US3732103A - Silver halide emulsions containing alkyl selenols and thiols as antifoggants - Google Patents

Silver halide emulsions containing alkyl selenols and thiols as antifoggants Download PDF

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US3732103A
US3732103A US00139941A US3732103DA US3732103A US 3732103 A US3732103 A US 3732103A US 00139941 A US00139941 A US 00139941A US 3732103D A US3732103D A US 3732103DA US 3732103 A US3732103 A US 3732103A
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silver halide
compounds
fog
hydrogen
organic
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A Herz
Wescott E Russell
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Eastman Kodak Co
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Eastman Kodak Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • 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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
    • 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
    • G03C1/492—Photosoluble emulsions
    • 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
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/32—Development processes or agents therefor
    • G03C8/36—Developers
    • G03C8/365—Developers containing silver-halide solvents

Definitions

  • R to R are each hydrogen or organic residues provided that at least one of said R to R is a sulfonic acid group or salt thereof and m and n are each about 0 to about 4 so that the sum of mi and n equals a positive integer up to about in which A is a cation, X is sulfur or selenium, R is an organic residue; R is hydrogen or an organic residue; 0!. and B are each hydrogen, organic residue or the electrons required to form double bonds between the carbon atoms; Y and Z are each hydrogen or an organic residue or together comprise atoms needed to complete a cyclic nucleus.
  • This invention relates to the stabilization of photographic elements and compositions. More particularly it relates in one aspect to the stabilization of silver halide containing compositions against spontaneous fog. In another aspect, the invention relates to certain new and known organic selenium derivatives and their sulfur-con taining analogs which are useful in stabilizing light sensitive silver halide emulsions and layers of photographic elements.
  • addenda have been employed in the past to increase the stability of the photosensitive silver halidecontaining elements and compositions. Some such addenda reduce the tendency to fog but likewise exhibit the disadvantage of decreasing the sensitivity and/or the contrast of the silver halide-containing element and composition. This is especially true in those photographic preparations which are optically sensitized to the various spectral regions, such as those preparations adapted for use in color photography.
  • British Pat. 1,115,048 issued May 22, 196 8, to Me- Veigh discloses the use of organic selenium compounds as sensitizers for silver halide emulsions.
  • British 1,098,466 issued to Dunn, Jan. 10, 1968 small amounts of organic selenium derivatives are used in con junction with noble metal sensitizers in order to produce unexpected increases in sensitivity.
  • This invention relates to new photographic compositions and elements comprising light sensitive silver halide which is fog stabilized by an effective concentration of a seleniumor sulfur-containing organic compound.
  • These compounds are generically described as sulfoalkyl selenols and their thiol analogs, fi-acylamino alkylene selenols and their thiol analogs and methylene bases such as 2-methyleneselenazolines and their thiazoline analogs.
  • a further object of the invention is to provide stabilized silver halide containing compositions and elements comprising development modifiers by employing certain seleninm-containing organic compounds and their sulfur analogs such as thiols or thiazolines.
  • A is an organic or inorganic cation
  • X is either sulfur or selenium
  • R is an organic residue such as hydrocarbon groups exemplified by alkyl residues like those having 1 to 6 carbon atoms like methyl; aryl residues like benzyl and the like or functionally-substituted alkyl residues such as sulfopropyl and the like in addition to carboxyalkyl like carboxydecyl and hydroxyalkyl like hydroxyethyl and the like;
  • R is hydrogen or an organic residue such as a hydrocarbon group like R", and a and B are hydrogen or an organic residue such as hydrocarbon groups like R" or can represent the electrons needed to link the carbon atoms to which they are attached by a double bond;
  • Y and Z are hydrogen or a hydrocarbon residue like R or together provide the linkage required for completion of a mono-cyclic nucleus like pyridine or benzene or polycyclic nuclei Where a -6 membercd
  • organic cation can be exemplified by ions such as guanidinium, tetraalkylammonium, trialkylsulfonium and the like and inorganic cations include those such as hydrogen, sodium, potassium and related ions.
  • Organic residues can be bydrocarbon residues like the alkyl groups such as lower alkyl like those having 1 to 6 carbons including methyl, ethyl, butyl, isopropyl and the like and functionally substituted hydrocarbon groups exemplified by substituted alkyls such as haloalkyl, hydroxyalkyl and various aryl substituted alkyls.
  • Mono-cyclic or polycyclic nuclei are well known and include phenyl, naphthyl, pyridyl and the like groups.
  • guanidinium-Z-selenylpropane sulfonate guanidinium-3-selenyl-3-methylpropanesulfonate
  • guanidinium-Z-mercaptoethane sulfonate guanidinium-4-mercaptobutane, sulfonate and the like.
  • Typical of compounds which are defined by the Formula II include for example:
  • the stabilizing compounds defined by these structural formulae can be utilized in a variety of ways such as being incorporated directly into silver halide containing elements, such as in the silver halide layer, silver halide emulsions or in various layers contiguous thereto such as overcoat, intermediate and the like layers. In this manner it can be said that these selenium containing antifoggant compounds or their sulfur analogs are incorporated into photographic elements and compositions in a concentration and manner sufficient to insurea fog-inhibiting effect. This relationship is likewise insured by use of said compounds in various solutions or sprays in which the finished or processed photographic material is so stabilized or in using various Wrapping or storage materials or environments juxtaposed to the layers, emulsion or elements.
  • the compounds within the scope defined by the above formulae are effective antifoggants and emulsion stabilizers when employed either in or contiguous to a photographic silver halide gelatin-containing emulsion layer.
  • a preferred concentration of said compounds is from about 0.005 to about 1.0 gram per mole of silver halide.
  • Still another preferred embodiment resides in photographic silver halide emulsions which further comprise color-coupler forming compounds such as those which are phenolic, pyrazolone and open-chain reactive methylene compounds which are capable of forming a dye with the oxidation product of an aromatic primary amine silver halide color developing agent.
  • a photographic element comprising a support bearing a fog stabilized light sensitive silver halide-containing layer and comprising a silver halide solvent concentration of a selenium-containing organic compound or its sulfur analog having the structural formula:
  • R to R are hydrogen or organic residues such as a hydrocarbon residue or functionally substituted hydrocarbon groups provided that at least one of said R to R groups is a. sulfonic acid group (SO H) or an organic or inorganic salt thereof, like sodium, potassium, guanidinium and the like; and m is about 0 to about 4 and n is from about 0 to 4 or (II) a Y-(LXA o z- -N R" (III) on X o-onn 2,695,310 and in J'ACS 77, 6321 (1955).
  • SO H sulfonic acid group
  • m is about 0 to about 4
  • n is from about 0 to 4 or (II) a Y-(LXA o z- -N R" (III) on X o-onn 2,695,310 and in J'ACS 77, 6321 (1955).
  • cornpounds are effective as antifoggants in a concentration range of from about 0.005 to about 1.0 gram/mole silver halide and preferably from about .01 to about 0.5. At higher concentrations, these compounds are unexpectedly effective as silver halide solvents. As will be seen hereafter, these compounds will stabilize the sensitivity of the emulsions and restrain the formation of development and incubation fog. In the examples following, these compounds can also restrain the fog associated with the presence of cationic (for example pyridinium) development accelerators.
  • cationic for example pyridinium
  • the p-acylamino thiols and selenols likewise have an effective antifoggant concentration in the range from about 0.005 to about 1.0 gram/mole of silver halide.
  • compounds having the structural formula of (II) having between about 4 and about 8 carbon atoms can be used at elevated concentrations, i.e. about 1 to about grams/mole of silver as silver halide solvents.
  • these compounds contain more than about 8 carbon atoms and also include a solubilizing group such as a carboxylic acid or a sulfonic acid substituent, they also are elfective as a silver halide solvent.
  • These compounds having structural Formula II can be obtained by a variety of methods such as by reduction of the corresponding disulfide or diselenide or by the hydrolysis of the corresponding quaternary azolium salt or their related methylene bases, which methods of preparation are disclosed in Larive et al., Chimia 15, 115, 1961 and in J. Chim. Phys. 60, 944, 1963 and by Mills and Clark in J. Chem. Soc. 2353 (1923); 2805 (1927) and 2313 (1928).
  • Preferred concentration ranges effective for antifoggant purposes similar to those above disclosed exist for the methylene bases described in Formula III, i.e. for fogrestraining purposes eifective ranges are 0.005 to about 1.0 gram/mole silver halide.
  • These antifoggants are conveniently prepared by methods disclosed in Belgian Pat. 744,886 issued Jan. 24, 1969, to Owen and can be likewise prepared as disclosed in I. Pr. Chem. 109, 324
  • the s-ulfoalkyl selenols and thiols having the structural Formula I can likewise serve as silver halide solvent ripening agents in the preparation of silver halide emulsions, as fixing agents, or as silver solvents in diffusion transfer processes. Because of their crystallizability the guanidinium sulfonates of these compounds have unexpectedly provided significantly good results. They are prepared conveniently by the Schramm method (supra) and include guanidinium 3 selenyl 3 methyl propane sulfonate, guanidinium 2 selenyl-propane sulfonate, guanidinium mercaptobutane sulfonate and the like.
  • these sulfur or selenium-containing addenda can be used with significant unexpected advantage to achieve enhanced ripening or digestion of the emulsion. As such, they can be added before the final digestion or the after-ripening.
  • the subject class of sulfur and selenium compounds are effective in concentrations of from about 1 to about 50 grams/mole of silver.
  • the various operations of emulsion making can be described briefly as in Mees, The Theory of the Photographic Process, 1954 as (1) emulsification and digestion of the silver halide; (2) freeing of the emulsion of excess watersoluble salts, suitably by Washing, with water; and (3) the second digestion or after-ripening in order to achieve increased emulsion speed or sensitivity.
  • Particularly useful addenda are those set forth above in 'Formula II wherein at least one R is an acid residue such as carboxylic, sulfinic, sulfonic acid substituents and the like.
  • silver halide solvent properties exist when the compounds contain more than 8 carbon atoms.
  • those compounds of Formula 1 provide when only 4 to 8 carbon atoms exist, no solubilizing group need appear and elevated temperatures, i.e. greater than ambient, are employed for preferred solvent action.
  • the silver halide emulsions used in the practice of this invention can be additionally protected against the production of fog and can be stabiilzed against loss of sensitivity during keeping.
  • Suitable other antifoggants and stabilizers each used alone or in combination include the azaindenes described in Piper U.S. Pat. 2,886,437 issued May 12, 1959 and Heimbach et al. U.S. Pat. 2,444,605 issued July 6, 1948; the mercury salts as descrbied in Allen et al. U.S. Pat. 2,728,663 issued Dec. 27, 1955; the urazoles described in Anderson et al. U.S. Pat. 3,287,135 issued Nov.
  • selenium-containing compounds are unexpectedly eflective as emulsion stabilizers and antifoggants.
  • sodium diphenyl-phosphinobenzene sulfonate selenide potassium 2 selenylbenzothiazole; 7-selenyl-1,3,4,6-tetraazaindene; 4 selenyl 6 methyl-1,3,3a,7-tetraazaindene; l-ethylnaphtho-[ l,2-d] selenazoline-Z-thione and the like.
  • the required '2-(3-sulfopropyl)-2-selen0pseudo-urea is prepared from 39 g. (0.25 mole) of 1-bromo-3-chloropropane and 25 g. (0.20 mole) of sodium sulfite which are stirred and refluxed for 2 hours in 300 ml. of a 1:1 mixture of ethyl alcohol and water. This mixture is concentrated to about 100 ml. and 20 g. (0.17 mole) of selenourea is added. This mixture is stirred and refluxed for /2 hour, concentrated to 75 m1., then chilled. From a mushy, oif-white cream, the final product is recrystallized from about 50 ml. of water in a 16 g. yield which has a melting point of 225 to 227 C.
  • the potassium salt of 2-selenylbenzothiazole is prepared by the novel process of keeping in a nitrogen atmosphere 27.6 g. (0.2 mole) of potassium carbonate, 8.5 g. (0.05 mole) of 2-chlorobenzothiazole and 6 g. (0.05 mole) of selenourea during reflux. This is stirred overnight and hot filtered, then concentrated to dryness. The resulting solid is recrystallized from ethyl alcohol and treated with decolorizing carbon to yield 6 g. of substance having a melting point of greater than 280 C.
  • various polyazaindenes can be used with good results.
  • triand tetraazaindenes such as 1,3,4 and 1,3,5- tri and l,2,3,4- and 1,2,3,5-tetraazaindenes are effective antifoggants when incorporated in the silver halide layer, a layer adjacent thereto and in various solutions, such as processing solutions and the like, used to contact the silver halide and other layers.
  • These polyazaindenes are conveniently prepared from their corresponding diaminopyridines by conventional methods.
  • An effective concentration range is from about 0.95 g. to about 4.0 g./mole of silver and preferably from about 0.75 g./mole to about 3.0 g./ mole.
  • these polyazaindenes are eflective in concentrations of from about 0.15 to about 0.75 gram/liter and preferably 0.25 to about 0.50 gram/liter of solution.
  • the silver halide emulsions used with this invention can comprise 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, e.g. single jet emulsions, double jet emulsions, such as Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions such as those described in Nietz et al. U.S. Pat. 2,222,264 issued Nov. 19, 1940; Illingsworth U.S. Pat. 3,320,069 issued May 16, 1967; and McBride U.S. Pat.
  • Negative type emulsions can be used or direct positive emulsions such as those described in Leermakers U.S. Pat. 2,184,013 issued Dec. 19, 1939; Kendall et al. U.S. Pat. 2,541,472 issued Feb. 13, 1951; Berriman U.S. Pat. 3,367,778 issued Feb. 6, 1968; Schouwenaars British Pat. 723,019 issued Feb. 2, 1955; Illingsworth et al. French Pat. 1,520,821 issued Mar. 4, 1968; Ives U.S. Pat. 2,563,785 issued Aug. 7, 1951; Knott et al. U.S. Pat. 2,456,953 issued Dec. 21, 1948, and Land U.S. Pat. 2,861,885 issued Nov. 25, 1958.
  • the emulsions can be regular grain emulsions such as the type described in Klein and Moisar, I. Phot. Sci., vol. 12, No. 5, September/October 1964, pp. 24225 1.
  • the emulsions used with this 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 in Sheppard et al. U.S. Pat. 1,623,499 issued Apr. 5, 1927; Waller et al. U.S. Pat. 2,399,083 issued Apr. 23, 1946; McVeigh U.S. Pat. 3,297,447 issued Jan. 10, 1967; and Dunn U.S. Pat. 3,297,446 issued Ian. 10, 1967.
  • the photographic and other hardenable layers used in the practice of this invention can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguar gum and the like.
  • various organic or inorganic hardeners such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines,
  • the photographic emulsions and elements described in the practice of this invention can contain various colloids alone or in combination as vehicles, binding agents and various layers.
  • Suitable hydrophilic materials include both 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 a photographic element employed in the practice of this 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 which increase the dimensional stability of the photographic materials.
  • Suitable synthetic polymers include those described, for example, in Nottor-f U.S. Pat. 3,142,568 issued July 28, 1964; White U.S. Pat. 3,193,386 issued July 6, 1965; Houck et al. U.S. Pat. 3,062,674 issued Nov. 6, 1962; Houck et al. U.S. Pat. 3,220,844 issued Nov. 30, 1965; Ream et al. U.S. Pat.
  • Typical supports include cellulose nitrate film, cellulose ester film, poly- (vinyl acetal) 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 orcoated with baryta and/or an alphaolefin polymer, particularly a polymer of an alpha-olefin containing 2 to carbon atoms such as polyethylene, polypropylene, ethylenebutane copolymers and the like.
  • the photographic layers employed in the practice of this invention can contain plasticizers and lubricants such as polyalcohols, e.g. glycerin and diols of the type described in Milton et al., U.S. Patent 2,960,404 issued Nov. 1, 1966; fatty acids or esters such as those described in Robijns U.S. Patent 2,588,765 issued Apr. 11, 1952, and Duane U.S. Patent 3,121,060 issued Feb. 11, 1964; and silicone resins such as those described in Du Pont British Patent 955,061 issued Apr. 15, 1964.
  • plasticizers and lubricants such as polyalcohols, e.g. glycerin and diols of the type described in Milton et al., U.S. Patent 2,960,404 issued Nov. 1, 1966; fatty acids or esters such as those described in Robijns U.S. Patent 2,588,765 issued Apr. 11, 1952, and Duane U.S. Patent 3,121,060 issued Feb. 11, 1964;
  • the compounds obtained in accordance with this invention can be used in a pod such as described in Land U.S. Patent 2,543,181 issued Feb. 27, 1951 or employed in the photographic element for diifusion transfer processes which utilize the undeveloped silver halide in nonimage areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a silver layer in close proximity to the original silver halide emulsion layer.
  • the compounds can also be used in diffusion transfer of an imagewise distribution of developer, coupler, or dye, from a light-sensitive layer to a second layer, while the two layers are in close proximity to one another.
  • the compounds of particular interest for diffusion transfer processes are the compounds of general Formula I since these compounds contain the solubilizers sulfonic acid substituents.
  • Example I In order to demonstrate the unexpected fog reduction and emulsion stabilization imparted by various organic selenium derivatives and their sulfur analogs, to a gold and sulfur sensitized silver bromoiodide gelatin emulsion containing a carbocyanine spectral sensitizer, the emulsion is first adjusted to approximately pBr 3 and a pH of 6.3. This emulsion is then coated on a film support at about 0.46 g. of silver and 0.84 g. gelatin per square foot. After the emulsion is dried down and exposed, the film is developed for 5 minutes in a hydroquinone methylated p-aminophenol developer at 20 C.
  • Example II Samples of the same silver halide emulsion as that of Example I are employed except that these samples also contain a polyethylene oxide and quaternary pyridinium development accelerator. Processing is accomplished in a methylated p-aminophenol hydroquinone developer.
  • Example TABLE v A gold and sulfur sensitized silver bromoiodide emulmethylated sion is coated on a film support at about 350 mg. silver g g i gggper ft. The emulsion is exposed and developed for 4 minutes in a high contrast hydroqiunone developer at 15 Compound 1n gJmole Ag Speed Fog C. This emulsion serves as the control and to por- N0 1 control 100 .22 tions of the same emulsion are added, in concentrations lwntaimng quaternary Pyndlmum 155 development accelerator. show hereafter, various selenium and sulfur compounds No. 3..- No.2with a g. Na salt of 4-hydroxy-6- 174 .57
  • Example IV A bromoiodide emulsion is prepared, coated and processed as previously described in Example III. To portions of the emulsion are added the various compounds as described in the following table at the indicated concentrations. The results are as follows:
  • a photographic element comprising a support bearing a light sensitive silver halide-containing layer and, in a concentration of from about 0.005 gram to about 50 grams per mole of silver, an organic compound having the structural formula:
  • A is a cation selected from the group consisting of hydrogen, sodium, potassium, guanidinium, tetraalkylammonium, and trialkylsulfonium;
  • X is sulfur or selenium;
  • R to R are each hydrogen, an alkyl group having 1 to 6 carbon atoms or a substituted alkyl selected from the group consisting of haloalkyl, hydroxyalkyl and aryl alkyl, provided that at least one of said R to R is a sulfonic acid group or salt thereof;
  • R is hydrogen, an alkyl residue having 1 to 6 carbon atoms, an aryl residue or a halo-, hydroxy-, or aryl-substituted alkyl residue;
  • R is an alkyl residue having 1 to 6 carbon atoms, an aryl residue or a halo-, hydroxy-, or aryl-substituted alkyl residue;
  • 0: and B are each hydrogen, an al
  • a photographic element comprising a support bearing a light sensitive silver halide-containing layer and, in a concentration of from about 0.005 to about 1.0 gram 13 per mole of silver, an organic compound having the structural formula:
  • A is a cation selected from the group consisting of hydrogen, sodium, potassium, guanidiniurn, tetraalkylammonium, and trialkylsulfonium;
  • X is sulfur or selenium;
  • -R to R are each hydrogen, an alkyl group having 1 to 6 carbon atoms or a substituted alkyl selected from the group consisting of haloalkyl, hydroxyalkyl and aryl alkyl, provided that at least one of said R to R is a sulfonic acid group or salt thereof;
  • R is hydrogen, an alkyl residue having 1 to 6 carbon atoms, an aryl residue or a halo-, hydroxy-, or aryl-substituted alkyl residue;
  • R is an alkyl residue having 1 to 6 carbon atoms, an aryl residue or a halo-, hydroxy-, or aryl-substituted alkyl residue;
  • at and ,B are each
  • At least one light sensitive silver halide-containing layer further comprises a phenolic, pyrazolone or open-chain reactive methylene coupler compound capable of forming a dye with an oxidation product of an aromatic primary amine silver halide color developing agent.
  • At least one light sensitive silver halide-containing layer further comprises a development modifier.
  • the element of claim 2 comprising the compound of Formula I corresponding to guanidinium-2-mercaptoethane sulfonate or guanidinium-Z-selenylpropane sulfonate.
  • the element of claim 2 comprising the compound of Formula II corresponding to o-(N-ethylacetamido)- selenaphenol, 2(N-ethylacetamido)propene 1 thiol or 2 (N-methylpropionamido propenel-selenol.
  • a photographic element comprising a support bearing a light sensitive silver halide-containing layer and, in a concentration of from about 1.0 gram to about 50 grams per mole of silver, an organic compound having the structural formula:
  • A is a cation selected from the group consisting of hydrogen, sodium, potassium, guanidinium, tetraalkylammonium, and trialkylsulfonium
  • X is sulfur or selenium
  • R to R are each hydrogen, an alkyl group having 1 to 6 carbon atoms or a substituted alkyl selected from the group consisting of haloalkyl, hydroxyalkyl and aryl alkyl, provided that at least one of said R to R is a sulfonic acid group or salt thereof;
  • R is hydrogen, an alkyl residue having 1 to 6 carbon atoms.
  • said silver halide containing layer is an emulsion layer comprising gelatin as a binder.

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4374196A (en) * 1981-02-20 1983-02-15 Eastman Kodak Company Silver halide emulsions containing latent image stabilizing compounds
US4423140A (en) * 1982-06-25 1983-12-27 Eastman Kodak Company Silver halide emulsions containing aromatic latent image stabilizing compounds
USRE32195E (en) * 1982-06-25 1986-07-01 Eastman Kodak Company Silver halide emulsions containing aromatic latent image stabilizing compounds

Citations (4)

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Publication number Priority date Publication date Assignee Title
US3042521A (en) * 1957-12-26 1962-07-03 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsion
US3506444A (en) * 1964-05-28 1970-04-14 Eastman Kodak Co Dry stabilization of photographic images
US3535115A (en) * 1967-12-11 1970-10-20 Eastman Kodak Co Silver halide systems containing stabilizer precursors
US3615621A (en) * 1968-08-12 1971-10-26 Eastman Kodak Co 4-pyrimidinethione compounds as fog inhibitors

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3042521A (en) * 1957-12-26 1962-07-03 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsion
US3506444A (en) * 1964-05-28 1970-04-14 Eastman Kodak Co Dry stabilization of photographic images
US3535115A (en) * 1967-12-11 1970-10-20 Eastman Kodak Co Silver halide systems containing stabilizer precursors
US3615621A (en) * 1968-08-12 1971-10-26 Eastman Kodak Co 4-pyrimidinethione compounds as fog inhibitors

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4374196A (en) * 1981-02-20 1983-02-15 Eastman Kodak Company Silver halide emulsions containing latent image stabilizing compounds
US4423140A (en) * 1982-06-25 1983-12-27 Eastman Kodak Company Silver halide emulsions containing aromatic latent image stabilizing compounds
USRE32195E (en) * 1982-06-25 1986-07-01 Eastman Kodak Company Silver halide emulsions containing aromatic latent image stabilizing compounds

Also Published As

Publication number Publication date
FR2117694B1 (show.php) 1977-12-23
BE782638A (fr) 1972-08-16
CA977600A (en) 1975-11-11
GB1395767A (en) 1975-05-29
FR2117694A1 (show.php) 1972-07-28

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