[go: up one dir, main page]

WO1987004534A2 - 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

Info

Publication number
WO1987004534A2
WO1987004534A2 PCT/US1987/000021 US8700021W WO8704534A2 WO 1987004534 A2 WO1987004534 A2 WO 1987004534A2 US 8700021 W US8700021 W US 8700021W WO 8704534 A2 WO8704534 A2 WO 8704534A2
Authority
WO
WIPO (PCT)
Prior art keywords
color developing
composition
agent
functions
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1987/000021
Other languages
English (en)
Other versions
WO1987004534A3 (fr
Inventor
Sheridan E. Vincent
Richard W. Berls
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25235131&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1987004534(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to DE8787900926T priority Critical patent/DE3769892D1/de
Priority to JP62500793A priority patent/JPH06100807B2/ja
Publication of WO1987004534A2 publication Critical patent/WO1987004534A2/fr
Publication of WO1987004534A3 publication Critical patent/WO1987004534A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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. BACKGROUND OF THE INVENTION
  • 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
  • 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: (1) a primary aromatic amino color developing agent. (2) an N,N-dialkylhydroxylamine,
  • 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. Examples of aminophenol developing agents include o-aminophenol. p-aminophenol.
  • 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.
  • useful p-phenylenediamine color developing agents include: N,N-diethyl-p-phenylenediamine monohydrochloride. 4-N,N-diethyl-2-methylphenylenediamine monohydrochloride.
  • 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.
  • p-phenylenediamines are the 3-alkyl-N-alkyl-N-alkoxyalkyl-p-phenylenediamines and the 3-alkoxy-N-alkyl-N-alkoxy-alkyl-p-phenylenediamines. These developing agents are described in United States Patents 3,656,950 and 3,658,525, and can be represented by the formula:
  • n is an integer having a value of from 2 to 4
  • R is an alkyl group of from 1 to 4 carbon atoms.
  • R 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:
  • N-ethyl-N-methoxyethyl-3-methoxy-p-phenylenediamine N-ethyl-N-butoxyethyl-3-methyl-p-phenylenediamine, and the like.
  • 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.
  • the N,N-dialkylhydroxylamine is preferably of the formula:
  • R 3 and R 4 represent the same or different alkyl groups of 1 to 4 carbon atoms.
  • Typical examples of 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. Thus, for example, they are used in the magenta color developing solutions described in Anselm. United States patent 3,489,566, issued January 13, 1970. However, in these magenta developing solutions, they are employed in combination with an unsubstituted or mono-alkylsubstituted 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.
  • Included within the broad class of aromatic polyhydroxy compounds which are useful in this invention are, for example, compounds of the benzene series and of the naphthalene series, which can be represented by the formula:
  • aromatic ring structure can be substituted with groups such as sulfo radicals, carboxy radicals, or halogen atoms.
  • aromatic polyhydroxy compounds useful in this invention include the following compounds: pyrocatechol,
  • 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).
  • 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.
  • M is hydrogen or a monovalent cation such as sodium or potassium.
  • 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 a.ir through the solution or by reaction with a persulfate. Aromatic polyhydroxy compounds have been used heretofore in photographic color developing compositions.
  • 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: nitrilotriacetic acid. (NTA), ethylenediaminetetraacetic acid, (EDTA), 1,3-diamino-2-propanol-N,N,N'.N'-tetraacetic acid.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • 1,3-diamino-2-propanol-N,N,N'.N'-tetraacetic acid 1,3-diamino-2-propanol-N,N,N'.N'-tetraacetic acid.
  • DPTA diethylenetriaminepentaacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • HBED N,N'-bis(2-hydroxybenzyl) ethylenediamine- N,N'-diacetic acid
  • hydroxyethylethylenediaminetriacetic acid cyclohexanediaminotetraacetic acid, aminomalonic acid, and the like.
  • 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 be very small, for example in the range of from zero to about 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. As described in Case et al. U. S. patent 4,170,478, issued October 9, 1979, preferred alkanolamines for use in photographic color developing compositions are compounds of the formula:
  • R 1 is an hydroxyalkyl group of 2 to 6 carbon atoms and each of R 2 and R 3 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
  • 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:
  • R 4 is an hydroxyalkyl group of 2 to 4 carbon atoms and each of R 5 and R 6 is an alkyl group of 1 to 4 carbon atoms or an hydroxyalkyl group of 2 to 4 carbon atoms.
  • alkanolamines which can be used in the color developing compositions of this invention include: ethanolamine diethanolamine triethanolamine di-isopropanolamine
  • a water-soluble sulfonated polystyrene a water-soluble sulfonated polystyrene.
  • the 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:
  • 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:
  • 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 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. and the like.
  • the sulfonated polystyrene can be used in the working developer solution in any effective amount.
  • 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:
  • amino-N,N-dimethylenephosphonic acids of the formula:
  • M is a hydrogen atom or a monovalent cation and R 3 is an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alicyclic group or a heterocyclic radical, and R 3 can be further substituted with substituents such as hydroxyl. halogen, an alkoxy group, a - PO 3 M 2 group, a
  • R 4 is an alkyl group, preferably of one to five carbon atoms
  • R 5 , R 6 and R 7 are hydrogen or an alkyl group, preferably alkyl of one to five carbon atoms.
  • N-acetyl-1-aminoethane-1,1-diphosphonic acid ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid. nitrilo-N,N,N-trimethylenephosphonic acid.
  • 1,2-cyclohexanediamine-N,N,N',N'-tetramethylenephosphonic acid 1,2-cyclohexanediamine-N,N,N',N'-tetramethylenephosphonic acid.
  • o-carboxyanilino-N,N-dimethylenephosphonic acid propylamino-N,N-dimethylenephosphonic acid.
  • 1,6-hexanediamine-N,N,N',N'-tetramethylenephosphonic acid 1,6-hexanediamine-N,N,N',N'-tetramethylenephosphonic acid. o-acetamidobenzylamino-N,N-dimethylenephosphonic acid, o-toluidine-N,N-dimethylenephosphonic acid. 2-pyridylamino-N',N'-dimethylenephosphonic acid. diethylenetriamine pentamethylenephosphonic acid, and the like.
  • 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. As described in
  • 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.
  • 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.
  • 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.
  • the present invention provides a method of rapid access processing of a high chloride silver halide photographic color print paper, which comprises the steps of:
  • bleach-fixing without washing between the developing and bleach-fixing steps, for a period of about 30 to about 60 seconds at a temperature of about 25oC to about 40oC in a bleach-fix composition having a pH in the range of from about 5 to about 8 and more preferably in the range of from about 6 to about 7 and comprising a thiosulfate fixing agent and a bleaching agent which is a ferric complex of an aminopolycarboxylic acid; and (3) stabilizing, without washing between the bleach-fixing and stabilizing steps, for a period of about 60 to about 120 seconds at a temperature of about 25 to about 40oC in a stabilizing composition having a pH in the range from about 5 to about 8 and comprising an aldehyde that functions as a stabilizing agent.
  • 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 sulfite.
  • 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.
  • 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 in these patents are unsubstituted hydroxylamines or mono-alkyl-substituted hydroxylamines.
  • dialkyl-substituted hydroxylamines are utilized rather than unsubstituted hydroxylamines or mono-alkyl-substituted hydroxylamines.
  • the 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.
  • 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 35oC and the print was dried for one minute at 60oC. 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 thiosulfate. sodium bisulfite, 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 15oC.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

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.
PCT/US1987/000021 1986-01-24 1987-01-08 Compositions photographiques de developpement en couleur, specialement utiles avec des elements photographiques a haute teneur en chlorure Ceased WO1987004534A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE8787900926T DE3769892D1 (de) 1986-01-24 1987-01-08 Photographische farbentwicklungszubereitungen zur verwendung insbesondere bei photographischen elementen mit hohem chloridgehalt.
JP62500793A JPH06100807B2 (ja) 1986-01-24 1987-01-08 発色現像組成物及び迅速アクセス処理方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US82209786A 1986-01-24 1986-01-24
US822,097 1986-01-24

Publications (2)

Publication Number Publication Date
WO1987004534A2 true WO1987004534A2 (fr) 1987-07-30
WO1987004534A3 WO1987004534A3 (fr) 1988-03-24

Family

ID=25235131

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1987/000021 Ceased WO1987004534A2 (fr) 1986-01-24 1987-01-08 Compositions photographiques de developpement en couleur, specialement utiles avec des elements photographiques a haute teneur en chlorure

Country Status (4)

Country Link
EP (1) EP0258288B1 (fr)
JP (1) JPH06100807B2 (fr)
CA (1) CA1314424C (fr)
WO (1) WO1987004534A2 (fr)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6462641A (en) * 1987-09-02 1989-03-09 Konishiroku Photo Ind Processing method for silver halide color photographic sensitive material
EP0243096A3 (en) * 1986-04-18 1989-03-15 Konishiroku Photo Industry Co. Ltd. Method for processing a light-sensitive silver halide color photographic material
US4837139A (en) * 1986-07-26 1989-06-06 Konishiroku Photo Industry Co., Ltd. Method for processing a light-sensitive silver halide color photographic material using at least one silver halide emulsion layer and at least one of a cyan coupler and magneta coupler
US4840878A (en) * 1986-01-23 1989-06-20 Fuji Photo Film Co., Ltd. Method of color image formation using a high chloride emulsion and a developer free of benzyl alcohol
EP0278003A4 (fr) * 1986-04-16 1989-09-19 Konishiroku Photo Ind Procede pour traiter un papier photographique couleur a base d'halogenure d'argent.
EP0330035A3 (en) * 1988-02-24 1989-12-06 Agfa-Gevaert Ag Colour-photographic developer solution, and process for developing a colour-photographic material
JPH0258A (ja) * 1987-10-30 1990-01-05 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料の処理方法
EP0312893A3 (en) * 1987-10-21 1990-03-28 Agfa-Gevaert Ag Colour-photographic developing solution and process for developing a colour-photographic material
EP0366954A3 (en) * 1988-10-03 1990-05-16 Fuji Photo Film Co., Ltd. Method for processing a silver halide color photosensitive material
EP0325278A3 (en) * 1988-01-21 1990-06-27 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials
EP0325277A3 (en) * 1988-01-21 1990-06-27 Fuji Photo Film Co., Ltd. A method for processing a silver halide color photograhic material
EP0325276A3 (en) * 1988-01-21 1990-06-27 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
EP0326030A3 (en) * 1988-01-21 1990-08-08 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
WO1990014615A1 (fr) * 1989-05-23 1990-11-29 Eastman Kodak Company Procede ameliore de developpement photographique en couleur
AU608071B2 (en) * 1987-10-19 1991-03-21 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
US5021326A (en) * 1989-04-18 1991-06-04 Agfa Gevaert Aktiengesellschaft Process for rapidly processing a color photography material
US5093226A (en) * 1988-10-03 1992-03-03 Fuji Photo Film Co., Ltd. Method for forming image of silver halide color photograph
WO1993011460A1 (fr) * 1991-12-03 1993-06-10 Kodak Limited Solutions de developpement
US5254442A (en) * 1988-07-21 1993-10-19 Konica Corporation Method of processing silver halide color photographic materials and a processing apparatus therefor
EP0578173A1 (fr) 1992-07-06 1994-01-12 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent et procédé de formation d'une image couleur
EP0512311A3 (fr) * 1991-05-03 1994-02-02 Agfa Gevaert Ag
EP0571935A3 (en) * 1992-05-25 1994-07-13 Fuji Photo Film Co Ltd Silver halide color photographic material and method for forming a color photographic image
US5445924A (en) * 1992-02-21 1995-08-29 Fuji Photo Film Co., Ltd. Laser color imaging method using a cyan dye coupler
US5478702A (en) * 1992-08-18 1995-12-26 Fuji Photo Film Co., Ltd. Method for forming a color image by scanning exposure using a photographic material containing a specific phenol derivative
EP0330442B1 (fr) * 1988-02-26 1996-05-29 EASTMAN KODAK COMPANY (a New Jersey corporation) Procédé de traitement de produits photographiques en couleurs
US5578426A (en) * 1992-07-15 1996-11-26 Fuji Photo Film Co., Ltd. Method for processing a silver halide color photographic material
US5702873A (en) * 1991-12-03 1997-12-30 Eastman Kodak Company Redox amplification solutions containing metal ion sequestering agents
US6284446B1 (en) 1999-06-16 2001-09-04 Fuji Photo Film Co., Ltd. Silver halide color photographic material and development processing method of the same

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59184343A (ja) * 1983-04-04 1984-10-19 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
JPS62253162A (ja) * 1986-01-29 1987-11-04 Konika Corp ハロゲン化銀カラ−写真感光材料の処理方法
JP2700236B2 (ja) * 1986-01-29 1998-01-19 コニカ株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JPS62253164A (ja) * 1986-01-29 1987-11-04 Konika Corp ハロゲン化銀カラ−写真感光材料の処理方法
JPH01180572A (ja) * 1986-01-30 1989-07-18 Konica Corp カラ−画像形成装置
JP2711319B2 (ja) * 1986-02-04 1998-02-10 コニカ株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JPH0830878B2 (ja) * 1986-03-20 1996-03-27 コニカ株式会社 ハロゲン化銀カラ−写真感光材料の迅速現像処理方法
JP2700237B2 (ja) * 1986-03-29 1998-01-19 コニカ株式会社 ハロゲン化銀カラー写真感光材料の迅速処理方法
JPH0746216B2 (ja) * 1986-04-04 1995-05-17 コニカ株式会社 迅速処理を可能にしたハロゲン化銀カラ−写真感光材料の処理方法
JP2546644B2 (ja) * 1986-04-22 1996-10-23 コニカ株式会社 ハロゲン化銀カラ−写真感光材料の処理方法
JPS62246048A (ja) * 1986-04-18 1987-10-27 Konika Corp ハロゲン化銀カラ−写真感光材料の処理方法
JPH0743524B2 (ja) * 1986-04-19 1995-05-15 コニカ株式会社 ハロゲン化銀カラ−写真感光材料の処理方法
JPH0827515B2 (ja) * 1986-04-19 1996-03-21 コニカ株式会社 カラ−画像の形成方法
JP2607364B2 (ja) * 1986-04-19 1997-05-07 コニカ株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JPH0830879B2 (ja) * 1986-04-21 1996-03-27 コニカ株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JPH0827516B2 (ja) * 1986-04-22 1996-03-21 コニカ株式会社 ハロゲン化銀カラ−写真感光材料の処理方法
JPS62249156A (ja) * 1986-04-22 1987-10-30 Konika Corp 水洗代替安定液および該水洗代替安定液を用いるハロゲン化銀カラ−写真感光材料の処理方法
JP2607082B2 (ja) * 1986-04-30 1997-05-07 コニカ株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JP2739314B2 (ja) * 1986-07-26 1998-04-15 コニカ株式会社 画像保存性が改良されるハロゲン化銀カラー写真感光材料の処理方法
JPH0789210B2 (ja) * 1986-11-19 1995-09-27 富士写真フイルム株式会社 ハロゲン化銀カラ−写真感光材料の処理方法
US4923782A (en) * 1988-06-03 1990-05-08 Eastman Kodak Company Photographic stabilizing bath containing hydrolyzed polymaleic anhydride
JP2976110B2 (ja) * 1989-01-17 1999-11-10 コニカ株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JP2976377B2 (ja) * 1989-04-27 1999-11-10 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3489566A (en) * 1966-02-01 1970-01-13 Eastman Kodak Co Magneta color developer solutions
DE2246610C3 (de) * 1972-09-22 1980-01-03 Agfa-Gevaert Ag, 5090 Leverkusen Photographischer Farbentwickler
JPS5943735B2 (ja) * 1976-09-07 1984-10-24 富士写真フイルム株式会社 カラ−写真処理方法
US4170478A (en) * 1977-06-06 1979-10-09 Eastman Kodak Company Photographic color developer compositions
US4264716A (en) * 1979-09-10 1981-04-28 Eastman Kodak Company Photographic color developer compositions
JPH0650381B2 (ja) * 1985-08-05 1994-06-29 富士写真フイルム株式会社 ハロゲン化銀カラ−感光材料の処理方法

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4840878A (en) * 1986-01-23 1989-06-20 Fuji Photo Film Co., Ltd. Method of color image formation using a high chloride emulsion and a developer free of benzyl alcohol
EP0278003A4 (fr) * 1986-04-16 1989-09-19 Konishiroku Photo Ind Procede pour traiter un papier photographique couleur a base d'halogenure d'argent.
EP0243096A3 (en) * 1986-04-18 1989-03-15 Konishiroku Photo Industry Co. Ltd. Method for processing a light-sensitive silver halide color photographic material
US4837139A (en) * 1986-07-26 1989-06-06 Konishiroku Photo Industry Co., Ltd. Method for processing a light-sensitive silver halide color photographic material using at least one silver halide emulsion layer and at least one of a cyan coupler and magneta coupler
JPS6462641A (en) * 1987-09-02 1989-03-09 Konishiroku Photo Ind Processing method for silver halide color photographic sensitive material
AU608071B2 (en) * 1987-10-19 1991-03-21 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
EP0312893A3 (en) * 1987-10-21 1990-03-28 Agfa-Gevaert Ag Colour-photographic developing solution and process for developing a colour-photographic material
JPH0258A (ja) * 1987-10-30 1990-01-05 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料の処理方法
EP0326030A3 (en) * 1988-01-21 1990-08-08 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
EP0325278A3 (en) * 1988-01-21 1990-06-27 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials
EP0325277A3 (en) * 1988-01-21 1990-06-27 Fuji Photo Film Co., Ltd. A method for processing a silver halide color photograhic material
EP0325276A3 (en) * 1988-01-21 1990-06-27 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
EP0330035A3 (en) * 1988-02-24 1989-12-06 Agfa-Gevaert Ag Colour-photographic developer solution, and process for developing a colour-photographic material
EP0330442B1 (fr) * 1988-02-26 1996-05-29 EASTMAN KODAK COMPANY (a New Jersey corporation) Procédé de traitement de produits photographiques en couleurs
US5254442A (en) * 1988-07-21 1993-10-19 Konica Corporation Method of processing silver halide color photographic materials and a processing apparatus therefor
US5093226A (en) * 1988-10-03 1992-03-03 Fuji Photo Film Co., Ltd. Method for forming image of silver halide color photograph
EP0366954A3 (en) * 1988-10-03 1990-05-16 Fuji Photo Film Co., Ltd. Method for processing a silver halide color photosensitive material
US5021326A (en) * 1989-04-18 1991-06-04 Agfa Gevaert Aktiengesellschaft Process for rapidly processing a color photography material
EP0393429A3 (fr) * 1989-04-18 1992-02-05 Agfa-Gevaert AG Procédé de traitement d'un matériau photographique couleur
WO1990014615A1 (fr) * 1989-05-23 1990-11-29 Eastman Kodak Company Procede ameliore de developpement photographique en couleur
US4975357A (en) * 1989-05-23 1990-12-04 Eastman Kodak Company Method of photographic color development using polyhydroxy compounds, metal ions and sequestering agents
EP0512311A3 (fr) * 1991-05-03 1994-02-02 Agfa Gevaert Ag
WO1993011460A1 (fr) * 1991-12-03 1993-06-10 Kodak Limited Solutions de developpement
US5702873A (en) * 1991-12-03 1997-12-30 Eastman Kodak Company Redox amplification solutions containing metal ion sequestering agents
US5445924A (en) * 1992-02-21 1995-08-29 Fuji Photo Film Co., Ltd. Laser color imaging method using a cyan dye coupler
EP0571935A3 (en) * 1992-05-25 1994-07-13 Fuji Photo Film Co Ltd Silver halide color photographic material and method for forming a color photographic image
US6136519A (en) * 1992-05-25 2000-10-24 Fuji Photo Film Co., Ltd. Silver halide color photographic material and method for forming a color photographic image
EP0578173A1 (fr) 1992-07-06 1994-01-12 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent et procédé de formation d'une image couleur
US5434033A (en) * 1992-07-06 1995-07-18 Fuji Photo Film Co., Ltd. Silver halide color photographic material and method for forming a color image
US5578426A (en) * 1992-07-15 1996-11-26 Fuji Photo Film Co., Ltd. Method for processing a silver halide color photographic material
US5478702A (en) * 1992-08-18 1995-12-26 Fuji Photo Film Co., Ltd. Method for forming a color image by scanning exposure using a photographic material containing a specific phenol derivative
US6284446B1 (en) 1999-06-16 2001-09-04 Fuji Photo Film Co., Ltd. Silver halide color photographic material and development processing method of the same
US6479229B2 (en) * 1999-06-16 2002-11-12 Fuji Photo Film Co. Ltd. Silver halide color photographic material and development processing method of the same

Also Published As

Publication number Publication date
EP0258288A1 (fr) 1988-03-09
JPH06100807B2 (ja) 1994-12-12
WO1987004534A3 (fr) 1988-03-24
JPS63502222A (ja) 1988-08-25
CA1314424C (fr) 1993-03-16
EP0258288B1 (fr) 1991-05-08

Similar Documents

Publication Publication Date Title
EP0258288B1 (fr) Compositions photographiques de developpement en couleur, specialement utiles avec des elements photographiques a haute teneur en chlorure
US4892804A (en) Photographic color developing compositions which are especially useful with high chloride photographic elements
EP0039752B1 (fr) Solutions de révélateurs chromogènes photographiques
CA1108912A (fr) Substance photographique contenant un agent aminoaromatique primaire revelateur de la couleur et un produit antioxydant comprenant de l'hydroxylamine
JP2552455B2 (ja) ハロゲン化銀カラ−写真感光材料の処理方法
EP0980024B1 (fr) Concentré homogène en une seule partie pour révélateur photographique en couleur et méthode de préparation
EP1037105A1 (fr) Développement en couleur avec taux de remplissage faible utilisant un révélateur couleur sous forme concentrée ne contenant pas d'ions chlorure
US6436618B2 (en) Multi-part photographic color developing composition and methods of manufacture and use
JPH04226451A (ja) 写真カラー現像用組成物およびハロゲン化銀カラー写真材料の処理方法
US4596765A (en) Composition of a photographic color forming agent
EP0530921B1 (fr) Composition pour un révélateur couleur en photographie contenant un acide alpha-aminé pour améliorer la stabilité de la solution
JPH068956B2 (ja) ハロゲン化銀カラ−感光材料の処理方法
EP1099980B1 (fr) Concentré de développateur photographique couleur stable envers les ions calcium et méthode de fabrication
US4975357A (en) Method of photographic color development using polyhydroxy compounds, metal ions and sequestering agents
JPH0419538B2 (fr)
JPH0251493B2 (fr)
US6037111A (en) Lithium and magnesium ion free color developing composition and method of photoprocessing
US6509143B2 (en) Concentrated photographic color developing composition containing stain reducing agent
JPH0257297B2 (fr)
JPS6141145A (ja) ハロゲン化銀カラ−写真感光材料の処理方法
US20060093970A1 (en) Combinations of preservatives and sequestrants to avoid formation of isonitrile malodor
JPS6150145A (ja) ハロゲン化銀カラ−写真感光材料の処理方法
GB2343009A (en) Colour developer for rapid processing comprising pyrazolidone
JPS6323532B2 (fr)
JPH0259974B2 (fr)

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): JP

AL Designated countries for regional patents

Kind code of ref document: A2

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

WWE Wipo information: entry into national phase

Ref document number: 1987900926

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1987900926

Country of ref document: EP

AK Designated states

Kind code of ref document: A3

Designated state(s): JP

AL Designated countries for regional patents

Kind code of ref document: A3

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

WWG Wipo information: grant in national office

Ref document number: 1987900926

Country of ref document: EP