EP0258288B1 - Compositions photographiques de developpement en couleur, specialement utiles avec des elements photographiques a haute teneur en chlorure - Google Patents

Compositions photographiques de developpement en couleur, specialement utiles avec des elements photographiques a haute teneur en chlorure Download PDF

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EP0258288B1
EP0258288B1 EP87900926A EP87900926A EP0258288B1 EP 0258288 B1 EP0258288 B1 EP 0258288B1 EP 87900926 A EP87900926 A EP 87900926A EP 87900926 A EP87900926 A EP 87900926A EP 0258288 B1 EP0258288 B1 EP 0258288B1
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Prior art keywords
color developing
composition
agent
photographic
acid
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EP0258288A1 (fr
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Sheridan E. Vincent
Richard W. Berls
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • 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
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers
    • G03C5/3053—Tensio-active agents or sequestering agents, e.g. water-softening or wetting agents

Definitions

  • This invention relates in general to photography and in particular to novel compositions and methods for processing photographic color elements. More specifically, this invention relates to novel photographic color developing compositions and to a novel method of rapid access processing of high chloride photographic elements utilizing such developing compositions.
  • the color-forming coupler may be either in the developer solution or incorporated in the light-sensitive photographic emulsion layer so that, during development, it is available in the emulsion layer to react with the color developing agent that is oxidized by silver image development.
  • Diffusible couplers are used in color developer solutions.
  • Nondiffusing couplers are incorporated in Photographic emulsion layers.
  • couplers are selected which form non-diffusing dyes.
  • couplers are used which will produce diffusible dyes capable of being mordanted or fixed in the receiving sheet.
  • Photographic color elements often utilize silver halide emulsions of the high bromide type, including silver bromide, silver bromoiodide and silver chlorobromide emulsions.
  • high chloride silver halide photographic elements _ that is, elements in which the silver halide grains are at least 80 mole percent silver chloride _ possess a number of highly advantageous characteristics.
  • silver chloride possesses less native sensitivity in the visible region of the spectrum than silver bromide, thereby permitting yellow filter layers to be omitted from multicolor photographic elements.
  • high chloride silver halides are more soluble than high bromide silver halides, thereby permitting development to be achieved in shorter times.
  • Photographic color developing compositions used heretofore have typically been adapted for use with high bromide silver halide photographic elements.
  • These conventional developing compositions can be used with high chloride silver halide photographic elements, but, in general, they tend to give less than satisfactory results.
  • hydroxylamine or a water-soluble acid salt thereof
  • hydroxylamine or a water-soluble acid salt thereof
  • it tends to act as a scavenger which reduces oxidized color developing agent before it can react with coupler to form dye. It also acts as a developing agent which competes with the color developing agent unless it is adequately restrained by bromide.
  • developing compositions heretofore used with high bromide silver halide elements often contain substantial concentrations of sulfite to also provide protection against oxidation of the developing agent.
  • the sulfite which is typically utilized in the form of an alkali metal sulfite or bisulfite, functions to sulfonate oxidized color developing agent and, when used in sufficient concentration, its competition with coupler for oxidized color developing agent seriously affects dye formation.
  • novel photographic color developing compositions of this invention are especially useful with high chloride silver halide emulsions. They are free, or at least substantially free, of bromides, since bromides in significant quantities can unduly restrain the development reaction. They are free of sulfite, or contain only a low concentration of sulfite, to minimize competition with the dye-forming reactions. They contain the following ingredients:
  • the aforesaid photographic color developing composition is free of benzyl alcohol and is used in a rapid access process for processing high chloride silver halide photographic color elements which employs the steps of color developing, bleach-fixing without washing between the color developing and bleach-fixing steps, and stabilizing without washing between the bleach-fixing and stabilizing steps.
  • Elimination of the benzyl alcohol from the developing composition allows the bleach-fix to be utilized at a lower pH than is otherwise permissible, without the risk of producing leuco cyan dye.
  • the low pH increases the rate of bleach-fix reactions, thereby enabling the use of a short bleach-fix time as is needed for a rapid access process.
  • the primary aromatic amino color developing agents that are utilized in the compositions and methods of this invention are well known and widely used in a variety of color photographic processes. They include aminophenols and p-phenylenediamines. They are usually used in the salt form, such as the hydrochloride or sulfate, as the salt form is more stable than the free amine, and are generally employed in concentrations of from about 0.1 to about 20 grams per liter of developing solution and more preferably from about 0.5 to about 10 grams per liter of developing solution.
  • aminophenol developing agents examples include o-aminophenol, p-aminophenol, 5-amino-2-hydroxy-toluene, 2-amino-3-hydroxy-toluene, 2-hydroxy-3-amino-1,4-dimethylbenzene, and the like.
  • Particularly useful primary aromatic amino color developing agents are the p-phenylenediamines and especially the N,N-dialkyl-p-phenylenediamines in which the alkyl groups or the aromatic nucleus can be substituted or unsubstituted.
  • Examples of useful p-phenylenediamine color developing agents include:
  • An especially preferred class of p-phenylenediamine developing agents are those containing at least one alkylsulfonamidoalkyl substitutent attached to the aromatic nucleus or to an amino nitrogen.
  • Other especially preferred classes of p-phenylenediamines are the 3-alkyl-N-alkyl-N-alkoxyalkyl-p-phenylenediamines and the 3-alkoxy-N-alkyl-N-alkoxy-alkyl-p-phenylenediamines.
  • n is an integer having a value of from 2 to 4
  • R is an alkyl group of from 1 to 4 carbon atoms
  • R1 is an alkyl group of from 1 to 4 carbon atoms or an alkoxy group of from 1 to 4 carbon atoms.
  • Illustrative examples of these developing agents include the following compounds:
  • the developing compositions of this invention contain an N,N-dialkylhydroxylamine.
  • the N,N-dialkylhydroxylamine can be used in the color developing composition in the form of the free amine, but is more typically employed in the form of a water-soluble acid salt.
  • Typical examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and the like.
  • N,N-dialkylhydroxylamine is preferably of the formula: wherein R3 and R4 represent the same or different alkyl groups of 1 to 4 carbon atoms.
  • N,N-dialkylhydroxylamines include:
  • N,N-dialkylhydroxylamine in the photographic color developing compositions of this invention provides fully adequate stability against oxidation, without the unwanted development and unwanted reaction with oxidized color developing agent that occurs with the use of unsubstituted hydroxylamines or mono-alkyl substituted hydroxylamines. This is believed to be a result of the two alkyl groups attached to the nitrogen atom serving to block the site at which reaction could otherwise take place.
  • N,N-dialkylhydroxylamines have been used heretofore in photographic color developing compositions.
  • they are used in the magenta color developing solutions described in Anselm, United States patent 3,489,566, issued January 13, 1970.
  • magenta developing solutions they are employed in combination with an unsubstituted or mono-alkyl substituted hydroxylamine, and they serve as balancing developing agents.
  • the novel color developing compositions of this invention contain at least one sequestering agent which functions to sequester iron.
  • the preferred sequestering agent for this purpose is an aromatic polyhydroxy compound that forms a complex with ferric ion in alkaline solution in which the molar ratio of the ferric ion to the aromatic polyhydroxy compound is 1 to 3.
  • the aromatic polyhydroxy compound is a compound having at least two hydroxy groups in ortho-position in relation to each other on an aromatic ring. Most preferably, it is a compound which has at least two hydroxy groups in ortho-position in relation to each other on an aromatic carbocyclic ring and which is free of exocyclic unsaturation.
  • the aromatic ring structure can be substituted with groups such as sulfo radicals, carboxy radicals, or halogen atoms.
  • Typical examples of aromatic polyhydroxy compounds useful in this invention include the following compounds:
  • the aromatic polyhydroxy compound is 5,6-dihydroxy-1,2,4-benzenetrisulfonic acid or a 5,6-dihydroxy-1,2,4-benzenetrisulfonate (also known as a catechol trisulfonate or pyrocatechol trisulfonate).
  • a 5,6-dihydroxy-1,2,4-benzenetrisulfonate also known as a catechol trisulfonate or pyrocatechol trisulfonate.
  • M is hydrogen or a monovalent cation such as sodium or potassium.
  • the most preferred compound of this class is 5,6-dihydroxy-1,2,4-benzenetrisulfonic acid trisodium salt.
  • the 5,6-dihydroxy-1,2,4-benzenetrisulfonic acid trisodium salt is advantageously employed in photographic color developing compositions in comparison with other similar aromatic polyhydroxy compounds, such as 4,5-dihydroxy-m-benzene disulfonic acid disodium salt in that it is more stable to aerial oxidation and has much less tendency to exhibit adverse sensitometric effects. It can be prepared by oxidation of 4,5-dihydroxy-m-benzene disulfonic acid disodium salt in an alkaline solution containing sulfite. Oxidation can be accomplished by bubbling air through the solution or by reaction with a persulfate.
  • Aromatic polyhydroxy compounds have been used heretofore in photographic color developing compositions. Thus, for example, they are used in Heilmann, U.S. patent 3,746,544, issued July 17, 1973, in combination with aminopolycarboxylic acid sequestering agents and in Vincent et al, U.S. patent 4,264,716, issued April 28, 1981, in combination with aminopolyphosphonic acid sequestering agents.
  • the primary function of the aromatic polyhydroxy compound in the photographic color developing compositions of this invention is to sequester iron but it can also function to sequester other heavy metals which can also catalyze the auto-oxidation of the N,N-dialkylhydroxylamine.
  • the aromatic polyhydroxy compound stabilizes the developing composition and enables the N,N-dialkylhydroxylamine to effectively perform its function as an anti-oxidant which protects the primary aromatic amino color developing agent.
  • the novel color developing compositions of this invention contain at least one sequestering agent which functions to sequester calcium and thereby prevent the formation of unwanted precipitates.
  • the preferred sequestering agent for this purpose is an aminopolycarboxylic acid sequestering agent.
  • aminopolycarboxylic acid sequestering agents are well known and widely used in photographic processing. Typical examples of the aminopolycarboxylic acid sequestering agents include:
  • the photographic color developing compositions of this invention are employed in the form of aqueous alkaline working solutions having a pH of above 7 and most typically in the range of from about 9 to about 13. To provide the necessary pH, they contain one or more of the well known and widely used pH buffering agents, such as the alkali metal carbonates or phosphates. Potassium carbonate is especially useful as a pH buffering agent.
  • the four essential components of the novel photographic color developing compositions of this invention are the primary aromatic amino color developing agent, the N,N-dialkylhydroxylamine, the sequestering agent which functions to sequester iron and the sequestering agent which functions to sequester calcium.
  • the N,N-dialkylhydroxylamine is preferably employed in an amount of from about 1.5 to about 6.0 moles per mole of the developing agent
  • the sequestering agent which functions to sequester iron is preferably employed in an amount of from about 0.04 to about 0.25 moles per mole of the developing agent
  • the sequestering agent which functions to sequester calcium is preferably employed in an amount of from about 0.3 to about 1.7 moles per mole of the developing agent.
  • a small amount of sulfite can optionally be incorporated in the developing compositions of this invention to provide additional protection against oxidation.
  • the amount of sulfite is in the range of from zero to 0.2 moles per mole of primary aromatic amino color developing agent.
  • the use of a small amount of sulfite is especially desirable when the color developing composition is packaged in the form of a concentrated solution, since such concentrates are especially susceptible to oxidation.
  • a further ingredient which can optionally be included in the color developing composition is an alkanolamine.
  • the alkanolamines are primarily useful in providing additional protection against oxidation.
  • preferred alkanolamines for use in photographic color developing compositions are compounds of the formula: wherein R1 is an hydroxyalkyl group of 2 to 6 carbon atoms and each of R2 and R3 is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an hydroxyalkyl group of 2 to 6 carbon atoms, a benzyl radical, or a wherein n is an integer of from 1 to 6 and each of X and Y is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms or an hydroxylalkyl group of 2 to 6 carbon atoms.
  • Alkanolamines which are especially preferred are compounds of the formula: wherein R4 is an hydroxyalkyl group of 2 to 4 carbon atoms and each of R5 and R6 is an alkyl group of 1 to 4 carbon atoms or an hydroxyalkyl group of 2 to 4 carbon atoms.
  • Typical examples of alkanolamines which can be used in the color developing compositions of this invention include:
  • a water-soluble sulfonated polystyrene can be used in the free acid form or in the salt form.
  • the free acid form of the sulfonated polystyrene is comprised of units having the formula: where X is an integer representing the number of repeating units in the polymer chain and is typically in the range from about 10 to about 3,000 and more preferably in the range from about 100 to about 1,000.
  • the salt form of the sulfonated polystyrene is comprised of units having the formula: where X is as defined above and M is a monovalent cation, such as, for example, an alkali metal ion.
  • the sulfonated polystyrenes utilized in the developing compositions of this invention can be substituted with substituents such as halogen atoms, hydroxy groups, and alkyl groups.
  • substituents such as halogen atoms, hydroxy groups, and alkyl groups.
  • they can be sulfonated derivatives of chlorostyrene, alpha methyl styrene, vinyl toluene, and the like.
  • substituents such as halogen atoms, hydroxy groups, and alkyl groups.
  • they can be sulfonated derivatives of chlorostyrene, alpha methyl styrene, vinyl toluene, and the like.
  • the molecular weight nor the degree of sulfonation are critical, except that the molecular weight should not be so high nor the degree of sulfonation so low as to render the sulfonated polystyrene insoluble in aqueous alkaline photographic color developing
  • the average degree of sulfonation that is the number of sulfonic acid groups per repeating styrene unit, is in the range from about 0.5 to 4 and more preferably in the range from about 1 to about 2.5.
  • a variety of salts of the sulfonated polystyrene can be employed, including, in addition to alkali metal salts, the amine salts such as salts of monoethanolamine, diethanolamine, triethanolamine, morpholine, pyridine, picoline, quinoline.
  • the sulfonated polystyrene can be used in the working developer solution in any effective amount. Typically, it is employed in amounts of from about 0.05 to about 30 grams per liter of developer solution, more usually in amounts of from about 0.1 to about 15 grams per liter, and preferably in amounts of from about 0.2 to about 5 grams per liter.
  • the photographic color developing compositions of this invention can contain an aminopolyphosphonic acid sequestering agent.
  • the aminopolyphosphonic acid sequestering agent can be utilized in the form of a free acid or in the form of a water-soluble salt.
  • useful aminopolyphosphonic acid sequestering agents are the following:
  • hydroxyalkylidenediphosphonic acid sequestering agents of the formula: where R is alkyl of 1 to 5 carbon atoms.
  • the hydroxyalkylidenediphosphonic acid sequestering agents can serve as both the sequestering agent which functions to sequester iron and the sequestering agent which functions to sequester calcium, as they have the ability to effectively sequester both iron and calcium.
  • they are preferably utilized in combination with small amounts of lithium salts, such as lithium sulfate.
  • Additional ingredients which can optionally be included in the photographic color developing compositions of this invention include thickening agents, brightening agents, wetting agents, stain reducing agents, and so forth.
  • the photographic color developing compositions of this invention are preferably free, or at least substantially free, of bromides.
  • substantially free is meant a concentration of bromide of not more than about 0.01 moles per mole of primary aromatic amino color developing agent.
  • bromides are very active development restrainers. To achieve the objective of a very short development time, it is necessary to have little or no bromide in the developing solution. Where the emulsions used are all-chloride emlsions, then there will not be any bromide present in the developing solution as a result of leaching from the element.
  • high chloride silver halide elements are elements in which the silver halide grains are at least 80 mole percent silver chloride.
  • high chloride silver halide elements can contain small amounts of silver bromide or silver bromoiodide, the amounts are low enough that the concentration of bromide in the developing solution that results from leaching is low, and the restraining effect is not pronounced.
  • Chloride will, of course, be leached from high chloride silver halide elements, but chloride is not nearly as active a development restrainer as bromide.
  • An important objective of the preferred embodiments of this invention is to have minimal development restraint from either developing composition components or from seasoning products that leach from the photographic element.
  • the working solution may contain chloride that has leached from the element, typically no chloride is incorporated in the replenisher solution.
  • the photographic color developing compositions of this invention be free of benzyl alcohol.
  • benzyl alcohol has typically been used in the processing of color print papers to function as a coupling accelerator. Since the developing compositions of this invention are designed to have minimal development restraint _ and since oxidation protection is provided by use of an N,N-dialkylhydroxylamine, optionally with the additional use of a small amount of sulfite, and therefore without introducing significant competition with coupler for oxidized developing agent _ they do not require the use of benzyl alcohol. Elimination of benzyl alcohol has several benefits. For example, it provides improved mixability of the developing composition components and it provides the environmental improvement of reduced biological oxygen demand.
  • a further advantage is that for those processes in which a bleach-fix is utilized, the elimination of benzyl alcohol from the developer enables the pH of the bleach-fix to be reduced without the risk of producing leuco cyan dye.
  • the reduced pH increases the rate of bleach-fix reactions, and thereby allows a very short bleach-fix time and, accordingly, facilitates accomplishment of the goal of a very short total processing time.
  • Yet another advantage of eliminating benzyl alcohol from the color developing composition is that this will help in avoiding or minimizing edge staining of the photographic print, as described for example in Tamagawa et al, United States Patent 4,433,030, issued February 21, 1984.
  • Color print papers are most commonly processed by use of a bleach-fixing solution.
  • the bleaching agent is typically a ferric complex of an aminopolycarboxylic acid, most usually the ferric complex of ethylenediaminetetraacetic acid (EDTA).
  • the fixing agent is typically a thiosulfate such as sodium thiosulfate or ammonium thiosulfate.
  • the bleach-fixing step can be followed by a stabilizing step in which the print is processed in a stabilizing bath to reduce fading of the dye images and staining of the print that can result from exposure to high humidities and/or high temperatures.
  • the stabilizing bath will typically contain an aldehyde, such as formaldehyde, which is known to react with the active methylene groups on residual color-forming couplers, and thus prevent them from reacting with the image dyes.
  • the stabilizing bath can contain a variety of other agents such as sequestering agents, buffering agents, and biocides. Particularly, effective stabilizing baths for use in the process of this invention are described in Mowrey, U.S. patent 3,676,136, issued July 11, 1972.
  • novel color developing compositions of this invention are especially useful in the processing of color print papers utilizing high chloride silver halide emulsion layers and particularly in the processing of such papers in a rapid access process comprising the steps of color developing, bleach-fixing without a wash step between the steps of color developing and bleach-fixing, and stabilizing without a wash step between the steps of bleach-fixing and stabilizing.
  • the bleach-fixing composition is comprised of a thiosulfate fixing agent and a ferric complex of an aminopolycarboxylic acid, which acts as a bleaching agent, while the stabilizing composition contains an aldehyde as the stabilizing agent.
  • Such a process involves only the three steps of color developing, bleach-fixing and stabilizing _ followed by a short drying step _ so it is especially well adapted to the very short total processing time that is needed in so-called "mini-lab” processing facilities.
  • the wash steps are omitted in the interest of achieving the shortest possible total processing time and reducing the total amount of effluent.
  • the present invention futhermore provides a method of rapid access processing of a high chloride silver halide photographic color print paper, which comprises the steps of:
  • the print is dried for a brief period. Drying for about one minute at a temperature of about 60°C is usually adequate.
  • the stabilizing bath advantageously comprises an aminopolycarboxylic acid sequestering agent, of the type hereinbefore described, and an aminopolyphosphonic acid sequestering agent or hydroxyalkylidenediphosphonic acid sequestering agent of the types hereinbefore described.
  • the aminopolyphosphonic acid or hydroxyalkylidenediphosphonic acid sequesters heavy metals, such as copper and iron, and thereby prevents such metals from catalyzing the oxidation of sulfile.
  • biocide Another useful ingredient in a stabilizing bath of this type is a biocide.
  • biocide examples include thiazoles such as 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one.
  • the individual ingredients employed in the photographic color developing compositions of this invention have been employed heretofore in one or other of the photographic color developing compositions described in the United States patents listed hereinabove.
  • the particular combination of ingredients utilized in the color developing compositions of this invention is a novel combination, and is unexpectedly advantageous in providing a developing composition which is especially adapted for use with high chloride silver halide elements, and is particularly well adapted for use in the rapid access process described herein in which total wet processing time is as little as three minutes.
  • N,N-dialkylhydroxylamine is utilized in the developing composition of this invention as an anti-oxidant.
  • This is in contrast with its typical use in the prior art, for example, in United States patent 3,489,566, in which it is used primarily as a balancing developing agent, that is as an agent which reacts with exposed silver halide so as to function as an auxiliary developing agent.
  • the hydroxylamines which are used in the color developing compositions described are hydroxylamines of the formula: where R is hydrogen or alkyl, and water-soluble acid salts thereof.
  • the hydroxylamines in these patents are unsubstituted hydroxylamines or monoalkyl-substituted hydroxylamines.
  • dialkyl-substituted hydroxylamines are utilized rather than unsubstituted hydroxylamines or mono-alkyl-substituted hydroxylamines.
  • dialkyl-substituted hydroxylamines have been unexpectedly found to provide satisfactory protection against oxidation, while having the advantage that they do not reduce oxidized developer before it can react to form dye, and the further advantage that they are much slower developing agents than unsubstituted hydroxylamines or mono-alkyl-substituted hydroxylamines.
  • competition with couplers in the dye-forming reactions is effectively avoided.
  • a photographic color print paper of the high chloride type as described in Atwell, U.S. patent 4,269,927 issued May 26, 1981, was processed in a three-step process consisting of a 45 second development step, a 45 second bleach-fix step and a 90 second stabilization step. Each of the three steps was carried out at a temperature of 35°C and the print was dried for one minute at 60°C. No washing steps were used in the process.
  • the developing composition exhibited excellent stability and the process provided excellent results, even though the total wet time was only three minutes, and thus achieved the objective of high quality rapid-access processing, which is especially useful in a "mini-lab" facility.
  • the color developing, bleach-fixing and stabilizing compositions used in the process were as follows:
  • the bleach-fixing composition had a pH of 6.2 and was comprised of ammonium thiosulfale, sodium bisulfile, and an ammonium salt of the ferric complex of ethylenediaminetetraacetic acid.
  • the stabilizing composition had a pH of 7.2 and was comprised of formaldehyde, sodium metabisulfite, potassium hydroxide, diethylene glycol, 5-chloro-2-methyl-4-isothiazolin-3-one, the disodium salt of ethylenediaminetetraacetic acid, and 1-hydroxyethylidene-1,1-diphosphonic acid.
  • the diethylene glycol serves as a solvent for the 5-chloro-2-methyl-4-isothiazolin-3-one).
  • An important feature of this invention is that there is minimal development restraint and this permits rapid access processing. Moreover, the rapid access processing does not require high development temperatures and can be achieved with development temperatures of as low as about 15°C.

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Abstract

Des compositions de développement photographique en couleur ci-décrites, particulièrement utiles dans le traitement d'éléments photographiques à halogénure d'argent à proportion élevée en chlorure d'argent sont exemptes ou au moins en grande partie exemptes de bromure. Elles peuvent contenir une petite quantité de sulfite et comprennent (1) un agent de développement couleur aminé aromatique primaire, (2) une N,N-dialkylhydroxylamine, (3) au moins un agent de séquestration qui séquestre le fer et (4) au moins un agent de séquestration qui séquestre le calcium. Les compositions de développement présentent une excellente stabilité. Leur retardement de développement étant minime, elles permettent d'obtenir des temps de développement très courts, ce dont on a besoin pour un traitement rapide.

Claims (23)

1. Composition photographique de révélateur chromogène, particulièrement utile pour le développement de produits photographiques aux halogénures d'argent à teneur élevée en chlorure, composition pratiquement sans bromures et comprenant:
(1) un développateur chromogène amine primaire aromatique,
(2) une N,N-dialkylhydroxylamine,
(3) au moins un sequestrant pour sequestrer le fer,
(4) au moins un sequestrant pour sequestrer le calcium, et
(5) de zéro à 0,2 mole de sulfite par mole de développateur chromogène amine primaire aromatique.
2. Composition photographique de révélateur chromogène selon la revendication 1, dans laquelle le sequestrant du fer est un composé aromatique polyhydroxy qui forme un complexe avec les ions ferriques en solution alcaline, complexe dans lequel le rapport molaire des ions ferriques au composé aromatique polyhydroxy est 1: 3 et le sequestrant du calcium est un acide aminopolycarboxylique.
3. Composition photographique de révélateur chromogène selon la revendication 1, dans laquelle on utilise l'acide hydroxyalkylidènediphosphonique pur sequestrer à la fois le fer et le calcium.
4. Composition photographique de révélateur chromogène selon la revendication 2, pratiquement sans bromures et sans alcool benzylique et comprenant:
(1) un développateur chromogène amine primaire aromatique,
(2) une N,N-dialkylhydroxylamine,
(3) un composé aromatique polyhydroxy qui forme un complexe avec les ions ferriques en solution alcaline, complexe dans lequel le rapport molaire des ions ferriques au composé aromatique polyhydroxy est 1: 3,
(4) au moins un sequestrant acide aminopolycarboxylique,
(5) de zéro à 0,2 moles de sulfite par mole de développateur chromogène amine primaire aromatique, et
(6) au moins un tampon de pH
5. Composition photographique de révélateur chromogène selon la revendication 1, comprenant de plus une alcanolamine.
6. Composition photographique de révélateur chromogène selon la revendication 5, dans laquelle l'alcanolamine est une triéthanolamine.
7. Composition photographique de révélateur chromogène selon la revendication 1, comprenant de plus un polystyrène sulfonate soluble dans l'eau.
8. Composition photographique de révélateur chromogène selon la revendication 4, comprenant de plus une triéthanolamine et un polystyrène sulfonate soluble dans l'eau.
9. Composition photographique de révélateur chromogène selon la revendication 1, dans laquelle le développateur chromogène amine primaire aromatique est le sesquisulfate monohydraté de la 4-(N-éthyl-N-2-méthane sulfonylaminoéthyl)-2-méthylphénylènediamine.
10. Composition photographique de révélateur chromogène selon la revendication 1, dans laquelle la N,N-dialkyl hydroxylamine a la formule
Figure imgb0020
 où R³ et R⁴ sont des groupes alkyles identiques ou différents ayant de 1 à 4 atomes de carbone.
11. Composition photographique de révélateur chromogène selon la revendication 4, dans laquelle le composé aromatique polyhydroxy a la formule:
Figure imgb0021
 où X représente le nombre d'atomes de carbone nécessaire pour compléter un noyau aromatique benzène ou naphtalène.
12. Composition photographique de révélateur chromogène selon la revendication 4, dans laquelle la N,N-dialkylhydroxylamine est la N,N-diéthylhydroxylamine.
13. Composition photographique de révélateur chromogène selon la revendication 11, dans laquelle le composé aromatique polyhydroxy est le sel trisodique de l'acide 5,6-dihydroxy-1,2,4-benzènetrisulfonique.
14. Composition photographique de révélateur chromogène selon la revendication 4, dans laquelle le sequestrant acide aminopolycarboxylique est l'acide éthylènediaminetétraacétique.
15. Composition photographique de révélateur chromogène selon la revendication 4, et comprenant:
(1) du sesquisulfate monohydraté de 4-(N-éthyl-N-2-méthanesulfonylaminoéthyl)-2-méthylphénylènediamine
(2) de la N,N-diéthylhydroxylamine,
(3) le sel trisodique de l'acide 5,6-dihydroxy-1,2,4-benzenetrisulfonique,
(4) le sel disodique de l'acide éthylènediaminetétraacétique,
(5) le sel de lithium d'un polystyrène sulfonate,
(6) de la triéthanolamine,
(7) du sulfite de potassium, et
(8) du carbonate de potassium.
16. Procédé pour le développement rapide de produits photographiques en couleurs aux halogénures d'argent à teneur élevée en chlorure, procédé comprenant les étapes suivantes:
(1) on développe le produit pendant 30 à 60 secondes à une température entre 30°C et 40°C dans une composition de révélateur chromogène ayant un pH compris entre 9 et 13,
(2) on effectue le blanchiment-fixage du produit, sans étape de lavage entre les étapes de développement et de blanchiment-fixage pendant 30 à 60 secondes à une température comprise entre 25 et 40°C dans une composition de blanchiment-fixage ayant un pH compris entre 5 et 8 et comprenant un fixateur thiosulfate et un complexe ferrique d'un acide aminopolycarboxylique comme agent de blanchiment; et
(3) on stabilise le produit, sans lavage entre les étapes de blanchiment-fixage et de stabilisation pendant 60 à 120 secondes, à une température comprise entre 25°C et 40°C dans une composition stabilisante ayant un pH compris entre 5 et 8 et comprenant un aldéhyde comme agent stabilisant, procédé dans lequel la composition de révélateur chromogène est la composition de la revendication 1
17. Procédé selon la revendication 16, dans lequel la composition de révélateur chromogène est la composition de l'une quelconque des revendications 2, 3, 5, 10.
18. Procédé selon la revendication 16, dans lequel la composition de révélateur chromogène est la composition de l'une quelconque des revendications 4, 8, 12, 13.
19. Procédé selon la revendication 18, dans lequel la composition de blanchiment-fixage a un pH compris entre 6 et 7.
20. Procédé selon la revendication 18, dans lequel la composition stabilisante comprend un additif qui est une combinaison bisulfitique d'un aldéhyde.
21. Procédé selon la revendication 18, dans lequel la composition stabilisante comprend un composé thiazole comme biocide.
22. Procédé selon la revendication 18, dans lequel la composition stabilisante comprend un sequestrant acide aminopolycarboxylique et un sequestrant choisi dans le groupe des sequestrants acides aminopolyphosphoniques et des sequestrants acides hydroxyalkylidène disphosphoniques.
23. Procédé selon la revendication 1, dans lequel le produit photographique aux halogénures d'argent à teneur élevée en chlorure est un papier couleur, procédé comprenant les étapes suivantes:
(1) on développe le papier couleur pendant 45 secondes à une température de 35°C dans une composition de révélateur chromogène ayant un pH de 10,
(2) on effectue le blanchiment-fixage du papier couleur, sans lavage entre les étapes de développement et de fixage pendant 45 secondes à une température de 35°C dans une composition de blanchiment-fixage ayant un pH de 6 et comprenant du thiosulfate d'ammonium et le sel d'ammonium d'un complexe ferrique d'acide éthylènediaminetétraacétique; et
(3) on stabilise le papier couleur, sans lavage entre l'étape de blanchiment-fixage et l'étape de stabilisation pendant 90 secondes à une température de 35°C dans une composition stabilisante ayant un pH de 7 et comprenant du formaldéhyde, du métabisulfite de sodium, de l'hydroxyde de potassium, du diéthylène glycol, de la 5-chloro-2-méthyl-4-isothiazolin-3-one, le sel disodique de l'acide éthylènediaminetétraacétique, et de l'acide 1-hydroxyéthylidène-1,1-diphosphonique, dans lequel la composition de révélateur chromogène est la composition de la revendication 15.
EP87900926A 1986-01-24 1987-01-08 Compositions photographiques de developpement en couleur, specialement utiles avec des elements photographiques a haute teneur en chlorure Expired - Lifetime EP0258288B1 (fr)

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WO1987004534A2 (fr) 1987-07-30
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JPH06100807B2 (ja) 1994-12-12
WO1987004534A3 (fr) 1988-03-24
JPS63502222A (ja) 1988-08-25

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