US3770432A - A photographic composition of 1,1-bis-sulfonyl alkane and hydroxylamine - Google Patents

A photographic composition of 1,1-bis-sulfonyl alkane and hydroxylamine Download PDF

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US3770432A
US3770432A US00185830A US3770432DA US3770432A US 3770432 A US3770432 A US 3770432A US 00185830 A US00185830 A US 00185830A US 3770432D A US3770432D A US 3770432DA US 3770432 A US3770432 A US 3770432A
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silver halide
photographic
bis
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developing agent
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D Yungkurth
Sweeney G Mc
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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
    • 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

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  • This invention relates to photographic processing compositions, elements and processes. In one of its aspects it relates to photographicprocessing compositions containing a combination of'ra l,l-bis-sulfonyl alemulsion layer; After exposure of the photographic layer, a processing composition is applied between the exposed photographic layer and the silver precipitating layer.
  • the processing composition usually contains a silver halide solvent which causes the unexposed silver salts, usually silver halides, to form a silver complex which diffuses to the image receiver or silver precipitatin g. layer where development nuclei or precipitating agent'within that layer causes the silver to be precipitated from the silver complex.
  • Development nuclei can be present in the image receiving layerbefore contact with the complex or the nuclei can be formed in situ.
  • Diffusion transfer photographic systems are described, for example, in US. Pat. No. 2,698,237 of Land issued Dec. 28, 1954; U.S. Pat. 'No. 2,647,056 ofLand issued July'28, 1953; U.-S.'Pat; No. 3,108,001 ofGreen issued Oct. 22, 1963; and U.S. Pat. No. 3,345,166 of Land issued Oct. 3,.
  • The'processing composition employed in a chemicaltransfer system normally contains a silver halide solubilizing agent and a silver halide developing agent'and' is usually applied as-a viscous fluid layer spread between the photosensitive layer and the image receiving layer.
  • silver halide complexing agents have been employed in monobaths wherein a single processing composition can be utilized to both develop and fix or stabilize a photographic silver halide emulsion layer.
  • compositions contain a silver halide developing agent in addition to the silver halide solubilizing agent.
  • silver halide solubilizing or complexing agent Many compounds have been tried as silver halide solubilizing or complexing agent in the described systems.
  • One commonly employed silver halide solubilizing or complexing agent employed is sodium-thiosulfate pentahydrate.
  • Other silver halide solubilizing or complexing agents which have been employed include potassium thiocyanate and certain mercaptans such as mercapto acetic acid.
  • These and other silver halide solubilizing or fixing agents have not been found satisfactory when employed with hydroxylamine silver halide developing agents due to the production of undesired maximum and minimum density in the developed image. This is illustrated in the following comparative exampies, 2, 3, 4, 5 and 6.
  • developing agents include hydroqu'inone, pyrocatechol, araboascorbic acid, or a reductone developing agent such as dihydro anhydro piperidino hexose reductone.
  • This combination of silver halide complexing agent with a hydroxylamine silver halide developing agent provides excellent silver halide solubilizing or fixing properties and developing properties in a range of photographic processes and products wherein silver halide solvents and developing agents are ordinarily employed in combination.
  • This combination can be employed with an auxiliary silver halidedeveloping agent DETAILED DESCRIPTION OF THE INVENTION
  • auxiliary silver halidedeveloping agent DETAILED DESCRIPTION OF THE INVENTION A range of the described l,l-biss ulfonyl alkanes, also known as beta-disulfones, can be employed in combination with a hydroxylamine silver halide developing agent according to the invention.
  • the betadisulfones and their chemical reactions have been described in the literature.
  • beta-disulfone compounds such as l,l-bis-sulfonyl alkanes are excellent silver halide solvents with hydroxylamine silver halide. developing agents.
  • Suitable 1,1- bis-sulfonyl alkanes employed according to the invention can be represented by the formula wherein R and R each represent an alkyl group containing one to four, carbon atoms and R represents hydrogen or an'alkyl group containing one to four carbon atoms.
  • alkyl as employed herein also includes substituted alkyl groups and preferably substituted lower alkyl group containing from one to four carbon atoms.
  • Substituted alkyl groups include hydroxyalkyl groups, e.g., hydroxyethyl or hydroxybutyl; alkoxyalkyl group such as methoxyethyl or butoxybutyl; carboxyalkyl such as a carboxyethyl or carboxybutyl; sulfoalkyl such as a sulfoethyl or sulfobutyl; sulfatoalkyl such as a sulfatoethyl or sulfatobutyl; an acyloxyalkyl such as beta-acetoxyethyl or butyloxybutyl; or alkoxycarbonylalkyl such as a beta-methoxycarbonylethyl or ethoxycarbonylbutyl.
  • 1,1-Bis-sulfonyl alkanes within the described formula include, for example, l,l-bis-(methylsulfonyl)ethane; 1 ,1 -bis-(ethylsulfonyl)ethane; l ,1 -bis-(methylsulfonyl )-propane; 1 -ethylsulfonyll methylsulfonylmethane; l-ethylsulfonyll -methylsulfonylethane and the like.
  • 1,1-bissulfonyl alkanes are bis(methylsulfonyl)methane, bis (ethysulfonyl)methane, bis(beta-hydroxyethylsulfonyl )methane, bis-(carboxymethylsulfonyl )methane, and bis(beta-carboxyethyl-sulfonyl)-methane.
  • hydroxylamine silver halide developing agents can be employed in the described combination also.
  • Useful hydroxylamine silver halide developing agents include, for example, compounds of the forwherein R, and R are each, individually, hydrogen, alkyl containing one to four carbon atoms, alkoxyalkyl containing three to six carbon atoms, or alkoxyalkoxyalkyl containing five to carbon atoms.
  • Typical hydroxylamine silver halide developing agents within this formula include hydroxylamine, N-methylhydroxylamine, N-ethylhydroxylamine, N-propylhydroxylamine, N-isopropylhydroxylamine, N,N-diethylhydroxylamine, N,N-dimethylhydroxylamine, N-methyl-N- propylhydroxylamine, N-methyl-N-isopropylhydroxylamine, N-ethyl-N-ri propylhydroxylamine, N,N-diisopropylhydroxylarnine, N,N-di-n-propylhydroxylamine, N-ethyl-N-methylbutylhydroxylamine, N-methyl-N-isobutylhydroxylamine, N-ethyl-N- hydroxyethylhydroxylam'ine, N-hydroxyethyl-N- carboxyethylhydroxylamine, N,N-di- (methoxyethyl)- hydroxylamine
  • Hydroxylamine silver halide developing agents are set out, for example, in U.S. Pat. No. 2,857,276 of Land et al., issued Oct. 21, 1958; U.S. Pat. No. 2,857,275 of Land et al., issued Oct. 21, 1958 and U.S. Pat. No. 2,857,274 of Land et al., issued Oct. 21, 1958, as well as a Netherlands Pat. No. 7015734 of Gevaert- Agfa; U.S. Pat. No. 3,343,958 of Morse, issued Sept. 26, 1967; British Pat. No. 902,314 of Polaroid, pubet al., issued Nov. 22, 1966; U.S. Pat. No.
  • One embodiment of the invention is accordingly a photographic processing composition comprising a 1,1- bis-sulfonyl alkane silver halide solubilizing agent with a hydroxylamine silver halide developing agent, as described.
  • a processing composition is typically an aqueous alkaline processing composition.
  • development activators can be employed in combination with the described beta-disulfone silver halide solubilizing agent and hydroxylamine silver halide developing agent. These include any of those which provide the desired activation of the described developing agents and desired silver halide solvent activity. These include, for example, alkaline development activators, such as inorganic alkalies including, for example, sodium hydroxide, potassium hydroxide,
  • alkali metal carbonates such as sodium carbonate, and potassium carbonate
  • alkali metal phosphates such as tri-.
  • sodium phosphate and/or organic alkaline development activators such as quaternary ammonium bases and salt, such as amino alkanols and similar alkaline materials and/or alkali releasing materials.
  • organic alkaline development activators such as quaternary ammonium bases and salt, such as amino alkanols and similar alkaline materials and/or alkali releasing materials.
  • the described hydroxylamine silver halide developing agent is alkaline and contributes to the alkalinity of the processing composition.
  • the described silver halide solubilizing agents can be utilized in a photographic processing composition in a concentration of at least about 1 gram of disulfone per liter of processing composition.
  • concentration of such silver halide solubilizing agents can vary over a wide range depending on the particular components of the processing composition, the desired image, the particular photographic silver halide emulsion employed, processing conditions and the like. Generally, however, the concentration of described disulfone utilized will vary between about 0.1 and about 1.0 moles of the described l,l-bis-sulfonyl alkane silver halide solubilizing agent per liter of processing composition.
  • disulfones When the described disulfones are employed in processing compositions for clearing or fixing silver halide in developed photographic elements, usually at least about 5 to' 200 grams of the beta-disulfone is employed per liter of processing composition to obtain the fixing within a practical time. Lower concentrations can be employed when the described disulfone is employed as a silver halide solubilizing agent in a silver salt chemical transfer system.
  • the described disulfone siiver halide complexing agents provide fixing or clearing action in alkaline or basic compositions.
  • alkaline compositions have a pH of at least 8 or 9, and preferably at least about 1 l, are employed.
  • the alkalinity of the processing compositions can vary over a wide range de pending upon the particular photographic element processed, particular processing condition, the hydroxylamine silver halide developing agent employed, processing time and the like.
  • a range of concentration of the described hydroxylamine silver halide developing agent can be employed in the combination according to the invention.
  • a suitable concentration is typically about 0.10 mole to about 1.50 mole of hydroxylamine silver halide developing agent per liter of processing composition.
  • An especially useful processing composition is an aqueous alkaline photographic processing solution containing bis(methylsulfonyl)methane with N,N-diethylhydroxylamine.
  • the disulfone silver halide solubilizing agent can be employed in one ormore layers of aphotographic element and/or in a processing composition, if desired.
  • the optimum location will depend upon the desired image, processing conditions, particular photographic system and the like.
  • An especially useful locaa a wide range depending, primarily, upon the concentration of silver halide present initially in the'photosensh tive element and the degree it is desired to dissolve or solubilize'the silver halide;
  • the fact that the described disulfones can be incorporated in a photosensitive element is an important characteristic of these compounds.
  • Silver halide solubilizing agent commonly employed such as sodium thiosulfate pentahydrate, cannot be successfully incorporated in a photographicelement,,especially in'a photographic silver halide emulsion layer since it provides undesired silver halide solvent action upon contact with the silver halide.
  • the described disulfones are relatively inert at a pH range below about 8 or 9 and, therefore, can be coated as a component of a photographic element at the pH or below. The disulfones become active silver halide solvents above this pH range. Alkaline activation of the described disulfone silver halide solubilizing agents with the hydroxylamine silver halide developing agents thus can provide both silver halide developing activity and silver halide solvent activity.
  • Another embodiment of the invention accordingly is a photographic element comprising a support, photographic silver halide, a 1,1-bis-sulfonyl alkane silver halide solubilizing agent with a hydroxylamine silver halide developing agent.
  • a typical photographic element comprises a support, photogrpahic silver halide, bis(methylsulfonyl)methane with N',N-diethylhydroxylamine.
  • a concentration of the described disulfone can vary dependprocessing condition and the like but is typically about 0.24 mole to about 4 moles of the described disulfone per mole of silver halide present in the photographic element.
  • a suitable range of hydroxylamine silver halide developing agent in a photographic element with the disulfone can also vary depending upon the deing upon the components of the photographic element, 5
  • photographicsilver halide by contacting the element with an alkaline photographic processing composition containing a silver halide solubilizing agent with a silver halide developing agent, the improvement which comprises employing a 1,1-bis-sulfonyl alkane as the silver halide solubilizing agent with a hydroxylamine developing agent as the silver halide developing agent.
  • This photographic element can provide a means for rapid access processing. 4
  • an alkaline solution containing conventional silver halide developing agents can be employed for activating the described hydroxylamine silver halide developing agent when employed in a photographic element.
  • web processing can be employed, as described, for example, in US. Pat. No. 3,179,517 of Tregillus et al issued Apr. 20, 1965 or so-called stabiliz a tio n processing as described in Russell et al., PSA
  • the practice of the invention which includes developing a desired latent image can vary over a wide range typically between about 1 second to several minutes depending-on the processing conditions, particular developing agents, particular silver halide solubilizing agent,
  • the conditionsfor processing can also vary, but usually ambient pressures and temperatures-of about 10C.
  • the described combinationof disulfones with hydroxylamine silver halide developing agents aredesirably employed in photographic chemical transfer systems, especially photographic silver s'alt chemicalv transfer systems.
  • the described combination can be employed individually or in combination in one or more layers of photographic elementand/or in a processing composition in ,such a system if desired.
  • Suitable chemical transfer systems, processes, processing compositions and elements therefor are described, for example, in 11.8. Pat. No. -2,452,l8l of Land issued Feb. 27, 1951; US. Pat. No. 3,337,342 ofGreen issued Aug. 27, 1967, the disclosures of which are incorporated herein by reference. They can be used in socalled high speed diffusion transfersystems, processes and compositions therefor as described, for example, in 11.8. Pat.
  • another embodiment of the invention is I in a process for developing and stabilizing an image in a photographic element comprising a support and exgraphicproducts suitable for diffusion transfer systems comprising in combination (a) a photographic element comprising photographic silver halide, (b) a processing composition containing a silver halidesolvent, typically in a rupturable container, and (c) an image receiving layer. Accordingly another embodiment of the.
  • a photographic diffusion transfer product comprising in combination (a) a photographic element comprising photographic silver halide, (b) a processing composition comprising a silver halide solubilizing agent and (c) an image receiving layer, the product containing a silver halide developing agent, the iniprovement comprising a combination of 1,1-bis-s ulfony alkane as the silver halide solubilizing agent and a hydroxylamine silver halide developing'agent as the described developing agent.
  • the described combination of silver halide solubilizing agent and silver halide developing agent is preferably present in the processing composition.
  • the described combination of disulfone with hydroxylamine silver halide developing agent can be employed in a photographic silver salt diffusion transfer process comprising developing a latent image in a photographic diffusion transfer product comprising (a) a photographic element comprising photographic silver halide, (b) a processing composition comprising a silver halide solvent, and (c) an image receiving layer wherein the l,l-bis sulfonyl alkane as described is em ployed as the silver halide solubilizing agent and a hydroxylamine is employed as the silver halide developing agent.
  • this process can, for example, comprise the steps of exposing a photographic silver halide layer to form a latent image therein; developing the latent image with a processing composition, such as at a pH of about 12 to about 14, comprising the described hydroxylamine silver halide developing agent;
  • development nuclei or silver precipitating agents can be employed in diffusion transfer systems as described. These can be physical development nuclei or chemical precipitants including, for example, heavy metal in colloidal form and salts of these metals, salts of amines which form silversalts and/or non-diffusing polymeric materials with functional groups capable of combining with silver amines.
  • Suitable development nuclei and/or silver image precipitating agents within the described classes include metal sulfides,-sulfonides, plysulfides, polyselenides, thiourea and its derivatives; stannous halides, sulfur, gold, platinum, palladium and mercury, colloidal silver sulfur, aminoguanidine sulfate, aminoguanidine carbonate, arsenous oxide, sodium stannate, hydrazines, xanthates and similar agents disclosed, for example, in U.S. Pat. No. 3,020,155 of Ya'ckel et al. issued Feb. 6, 1962.
  • a typical non-diffusing polymeric silver precipitant is poly (vinylmercaptoacetate).
  • a range of concentration of development nuclei or silver precipitating agent can be employed.
  • a concentration of the development nuclei or silver precipitant in the imagereceiving layer must be at least sufficient to insure the development of a positive image and sufficient removal of undeveloped silver salt from the light sensitive layer to be processed.
  • the described silver precipitating agents or development nuclei can beutilized in image reception layers that are separate elements from the light sensitive silver halide element processed or they can be utilized as reception layers integral with the light sensitive element.
  • the reception layer is integral with the light sensitive element, the reception layer is generally a sublayer over which is coated the silver halide in a vehicle that is readily removable during processing, such as a hydrophilic colloid soluble in aqueous alkali such as cellulose ether phthalate.
  • the concentration of the disulfone can vary over a wide range depending on the concentration of the silver halide present in the system to be dissolved.
  • the concentration can be about 0.25 to about 4 moles of described disulfone per mole of silver halide-in the light sensitive element.
  • the described photographic element, receiving layers and/or processing compositions can also contain toning agents.
  • Typical toning agents which can be employed include, for example, polyvalent inorganic-salts as described in U.S. Pat. No. 2,698,236 of Land issued Dec. 28, 1954; silica as described in U.S. Pat. No. 2,698,237 of Land issued Dec. 28, 1954 and heterocyclic mercaptans such as mercaptoazoles, such as mercaptodiazoles, mercaptotriazoles, mercaptotetrazoles and corresponding selenazoles.
  • a processing composition employed in a diffusion transfer system as described is typically a viscous processing composition.
  • a wide range of viscosity can be employed The viscosity can be about 20 to about 100,000centipoise typically about 100 to about 10,000 centipoise.
  • Various thickening agents are suitable in the described processing compositions and processes of the invention. Any of those commonly employed in diffusion transfer photographic systems can be employed as well as those employed in viscous monobaths. These include those described, for example, in U.S. Pat. No. 3,120,795 of Land issued Feb. 11, 1964 such as hydroryethylcellulose and carboxymethylcellulose.
  • the described combination of a l,l-bis-sulfonyl alkane silver halide solubilizing agent with a hydroxylamine silver halide developing agent can be employed in combination with silver halide developing agents which are not hydroxylamines.
  • the developing agents can be employed in such combinations as auxiliary developing agents or as the main component of a developing combination.
  • Suitable silver halide developing agents which can be employed include, for example, polyhydroxybenzenes, such as hydroquinone silver halide developing agents, e.g., hydroquinone, alkylsubstituted hydroquinones as exemplified by tertiary butyl hydroquinone, methyl hydroquinone, 2,5- dimethyl hydroquinone and 2,6-dimethyl hydroquinone; catechols and pyrogallols; chloro-substituted hydroquinones, such as chlorohydroquinone or dichlorohydroquinone; alkoxy-substituted hydroquinone British Pat. No. 1,045,303 published Oct. 12, 1966 and V the like. Combinations of these developing agents can be employed, if desired.
  • hydroquinone silver halide developing agents e.g., hydroquinone, alkylsubstituted hydroquinones as exemplified by tertiary butyl hydroquinone, methyl hydro
  • 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 orfine-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 Lippmann, 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. 4, 1940; U.S. Pat. No. 3,320,069 of lllingsworth issued May 15, 1967 and U.S.
  • 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.
  • the silver halide emulsions employed in the practice of the invention can be unwashed or washed to remove soluble salts. 1n the latter case the soluble salts can be removed by chill-setting 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; silver, selenium, or tellurium compounds; gold, platinum or palladium compounds; or combinations of these.
  • chemical sensitizers such as with reducing-agents; silver, 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 Shepardyissued Apr. 5, 1927; U.S. Pat. No. 2,399,083 of Waller et al. issued Apr. 23, 1946;
  • the silver halide emulsions and/orproc essing com-- positions employed in thepractice of the invention can contain speed increasing comounds such as polyalkylene glycols, cationic surfactants andthioethers or comfor example, thiazolium salts; azaindenes, mercury salts as described, for example, in U.S. Pat. No. 2,728,663
  • nates carbodiimides, mixed function hardeners and 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 U.S. Pat. No. 2,839,405 of Jones issued June. 17, 1958; palladium, platinum and gold salts described, for
  • polymeric hardeners such as oxidized polysaccharides such'as dialdehyde starch and oxyguargum and the like.
  • 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 mate-, rials 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 which increase 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.
  • the photographicelments 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 ester 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, poly-propylene, ethylene-butene copolymers and the like.
  • the photographic 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.
  • 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 Duan
  • 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, 1962 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, 1962 and amphoteric compounds such as those described in U.S. Pat. No. 3,133,816 of Ben-Ezra issued May 19, 1964.
  • the photographic elements employed in the practice of the invention can contain matting agents such as startch, titanium dioxide, zinc oxide, silica, and polymeric beads including beads described, for example, in U.S. Pat. No. 2,992,101 of Jelley et al. issued July 11, 1961 and U.S. Pat. No. 2,701,245 of Lynn issued Feb. 1, 1955.
  • matting agents such as startch, titanium dioxide, zinc oxide, silica, and polymeric beads including beads described, for example, in U.S. Pat. No. 2,992,101 of Jelley et al. issued July 11, 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 brightening agents including stilbene, triazine, oxazole, and/or coumarin brightening agents.
  • Water-soluble brightenlide emulsions can conveniently be ortho-sensitized or pan-sensitized 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 groups as the thia'zolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles.
  • Such groups can contain alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine substituents 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 groups described as well as acid groups such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones and malononitrile. These acid groups can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups or heterocyclic groups. 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 used in the practiceoftheinvention 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.
  • EXAMPLE 1 This example illustrates use of the combination of the described disulfones with a hydroxylamine silver halide developing agent and producing a positive image in a photographic chemical transfer system.
  • a processing composition is prepared by mixing the following components.
  • processing composition is spread between the photographic element and the image receiver so as to have the image and receiver contact the processing composition simultaneously. After 30 seconds contact time at 22C the photographic element with the processing layer is stripped away from the image receiver. A positive image of good discrimination is observed on the image receiver. The minimum reflection density of the image on the image receiver is 0.08 and the maximum reflection density of this image is 1.69.
  • EXAMPLE 2 This is a comparative example.
  • Example 2 The procedure set out in Example 1 is repeated with the exception that 1.08 grams of uracil is employed in place of bis( methylsulfonyl)methane. A transfer image is produced having a minimum reflection density of 0.10 and a maximum reflection density of 0.79.
  • Example 2 The procedure set out in Example 1 is repeated with the exception that 2.38 grams of sodium thiosulfate pentahydrate is employed in place of bis(methylsulfonyl)methane. A transfer image isproduced on the image receiver having a minimum reflection density of 0.30 and a maximum reflection density of .57.
  • Example 1 The procedure set out in Example 1 is repreated with the exception that 0.93 grams of potassium thiocyanate is employed in place of the bis(methylsulfonyl)methane. A transfer image is produced on the image receiver having a minimum reflection density of 0.10 and a maximum reflection density of 0.16.
  • Example 1 The procedure set out in Example 1 is repeated with the exception that 1.10 ml of an 80 percent by weight aqueous m'ercaptoacetic acid solution is employed in place of the bis(methylsulfonyl)methane. A transfer image is produced on the image receiver having a minimum reflection density of 0.10 and a maximum reflection density of 0.10. This indicates no satisfactory image transfer.
  • Example 1 The procedure set out in Example 1 is repeated with the exception that 1.69 grams of cysteine hydrochloride monohydrate is employed in place of thebis(methylsulfonyl)-methane. N0 satisfactory image transfer is observed.
  • EXAMPLE 7 This is a comparative example.
  • Example 1 The procedure set out in Example 1 is repeated with the exception that 3.10 grams of hydroquinone is employed in place of the N,N-diethylhydroxylamine. An image transfer is obsreved on the image receiver having a minimum reflection density of 0.20 and a maximum reflection density of 1.10.
  • EXAMPLE 8' This is a comparative example.
  • Example 2 The procedure set out in Example 1 is repeated with the exception that 4.98 grams of D-(-)-araboascorbic acid is employed in place of the N,N-diethylhydroxylamine. A transfer image is produced on the image receiver having a minimum reflection density of 0.16 and a maximum reflection density of 0.8.6.
  • EXAMPLE 9 This examplesillustrates image stability of the image produced according to Example 1.
  • a print as produced according to Example 1 is subjected to the following conditions:
  • Treatment Condition 22C. about 50% relative humidity, no light 38C.; about 90% relative humidity, 1800 foot-candles fluorescent illumination Identification Fresh Light incubated After 48 hours at the described conditions, sensitometric-curves are plotted for the fresh and light incubated samples.
  • Table 1 indicates the stability of prints producedaccording-to Example 1 as measured by the gain in speed at adensity of 0.20.
  • EXAMPLE 26 l, l -Bis-(methylsulfonyl)ethane EXAMPLE 27 l,l-Bis-(ethylsulfonyl)ethane v EXAMPLE 2 8 l,l -Bis-(methylsulfonyl )propane I EXAMPLE 29 l-e'thylsulfonyll -methyl sulfonylmethane EXAMPLE 30 l-eth'ylsulfonyll -methylsulfonylethane EXAMPLE 31 l ,1 -Bis-(beta-hydroxyethylsulfonyl)methane EXAMPLE 32 l, l -Bis-(carboxymethylsulfonyl)methane EXAMPLE 33 l, l -Bis-( beta-carboxyethylsulfonyl)methane EXAMPLE 34
  • a photographic element comprising a support, photographic silver halide, a l,l-bis-sulfonyl alkane silver halide solubilizing agent with a hydroxylamine silver halide developing agent.
  • Aphotographic element as in claim 1 comprising a support, photographic silver halide, bis(methylsulwherein R and R each represent an alkyl group containing one to four carbon atoms and R represents hydrogen or an alkyl group containing one to four carbon atoms, andsaid hydroxylamine silver halide developing agent is a compound of the formula:'
  • R, and R are each hydrogen, alkyl containing one to four carbon atoms, alkoxyalkyl containing three to six carbon atoms, or alkoxyalkoxyalkyl containing five to 10 carbon atoms.
  • a photographic diffusion transfer process comprising developing a latent image in a photographic diffusion transfer product comprising (a) a photographic element comprising photographic silver halide, (b) a processing composition comprising a silver halide solubilizing agent and (c) an image receiving layer, said product also comprising a silver halide developing agent, and forming an imagewise distribution of a silver complex in said element by contacting undeveloped silver halide in said element with said silver halide solubilizing agent and transferring at least part of the silver complex to said image receiver layer, the improvement comprising employing a 1,1-bis-sulfonyl alkane as said silver halide solubilizing agent and hydroxylamine as said silver halide developing agent.
  • R and R each representan alkyl giofiiicdfi-i taining one to four carbon atoms and R represents hydrogen or an alkyl group containing one to four carbon atoms
  • said hydroxylamine silver halide developing agent is a compound of the formula:
  • R and R are each hydrogen, alkyl containing one to four carbon atoms, alkoxyalkyl containing three 1 agent.
  • I I I is QERTWMATE FQQRREQTTE I I -7?O. v Emma Ngvember 63 197i Imnntofls) 90mm Gn Yenglwrich and 2m ⁇ ! 5, Mcfiweeney I: is certitiafiqm @3250? eppeen'e m em ebesvve fidemaifia wfient ind that and Lemma esteem em hemby emrmew ma mew Mime:

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US00185830A 1971-10-01 1971-10-01 A photographic composition of 1,1-bis-sulfonyl alkane and hydroxylamine Expired - Lifetime US3770432A (en)

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BE (1) BE789563A (ja)
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JPS5522071A (en) * 1978-08-01 1980-02-16 Kuraray Co Polymer sheet article similar to natural leather and method
US4382119A (en) * 1981-08-19 1983-05-03 Polaroid Corporation Novel photographic products and processes

Citations (2)

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Publication number Priority date Publication date Assignee Title
US3293034A (en) * 1963-06-26 1966-12-20 Polaroid Corp Alkoxy hydroxylamines as photographic developers
US3647453A (en) * 1970-06-01 1972-03-07 Eastman Kodak Co Stabilization of silver halide emulsions with 1,1 bis-sulfonyl alkanes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293034A (en) * 1963-06-26 1966-12-20 Polaroid Corp Alkoxy hydroxylamines as photographic developers
US3647453A (en) * 1970-06-01 1972-03-07 Eastman Kodak Co Stabilization of silver halide emulsions with 1,1 bis-sulfonyl alkanes

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CA976798A (en) 1975-10-28

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