US3625699A - Sensitization of photographic silver halide emulsions containing colorforming compounds by 1 1-bis-sulfonyl alkanes - Google Patents

Sensitization of photographic silver halide emulsions containing colorforming compounds by 1 1-bis-sulfonyl alkanes Download PDF

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US3625699A
US3625699A US42605A US3625699DA US3625699A US 3625699 A US3625699 A US 3625699A US 42605 A US42605 A US 42605A US 3625699D A US3625699D A US 3625699DA US 3625699 A US3625699 A US 3625699A
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pat
silver halide
bis
emulsion
photographic
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Paul H Stewart
Donald W Heseltine
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39236—Organic compounds with a function having at least two elements among nitrogen, sulfur or oxygen

Definitions

  • This invention relates to the art of photography and to photographic silver halide emulsions employed therein. More particularly, this invention relates to sensitizing photographic silver halide emulsions containing colorforming compounds, or couplers.
  • the couplers may be contained either in the processing solution or in the photographic emulsion.
  • the color-forming compounds employed include, for example, pyrazolone couplers for the formation of a magenta image, phenolic couplers for the formation of a cyan image, and open-chain couplers containing a reactive methylene group for the formation of a yellow image. If the couplers are incorporated in a photographic silver halide emulsion layer, they are characterized by nondiffusing properties with respect to the particular silver halide emulsions in which they are incorporated.
  • Another object of the present invention is to provide a process for increasing the speed of photographic silver halide emulsions containing a color-forming compound.
  • Suitable 1,1 bis-sulfonyl alkanes used in the present invention can be represented by the general formula wherein R and R each represents 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 1 to 4 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 1 to 4 carbon atoms.
  • substituted lower alkyl groups such as a hydroxyalkyl group, e.g., B-hydroxyethyl, w-hydroxybutyl, etc.; an alkoxyalkyl group, e.g., fi-methoxyethyl, w-butoxybutyl, etc.; a carboxyalkyl group, e.g., p-carboxyethyl, w-carboxybutyl, etc.; a sulfoalkyl group, e.g., fi-sulfoethyl, w-sulfobutyl, etc.; a sulfatoalkyl group, e.g., B-sulfatoethyl, w-sulfatobutyl, etc.; an acryloxyalkyl group, e.g., fl-acetoxyethyl, w-butyryloxybutyl, etc.; an alkoxycarbonyl group
  • 1,1 bis-sulfonyl alkanes within the above formula include 1,1 bis-(methylsulfonyl)ethane; 1,1 bis-(ethylsulfonyl)- ethane; 1,1 bis-(methylsulfonyl)propane; 1,1 bis- (ethylsulfonyl propane; l-ethylsulfonyll-methylsulfonyl methane; l-ethylsulfonyl-l-methylsulfonyl ethane; etc.
  • 1,1 bis-sulfonyl alkanes are bis(methylsulfonyl)methane, bis(ethylsulfonyl)methane, bis(fi-hydroxyethylsulfonyl methane, bis (carboxymethylsulfonyl) methane, and bis(fi-carboxyethylsulfonyl)methane.
  • the disulfones of the present invention are efiectively employed in photographic silver halide emulsions in combination with various color-forming compounds or couplers, which react with the oxidation products of color developers, such as aromatic primary amino color developing agents e.g., p-phenylenediarnine developers, to provide subtractively-colored images.
  • color developers such as aromatic primary amino color developing agents e.g., p-phenylenediarnine developers
  • the disulfones of the invention can be utilized in one or more layers of a photosensitive element contiguous to the silver halide emulsion.
  • the amount of disulfone to be employed may vary over a fairly wide range. The optimum amount of the particular disulfone employed will vary somewhat from emulsion to emulsion and from disulfone to disulfone. Generally, an effective sensitizing concentration is from about 0.1 to about 1.0 mole of the disulfone per mole of silver halide in the silver halide emulsion.
  • any of the customary types of color-forming couplers can be employed in the present invention.
  • Such couplers can be of the type which can be dispersed in a high-boiling crystalloidal compound, which may be used as a vehicle for incorporating the color-forming compound in the photographic emulsion.
  • the couplers may be of the fat-tail varieties (for example, see F.I.A.T., Final Report, No. 721) which may be dispersed in the photographic silver halide emulsions. Both of these types of couplers are characterized by non-diffusing properties in the particular silver halide emulsions in which they are incorporated.
  • the couplers, or color-forming compounds can be incorporated in the silver halide emulsion by any of the common methods known to those skilled in the art.
  • the disulfones of the present invention may be added to photographic emulsions using any of the techniques well known in emulsion making.
  • the disulfones can be dissolved in a suitable solvent and added to the silver halide emulsion or they may be added to the emulsion in the form of a finely divided dispersion, such as is described in Fierke et al., U.S. Patent 2,801,171 issued July 30, 1957.
  • Suitable color-forming compounds or couplers which can be used in practicing the present invention include couplers producing cyan images, magenta images and yellow images such as those disclosed in columns 15-18 of U.S. Patent 3,046,129 of Graham et al.
  • the above-mentioned color-forming compounds produce dyes upon development of the exposed emulsion with color developers such as aromatic primary amino color developing agents, e.g., p-phenylenediamine color developing agents.
  • color developers such as aromatic primary amino color developing agents, e.g., p-phenylenediamine color developing agents. Examples of such developing agents are shown, for example, in column 18 of the abovementioned Graham et al. U.S. Patent 3,046,129.
  • the silver halide emulsions employed in the present invention are of the developing-out type and can comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
  • the emulsions can be coarse or fine grain and may be prepared by any of the Well known procedures, e.g., single jet emulsions, double jet emulsions, Lippmann emulsions, ammoniacal eitnulsions, thiocyanate or thioether ripened emulsions, e c.
  • the emulsions can also be sensitized with 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; Waller et al. U.S. Pat. 2,399,083; McVeigh U.S. Pat. 3,297,447; and Dunn U.S. Pat. 3,297,446.
  • the silver halide emulsions can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping.
  • Suitable antifoggants and stabilizers each used along or in combination include thiazolium salts described in Brooker et al. U.S. Pat. 2,131,038 and Allen et al. U.S. Pat. 2,694,716; the azaindenes described in Piper U.S. Pat. 2,886,437 and Heimbach et al. U.S. Pat. 2,444,605; the mercury salts as described in Allen et al. U.S. Pat. 2,728,663; the urazoles described in Anderson et al. U.S. Pat.
  • Spectral sensitizing dyes can be used to confer additional sensitivity to the light-sensitive silver halide emulsion of the multilayer photographic elements of the invention.
  • additional spectral sensitization can be obtained by treating the emulsion with a solution of a sensitizing dye in an organic solvent or the dye may be added in the form of a dispersion as described in Owens et al. British Pat. 1,154,781.
  • the dye may either be added to the emulsion as a final step or at some earlier stage.
  • sensitizing dyes useful in sensitizing such emulsions are described, for example, in Brooker et al. U.S. Pat. 2,526,632, issued Oct. 24, 1950; Sprague U.S. Pat. 2,503,776, issued Apr. 11, 1950; Brooker et al. U.S. Pat. 2,493,748; and Taber et al. U.S. Pat. 3,384,486.
  • Spectral sensitizers which can be used include the cyanines, merocyanines, complex (tri or tetranuclear) merocyanines, complex (tri or tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines (e.g. enamine hemicyanines),
  • Dyes of the cyanine classes may contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles.
  • Such nuclei may contain alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine groups and may be fused to carbocyclic or heterocyclic ring sysetms either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano, or alkoxy groups.
  • the dyes may be symmetrical or unsymmetrical and may contain alkyl, phenyl, enamine or heterocyclic substituents on the methine or polymethine chain.
  • the merocyanine dyes may contain the basic nuclei mentioned above as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones, and malononitrile.
  • These acid nuclei may be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups, or heterocyclic nuclei. Combinations of these dyes may be used, if desired.
  • supersensitizing addenda which do not absorb visible light may be included, for instance, ascorbic acid derivatives, azaindenes, cadmium salts, and organic sulfonic acids as described in McFall et al. U.S. Pat. 2,933,390 and Jones et al. U.S. Pat. 2,937,089.
  • the various layers, including the photographic layers, employed in the practice of this invention can contain light absorbing materials and filter dyes such as those described in Sawdey U.S. Pat. 3,253,921; Gaspar U.S. Pat. 2,274,782; Silberstein et al. U.S. Pat. 2,527,583 and Van- Campen U.S. Pat. 2,956,879.
  • the dyes can be mordanted, for example, as described in Jones et al. U.S. Pat. 3,282,699.
  • the sensitizing dyes and other addenda used 1n the practice of this invention may be added from water solutions or suitable organic solvent solutions may be used.
  • the compounds can be added using various procedures including those described in Collins et al. US. Pat. 2,912,343; McCrossen et al. U.S. Pat. 3,342,604; Audran U.S. Pat. 2,996,287 and Johnson et al. U.S. Pat. 3,425,835.
  • 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 or coated with baryta and/or an alphaolefin polymer, particularly a polymer of an alpha-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.
  • the silver bromoiodide emulsion contains the cyanforming coupler 5 [0c (2,4 di-n-amylphenoxy)butyramido]-2-heptafluorobutyramidophenol.
  • the emulsion contains the cyan-forming coupler 1-hydroxy-2- [oc-(2',4'di-t6lt. amylphenoxy)-n-butyl]naphthamide.
  • the couplers are added to the emulsion in the form of a finelydivided dispersion according to the procedure described in Example 2 of U.S. 2,801,171 to Fierke.
  • a second portion of the foregoing emulsion is coated over a cellulose acetate support having thereon a layer of gelatin (454 mg./ft. containing bis(methylsulfonyl )methane at a coverage of 50 milligrams per square foot.
  • a third portion of the emulsion is admixed with 50 milligrams per square foot of his (methylsulfonyl)methane and coated on a cellulose acetate film support coated with gelatin at a coverage of 454 mg./ft.
  • the three elements are exposed on an Eastman Ib sensitometer for approximately second. The exposed elements are developed for 60 seconds at about 68 F. in a developer having the composition set forth below:
  • the elements are again washed and treated once again with the clearing and fixing bath identified above.
  • the elements are again washed and treated in a stabilizing bath having the following composition:
  • 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 ole-fins, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguargum 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, azi
  • the photographic emulsions and elements described in the practice of this invention may 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 photographic elements used with this invention may contain antistatic or conducting layers, such layers may comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Trevoy U.S. Pat. 3,428,451.
  • the various photographic layers may contain plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton et al. U.S. Pat. 2,960,404; fatty acids or esters such as those described in Robijns U.S. Pat. 2,588,765 and Duane U.S. Pat. 3,121,- 060; and silicone resins such as those described in Du Pont British Pat. 955,061.
  • plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton et al. U.S. Pat. 2,960,404; fatty acids or esters such as those described in Robijns U.S. Pat. 2,588,765 and Duane U.S. Pat. 3,121,- 060; and silicone resins such as those described in Du Pont British Pat. 955,061.
  • the various photographic layers employed in the practice of this invention may contain surfactants such as saponin; anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen U.S. Pat. 2,600,831; amphoteric compounds such as those described in Ben- Ezra U.S. Pat. 3,133,816; and water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson British Pat. 1,022,878.
  • the photographic elements may contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et al., U.S. Pat. 2,992,101 and Lynn U.S. Pat. 2,701,245.
  • the photosensitive elements of the invention can contain brightening agents including stilbenes, triazines, ox-
  • Water soluble brightening agents may be used such as those described in Albers et al. German Pat. 972,067 and McFall et al. U.S. Pat. 2,933,390 or dispersions of brighteners may be used such as those described in Jansen Germany Pat.
  • a process for increasing the speed of a photographic silver halide emulsion which comprises developing an exposed silver halide emulsion with an aromatic primary amino color developing agent in the presence of a coupler capable of coupling with the oxidation products of said color developing agent to form a dye and a 1,1 bis sulfonyl-alkane speed increasing agent.
  • said 1,1 bis sulfonyl alkane has the formula a Rr-S O2C 1HSO2-Rz wherein R and R each represent an alkyl group containing 1 to 4 carbon atoms and R represents H or an alkyl group containing 1 to 4 carbon atoms.
  • R and R each represent methyl, ethyl, hydroxyethyl, carboxymethyl, or carboxyethyl groups and R represents H.
  • a photographic silver halide emulsion having a color-forming coupler compound contiguous thereto which is capable of coupling with the oxidation products of an aromatic primary amino color developing agent to produce a colored compound, said emulsion containing a sensitizing amount of a 1,1 bis sulfonyl alkane.
  • R and R each represent methyl, ethyl, hydroxyethyl, carboxymethyl, or carboxyethyl groups and R represents H.
  • a photosensitive element comprising a support having thereon a photographic silver halide emulsion layer having a color-forming coupler compound contiguous thereto which is capable of coupling with the oxidation products of anaromatic primary amino color developing agent to produce a colored compound, said photosensitive element containing a sensitizing amount of a 1,1 bis sulfonyl alkane speed increasing agent.
  • said 1,1 bis sulfonyl alkane has the formula a R1-SOg( )HSOg-Rg wherein R and R each represent an alkyl group containing l to 4 carbon atoms and R represents H or an alkyl group containing 1 to 4 carbon atoms.
  • R and R each represent methyl, ethyl, hydroxyethyl, carboxymethyl, or carboxyethyl groups and R represents H.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
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US42605A 1970-06-01 1970-06-01 Sensitization of photographic silver halide emulsions containing colorforming compounds by 1 1-bis-sulfonyl alkanes Expired - Lifetime US3625699A (en)

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US (1) US3625699A (fr)
JP (1) JPS5110782B1 (fr)
BE (1) BE767950A (fr)
CA (1) CA948015A (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4367279A (en) * 1974-09-06 1983-01-04 Eastman Kodak Company Silver halide complexing agents of sulfones, nitriles, and onium salts
US5232821A (en) * 1991-04-01 1993-08-03 Eastman Kodak Company Photographic coupler compositions containing ballasted sulfoxides and sulfones and methods

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4367279A (en) * 1974-09-06 1983-01-04 Eastman Kodak Company Silver halide complexing agents of sulfones, nitriles, and onium salts
US5232821A (en) * 1991-04-01 1993-08-03 Eastman Kodak Company Photographic coupler compositions containing ballasted sulfoxides and sulfones and methods

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GB1344842A (en) 1974-01-23
FR2095639A5 (fr) 1972-02-11
BE767950A (fr) 1971-11-03
CA948015A (en) 1974-05-28
DE2126722B2 (de) 1976-05-06
JPS5110782B1 (fr) 1976-04-06
DE2126722A1 (de) 1971-12-09

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