EP0738919B1 - Stabilisierte Peroxid-Bleichlösungen und deren Verwendung zur Verarbeitung von photographischen Elementen - Google Patents

Stabilisierte Peroxid-Bleichlösungen und deren Verwendung zur Verarbeitung von photographischen Elementen Download PDF

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EP0738919B1
EP0738919B1 EP19960200947 EP96200947A EP0738919B1 EP 0738919 B1 EP0738919 B1 EP 0738919B1 EP 19960200947 EP19960200947 EP 19960200947 EP 96200947 A EP96200947 A EP 96200947A EP 0738919 B1 EP0738919 B1 EP 0738919B1
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Prior art keywords
carbon atoms
group
acid
mol
bleaching
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French (fr)
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EP0738919A3 (de
EP0738919A2 (de
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Shirleyanne Elizabeth Haye
Mayra Beatriz Reyes
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Eastman Kodak Co
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Eastman Kodak Co
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Priority claimed from US08/422,468 external-priority patent/US5550009A/en
Priority claimed from US08/423,257 external-priority patent/US5541041A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421—Additives other than bleaching or fixing agents
    • 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

  • the present invention relates generally to the processing of color photographic elements. More particularly, it relates to the use of stabilized peroxide bleaching solutions comprising a certain amount of chloride ion and two distinct sequestering acidic compounds.
  • the compositions and the methods for their use in photography are the subject of this invention.
  • the developed silver is oxidized to a silver salt by a suitable bleaching agent.
  • the oxidized silver is then removed from the element in a fixing step.
  • the most common bleaching solutions contain complexes of ferric ion and various organic ligands.
  • One primary desire in this industry is to design bleaching compositions which are more compatible with the environment, and thus it is desirable to reduce or avoid the use of ferric complex bleaching agents.
  • Peracid bleaching solutions such as those containing peroxide, persulfate, perborate, perphosphate, perhalogen, percarboxylic acid or percarbonate bleaching agents, offer an alternative to the ferric complex bleaching solutions. They are less expensive and present lower chemical and biological demands on the environment since their by-products can be less harmful.
  • persulfate bleaching agents While persulfate bleaching agents have low environmental impact, they have the disadvantage that their bleaching activity is slow and thus require the presence of a bleaching accelerator.
  • the most common bleaching accelerators are thiol compounds that have offensive odors.
  • peroxide bleaching solution offers many environmental advantages over persulfate and ferric complex bleaching solutions.
  • peroxide bleaching solutions including US-A-4,277,556, US-A-4,301,236, US-A-4,454,224, US-A-4,717,649, and WO-A-92/01972.
  • WO-A-92/07300 and EP 0 428 101A1 describe hydrogen peroxide compositions for bleaching high chloride emulsions. These compositions comprise up to 0.4 mole of chloride ions per liter of solution and have a pH in the range of 5 to 11. These particular bleaching solutions, however, cause vesiculation in the processed element.
  • WO-A-93/11459 describes hydrogen peroxide bleaching solutions that include two or more water-soluble sequestering agents for complexing with transition metals. These solutions appear suitable for use with low silver paper materials.
  • This invention provides a hydrogen peroxide bleaching solution having a pH of from 7 to 13 and comprising:
  • the method of this invention for processing a color photographic element comprises:
  • the bleaching solution of this invention provides all of the advantages of no vesiculation and efficient and rapid bleaching. In addition, however, the bleaching solution of this invention has improved stability. That is, the loss in hydrogen peroxide over time is considerably reduced. Thus, the solution has improved shelf life during shipping and storage.
  • FIG. 1 is a graphical plot of relative hydrogen peroxide concentration versus storage time for two bleaching solutions of this invention and a bleaching solution of the prior art, as discussed in Examples 1-2 below.
  • Hydrogen peroxide bleaching solutions of this invention include a conventional hydrogen peroxide bleaching agent including, but not limited to hydrogen, alkali and alkaline earth salts of peroxide, or a compound which releases or generates hydrogen peroxide.
  • a conventional hydrogen peroxide bleaching agent including, but not limited to hydrogen, alkali and alkaline earth salts of peroxide, or a compound which releases or generates hydrogen peroxide.
  • Such hydrogen peroxide precursors are well known in the art, and include for example, perborate, perphosphate, percarbonate, percarboxylate, and hydrogen peroxide urea.
  • hydrogen peroxide can be generated on site by electrolysis of an aqueous solution. Examples of peroxide bleaching solutions are described, for example, in Research Disclosure, publication 36544, pages 501-541 (September, 1994).
  • Research Disclosure is a publication of Kenneth Mason Publications Ltd., Dudley House, 12 North Street, Emsworth, Hampshire PO10 7DQ England (also available from Emsworth Design Inc., 121 West 19th Street, New York, N.Y. 10011). This reference will be referred to hereinafter as "Research Disclosure”. Hydrogen peroxide is a preferred bleaching agent.
  • the amount of peroxide (or its precursor) is generally at least 0.15 mol/l, and from 0.15 to 5 mol/l is preferred. The optimum amount will depend upon the type of photographic element being processed. For example, for color negative films that contain silver bromoiodide emulsions, more preferred amounts are from 0.9 to 3 mol/l. The most preferred amounts for silver bromoiodide emulsions are from 1.45 to 2.0 mol/l. For motion picture print films, the more preferred amount is from 0.15 to 1 mol/l, and a most preferred amount is from 0.35 to 0.6 mol/l. For photographic color papers, the preferred amounts would be from 0.15 to 3 mol/l.
  • Chloride ions can be supplied to the bleaching solution as part of a simple inorganic salt, for example, sodium chloride, potassium chloride, ammonium chloride and lithium chloride. In addition, they can be supplied as organic complexes such as tetraalkylammonium chlorides.
  • the preferred salts are sodium chloride and potassium chloride.
  • the chloride ion concentration is at least 0.35 mol/l, with from 0.45 to 2 mol/l being preferred, and from 0.45 to 1 mol/l being most preferred.
  • the bleaching solutions of this invention are quite simple, having four essential components: the peroxide bleaching agent, the chloride ions, and two distinct sequestrant acidic compounds, as defined below.
  • An optional but preferred component is a buffer.
  • the bleaching solution of this invention is alkaline, having a pH within the general range of from 7 to 13, with a pH of from 8 to 11 being preferred.
  • the pH can be provided by adding a conventional weak or strong base, and can be maintained by the presence of one or more suitable buffers including, but not limited to, sodium carbonate, potassium carbonate, sodium borate, potassium borate, sodium phosphate, calcium hydroxide, sodium silicate, beta-alaninediacetic acid, arginine, asparagine, ethylenediamine, ethylenediaminetetraacetic acid, glycine, histidine, imidazole, isoleucine, leucine, methyliminodiacetic acid, nicotine, nitrilotriacetic acid, piperidine, proline, purine and pyrrolidine.
  • Sodium or potassium carbonate are preferred.
  • the first acidic compound can be one or more organic phosphonic acids or salts thereof.
  • organic phosphonic acids or salts thereof are represented by the structure (I): R 1 N(CH 2 PO 3 M 2 ) 2 or (II): R 2 R 3 C(PO 3 M 2 ) 2 wherein
  • useful substituents include, but are not limited to, an alkyl group, hydroxy, sulfo, carbonamido, sulfonamido, sulfamoyl, sulfonato, thioalkyl, alkylcarbonamido, alkylcarbamoyl, alkylsulfonamido, alkylsulfamoyl, carboxyl, amino, halo (such as chloro or bromo) sulfono, or sulfoxo, alkoxy of 1 to 5 carbon atoms (linear or branched) . , -PO 3 M 2 , -CH 2 PO 3 M 2 or -N(CH 2 PO 3 M 2 ) 2 wherein the alkyl (linear or branched) for any of these groups has 1 to 5 carbon atoms.
  • Representative phosphonic acids useful in the practice of this invention include, but are not limited to the compounds listed in EP 0 428 101A1.
  • Representative useful compounds are 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepentaphosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, 1,2-cyclohexanediamine-N,N,N',N'-tetramethylenephosphonic acid, o-carboxyaniline-N,N-dimethylenephosphonic acid, propylamine-N,N-dimethylenephosphonic acid, 4-(N-pyrrolidino)butylamine-N,N-bis(methylenephosphonic acid), 1,3-diamine-2-propanol-N,N,N',N'-tetramethylenephosphonic acid, 1,3-propanediamine-N,N,N',N'-t
  • Particularly useful first acidic compounds are 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, diethylenetriamine-N,N,N',N",N"-penta(methylenephosphonic acid), or salts thereof.
  • the amount of organic phosphonic acid used in the practice of the invention is at least 0.0005 mol/l and generally up to 0.03 mol/l. An amount of from 0.0025 to 0.012 mol/l is preferred.
  • a second acidic compound in the bleaching solution can be any of a number of compounds described below.
  • it is a compound that is water-soluble and preferably biodegradable, and can be a substituted or unsubstituted 2-pyridinecarboxylic acid or substituted or unsubstituted 2,6-pyridinedicarboxylic acid (or equivalent salt).
  • the substituents which may be on the pyridinyl ring include substituted or substituted alkyl, substituted or unsubstituted cycloalkyl or substituted or unsubstituted aryl groups (as defined above for structures I-II), hydroxy, nitro, sulfo, amino, carboxy, sulfamoyl, sulfonamide, phospho, halo or any other group that does not interfere with ferric ion ternary complex formation, stability, solubility or catalytic activity.
  • the substituents can also be the atoms necessary to form a 5- to 7-membered fused ring between any of the positions of the pyridinyl nucleus.
  • the monovalent and divalent radicals defining Structures III and IV can have substituents like those defining the radicals for Structures I-II above.
  • M is as defined above.
  • R, R', R'' and R''' are independently hydrogen, hydroxy or carboxy.
  • the most preferred compounds are unsubstituted 2-pyridinecarboxylic acid and 2,6-pyridinedicarboxylic acid or salts thereof.
  • the second acidic compound is an aminopolycarboxylic acid that has at least one secondary amino group at a pH of from 8 to 11, and at least two carboxyl groups (polydentate), or their corresponding salts.
  • Such acids can be bidendate, tridentate, tetradentate, pentadentate and hexadentate ligands. These acids must be water-soluble also, and are preferably biodegradable (defined below).
  • these compounds include, but are not limited to, alkylenediaminetetracarboxylic acids having at least one secondary nitrogen atom, and alkylenediaminepolycarboxylic acids having at least one secondary nitrogen atom.
  • the "divalent substituted or unsubstituted aliphatic linking group" in the definition of "W” and “L” noted above includes any nonaromatic linking group comprised of one or more alkylene, cycloalkylene, oxy, thio, amino or carbonyl groups that form a chain of from 1 to 6 atoms.
  • Examples of such groups include, but are not limited to, alkylene, alkyleneoxyalkylene, alkylenecycloalkylene, alkylenethioalkylene, alkyleneaminoalkylene, alkylenecarbonyloxyalkylene, all of which can be substituted or unsubstituted, linear or branched, and others that would be readily apparent to one skilled in the art.
  • substituted is meant the presence of one or more substituents on the group, such as an alkyl group of 1 to 5 carbon atoms (linear or branched), hydroxy, carboxy, sulfo, sulfonato, thioalkyl, alkylcarbonamido, alkylcarbamoyl, alkylsulfonamido, alkylsulfamoyl, carbonamido, sulfonamido, sulfamoyl, amino, halo (such as chloro or bromo), sulfono (-SO 2 R) or sulfoxo [-S(O)R] wherein R is a branched or linear alkyl group of 1 to 5 carbon atoms.
  • substituents on the group such as an alkyl group of 1 to 5 carbon atoms (linear or branched), hydroxy, carboxy, sulfo, sulfonato, thioalkyl, al
  • More preferred second acidic compounds are N,N-ethylenediaminedisuccinic acid, N,N-ethylenediaminediacetic acid, and N-(2-carboxyethyl)aspartic acid, or salts thereof.
  • the amount of the second acidic compound used in the practice of this invention is at least 0.0005 to 0.05 mol/l. Preferred amounts are from 0.001 to 0.05, mol/l.
  • Mixtures of each type of first or second acidic compound can be used if desired.
  • biodegradable or “biodegradability” refer to at least 80% decomposition in the standard test protocol specified in by the Organization for Economic Cooperation and Development (OECD), Test Guideline 302B (Paris, 1981), also known as the "Modified Zahn-Wellens Test”.
  • the color photographic elements to be processed using the present invention can contain any of the conventional silver halide emulsions. They can be “high chloride” or “low chloride” emulsions, but preferably they are “high chloride” emulsidns. Thus, other emulsions are also useful, including but not limited to, silver bromide, silver iodide, silver bromoiodide, silver chloroiodide, silver chlorobromide, silver bromochloroiodide and silver chlorobromoiodide.
  • high chloride” emulsions is meant those having at least 50 mol % of chloride as the halide component of the emulsion grains.
  • Low chloride emulsions mean those having less than 30 mol % of chloride, and preferably less than 10 mol % of chloride.
  • the high chloride emulsions contain less than 5 mol % of iodide, and preferably no iodide.
  • the silver coverage can be any suitable amount known in the art, for example, 10 g/m 2 or less.
  • the amount is less than 2 g/m 2 , and more preferably, it is less than 0.8 g/m 2 (such as from 0.3 to 0.8 g/m 2 ), especially when "high" silver chloride emulsions are used.
  • the photographic elements processed in the practice of this invention can be single or multilayer color elements.
  • Multilayer color elements typically contain dye image-forming units sensitive to each of the three primary regions of the visible spectrum. Each unit can be comprised of a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum.
  • the layers of the element can be arranged in any of the various orders known in the art.
  • the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer.
  • the elements can also contain other conventional layers such as filter layers, interlayers, subbing layers, overcoats and other layers readily apparent to one skilled in the art.
  • a magnetic backing can be used as well as conventional supports.
  • emulsions can be used in the elements, including but not limited to, thin tabular grain emulsions, and either positive-working or negative-working emulsions.
  • the elements can be either photographic film or paper elements.
  • the elements are typically exposed to suitable radiation to form a latent image and then processed to form a visible dye image.
  • Processing includes the step of color development in the presence of a color developing agent to reduce developable silver halide and to oxidize the color developing agent. Oxidized color developing agent in turn reacts with a color-forming coupler to yield a dye.
  • Color developers are well known and described in many publications including the Research Disclosure noted above.
  • the color developer generally contains a buffer (such as potassium carbonate), a sulfite, chelating agents, halides, and one or more antioxidants as preservatives.
  • a buffer such as potassium carbonate
  • a sulfite such as sodium carbonate
  • chelating agents such as sodium sulfite
  • halides such as sodium sulfite
  • antioxidants as preservatives.
  • useful antioxidants including, but not limited to, hydrazines and substituted or unsubstituted hydroxylamines.
  • substituted hydroxylamines is meant, for example, those having one or more alkyl or aryl groups connected to the nitrogen atom. These alkyl or aryl groups can be further substituted with one or more groups such as sulfo, carboxy, hydroxy, alkoxy, and other groups known in the art which provide solubilizing effects.
  • hydroxylamines examples include US-A-4,876,174, US-A-4,892,804, US-A-5,178,992 and US-A-5,354,646.
  • One particularly useful hydroxylamine is N-isopropyl-N-ethylsulfonic acid hydroxylamine, or a salt thereof.
  • Development can also be carried out using what is known in the art as a "developer/amplifier” solution, as described in US-A-5,324,624.
  • bleaching and fixing steps can be carried out in any suitable fashion, as is known in the art. Subsequent to bleaching and fixing, a final washing or stabilizing step may be employed. Color prints and films can be processed using a wide variety of processing protocols, as described for example, in Research Disclosure, noted above, and thus can include various combinations of one or more bleaching, fixing, washing or stabilizing steps in various orders, and lastly, drying. Additionally, reversal processes include additional steps of black and white development, chemical fogging, re-exposure and washing prior to color development.
  • Processing according to the present invention can be carried out using conventional deep tanks holding processing solutions. Alternatively, it can be carried out using what is known in the art as "low volume thin tank” processing systems having either rack and tank or automatic tray designs. Such processing methods and equipment are described, for example, in US-A-5,436,118 and publications noted therein.
  • EKTACOLOR EDGETM photographic color paper were subjected to a step wedge test object for 1/10 second with HA-50 and NP-11 filters, a 0.3 Inconel and a 3000K color temperature lamp on a conventional lB-sensitometer. They were then processed using the following protocol (under nitrogen) wherein the bleaching time was varied to determine bleaching effectiveness. 45 seconds Development 30 seconds Stop solution (1% v/v H 2 SO 4 ) 30 seconds Water wash 0-2 minutes Bleaching 30 seconds Water wash 1 minute Fixing 2 minutes Water wash 5 minutes Dry.
  • a Control A bleaching solution contained hydrogen peroxide (0.98 mol/l. 3% w/w), potassium chloride (0.35 mol/l), potassium carbonate (0.025 mol/l), potassium bicarbonate (0.025 mol/l) and 1-hydroxyethylidene-1,1-diphosphonic acid (0.004 mol/l), and was adjusted to pH 10 using potassium hydroxide.
  • a Control B bleaching solution contained hydrogen peroxide (0.98 mol/l, 3% w/w), potassium chloride (0.35 mol/l), potassium carbonate (0.025 mol/l), potassium bicarbonate (0.025 mol/l) and 2-pyridinecarboxylic acid (0.035 mol/l), and was adjusted to pH 10 using potassium hydroxide.
  • a Control C bleaching solution contained hydrogen peroxide (0.98 mol/l, 3% w/w), potassium chloride (0.35 mol/l), potassium carbonate (0.025 mol/l), potassium bicarbonate (0.025 mol/l) and 2,6-pyridinedicarboxylic acid (0.035 mol/l), and was adjusted to pH 10 using potassium hydroxide.
  • Control D bleaching solution was like Control A except that the phosphonic acid was omitted.
  • An Example 1 bleaching solution contained hydrogen peroxide (0.98 mol/l, 3% w/w), potassium chloride (0.35 mol/l), potassium carbonate (0.025 mol/l), potassium bicarbonate (0.025 mol/l), 1-hydroxyethylidene-1,1-diphosphonic acid (0.004 mol/l) and 2-pyridinecarboxylic acid (0.035 mol/l), and was adjusted to pH 10 using potassium hydroxide.
  • An Example 2 bleaching solution contained hydrogen peroxide (0.98 mol/l, 3% w/w), potassium chloride (0.35 mol/l), potassium carbonate (0.025 mol/l), potassium bicarbonate (0.025 mol/l), 1-hydroxyethylidene-1,1-diphosphonic acid (0.004 mol/l) and 2,6-pyridinedicarboxylic acid (0.035 mol/l), and was adjusted to pH 10 using potassium hydroxide.
  • FIG. 1 shows stability data for the Controls, Example 1 and Example 2 bleaching solutions. These solutions were stored at room temperature for a number of days. After certain number of days, samples of the solutions were evaluated for the amount of hydrogen peroxide remaining. This evaluation was achieved electroanalytically by cyclic voltammetry using a mercury drop electrode. The electroanalytical data were recorded using a conventional EG&G Princeton Applied Research Potentiostat/Galvanostat, Model 273A. The results were plotted as Relative Peroxide Concentration (%) versus time (days). The data for Controls B, C and D were the same, as shown in FIG. 1.
  • Residual silver (g/m 2 ) was determined by X-ray fluorescence using conventional procedures. The results are tabulated below in Table I for certain density exposures after 45 seconds. Results are also presented for the use of the conventional KODAK EKTACOLORTM RA bleach-fixing solution.
  • Step Number RA (g/m 2 ) Control A (g/m 2 ) Control B (g/m 2 ) Control C (g/m 2 ) Example 1 (g/m 2 ) Example 2 (g/m 2 ) 1 0.04 0.03 0.67 0.67 0.01 0.02 3 0.05 0 0.62 0.61 0.03 0.02 5 0.05 0.02 0.60 0.56 0.05 0.02 7 0.03 0 0.49 0.44 0.01 0.01 9 0.03 0 0.26 0.2 0.02 0 11 0 0 0.06 0.02 0.01 13 0 0.01 0.01 0 0 0 15 0 0 0.01 0 0 0 17 0 0 0.01 0 0.02 0 19 0 0.02 0.02 0.01 0 0.02 21 0 0 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01
  • Control B and C bleaching solutions containing only a "second" acid did not provide effective bleaching after 45 seconds.
  • the Control A bleaching solution containing only a "first” acid did provide acceptable bleaching.
  • the Control A bleaching solution was not acceptably stable after storage for 14 days at room temperature.
  • the Example 1 and 2 bleaching solutions demonstrated considerably better storage stability over the test period. No vesiculation was observed with use of the present invention.
  • the results also show that use of the present invention provided comparable bleaching to the conventional KODAK EKTACOLORTM RA bleach-fixing solution after storage for 21 days.
  • bleaching solutions of this invention were evaluated for bleaching effectiveness according to the present invention. They were also evaluated for stability. Several comparison bleaching solutions were also evaluated.
  • the bleaching solutions contained hydrogen peroxide (0.98 mol/l), potassium chloride (0.35 mol/l), potassium carbonate (0.025 mol/l), potassium bicarbonate (0.025 mol/l) and the sequestering agents and amounts listed in Table II below, and were adjusted to pH 10 using potassium hydroxide.
  • Example 4 1-hydroxyethylidene-1,1-diphosphonic acid 0.004 mol/l 0.0 0.0 0.0 0.004 mol/l 0.004 mol/l 0.004 mol/l N,N-ethylenediamine disuccinic acid 0.0 0.002 mol/l 0.0 0.0 0.002 mol/l 0.0 0.0 N,N-ethylenediamine diacetic acid 0.0 0.0 0.002 mol/l 0.0 0.0 0.002 mol/l 0.0 N-(2-carboxyethyl)-aspartic acid 0.0 0.0 0.0 0.002 mol/l 0.0 0.0 0.002 mol/l
  • the bleaching solutions described above were evaluated for stability over time.
  • the molar concentration (mol/l) of the peroxide bleaching agent was measured electroanalytically by cyclic voltammetry using a mercury drop electrode.
  • the electroanalytical data were recorded using a conventional EG&G Princeton Applied Research Potentiostat/Galvanostat, Model 273A. The results of these measurements over time are provided in Table III below.
  • Each solution was normalized to 0.98 mol of hydrogen peroxide per liter of solution prior to the first measurement.
  • the bleaching compositions of this invention were also evaluated for bleaching activity after 21 days of storage at room temperature.
  • Samples of KODAK EKTACOLOR EDGETM photographic color paper were subjected to a step wedge test object for 1/10 second with HA-50 and NP-11 filters, a 0.3 Inconel and a 3000K color temperature lamp on a conventional lB-sensitometer. They were then processed using the following protocol (under nitrogen). 45 seconds Development 30 seconds Stop solution (1% v/v H 2 SO 4 ) 30 seconds Water wash 45 seconds Bleaching 30 seconds Water wash 1 minute Fixing 2 minutes Water wash 5 minutes Dry.
  • Residual silver (g/m 2 ) at maximum density was determined by X-ray fluorescence using conventional procedures. The results are tabulated below in Table IV after 45 seconds for certain exposure densities. Results are also presented for the use of the conventional KODAK EKTACOLORTM RA bleach-fixing solution, and for the Control E solution, both freshly prepared. Of course, in the use of the KODAK EKTACOLORTM RA bleach-fixing solution, the noted fixing and preceding wash steps were omitted from the processing protocol.
  • Step Number RA-4 (g/m 2 ) Control E (g/m 2 ) Example 3 (g/m 2 ) Example 4 (g/m 2 ) Example 5 (g/m 2 ) 1 0.05 0 0.02 0.01 0 2 0.03 0.01 0 0.01 0.01 3 0.04 0 0.02 0 0.01 11 0.01 0.01 0.02 0.02 0 18 0.01 0 0.02 0 0 19 0.01 0.04 0.01 0.01 0 20 0 0.01 0.01 0 0 0

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Claims (16)

  1. Wasserstoffperoxid-Bleichlösung mit einem pH-Wert von 7 bis 13, die enthält:
    ein Wasserstoffperoxid-Bleichmittel und Chloridionen, die in einer Menge von mindestens 0,35 Mol/l vorhanden sind,
    wobei die Bleichlösung weiter dadurch gekennzeichnet ist, daß sie enthält:
    a) eine erste saure Verbindung, die eine organische Phosphonsäure oder ein Salz hiervon ist, und
    b) eine zweite saure Verbindung, die entweder ist:
    eine 2-Pyridincarboxylsäure oder eine 2,6-Pyridindicarboxylsäure oder ein Salz hiervon, oder
    eine Aminopolycarboxylsäure mit mindestens einer sekundären Amingruppe bei einem pH-Wert von 8 bis 11 oder ein Salz hiervon.
  2. Lösung nach Anspruch 1 mit einem pH-Wert von 8 bis 11, und in der das Bleichmittel Wasserstoffperoxid ist.
  3. Lösung nach einem der Ansprüche 1 oder 2, worin die Chloridionen in einer Menge von 0,45 bis 2 Mol/l vorhanden sind, in der die erste saure Verbindung in einer Menge von 0,0005 bis 0,03 Mol/l vorliegt, und in der die zweite saure Verbindung in einer Menge von 0,0005 bis 0,05 Mol/l vorhanden ist.
  4. Lösung nach einem der Ansprüche 1 bis 3, in der die organische Phosphonsäure oder das Salz hiervon der Struktur (I) entspricht: R1N(CH2PO3M2)2 oder der Struktur (II): R2R3C(PO3M2)2 worin
    R1 ein Wasserstoffatom ist, eine Alkylgruppe mit 1 bis 12 Kohlenstoffatomen, eine Alkylaminoalkylgruppe, eine Alkoxyalkylgruppe mit 1 bis 12 Kohlenstoffatomen, eine Cycloalkylgruppe mit 5 bis 10 Kohlenstoffatomen, eine Arylgruppe mit 6 bis 10 Kohlenstoffatomen oder eine 5- bis 10-gliedrige heterocyclische Gruppe, worin
    R2 steht für Wasserstoff, eine Alkylgruppe mit 1 bis 12 Kohlenstoffatomen, eine Arylgruppe mit 6 bis 10 Kohlenstoffatomen, eine Cycloalkylgruppe mit 5 bis 10 Kohlenstoffatomen, eine 5- bis 10-gliedrige heterocyclische Gruppe, oder -PO3M2 oder -CHR4PO3M2, worin
    R3 steht für Wasserstoff, Hydroxyl, eine Alkylgruppe mit 1 bis 12 Kohlenstoffatomen oder -PO3M2,
    R4 steht für Wasserstoff, Hydroxyl, eine Alkylgruppe mit 1 bis 12 Kohlenstoffatomen oder -PO3M2, und worin
    M steht für Wasserstoff oder ein wasserlösliches monovalentes Kation.
  5. Lösung nach einem der Ansprüche 1 bis 4, in der die zweite saure Verbindung eine der Strukturen hat:
    Figure 00340001
    Figure 00340002
    worin R, R', R" und R"' unabhängig voneinander stehen für Wasserstoff, eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, eine Arylgruppe mit 6 bis 10 Kohlenstoffatomen, eine Cycloalkylgruppe mit 5 bis 10 Kohlenstoffatomen, Hydroxy, Nitro, Sulfo, Amino, Phospho, Carboxy, Sulfamoyl, Sulfonamido oder Halo, oder
    wobei zwei von R, R', R" und R"' die Kohlenstoffatome darstellen können, die erforderlich sind zur Bildung eines 5- bis 7-gliedrigen Ringes, der an den Pyridinylkern ankondensiert ist, und worin
    M steht für Wasserstoff oder ein monovalentes Kation, oder
    Figure 00340003
    worin
    R5, R6, R7, R8, R9 und R10 unabhängig voneinander stehen für Wasserstoff, Hydroxy, eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, eine Cycloalkylgruppe mit 5 bis 10 Kohlenstoffatomen oder eine Arylgruppe mit 6 bis 10 Kohlenstoffatomen im aromatischen Kern,
    M die oben angegebene Bedeutung hat, und
    W eine kovalente Bindung oder eine divalente aliphatische verbindende Gruppe ist,
    Figure 00350001
    worin mindestens zwei von R11, R12 und R13 Carboxymethylgruppen oder äquivalente Salze sind, und worin die dritte Gruppe für Wasserstoff steht,
    Figure 00350002
    worin
    einer von R14 und R15 eine Carboxymethyl- oder 2-Carboxyethylgruppe oder ein äquivalentes Salz hiervon ist, und der andere Rest für Wasserstoff steht, und
    R16, R17, R18 und R19 unabhängig voneinander stehen für Wasserstoff, eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, Hydroxy, Carboxymethylamino, Carboxy oder Carboxymethyl, oder ein äquivalentes Salz hiervon, wobei gilt, daß ein Rest und nur ein Rest von R16, R17, R18 und R19 steht für Carboxy, Carboxymethylamino oder Carboxymethyl oder ein äquivalentes Salz hiervon,
    Figure 00350003
    worin
    einer der Reste R20 und R21 steht für Wasserstoff und der andere Rest steht für eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen, eine Hydroxyethylgruppe, eine Carboxymethylgruppe oder eine 2-Carboxyethylgruppe oder ein äquivalentes Salz hiervon,
    M hat die oben angegebene Definition, und
    p und q stehen unabhängig voneinander für 0, 1 oder 2, wobei gilt, daß die Summe von p und q Zwei nicht übersteigt, oder
    Figure 00360001
    worin
    Z für eine Arylgruppe mit 6 bis 10 Kohlenstoffatomen im Kern steht oder eine heterocyclische Gruppe mit 5 bis 7 Kohlenstoff-, Stickstoff-, Schwefel- und Sauerstoffatomen im Kern,
    L steht für eine divalente aliphatische verbindende Gruppe,
    einer der Reste R22 und R23 steht für Wasserstoff und der andere Rest steht für eine Carboxyalkylgruppe mit 2 bis 4 Kohlenstoffatomen oder eine Hydroxy-substituierte Carboxyalkylgruppe mit 2 bis 4 Kohlenstoffatomen oder ein äquivalentes Salz hiervon, und r steht für 0 oder 1, wobei gilt, daß mindestens zwei Carboxygruppen im Molekül vorliegen.
  6. Lösung nach einem der Ansprüche 1 bis 5, in der die erste saure Verbindung 1-Hydroxyethyliden-1,1-diphosphonsäure, Nitrilo-N,N,N-trimethylenphosphonsäure, Diethylentriamin-N,N,N',N",N"-penta(methylenphosphonsäure) oder ein Salz der Säuren ist, und
    die zweite saure Verbindung 2-Pyridincarboxylsäure, 2,6-Pyridindicarboxylsäure, N,N-Ethylendiamindisuccinsäure, N,N-Ethylendiamindiessigsäure, N-(2-carboxyethyl)aspartinsäure oder ein Salz der Säuren ist.
  7. Verfahren zur Entwicklung eines farbphotographischen Elementes, das umfaßt:
    das Ausbleichen eines bildweise exponierten und entwickelten farbphotographischen Elementes mit einer Wasserstoffperoxid-Bleichlösung nach einem der Ansprüche 1 bis 6.
  8. Verfahren nach Anspruch 7, in dem die Bleichlösung die Chloridionen in einer Menge von 0,45 bis 1 Mol/l enthält.
  9. Verfahren nach einem der Ansprüche 7 oder 8, bei dem die organische Phosphonsäure oder ein Salz hiervon in einer Menge von 0,0025 bis 0,012 Mol/l vorliegt, und die zweite saure Verbindung in einer Menge von 0,001 bis 0,05 Mol/l vorhanden ist.
  10. Verfahren nach einem der Ansprüche 7 bis 9, bei dem das Bleichmittel in einer Menge von 0,15 bis 5 Mol/l vorliegt.
  11. Verfahren nach einem der Ansprüche 7 bis 10, bei dem das photographische Element eine Silberhalogenidemulsion aufweist mit mehr als 50 Mol-% Silberchlorid und weniger als 5 Mol-% Silberiodid.
  12. Verfahren nach einem der Ansprüche 7 bis 10, bei dem das photographische Element eine Silberhalogenidemulsion mit mehr als 90 % Silberchlorid enthält.
  13. Verfahren nach einem der Ansprüche 7 bis 12, das in einem Entwicklungssystem mit einem dünnen Tank eines geringen Volumens durchgeführt wird.
  14. Verfahren nach einem der Ansprüche 7 bis 13, in dem das zu entwickelnde photographische Element weniger als 0,8 g Silber pro m2 enthält.
  15. Verfahren nach einem der Ansprüche 7 bis 14, bei dem dem Bleichen mit der Peroxid-Bleichlösung eine Farbentwicklung mit einer Entwickler-/Verstärkerlösung vorangestellt wird.
  16. Verfahren nach einem der Ansprüche 7 bis 15, bei dem dem Bleichen mit der Bleichlösung eine Farbentwicklung mit einer Farbentwicklerlösung vorangestellt wird, die N-Isopropyl-N-ethylsulfonsäurehydroxylamin oder ein Salz hiervon enthält.
EP19960200947 1995-04-17 1996-04-15 Stabilisierte Peroxid-Bleichlösungen und deren Verwendung zur Verarbeitung von photographischen Elementen Expired - Lifetime EP0738919B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US08/422,468 US5550009A (en) 1995-04-17 1995-04-17 Stabilized peroxide bleaching solutions and their use for processing of photographic elements
US08/423,257 US5541041A (en) 1995-04-17 1995-04-17 Stabilized peroxide bleaching solutions containing multiple chelating ligands and their use for processing of photographic elements
US423257 1995-04-17
US422468 1995-04-17

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EP0738919A3 EP0738919A3 (de) 1997-01-15
EP0738919B1 true EP0738919B1 (de) 1998-12-30

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EP0738919A2 (de) 1996-10-23
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DE69601244D1 (de) 1999-02-11

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