US3647453A - Stabilization of silver halide emulsions with 1,1 bis-sulfonyl alkanes - Google Patents

Stabilization of silver halide emulsions with 1,1 bis-sulfonyl alkanes Download PDF

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US3647453A
US3647453A US42580A US3647453DA US3647453A US 3647453 A US3647453 A US 3647453A US 42580 A US42580 A US 42580A US 3647453D A US3647453D A US 3647453DA US 3647453 A US3647453 A US 3647453A
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silver halide
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carbon atoms
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Grant M Haist
James R King
David A Pupo
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/42—Developers or their precursors

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  • ABSTRACT Silver halide emulsions and photographic elements containing a 1,1 bis-sulfonyl alkane stabilizing agent are stabilized after exposure by an alkaline activation treatment.
  • the silver halide in the unexposed areas is conventionally washed out as a soluble complex with a fixing solution. It would be convenient to have the fixing agent incorporated directly in the emulsion.
  • a fixing agent for incorporation in an emulsion depends on many factors, but it has been difficult to find compounds which are satisfactory because of the sensitive nature of the element.
  • Most active fixing agents such as hypo, for example, cannot be incorporated into the light-sensitive element because of the prefixing which takes place, that is, the compound reacts to fix the silver halide prematurely and light sensitivity is lost.
  • Other less active fixing compounds may show such inactivation (prestabilization) on long-term keeping, so that light sensitivity is lost after a period of time.
  • Other still less active fixing agents, while they do not react prematurely may act with only insufficient completeness so that they do not do a satisfactory fixing job. This results in subsequent background printup and instability in the processed image.
  • Still other known fixing agents cannot be incorporated in light-sensitive coatings because of solubility relationships or because of interaction with other components of the system. It would be highly desirable to have a fixing agent which could be satisfactorily incorporated into a light-sensitive coating and which would not interfere with sensitometric properties so that stable coatings could be made.
  • the fl-disulfones used in the present invention do not desensitize the emulsion or stabilize the emulsion prior to development.
  • the disulfones then act as effective stabilizers.
  • Suitable l,1 bis-sulfonyl alkanes used in the present invention can be represented by the general formula Rr-S Or-CH-S Or -R2 wherein R and R each represent a lower alkyl group and R represents H or a lower alkyl group.
  • the term lower alkyl as employed herein is preferably an alkyl group containing from about one to four carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl and the like.
  • alkyl as employed herein also includes substituted alkyl groups, and is preferably a substituted lower alkyl group containing from one to four carbon atoms.
  • substituted lower alkyl groups such as a hydroxyalkyl group, e.g., B-hydroxyethyl, mhydroxybutyl, etc.; an alkoxyalkyl group, e.g., B-methoxyethyl, w-butoxybutyl, etc.; a carboxyalkyl group, e.g., B-carboxyethyl, m-carboxybutyl, etc.; a sulfoalkyl group, e.g., B-sulfoethyl, w-sulfobutyl, etc.; a sulfatoalkyl group, e.g., B-sulfatoethyl, w-sulfatobutyl,
  • an acryloxyalkyl group e.g., fl-acetoxyethyl. w-butyryloxybutyl, etc.
  • an alkoxycarbonylalkyl group e.g., B- methoxycarbonyl-ethyl, w-ethoxycarbonylbutyl, etc, are preferred.
  • l,l Bis-sulfonyl alkanes within the above formula include 1,1 bis-(methylsulfonyl)ethane; l,l bis-(ethylsulfonyl)ethane; l,l bis-(methylsulfonyl) propane; 1,1 bis-(ethylsulfonyl)propane; l-ethylsulfonyl-l-methylsulfonyl methane; lethylsulfonyl-l-methylsulfonyl ethane; etc.
  • l,l bis-sulfonyl alkanes are bis(methylsulfonyl)methane, bis (ethylsulfonyl)methane, bis(/3'hydroxyethylsulfonyl)methane, bis(carboxymethylsulfonyl)methane, and bis(B-carboxyethylsulfonyl)methane.
  • novel disulfone stabilizers described herein When the novel disulfone stabilizers described herein are incorporated in a silver halide emulsion, or contiguous to the silver halide, they serve as incorporated fixing agents. These addenda do not prevent development of exposed areas of the emulsion but protect the unexposed areas of the emulsion against printout after development of the emulsion. Thus, with emulsions containing the addenda of the invention, silver images can be formed and stabilized without the use of a conventional fixing process.
  • the subject addenda are stable and do not act as fixing agents in acidic or neutral media such as in emulsions. However, under aqueous alkaline conditions which usually occurs during development, the subject addenda become active fixing agents. If the developing solution is not sufficiently alkaline to activate the disulfones of the invention at the rate desired, the developed element can thereafter be immersed in a stronger alkaline bath for fixing.
  • the concentration of the novel disulfone stabilizers described herein which may be incorporated into photosensitive elements should be sufficient to stabilize all undeveloped silver halide and is usually at least about one mole of stabilizer per mole of silver halide in the silver halide emulsion or photosensitive element, preferably about 2 to about 10 moles of stabilizer per mole of silver halide depending upon the solubility of the particular agent employed.
  • a photosensitive element comprises a support having thereon a photographic silver halide emulsion layer, the element containing either in the emulsion layer or in a separate layer, preferably contiguous to the emulsion layer, at least one mole per mole of silver halide of the novel disulfone stabilizing agents described herein.
  • the developing step can be omitted by incorporating a developing agent directly into the photographic element or silver halide emulsion.
  • the alkaline treatment thus serves to initiate development and then complexing of the unexposed and undeveloped silver halide with the stabilizing agent to provide a stable image.
  • Suitable developing agents useful in the present invention hydroquinones, catechols, aminophenols, 3- pyrazolidones, ascorbic acid and its derivatives, reductones, phenylenediamines, combinations thereof, etc.
  • the amount of developer to be employed can be varied over a wide range as is well known to those skilled in the art, depending upon the particular developer employed, its location in the system, etc.
  • the novel disulfones of the invention are relatively inert at pHs below about 8 or 9 and can be coated at that pH or below.
  • alkaline activation at pH s at about l0 or above renders these disulfones very effective stabilizers.
  • auxiliary developing agent present in the photographic element of the invention, such auxiliary developing agent can be employed, if desired, to improve maximum density of the developed image.
  • the silver halide emulsions which can be employed with this invention can be silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
  • the emulsions can be coarse or fine-grain and can be prepared by any of the well-known procedures in emulsion making such as single-jet emulsions, double-jet emulsions, such as Lippman, ammoniacal emulsions, thiocyanate or thioether ripened emulsions, such as those described in U.S. Pat. No. 2,222,264 of Nietz et al. issued Nov. 19, 1940; U.S. Pat. No. 3,320,069 of lllingsworth issued May 15, 1967; and U.S. Pat. No. 3,271,157 of McBride issued Sept. 6, 1966.
  • Surface image emulsions can be used or internal image emulsions can be used such as those described in U.S. Pat. No. 2,592,250 of Davey et al. issued Apr. 8, 1952; U.S. Pat. No. 3,206,313 of Porter et a1. issued Sept. 14, 1965; and Belgian Pat. No. 704,255.
  • the emulsions can be regular grain emulsions such as those described in Klein and Moisar, Journal of Photographic Science, Volume 12, No. 5, September-October (1964 pages 242-251. If desired, mixtures of surface and internal image emulsions can be used as described in U.S. Pat. 'No. 2,996,382 of Luckey et al. issued Aug. 15, 1961.
  • Negativetype emulsions can be used or direct positive emulsions can be used such as those described in U.S. Pat. No. 2,184,013 of Leermakers issued Dec. 19, 1939; U.S. Pat. No. 2,541,472 of Kendall et al. issued Feb. 13, 1951; U.S. Pat. No. 3,367,778 of Berriman et al. issued Feb. 6, 1968; British Pat. 723,019; French Pat. No. 1,520,821; U.S. Pat. No. 2,563,785 of lves issued Aug. 7, 1951; U.S. Pat. No. 2,456,953 of Knott et al. issued Dec. 21, 1968; and U.S. Pat. No. 2,861,885 of Land issued Nov.25, 1958.
  • the silver halide emulsions employed in the practice of the invention can be unwashed or washed to remove soluble salts. In the latter case the soluble salts can be removed by chillsetting and leaching or the emulsion can be coagulation washed.
  • the silver halide emulsions employed in the practice of the invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these.
  • chemical sensitizers such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these.
  • Suitable procedures are described, for example, in U.S. Pat. No. 1,623,499 of Sheppard issued Apr. 5, 1927; U.S. Pat. No. 2,399,083 of Waller et al. issued Apr. 23, 1946; U.S. Pat. No. 3,297,447 of McVeigh issued Jan. 10, 1967 and U.S..Pat. No. 3,297,446 of Dunn issued Jan. 10, 1967.
  • spectral sensitizers can be added to the emulsion before a chemical sensitizer is added. This can result in a speed increase as compared to an emulsion wherein the chemical sensitizer is added before the spectral sensitizer.
  • the silver halide emulsion can be spectrally sensitized with anhydro-S,5'-dichloro3,9-diethyl-3'-(3-sulfobutyl) thiacarbocyanine hydroxide; 5-[di-( l-ethyl-2( ll-l)-%-naphthothiazolylidene) iso-propylidene]-1,3-di-(B-methoxyethyl) barbituric acid; anhydro'S,5-dichloro-9-ethyl-3,3 -di( 3-sulfopropyl) oxacarbocyanine hydroxide, sodium salt; or anhydro5,5,6,6'- tetrachloro-1,l -diethyl-3,3'-di(3-sulfobutyl) benzimidazolocarbocyanine hydroxide and then chemically sensitized with sulfur
  • Cationic hydroxyalkyl surfactants such as quaternary salts, which contain an omega-hydroxyalkyl group can be employed as chemical sensitizers for silver halides, e.g., a silver halide dispersed in gelatin or synthetic polymeric vehicles.
  • Compounds which are cationic surfactant sulfonium compound chemical sensitizers are set out in U.S. Pat. No. 2,271,623 and U.S. Pat. No. 2,275,727 as well as various quaternary ammonium compounds.
  • Tetraalkyl quaternary ammonium salts, pyridinium quaternary salts, piperidinium salts, pyrazolium quaternary salts, and quinolinium salts which contain an omega-hydroxyalkyl group are suitable compounds which can be employed to increase the photographic speed of silver halide.
  • the silver halide emulsions employed in the practice of the invention can contain speed increasing compounds such as polyalkylene glycols, cationic surfactants and thioethers or combinations of these as described, for example, in U.S. Pat. No. 2,886,437 of Piper issued May 12, 1959; U.S. Pat. No. 3,046,134 of Dann et al. issued July 24, 1962; U.S. Pat. No. 2,944,900 of Carroll et al. issued July 12, 1960; and U.S. Pat. No. 3,294,540 ofGoffe issued Dec. 27, 1966.
  • speed increasing compounds such as polyalkylene glycols, cationic surfactants and thioethers or combinations of these as described, for example, in U.S. Pat. No. 2,886,437 of Piper issued May 12, 1959; U.S. Pat. No. 3,046,134 of Dann et al. issued July 24, 1962; U.S. Pat. No. 2,944,900 of Carroll et al. issued July 12, 1960; and
  • Suitable antifoggants and stabilizers each used alone or in combination include, for example, thiazolium salts; azaindenes; mercury salts as described, for example, in U.S. Pat. No. 2,728,663 of Allen et al. issued Dec. 27, 1955; urazoles; sulfocatechols; oximes described, for example, in British Pat. No. 623,448; nitron; nitroindazoles; mercaptotetrazoles; polyvalent metal salts described, for example, in
  • the photographic and other hardenable layers of a photographic element used in the practice of the invention can be hardened by various organic or inorganic hardeners alone or in combination, such as aldehyde hardeners and blocked a1- dehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfones, active halogen compounds, epoxy compounds, azirindenes, active olefins, isocyanates, carbodiimides, mixed-function hardeners and polymeric hardeners such as oxidized polysaccharides such as dialdehyde starch and oxyguargum and the like.
  • various organic or inorganic hardeners such as aldehyde hardeners and blocked a1- dehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfones, active halogen compounds
  • a photographic element and emulsions described in the practice of the invention can contain various colloids alone or in combination as vehicles, binding agents and in various layers.
  • Suitable hydrophilic materials include those naturally occurring substances such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as water-soluble polyvinyl compounds like poly(vinylpyrrolidone), acrylamide polymers and the like.
  • the described photographic emulsion layers and other layers of the photographic element employed in the practice of the invention can also contain, alone or in combination with hydrophilic, water-permeable colloids, other synthetic polymeric compounds such as dispersed vinyl compounds, such as in latex form, and particularly those whichincrease the dimensional stability of the photographic materials.
  • Suitable synthetic polymers include those described in U.S. Pat. No. 3,142,586 of Nottorf issued July 28, 1964; U.S. Pat. No.
  • the photographic elements employed in the practice of the invention can contain antistatic or conducting layers.
  • Such layers can comprise soluble salts such as chloride, nitrate and the like evaporated metal layers, ionic polymers such as those described in U.S. Pat. No. 2,861,056 of Minsk issued Nov. 18, 1958 and U.S. Pat. No. 3,206,312 of Sterman et al. issued Sept. 14, 1965 or insoluble organic salts such as those described in U.S. Pat. No. 3,428,451 of Trevoy issued Feb. 18, 1969.
  • Typical supports include cellulose nitrate film, cellulose acetate film, poly(vinylacetal) film, polystyrene film, poly(ethylene terephthalate) film, polycarbonate film and related films or resinous materials as well as glass, paper, metal and the like.
  • a flexible support is employed, especially a paper support which can be partially acetylated or coated with baryta and/or an alpha olefin polymer, particularly a polymer of an alpha olefin containing two to carbon atoms such as polyethylene, polypropylene, ethylene-butene copolymers and the like.
  • Paper supports which can contain acidic materials to control pl-l can be especially useful.
  • Such paper supports can contain acids such as boric acid and phthalic acids, as described, for example, in U.S. Pat. No. 3,250,619 and U.S. Pat. No. 3,326,744.
  • the photograph elements employed in the practice of the invention can contain plasticizers and lubricants such as polyalcohols, glycerin and diols as described, for example, in U.S. Pat. No. 2,960,404 of Milton et al. issued Nov. 1, 1966; fatty acids or esters such as described in U.S. Pat. No. 2,588,765 of Robijns issued Mar. 11, 1952; and U.S. Pat. No. 3,121,160 of Duane issued Feb. 11, 1964; and silicone resins such as those described in British Pat. No. 955,061
  • the photographic elements employed in the practice of the invention can contain surfactants such as saponin, anionic compounds, such as alkyl aryl sulfonates described, for example, in U.S. Pat. No. 2,600,831 of Baldsiefen issued June 17, 1952 and amphoteric compounds such as those described in U.S. Pat. No. 3,133,816 of Ben-Ezra issued May 19, 1964.
  • surfactants such as saponin, anionic compounds, such as alkyl aryl sulfonates described, for example, in U.S. Pat. No. 2,600,831 of Baldsiefen issued June 17, 1952 and amphoteric compounds such as those described in U.S. Pat. No. 3,133,816 of Ben-Ezra issued May 19, 1964.
  • the described photographic elements containing an incorporated developing agent can contain an antioxidant such as a water-soluble sulfite or bisulfite, e.g., sodium formaldehyde bisulfite,such as described in U.S. Pat. No. 3,212,895 of Barbier et al. and U.S. Pat. No. 3,418,132 of Kitze.
  • an antioxidant such as a water-soluble sulfite or bisulfite, e.g., sodium formaldehyde bisulfite, such as described in U.S. Pat. No. 3,212,895 of Barbier et al. and U.S. Pat. No. 3,418,132 of Kitze.
  • the photographic elements employed in the practice of the invention can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, and polymeric beads including beads described, for example, in U.S. Pat. No. 2,922,101 of .lelley et al. issued July 1 1, 1961 and U.S. Pat. No. 2,701,245 of Lynn issued Feb. 1, 1955.
  • matting agents such as starch, titanium dioxide, zinc oxide, silica, and polymeric beads including beads described, for example, in U.S. Pat. No. 2,922,101 of .lelley et al. issued July 1 1, 1961 and U.S. Pat. No. 2,701,245 of Lynn issued Feb. 1, 1955.
  • the described photographic elements employed in the practice of the invention can also contain a brightening agent including stilbene, triazine, oxazole] and/or coumarin brightening agents.
  • a brightening agent including stilbene, triazine, oxazole] and/or coumarin brightening agents.
  • Water-soluble brighteners such as those described in German Pat. No. 972,067 and U.S. Pat. No. 2,933,390 of McFall et al. issued Apr. 19, 1960 or dispersions of brighteners can be used such as those described in German Pat. No. 1,150,274 and U.S. Pat. No. 3,406,070 of Oetiker et al. issued Oct. 15, 1968 and French Pat. No. 1,530,244.
  • the photographic silver halide emulsions employed in the practice of the invention can be X-ray or other nonspectrally sensitized emulsions or they can contain spectral sensitizing dyes.
  • the photographic silver halide emulsions can conveniently be orthosensitized or pansensitized with spectral sensitizing dyes.
  • these emulsions can be spectrally sensitized by treating with a solution of a sensitizing dye in an organic solvent or the dye can be added in the form of a dispersion such as described in French Pat. No. 1,482,774.
  • Spectral sensitizing dyes useful in sensitizing such emulsions are described, for example, in U.S. Pat. No.
  • Spectral sensitizers which can be used include the cyanines, merocyanines, complex (trinuclear or tetranuclear) cyanines, complex (trinuclear or tetranuclear) merocyanines, holopolar cyanines, styryls, hemicyanines, such as enamine hemicyanines, oxonols and hemioxonols.
  • Dyes of the cyanine classes can contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles.
  • Such nuclei can contain alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine groups and can be fused to carbocyclic or heterocyclic ring systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano or alkoxy groups.
  • the dyes can be symmetrical or unsymmetrical and can contain alkyl, phenyl, enamine or heterocyclic substituents on the methine or polymethine chain.
  • the merocyanine dyes can contain the basic nuclei described as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolinones and malononit'rileI
  • acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups or heterocyclic nuclei. Combinations of these dyes can be used if desired.
  • supersensitizing addenda which do not absorb visible light can be included, such as ascorbic acid derivatives, azaindenes, cadmium salts and organic sulfonic acids as described in U.S. Pat. No. 2,933,390 of McFall et al. issued Apr. 19, 1960 and U.S. Pat. No. 2,937,089 of Jones et al. issued May 17, 1960.
  • the various layers including the photographic emulsion layer of the photographic element employed in the practice of the invention can contain light absorbing materials and filter dyes such as those described in U.S. Pat. No. 3,253,921 of Sawdey issued May 31, 1966; U.S. Pat. No. 2,274,782 of Gaspar issued Mar. 3, 1942; U.S. Pat. No. 2,527,583 of Silberstein et al. issued Oct. 31, 1950; and U.S. Pat. No. 2,956,879 of VanCampen issued Oct. 18, 1960.
  • the dyes can be mordanted, for example, as described in U.S. Pat. No. 3,282,699 of Jones et al. issued Nov. 1, 1966.
  • the sensitizing dyes and other addenda such as the described silver halide developing agents and silver halide stabilizer precursors used in the practice of the invention can be added from water solutions or suitable organic solvent solutions can be used.
  • the compounds can be added using various procedures including those described in U.S. Pat. No. 2,912,343 of Collins et al. issued Nov. 10, 1959; U.S. Pat. No. 3,342,605 of McCrossen et al. issued Sept. 19, 1967; U.S. Pat. No. 2,996,287 of Audran issued Apr. 15, 1961; and U.S. Pat. No. 3,425,835 of Johnson et al. issued Feb. 4, 1969.
  • the resulting latent image in a photographic element according to the invention can be developed and stabilized by contacting the element with an alkaline activator.
  • An especially suitable activator is an aqueous alkaline solution comprising potassium hydroxide at a pH of about 10 to about 14.5, especially 12 to 14.5.
  • Alkaline activators which can be employed in developing a latent image in a photographic element as described include any of those which provide the desired activation of the described silver halide developing agents and silver halide stabilizer precursors. These include, for instance, aqueous alkaline activator solutions commonly employed in rapid access processing of photographic elements, such as those employed in so-called reader-printers.
  • Alkaline activators which are suitable include inorganic alkali such as alkali metal hydroxides, especially sodium hydroxide, potassium hydroxide and/or lithium hydroxide, alkali metal carbonates, such as sodium carbonate and potassium carbonate, sodium or potassium phosphates, and organic alkaline development activators such as quaternary ammonium bases and salts and alkanolamines such as ethanol amine, and similar alkaline materials and/or alkali releasing materials.
  • Such development activators can be applied to the photographic element employed in the practice of the invention in any suitable manner, including for example, dipping, spraying and/or surface applications such as with rollers, as described in U.S. Pat. No. 3,025,779 of Russell et al. issued Mar. 20, 1962 or by surface application processing as described in U.S. Pat. No. 3,418,132 of Kitze issued Dec. 24, 1968.
  • an alkaline solution can be employed containing conventional silver halide developing agents such as those described.
  • web processing can be employed as described, for example, in U.S. Pat. No. 3,179,517 of Tregillus et al. issued Apr. 20, 1965 or so-called stabilization processing as described in Russell et al., PSA Journal, Volume 16b, Aug. 1950.
  • the alkaline activator especially an aqueous alkaline activator solution can contain a hardener as described.
  • the time for processing a photographic element in the practice of the invention can vary over a wide range, typically between about 1 second to several minutes depending on the desired image, processing conditions and the like.
  • the conditions for processing can also vary, but usually ambient pressures and temperatures of about 20 C. to about 30 C. are employed. If desired, higher temperatures can be used such as temperatures up to about 90 C.
  • EXAMPLE 1 The following coating composition is prepared and coated at 0.004 inch wet thickness on a baryta-coated paper base:
  • This composition contains approximately 8 moles of the stabilizer compound per mole of silver.
  • the resulting photographic element is then exposed to an image and then immersed for 10 seconds in a solution at 75 F. containing 5 percent sodium hydroxide, 5 percent sodium sulfite and 5 percent sodium sulfate. The element is then washed in water. A blue-black image of excellent density and emulsion speed is obtained with a white background that is stable to the continued effect of light.
  • EXAMPLE 5 A photographic element is prepared according to the procedure of Example I. A portion of the element is incubated for 7 days at 120 F. and 35 percent Relative Humidity. Both portions of the element are then processed as in Example 1. The following sensitometric values are obtained:
  • a photographic silver halide emulsion containing at least one mole per mole of silver halide of a l,l bis-sulfonyl alkane stabilizing agent 1.
  • stabilizing agent has the formula wherein R, and R each represent an alkyl group containing one to four carbon atoms and R represents H or an alkyl group containing one to four carbon atoms.
  • a photosensitive element comprising a support having thereon a photographic silver halide emulsion layer, said element containing at least one mole per mole of silver halide of a l,l bis-sulfonyl alkane stabilizing agent.
  • said stabilizing agent has the formula Ra Rr-S 0r- JH-s 02-11 wherein R, and R each represent an alkyl group containing one to four carbon atoms and R represents H or an alkyl group containing one to four carbon atoms.
  • R, and R each represent methyl, ethyl, hydroxyethyl, carboxymethyl or carboxyethyl groups and R represents H.
  • the photosensitive element of claim 5 which includes a photographic silver halide developing agent incorporated therein.
  • said stabilizing agent has the formula wherein R, and R each represent an alkyl group containing one to four carbon atoms and R represents H or an alkyl group containing one to four carbon atoms.
  • R, and R each represent methyl, ethyl, hydroxyethyl, carboxymethyl or carboxyethyl groups and R represents H.
  • a process for stabilizing a photographic element comprising:
  • exposing a photosensitive element comprising a support having thereon a photographic silver halide emulsion layer, said element containing at least 1 mole per mole of silver halide of a l,l bis-sulfonyl alkane stabilizing agent.
  • said stabilizing agent has the formula wherein R, and R each represent an alkyl group containing one to four carbon atoms and R represents H or an alkyl group containing one to four carbon atoms.
  • R, and R each represent methyl, ethyl, hydroxyethyl, carboxymethyl or carboxyethyl groups and R represents H.
  • a process for stabilizing a photographic element comprising:
  • V exposing a photosensitive element comprising a support having thereon a photographic silver halide emulsion E layer, said element containing at least one mole per mole a.
  • V a r of Silver Palide of a 1,1 q y stabilizing wherein R and R each represent an alkyl group containing agent element also a Sllver halide 5 one to four carbon atoms and R represents H or an alkyl developmg agent Incorporated therem and group containing one to four carbon atoms.
  • stabilizing agent has the formula 19.
  • R, and R each represent methyl, ethyl, hydroxyethyl, carboxymethyl or carboxyethyl groups and R represents H.

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770432A (en) * 1971-10-01 1973-11-06 Eastman Kodak Co A photographic composition of 1,1-bis-sulfonyl alkane and hydroxylamine
US3839042A (en) * 1972-09-29 1974-10-01 Eastman Kodak Co Hardening hydrophilic colloid silver halide emulsion layer with a 2-haloethylsulfonyl compound
US4126459A (en) * 1976-05-14 1978-11-21 Polaroid Corporation Thioether substituted silver halide solvents

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3866259D1 (de) * 1987-02-24 1992-01-02 Agfa Gevaert Nv Entwicklung von photographischen silberhalogenidemulsionsmaterialien.

Citations (2)

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Publication number Priority date Publication date Assignee Title
US3220839A (en) * 1961-08-25 1965-11-30 Eastman Kodak Co Photographic emulsions containing isothiourea derivatives
US3301678A (en) * 1964-05-28 1967-01-31 Eastman Kodak Co Process for stabilizing photographic images with heat

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3220839A (en) * 1961-08-25 1965-11-30 Eastman Kodak Co Photographic emulsions containing isothiourea derivatives
US3301678A (en) * 1964-05-28 1967-01-31 Eastman Kodak Co Process for stabilizing photographic images with heat

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770432A (en) * 1971-10-01 1973-11-06 Eastman Kodak Co A photographic composition of 1,1-bis-sulfonyl alkane and hydroxylamine
US3839042A (en) * 1972-09-29 1974-10-01 Eastman Kodak Co Hardening hydrophilic colloid silver halide emulsion layer with a 2-haloethylsulfonyl compound
US4126459A (en) * 1976-05-14 1978-11-21 Polaroid Corporation Thioether substituted silver halide solvents

Also Published As

Publication number Publication date
JPS5038329B1 (OSRAM) 1975-12-09
FR2095613A5 (OSRAM) 1972-02-11
DE2126685B2 (de) 1979-01-11
GB1344525A (en) 1974-01-23
DE2126685C3 (de) 1979-09-06
DE2126685A1 (de) 1971-12-09
CA972209A (en) 1975-08-05
BE767948A (fr) 1971-11-03

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