications of JP-A-56-25738 and JP-A-62-63936.
  • the layers in a layer of the same color sensitivity may be arranged in the order, from the side furthest from the support, of intermediate speed emulsion layer/high speed emulsion layer/low speed emulsion layer, as disclosed in the specification of JP-A-59-202464.
  • the layers can be arranged in the order high speed emulsion layer/low speed emulsion layer/intermediate speed emulsion layer, or low speed emulsion layer/intermediate speed emulsion layer/high speed emulsion layer for example.
  • the dry film thickness of all the structural layers (photographic structural layers) except the support, the under-layer of the support and the backing layer is 23.0 ⁇ m or less.
  • the lower limiting value for the film thickness specification is preferably such that the film thickness is reduced within a range in which there is no pronounced loss of performance of the photosensitive materials.
  • the lower limit for the total dry film thickness of the structural layers other than the support and the under-layer of the support of the sensitive material is preferably 12.0 ⁇ m, and the lower limit for the total dry film thickness of the structural layer which is established between the photosensitive layer which is located closest to the support and the under-layer of the support is preferably 1.0 ⁇ m.
  • the film thickness of a multi-layer color photosensitive material in the present invention is measured using the method described below.
  • the sensitive material which is to be measured is stored for 7 days after preparation under conditions of 25°C and 50% RH. First of all, the total thickness of the sensitive material is measured and then the thickness is measured again after removing the coated layers from the support and the difference is taken to be the total film thickness of the coated layers except for the support of the sensitive material.
  • the measurement of this thickness can be achieved using a film thickness gauge of the contact type with a voltage conversion element for example (Anritsu Electric Co. Ltd., K-402B Stand.)
  • the removal of the coated layer from the support can be achieved using an aqueous solution of sodium hypochlorite.
  • a cross sectional photograph of the above mentioned sensitive material is taken using a scanning electron microscope (magnification preferably at least 3,000 times), the total thickness and the thickness of each layer on the support is measured and the thickness of each layer can then be calculated as a proportion of the measured value of the total thickness obtained beforehand with the film thickness gauge (the absolute value of the thickness as measured).
  • the swelling factor of the sensitive material in this present invention is preferably from 50 to 200%, and most desirably from 70 to 150%.
  • the swelling factor can be calculated from the equilibrium swelled film thickness in water at 25°C and the total dry film thickness at 25°C, 55% RH using the following expression: Equilibrium Swelled Film Thickness - Total Dry Film Thickness Total Dry Film Thickness ⁇ 100 (%)
  • the amount of residual color developing agent increases when the swelling factor varies from the above mentioned numerical values and there is an adverse effect on photographic performance, on the image, on the desilvering properties, and on the properties of the film such as the film strength, for example.
  • the film swelling rate T 1/2 of the photosensitive material in the present invention is preferably not more than 15 seconds and most preferably not more than 9 seconds.
  • the film thickness T 1/2 can be measured using methods well known in the art. For example, measurements can be made using a swellometer of the type described by A. Green in Photogr. Sci. Eng. , Volume 19, Number 2, pages 124 - 129, and T 1/2 is defined as the time taken to reach half the saturated film thickness, taking 90% of the maximum swelled film thickness arising on processing the material for 3 minutes 15 seconds in a color developer at 30°C as the saturated film thickness.
  • Preferred silver halides for the photographic emulsion layers of a color photographic photosensitive material for camera use which is used in the present invention are silver iodobromides, silver iodochlorides and silver iodochlorobromides which contain not more than about 30 mol% of silver iodide. Most preferably they are silver iodobromides which contain from about 2 mol% to about 25 mol% of silver iodide.
  • the silver halide grains in the photographic emulsion may have a regular crystalline form such as a cubic, octahedral or tetradecahedral form, an irregular crystalline form such as a spherical or plate-like form, a form which has crystal defects such as twinned crystal planes, or a form which is a composite of these forms.
  • the grain size of the silver halide may be very fine, about 0.2 ⁇ m or less or large with a projected area diameter of up to about 10 ⁇ m.
  • the emulsions may be poly-disperse emulsions or mono-disperse emulsions.
  • the silver halide photographic emulsions which can be used in the present invention can be prepared, for example, using the methods disclosed in Research Disclosure (RD) No. 17643 (December, 1978), pages 22 - 23, "I. Emulsion Preparation and Types", and Research Disclosure No. 18716 (November 1979), page 648, in P. Glafkides, Chimie et Physique Photopraphique , published by Paul Montel, 1967, in G.F. Duffin, Photographic Emulsion Chemistry , published by Focal Press, 1966, and in V.L. Zelikmann et al., Making and Coating Photographic Emulsions , published by Focal Press, 1964.
  • tabular grains which have an aspect ratio of at least about 5 can be used in the present invention.
  • Tabular grains can be prepared easily using the methods described, for example, in Gutoff, Photographic Science and Engineering , Volume 14, pages 248 - 257 (1970), and in U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520, and British Patent 2,112,157.
  • the crystal structure may be uniform, or the interior and exterior parts of the grains may have different halogen compositions, or the grains may have a layer-like structure.
  • silver halides which have different compositions may be joined with an epitaxial junction or they may be joined with compounds other than silver halides, such as silver thiocyanate or lead oxide, for example.
  • mixtures of grains which have various crystalline forms can be used.
  • the silver halide emulsions used generally are subjected to physical ripening, chemical ripening and spectral sensitization. Additives which are used for these purposes are disclosed in Research Disclosure No. 17643 and ibid. , No. 18716, and these disclosures are summarized in the table below.
  • Type of Additive RD 17643 RD 18716 1. Chemical Sensitizers Page 23 Page 648, right col. 2. Speed Increasing Agents As above 3. Spectral Sensitizers and Super-Sensitizers Pages 23 - 24 Pages 648 right col. to 649 right col. 4. Whiteners Page 24 5. Anti-Foggants and Stabilizers Pages 24 - 25 Page 649, right col. 6. Light Absorbers, Filter Dyes and UV Absorbers Pages 25 - 26 Pages 649, right col. to 650, left col. 7.
  • 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 3,725,067, 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 International Patent WO 88/04795 are especially preferred.
  • Phenol 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 Patent Laid Open 3,329,729, European Patents 121,365A and 249,453A, U.S. Patents 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212 and 4,296,199, and JP-A-61-42658 are preferred.
  • the colored couplers for correcting the unwanted absorptions of colored dyes disclosed, for example, in section VII-G of Research Disclosure No. 17643, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258, and British Patent 1,146,368 are preferred. Furthermore, the use of couplers which correct for unwanted absorption of colored dyes by means of fluorescent dyes which are released on coupling as disclosed in U.S. Patent 4,774,181, and couplers which have, as leaving groups, dye precursor groups which can form dyes on reaction with the developing agent disclosed in U.S. Patent 4,777,120 is also preferred.
  • couplers disclosed in U.S. Patent 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Laid Open) 3,234,533 are preferred as couplers where the colored dyes formed have a suitable degree of diffusibility.
  • Typical examples of polymer dye forming couplers are disclosed, for example, in U.S. Patents 3,451,820, 4,080,211, 4,367,282, 4,409,320 and 4,576,910, and British Patent 2,102,173.
  • 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 Research Disclosure 17643, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350 and U.S. Patents 4,248,962 and 4,782,012 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 correspondence to the image formed during development.
  • Other compounds which can be used in photosensitive materials of this present invention include the competitive couplers disclosed, for example, in U.S. Patent 4,130,427, the poly-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 which release dyes whose color is restored after elimination disclosed in European Patent 173,302A, the bleach accelerator releasing couplers disclosed, for example, in Research Disclosure No.
  • the couplers which are used in the present invention can be introduced into the photosensitive material using a variety of known dispersion methods.
  • high boiling point solvents which can be used in the oil in water dispersion method are disclosed, for example, in U.S. Patent 2,322,027.
  • Specific examples of high boiling point organic solvents which have a boiling point of at least 175°C at normal pressure which can be used in the oil in water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-tert-amylphenyl)phthalate, bis(2,4-di-tert-amylphenyl)isophthalate and bis(1,1-diethylpropyl)phthalate), phosphate or phosphonate esters (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-eth
  • organic solvents which have a boiling point of about 30°C or more and preferably of at least 50°C, but about 160°C or less can be used as auxiliary solvents.
  • auxiliary solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.
  • couplers can be loaded into a loadable latex in the presence or absence of the above-described high boiling point organic solvents (for example, as disclosed in U.S. Patent 4,203,716), or they can be dissolved in a water insoluble but organic solvent soluble polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution.
  • high boiling point organic solvents for example, as disclosed in U.S. Patent 4,203,716
  • Suitable supports which can be used in the present invention are disclosed, for example, on page 28 of Research Disclosure No. 17643, and from the right hand column of page 647 to the left hand column of page 648 of Research Disclosure No. 18716.
  • This present invention is applicable to a variety of color photosensitive materials. Its application to color negative films for general and cinematographic purposes and to color reversal films for slides and television purposes is especially preferred.
  • a multi-layer color photosensitive material was prepared by lamination coating of each of the layers of whose composition is shown below on a triacetylcellulose film support on which an under-layer had been established.
  • the numerical value corresponding to each component below indicates the coated weight in g/m 2 .
  • this is shown as the coated weight as silver.
  • the coated weights are shown as mol per mol of silver halide in the same layer.
  • Second Layer Anti-halation Layer Black Colloidal Silver as silver 0.18 Gelatin 0.40 Second Layer Intermediate Layer 2,5-Di-tert-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third Layer First Red Sensitive Emulsion Layer Mono-disperse Silver Iodobromide Emulsion (6 mol% AgI, average grain size 0.6 ⁇ m, variation coefficient for grain size 0.15) as silver 0.55 Sensitizing Dye I 6.9 ⁇ 10 -5 Sensitizing Dye II 1.8 ⁇ 10 -5 Sensitizing Dye III 3.1 ⁇ 10 -4 Sensitizing Dye IV 4.0 ⁇ 10 -5 EX-2 0.350 HBS-1 0.005 EX-10 0.020 Gelatin 1.20 Fourth Layer Second Red Sensitive Emulsion Layer Tabular Silver Iodobromide Emulsion (10 mol% AgI, average grain diameter 0.7
  • Gelatin Hardening Agent H-1 and surfactant were added to each layer.
  • the color film prepared in the manner described above was cut into strips of a width of 35 mm and then subjected to a standard exposure in a camera. Then the films were processed under various conditions with the processing operations shown below using a small type cine automatic processor. Each process was carried out continuously using 3.5 square meters (100 m length of 35 mm wide) of the above-described exposed film.
  • Processing was carried out under conditions in which the bleaching agent in the bleach was modified in the manner indicated in Table 1 and the reverse osmosis membrane treatment apparatus as shown schematically in Figure 1 was or was not used with the water washing process.
  • the reverse osmosis membrane treatment involved a synthetic composite membrane made by Daicel Chemical Industries, namely a DRA-80-SW-03 model spiral module (effective membrane area 1.1 m 2 ), housed in a PSV-03 pressure resistant vessel made by the same company and the liquid was treated at a liquid feed pressure of 3.5 kg/cm 2 and a liquid feed rate of 1.3 liters/minute using a magnetic gear pump.
  • the amount of permeating liquid when the reverse osmosis membrane treatment started was 230 ml/minute.
  • the fluorescence X-ray method was used to measure the amount of residual silver and the increase in magenta density was measured using an "Exlite 310" model photographic densitometer.
  • a multi-layer color photosensitive material comprising the layers of the compositions shown below was prepared on a cellulose triacetate film on which an underlayer had been established.
  • the coated weights are indicated as g.Ag/m 2 in the case of silver halides and colloidal silver, as g/m 2 in the case of the couplers, additives and gelatin, and in mol per mol of silver halide in the same layer in the case of the sensitizing dyes.
  • Second Layer (Intermediate Layer) Gelatin 1.5 UV-1 0.03 UV-2 0.06 UV-3 0.07 ExF-1 0.004 Solv-2 0.07 Cpd-5 6 ⁇ 10 -4
  • Third Layer (First Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion (AgI 2 mol%, high internal AgI type, corresponding sphere diameter 0.3 ⁇ m, variation coefficient of corresponding sphere diameter 29%, regular crystal grain/twinned crystal grain mixture, diameter/thickness ratio 2.5) 0.5 as silver Gelatin 0.8 ExS-1 1.0 ⁇ 10 -4 ExS-2 3.0 ⁇ 10 -4 ExS-3 1 ⁇ 10 -5 ExC-3 0.22 ExC-4 0.02 Cpd-5 3 ⁇ 10 -4 Fourth Layer (Second Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion
  • the color negative film which had been prepared in the manner as described above was cut into strips of a width of 35 mm and then subjected to a standard exposure in a camera. Then, the material was processed under various processing conditions with the processing operations shown below using a small cine type automatic processor. Each processing run was continued until 3.5 m 2 (100 m long by 35 mm wide) of the a above-described exposed film had been processed.
  • Processing was carried out under conditions in which the bleaching agent in the bleach-fix was changed in the manner shown in Table 2 below and the reverse osmosis membrane treatment apparatus as shown schematically in Figure 2 was or was not used in the stabilization process.
  • the reverse osmosis membrane treatment involved a synthetic composite membrane made by the Toray Co., namely an SU-210 model spiral module (effective membrane area 0.8 m 2 ), and the liquid was treated at a liquid feed pressure of 5 kg/cm 2 and a liquid feed rate of 4 liters/minute.
  • the amount of permeating liquid when the reverse osmosis membrane treatment started was 340 ml/minute.
  • compositions of the processing baths used were as indicated below.

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Claims (6)

  1. Verfahren zur Behandlung von silberhalogenidhaltigen farbphotographischen lichtempfindlichen Materialien zur Benutzung in Kameras, wobei besagte farbphotographische lichtempfindliche Materialien eine Trockenfilmdichte aller photographischen strukturellen Schichten, mit Ausnahme des Trägers, der Unterschicht des Trägers und der Stützschicht, von 23,0 pm oder weniger aufweisen, umfassend Behandlung des Material in einem Bad, das Bleichfunktion hat und als Bleichmittel ein Aminopolycarboxylsäure-Eisen(III)-Komplexsalz enthält, anschließende Mehrstufengegenflußwasserwaschung und/oder Stabilisierungsbehandlung, wobei das Molekulargewicht der Aminopolycarboxylsäure des Aminopolycarboxylsäure-Eisen(III)-Komplexsalzes von 300 bis 450 beträgt, und das Waschwasser und/oder der Stabilisator mit Umkehrosmosemembranen behandelt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Bleichmittel mindestens ein Bleichmittel, ausgewählt aus der Gruppe bestehend aus 1,3-Diaminopropantetraessigsäure-Eisen(III)-Komplexsalz, 1,4-Diaminobutantetraessigsäure-Eisen(III)-Komplexsalz, 1,4-Diaminobutantetraessigsäure-Eisen(III)-Komplexsalz, 1,5-Diaminopentantetraessigsäure-Eisen(III)-Komplexsalz, trans-Cyclohexandiamintetraessigsäure-Eisen(lll)-Komplexsalz, Glycoletherdiamintetraessigsäure-Eisen(III)-Komplexsalz und Diethylentriaminpentaessigsäure-Eisen(III)-Komplexsalz ist.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Behandlungszeit nach Behandlung in dem Bad mit Bleichfunktion bis zum Erreichen der Trocknung 6 Minuten oder weniger beträgt.
  4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Nachfüllrate des Wasserwaschwassers und/oder Stabilisators, die Umkehrosmose unterworfen werden, 800 ml oder weniger pro m2 photoempfindlichen Materials ist.
  5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Molekulargewicht zwischen mindestens 300 und nicht mehr als 400 liegt.
  6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Menge des Aminopolycarboxylsäure-Eisen(III)-Komplexsalzes von 0,1 bis 1 mol/l des Bleichbades oder 0,05 bis 0,5 mol/l des Bleich-Fixierungsbades ist.
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Publication number Priority date Publication date Assignee Title
EP0409065A1 (de) * 1989-07-20 1991-01-23 Fuji Photo Film Co., Ltd. Verfahren zur Verarbeitung von photoempfindlichen Silberhalogenidmaterialien
EP0410388A1 (de) * 1989-07-25 1991-01-30 Fuji Photo Film Co., Ltd. Verfahren zur Verarbeitung von photoempfindlichen Silberhalogenidmaterialien

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JPH03200145A (ja) 1991-09-02
JP2676638B2 (ja) 1997-11-17
DE69032178D1 (de) 1998-04-30
DE69032178T2 (de) 1998-07-09
EP0435352A1 (de) 1991-07-03

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