Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
• • 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
  • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/156—Precursor compound
  • Y10S430/159—Development dye releaser, DDR

Definitions

• ABSTRACT Color images are prepared by silver-dye bleach processing of a photosensitive element comprising a nondiffusible redox dye releaser such as a psulfonamidoaniline or p-sulfonamidophenol which is alkali-cleavable upon oxidation to release a diffusible dye such as an azo dye.
• a nondiffusible redox dye releaser such as a psulfonamidoaniline or p-sulfonamidophenol which is alkali-cleavable upon oxidation to release a diffusible dye such as an azo dye.
• This invention relates to photography, and more particularly to color photography employing dye imageproviding materials comprising nondiffusible redox dye releasers such 'as p-sulfonamidoanilines and p-sulfonamidophenols which are alkalicleavable upon oxidation to release a diffusible, bleachable dye,-such as an azo dye from" the benzene nucleus.
• a silver-dye bleach bath is employed with such materials in order to produce color images, such as positive transparency or a motion-picture film.
• the silver-dye bleach process has been known for many years. Such a process employs a photographic material comprising at least one photosensitive silver halide-emulsion layer whichis associated with a preformed bleachable dye.
• a typical multicolor-silver-dye bleach element is composed of three silver halide layers respectively sensitized to red, green, and blue radiation, and having associated therewith; respectively, a bleachable cyan, magenta and yellow dye.
• the processing such an element for obtaining a positive multicolored photographic reproduction generally includes exposing said element to a light pattern, developing it to a negative silver image in a black-and-white silver halide developer solution, treating it in a dye bleach bath which oxidizes the silver image to a silver salt andconcurrently decolorizes the associated pattern of dye, and, finally removing the residual silver salt by fixing and washing.
• a dye image is left which is photographically the inverse of the initial silver image.
• General descriptions of this well known silver-dye bleach process are found in U.S. Pat. No. 3,498,787 of Wilson et al, issued Mar. 3, 1970; U.S. Pat. No.,3,414,411 of Michel et al, issued Dec. 3, 1968; U.S. Pat.
• a process for producing a color image comprises:
• a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, the emulsion layer having associated therewith a nondiffusible redox dye releaser;
• the nondiffusible redox dye releasers useful in my invention are, generally speaking, compounds which will redox with oxidized developing agent to release a dye, such as by alkaline hydrolysis.
• redox dye releasers are described in U.S. Pat. No. 3,725,062 of Anderson and Lum, issued Apr. 3, 1973; U.S. Pat. No. 3,698,897 of Gompf and Lum, issued Oct. 17, 1972; U.S. Pat. No. 3,628,952 of Puschel et al, issued Dec. 21, 1971; U.S. Pat. No.
• a process for producing a color image comprises:
• a photosensitive element comprising a support havingth ereon at least one photosensitive silver halide emulsion layer, the emulsion layer having associated therewith a nondiffusible p-sulfonamidoaniline or p-sulfonamidophenol which is alkali-cleavable upon oxidation to release 3 a diffusible dye from the benzene nucleus and having the formula:
• Z is a bleachable dye having a predominant spectral absorption within the region of the visible spectrum to which the associated silver halide emulsion is sensitive to a dye precursor;
• Ballast is an organic ballasting radical of such molecular size and configuration (e.g., simple organic groups or polymeric groups) as to render the sulfonamido compound nondiffusible during development in an alkaline processing composition;
• G is OR or Nl-lR wherein R is hydrogen or a hydrolyzable moiety and R is a hydrogen or a substituted or unsubstituted alkyl group of l to 22 carbon atoms, such as methyl, ethyl, hydroxyethyl, propyl, butyl, secondary butyl, tert-butyl cyclopropyl, 4-chlorobutyl, cyclobutyl, 4-nitroamyl, hexyl, cyclohexyl, octyl, decyl, octadecyl, dodecyl, benzyl, phenethyl, etc., (when R is an alkyl group of greater than 6 carbon atoms, it can serve as a partial or sole Ballast group); and
• n is a positive integer of l to 2 and is 2 when G is OR or when R is hydrogen or an alkyl group of less than 8 carbon atoms;
• the photosensitive element in the above-described processes can be treated with an alkaline processing composition to effect or initiate development in any manner.
• a preferred method for applying processing composition is by employing a bath which contains the composition.
• the alkaline composition could also be employed in a rupturable container such as those used in diffusion transfer processes. In that case, the composition is applied to the element by passing it and a spreader sheet through pressure-applying members to rupture the container and spread the composition therebetween.
• the processing composition employed in my system contains the developing agent for development, although the composition could also just be an alkaline solution when the developer is incorporated in the photosensitive element, in which case the alkaline solution serves to activate the incorporated developer.
• R is preferably hydrogen, although it could be any hydrolyzable entity well-known to those skilled in the art, e.g., acetyl, mono-, dior trichloroacetyl radicals, perfluoroacyl, pyruvyl, alkoxyacyl, nitrobenzoyl, cyanbenzoyl, sulfonyl, sulfmyl, etc.
• ballast group in the formula for the compounds described above (Ballast) is not critical as long as it confers nondiffusibility to the compounds.
• Typical ballast groups include long-chain alkyl radicals linked directly or indirectly to the compound as well as aromatic radicals of the benzene and naphthalene series indirectly attached or fused directly to the benzene nucleus, etc.
• Useful ballast groups generally have at least 8 carbon atoms such as a substituted or unsubstituted alkyl group of 8 to 22 carbon atoms, an amide radical having 8 to 30 carbon atoms, a keto radical having 8 30 carbon atoms, etc., and may even comprise a polymer backbone or a dye or dye precursor (Z) as defined below, e.g.,
• the benzene nucleus in the above formula may have groups or atoms attached thereto such as the halogens, alkyl, aryl, alkoxy, aryloxy, nitro, amine, alkylamino, arylamino, amido, cyano, alkylmercapto, keto, carboalkoxy, heterocyclic groups, etc.
• groups may combine together with the carbon atoms to which they are attached on the ring to form another ring which may be saturated or unsaturated including a carbocyclic ring, a heterocyclic ring, etc.
• an aromatic ring. is directly fused to the benzene nucleus which would form, for example, a naphthol.
• Such a p-sulfonamidonaphthol is considered to be a species of a p-sulfonamidophenol and thus included within the definition. The same is true for p-sulfonamidoanilines employed in the invention.
• Z in the above formula represents a bleachable dye haaving a predominant spectral absorption within the region of the visible spectrum l to which the associated silver halide emulsioniis sensitive, or a dye precursor.
• Such bleachable dyes are pref- 5 i i l e'rably azo dyes although other bleachable dyes, such as N formazan dyes described in US. Pat. No. 3,503,741, CH
• Dye precursors can also be employed in my invention so long as they provide a l bleachable dye at some stage of the process, preferably 10 C H --1-l---C I'1 l ⁇ l'1-1---SO CH during development.
• Dye precursor moieties which could be used include leuco dyes, shifted dyes which shift hypsochromically or bathochromically when subjected to a different environment such as a change in pH, reaction with a material to form a complex, etc. These compounds may contain a solubilizing group if When dye precursor moieties are employed in my invention instead of dyes, they are converted to dyes by desired.
• dye groups include the folmeans well'known to those l l the lowing; dation, either in the photosensitlve element, in the processing composition or at some stage in the process to L-Hydroxy azobenzene form a visible dye.
• dation either in the photosensitlve element, in the processing composition or at some stage in the process to L-Hydroxy azobenzene form a visible dye.
• Such techniques are disclosed, for example, in British Pat. Nos. 1,157,501; 1,157,502; 1,157,503; 1,157,504; 1,157,505; 1,157,506;
• Expecially preferred compounds which can be employed in the process of my invention include the following:
• the process of the present invention may be used to produce positive images in singleor multicolors.
• the blue-sensitive silver halide emulsion layer will have a yellow sulfonamido compound associated therewith
• the green-sensitive silver halide emulsion layer will have a magenta sulfonamido compound associated therewith
• the red-sensitive silver halide emulsion layer will have a cyan sulfonamido compound associated therewith.
• the sulfonamido compound associated with each silver halide emulsion layer may be contained either in the silver halide emulsionlayer itself or in a layer contiguous the silver halide emulsion layer.
• the concentration of the sulfonamido compounds, which are alkali-cleavable upon oxidation, employed in a preferred process of the present invention may be varied over a wide range depending upon the particular compound employed and the results which are desired.
• the sulfonamido compounds employed in the present invention may be coated in layers by using coating solutions containing between about 0.5 and about 8 percent by weight of the sulfonamido compound distributed in a hydrophilic film-forming natural material or synthetic polymer, such as gelatin, polyvinyl alcohol, etc., which is adapted to be permeated by an aqueous alkaline processing composition.
• Any silver halide developing agent can be employed in the process of my invention as long as it cross-oxidizes with the redox dye releaser compounds described herein.
• the developer may be employed in the photosensitive element to be activated by the alkaline processing composition. Specific examples of developers which can be employed in my invention include:
• black-and-white developers in this list are preferred, however, since they usually develop the emulsion faster.
• the alkaline processing composition employed in the process of this invention is the conventional aqueous solution of an alkaline material, eg. sodium hydroxide, sodium carbonate, an amine such as diethylamine, potassium hydroxide, etc.; preferably possessing a pH in excess of 12 and preferably containing a developing agent as described above.
• an alkaline material eg. sodium hydroxide, sodium carbonate, an amine such as diethylamine, potassium hydroxide, etc.
• a thickener can be added to the processing composition to increase the viscosity of the composition and make it more adaptable for continuous processing.
• the viscuous composition can then be removed by squeegeeing or water spraying.
• Thedye-bleach bath employed in the process of my invention is composed of any of the conventional materials heretofore used for such purpose. Reference is made, for example, to the materials disclosed in U.S. Pat. Nos. 3,414,411; 3,503,741; 3,498,787 and Canadian Pat. No. 790,533 referred to above.
• a catalyst is usually employed in such a bath such as a phenazine, a quinoxaline or an anthraquinone.
• Other catalysts are disclosed in U.S. Pat. Nos. 2,183,395 and 2,270,118.
• the catalyst may be incorporated in the emulsion, the alkaline processing composition, the dye-bleach bath,
• the film unit is exposed and the alkaline processing composition is applied to the fluid unit.
• the processing composition then permeates the various layers to initiate development of the exposed photosensitive silver halide emulsion layers.
• the developing agent develops each of the silver halide emulsion layers in the exposed areas, reducing silver halide to silver metal, and causing the developing agent to become oxidized imagewise.
• the oxidized developing agent then cross-oxidizes the redox dye releaser compounds, the oxidized form of which undergoes a base-catalyzed reaction to release the preformed dyes or the dye precursors imagewise as a function of the imagewise exposure of each of the silver halide emulsion layers.
• the diffusible moiety is transferable in the alkaline processing composition either by virtue of its self-diffusivity or by having attached to it one or more solubilizing groups such as COOH, SO H, OH, SH, etc.
• diffusible dye which diffuses out of the element would be deposited on an image-receiving sheet which may or may not be the same as the spreader sheet mentioned above. This image-receiving sheet would then be peeled apart from the reset of the film unit so that the positive dye image in the photographic element may be viewed.
• the various silver halide emulsion layers of a color film assembly employed in the process of the invention can be disposed in the usual order, i.e., the blue-sensitive silver halide emulsion layer first with respect to the exposure side, followed by the green-sensitive and redsensitive silver halide emulsion layers.
• a yellow dye layer or a Carey Lea silver layer can be present between the blue-sensitive and green-sensitive silver halide emulsion layer for absorbing or filtering blue radiation that may be transmitted through the blue-sensitive layer.
• the selectively sensitized silver halide emulsion layers can be disposed in a different order, e.g., the blue-sensitive layerfirst with respect to the exposure side, followed by the red-sensitive and green-sensitive layers.
• the silver halide emulsions used in this invention are the conventional, negative-working silver halide emulsions and comprise, for example, silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
• the emulsions can be coarseor fine-grain and can be prepared by any of the well-known procedures, e.g., single-jet emulsions such as those described in Trivelli and Smith. The Photographic Journal, Vol.
• doublejet emulsions such as Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions such as those described in Nietz et al US. Pat. No. 2,222,264 issued Nov. 19, 1940; Illingsworth U.S. Pat. No. 3,320,069 issued May 16, 1967; and McBride U.S. Pat. No. 3,271,157 issued Sept. 6, 1966.
• the emulsions may be regular-grain emulsions such as the type described in Klein and Moisar, J. Phat. Sci., Vol 12, No.
• the supports for the photographic elements employed in the process of this invention can be any material as long as it does not deleteriously effect the photo graphic properties of the film unit and is dimensionally stable.
• transparent supports are preferred such as cellulose nitrate film, cellulose acetate film, poly(vinyl acetal) film, polystyrene film, poly(ethyleneterephthalate) film, polycarbonate film, poly-a-olefins such as polyethylene and polypropylene film, and related films or resinous materials.
• the support is usually about 2 to 6 mils in thickness.
• the silver halide emulsions useful in the process of my invention are well-known to those skilled in the art and are described in Product Licensing Index, Vol. 92, December, 1971, publication 9232, p. 107, paragraph I, Emulsion types; they may be chemically and spectrally sensitized as described on p. 107, paragraph III, Chemical sensitization, and pp. 108-109, paragraph XV, Spectral sensitization, of the above article; they can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping by employing the materials described on p.
• a multilayer, multicolor photographic element is prepared by coating the following layers in the order recited on a transparent cellulose acetate film support:
• red-sensitive, negative-working, gelatin-silver bromide emulsion 200 mg gelatin/ft and 100 mg silver/ft and compound 4 (140 mg/ft which is 1.3 X 10' M);
• interlayer of gelatin 100 mg/ft developing agent 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (10 mg/ft and 2,5-di-sec-dodecylhydroquinone (100 mg/ft 3.
• green-sensitive, negative-working, gelatin-silver bromide emulsion 200 mg gelatin/ft and 100 mg silver/ft compound 2 (125 mg/ft which is 1.3 X 10 M) and diethyl lauramide (125 mglft 4.
• EXAMPLE II A second multilayer, multicolor, photographic element is prepared similar to Example 1 except that compound 4 is replaced with compound 3 at equimolar amount in layer 1 The element is exposed and processed as in Example I except that the Dye-Bleach treatment of step 3 is for two minutes. The following sensitometric results are obtained:
• Example I the above results reveal a significant improvement in D,,,,-, without adversely affecting D when the Dye-Bleach bath is employed.
• EXAMPLE 111 Combined Dye-Bleach and Bleach-Fix Stops A multilayer, multicolor, photographic element is prepared similar to Example I. The element is exposed as in Example I and processed as follows:
• a process for producing a color image comprising:
• a photosensitive element com prising a support having thereon at least one photosensitive silver halide emulsion layer, said emulsion layer having associated therewith a nondiffusible redox dye releaser which will redox with oxidized developing agent to release a diffusibl e, bleachable dye, said redox dye releaser being a ballasted, bleachable dye wherein the ballast group is linked to the dye through a linkage which is cleavable upon oxidation;
• said redox dye releaser is a nondiffusible p-sulfonamidoaniline or p-sulfonamidophenol which is alkali-cleavable upon oxidation to release a diffusible dye from the benzene nucleus and having the formula:
• Ballast is an organic ballasting radical of such molecular size and configuration as to render the sul' 5 fonamido compound nondiffusible during development in an alkaline processing composition;
• G is OR or NHR wherein R is hydrogen or a hydrolyzable moiety and R is hydrogen or an alkyl group of 1 to 22 carbon atoms;
• n is a positive integer of l. to 2 and is 2 when G is OR or when R, is hydrogen or an alkyl group ofless than 8 carbon atoms.
• said photosensitive element comprises a support having thereon red-, greenand bluesensitive silver halide emulsion layers having associated therewith a nondiffusible p-sulfonamidoaniline or p-sulfonamidophenol which is alkali-cleavable upon oxidation to release a diffusible cyan, magenta and yellow dye, respectively, from the benzene nucleus, said dyes being azo dyes.
• a process for producing a color image comprising- I. imagewise exposing a photosensitive element com- 50 prising a support having thereon at least one photosensitive silver halide emulsion layer, said emulsion layer having associated therewith a nondiffusible p-sulfonamidoaniline or p-sulfonamidophenol which is alkali-cleavable upon oxidation to release a diffusible, bleachable dye from the benzene nucleus and having the formula:
• Ballast is an organic ballasting radical of such molecular size and configuration as to render the sulfonamido compound nondiffusible during development in an alkaline processing composition
• G is OR or NHR wherein R'is hydrogen or a hydrolyzable moiety and R is hydrogen or an alkyl group of l to 22 carbon atoms;
• n is a positive integer of l to 2 and is 2 when G is OR or when R, is hydrogen or an alkyl group of less than 8 carbon atoms;
• treating said photosensitive element with an alkaline processing composition in the presence of a silver halide developing agent to: (1) cause any dye precursor present to become a dye having a predominant spectral absorption within the region of the visible spectrum to which said associated silver halide emulsion is sensitive, said dye being bleachable; and (2) to effect development of each of said exposed silver halide emulsion layers, thereby oxidizing said developing agent and forming a metallic silver image;
• said photosensitive element comprises a support having thereon red-, greenand blue-sensitive silver halide emulsion layers having associated therewith a nondiffusible p-sulfonamidoaniline or p-sulfonamidophenol which is alkali-cleavable upon oxidation to release a diffusible cyan, magenta and yellow dye, respectively, from the benzene nucleus, said dyes being azo dyes.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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Citations (8)

• 1973
  • 1973-12-06 US US422390A patent/US3923510A/en not_active Expired - Lifetime
• 1974
  • 1974-11-05 CA CA213,004A patent/CA1052613A/en not_active Expired
  • 1974-12-04 DE DE19742457307 patent/DE2457307A1/de active Pending
  • 1974-12-05 GB GB5266474A patent/GB1477376A/en not_active Expired
  • 1974-12-05 FR FR7439764A patent/FR2254046B1/fr not_active Expired
  • 1974-12-06 BE BE151274A patent/BE823080A/xx unknown
  • 1974-12-06 JP JP49139681A patent/JPS5092133A/ja active Pending

Patent Citations (8)

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