US3698897A - Diffusion transfer processes and film units comprising compounds which are cleavable upon oxidation in alkali media to produce diffusible dyes or dye precursors - Google Patents

Diffusion transfer processes and film units comprising compounds which are cleavable upon oxidation in alkali media to produce diffusible dyes or dye precursors Download PDF

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US3698897A
US3698897A US160068A US3698897DA US3698897A US 3698897 A US3698897 A US 3698897A US 160068 A US160068 A US 160068A US 3698897D A US3698897D A US 3698897DA US 3698897 A US3698897 A US 3698897A
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dye
pat
silver halide
image
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Thomas E Gompf
Kin Kwong Lum
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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
    • 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
    • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors

Definitions

  • R is H or a hydrolyzable entity
  • n is 1 to 3 and m is 1 to 3.
  • This invention relates to photography and more particularly to color, diffusion transfer photography employing dye image-providing materials which are cleavable upon oxidation in an alkaline medium.
  • Color, diffusion transfer processes of the prior art such as US. Pats. 2,983,606 and 3,222,169 generally involve the use of a photographic element comprising a support, at least one silver halide emulsion layer, and contained therein or contiguous thereto, a dye developer.
  • a liquid processing composition is applied to the photosensitive element and permeates the emulsion to provide a solution of the dye developer substantially uniformly distributed therein.
  • the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, thereby providing an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition.
  • This immobilization is apparently due, at least in part, to a change in the solubility charatceristics of the dye developer upon oxidation, and particularly as regards its solubility in alkaline solutions. At least part of this imagewise distribution of unoxidized dye developer is transferred to a superposed image-receiving layer to provide the transfer image.
  • the developer moiety of the dye developer is transferred with the dye to the imagereceiving layer.
  • the developer moiety can undergo aerial oxidation which will have a substantial efiect upon the stability to light of the resulting dye developer image. Accordingly, it would be highly desirable to provide a transfer system in which only the desired chemical entity, i.e., the dye, is transferred to the receiver.
  • a photographic film unit according to our invention which is adapted to be processed by passing the unit between a pair of juxtaposed pressure-applying members comprises:
  • a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, each silver halide emulsion layer having associated therewith a dye image-providing material comprising a compound which is cleavable upon oxidation in an alkaline medium having the formula:
  • Ballast is a photographically inert organic ballasting radical of such molecular size and configuration as to render the cleavable compound nondiffusible during development in an alkaline processing composition
  • Dye is a dye or dye precursor
  • n is an integer of 1 to 3;
  • m is an integer of 1 to 3;
  • a rupturable container containing an alkaline processing composition said container being adapted to be positioned during processing of said film unit so that a compressive force applied to said container by said pressure-applying members will effect a discharge of the containers contents within said film unit; said film unit containing a silver halide developing agent.
  • a photosensitive element according to our invention is set forth in (a) in the film unit described above.
  • a process for producing a photographic transfer image in color according to our invention comprises:
  • the photosensitive element in the above-described process 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 use of a rupturable container or pod which contains the composition.
  • the processing composition employed in our system contains the developing agent for development although the composition could also just be an alkaline solution where the developer is incorporated in the photosensitive element, in which case the alkaline solution serves to activate the incorporated developer.
  • the dye image-receiving layer in the above-described film unit can be located on a separate support adapted to be superposed on the photosensitive element after exposure thereof.
  • image-receiving elements are generally disclosed, for example, in U.S. Pat. 3,362,819.
  • a rupturable container is employed and is positioned in relation to the photosensitive element and the image-receiving element so that a compressive force applied to the container by pressure-applying members, such as would be found in a typical camera used for in-camera processing, will effect a discharge of the containers contents between the image-receiving element and the outermost layer of the photosensitive element. After processing, the dye image-receiving element is separated from the photosensitive element.
  • the dye image-receiving layer in the above-described film unit can also be located integral with the photosensitive element between the support and the lowermost photosensitive silver halide emulsion layer.
  • a general format for integral receiver-negative photosensitive elements is disclosed in copending U.S. application Ser. No. 27,991 of Barr, Bush and Thomas filed Apr. 13, 1970 and now abandoned.
  • the support for the photosensitive element is transparent and is coated with an image-receiving layer, a substantially opaque light-reflective layer, e.g., TiO and then the photosensitive layer or layers described above. After exposure of the photosensitive element, a rupturable container containing an alkaline processing composition and an opaque process sheet are brought into superposed position.
  • the support for the photosensitive element is transparent and is coated with the image-receiving layer, a substantially opaque, light-reflective layer, the photosensitive layer or layers described above, and a top transparent sheet.
  • a rupturable container containing an alkaline processing composition and an opacifier is positioned adjacent to the top layer and sheet. The film unit is placed in a camera, exposed through the top transparent sheet and then passed throuhg a pair of pressureapplying members in the camera as it is being removed therefrom.
  • the pressure-applying members rupture the container and spread processing composition and opacifier over the negative portion of the film unit to render it light-insensitive.
  • the processing composition develops each silver halide layer and dye images are formed as a result of development which diffuse to the image-receiving layer to provide a right-reading image which is viewed through the transparent support on the opaque reflecting layer background.
  • 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, per-fluoroacyl, pyruvyl, alkoxyacyl, nitrobenzoyl, cyanobenzoyl, sulfonyl, sulfinyl, 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, etc.
  • Useful ballast groups generally have at least 8 carbon atoms and may even comprise a Dye as defined below.
  • the benzene nucleus in the above formula may be substituted with groups such as the halogens, alkyl, aryl, alkoxy, aryloxy, nitro, amino, alkylamino, arylamino, amido, cyano, alkylmercapto, keto, carboalkoxy, etc.
  • Dye in the above formula represents a dye or dye precursor.
  • Such compounds are well-known to those skilled in the art and include dyes such as azo, azomethine, indoaniline, indophenol, anthraquinone, triarylmethane, alizarin, etc., and dye precursors such as a leuco dye, a shifted dye which shifts hyposochromically or bathochromically when subjected to a different environment such as a change in pH, reaction with a material to form a complex, etc., couplers such as a phenol, naphthol, indazolone, open-chain benzoyl acetanilide, pivalylacetanilide, malonamide, malonanilide, cyanoacetyl coumarone, pyrazolone, compounds described in U.S. Pat. 2,756,142, etc.
  • dyes include the following:
  • YELLOW DYES 4-hydroxy azobenzene 3-methy1-4-hydroxy azobenzene p-sulfhydryl azobenzene MAGENTA DYES a CH(CH3)2 OH NH-C CH3
  • dye precursors are employed in our process instead of dyes, they are converted to dyes by means well known to those skilled in the art either in the photosensitive element, in the processing composition or in the dye image-receiving layer to form a visible absorbing dye.
  • each silver halide emulsion layer of the film assembly will have associated therewith a dye image-providing material possessing a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion, i.e., the bluesensitive silver halide emulsion layer will 'have a yellow dye image-providing material associated therewith, the green-sensitive silver halide emulsion layer will have a magenta dye image-providing material associated therewith, and the red-sensitive silver halide emulsion layer will have a cyan dye image-providing material associated therewith.
  • the dye image-providing material associated with each silver halide emulsion layer may be contained either in the silver halide emulsion layer itself or in a layer continguous to the silver halide emulsion layer.
  • cleavable dye image providing compounds of 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 dye image-providing 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 aqueous alkaline processing composition.
  • a hydrophilic film-forming natural material or synthetic polymer such as gelatin, polyvinyl alcohol, etc.
  • Any silver halide developing agent can be employed in our invention as long as it cross-oxidizes with the cleasvable compounds described herein.
  • the developer may be employed in the photosensitive element to be actuated by the alkaline processing composition.
  • Specific examples of developers which can be employed in our invention include:
  • sulfite ions in the processing composition enhances the cleavage reaction.
  • sulfite ions can be conveniently employed in the processing composition in the form of their alkali metal salts, e.g., sodium sulfite, potassium sulfite, etc.
  • the silver halide developer in our process becomes oxidized upon development and reduces silver halide to silver metal.
  • the oxidized developer then cross-oxidizes the cleavable compound causing it to cleave at the S0 linkage, thus forming an imagewise distribution of diifusible dye or dye precursor containing the S0 solubilizing group which then diflfuses to the receiving layer to provide the dye image.
  • the silver halide emulsion employed is a direct-positive silver halide emulsion, such as an internal-image emulsion or a solarizing emulsion, which is developable in unexposed areas, a positive image can be obtained on the dye image-receiving layer.
  • the alkaline processing composition permeates the various layers to initiate development of the exposed photosensitive silver halide emulsion layers.
  • the developing agent present in the film unit develops each of the silver halide emulsion-layers in the unexposed areas (since the silver halide emulsions are direct-positive ones), thus causing the developing agent to become oxidized imagewise corresponding to the unexposed areas of the direct positive silver halide emulsion layers
  • the oxidized developing agent then cross-oxidizes the cleavable compounds and the oxidized form of the compounds then undergoes a base-catalyzed elimination 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.
  • At least a portion of the imagewise distributions of diffusible dyes or dye precursors containing an S0 solubilizing group as a result of cleavage diffuse to the image-receiving layer to form a positive image of the original subject.
  • a pH-lowering layer in the film unit or image-receiving unit (if such a layer is needed) lowers the pH of the film unit or image-receiver to stabilize the image.
  • Internal-image silver halide emulsions useful in the above-described embodiment are direct-positive emulsions that form latent images predominantly inside the silver halide grains, as distinguished from silver halide grains that form latent images predominantly on the surface thereof. Such internal-image emulsions were described by Davey et al. in U.S. Pat. 2,592,250 issued Apr. 8, 1952, and elsewhere in the literature. Internalimage silver halide emulsions can be defined in terms of the increased maximum density obtained when developed with internal-type developers over that obtained when developed with surface-type developers.
  • Suitable internal-image emulsions are those which, when measured according to normal photographic techniques by coating a test portion of the silver halide emulsion on a transparent support, exposing to a light intensity scale having a fixed time between 0.01 and 1 second, and developing for 3 minutes at 20 C.
  • Developer A (internal-type developer)
  • Developer B dmcribed below (surface-type developer).
  • the maximum density in Developer A is at least 0.5 density unit greater than the maximum density in Developer B.
  • the solarizing direct-positive silver halide emulsions useful in the above-described embodiment are well-known silver halide emulsions which have been effectively fogged either chemically or by radiation to a point which corresponds approximately to the maximum density of the reversal curve as shown by Mees, The Theory of the Photographic Process, published by the Macmillan Co., New York, N.Y., 1942, pp. 261-297.
  • Typical methods for the preparation of solarizing emulsions are shown by Groves British Pat. 443,245, Feb.
  • Suitable fogging agents include the hydrazines disclosed in Ives U.S. Pats. 2,588,982 issued Mar. 11, 1952 and 2,563,785 issued Aug. 7, 1951; the hydrazides and hydrazones disclosed in Whitmore U.S. Pat. 3,227,- 552 issued Jan. 4, 1966; hydrazone quaternary salts described in Lincoln and Heseltine application Ser. No. 828,064, filed Apr. 28, 1969, now abandoned; or mixtures thereof.
  • the quantity of fogging agent employed can be widely varied depending upon the results desired. Generally, the concentration of fogging agent is from about 1 to about 20 mg. per square foot of photosensitive layer in the photosensitive element or from about 0.1 to about 2 grams per liter of developer if it is located in the developer.
  • imaging chemistry can be employed include the techniques described in U.S. Pats. 3,227,550; 3,227,551; 3,227,552; and in British Pat. 904,364, page 19, lines 1-41, wherein our dye imageproviding materials are substituted for the nondiifusible couplers described therein.
  • a film unit using development inhibitor-releasing couplers as described in U.S. Pat. 3,227,551 may be employed in conjunction with the dye image-providing materials described herein.
  • the developing agent employed is restricted to one which oxidatively couples to release the inhibitor compounds.
  • These developing agents are generally selected from the class of aromatic primary amino developing agents such as p-aminophenols or p-phenylenediamines.
  • Another embodiment of our invention uses the imagereversing technique disclosed in British Pat. 904,364, page 19, lines 1-41.
  • our cleavable compounds are used in combination with physical development nuclei in a nuclei layer contiguous to the photosensitive silver halide emulsion layer.
  • the film unit contains a silver halide solvent, preferably in a rupturable container with the alkaline processing composition, and the photosensitive element contains an immobilizing coupler, which is capable of reacting with oxidized developer to form an immobile product.
  • This embodiment also restricts the choice of developing agents to one which is reactive with the immobilizing coupler.
  • Preferred compounds include the primary aromatic amines described above.
  • Spectral-sensitizing dyes can be used conveniently 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 issued June 11, 1969.
  • the dye can 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, issued Jan. 10, 1950; and Taber et al., U.S. Pat. 3,3 84,486 issued May 21, 1968.
  • Spectral sensitizers which can be used include the cyanines, merocyanines, complex (trior tetranuclear) merocyanines, complex (tri-or tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines (e.g. enamine hemicyanines), oxonols and hemioxonols.
  • Dyes of the cyanine classes can contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles.
  • Such nuclei can contain alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine groups and can be fused to carbocyclic or heterocyclic ring system either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano, or alkoxy groups.
  • the dyes can be symmetrical or unsymmetrical and can contain alkyl, phenyl, enamine or heterocyclic substituents on the methine or polymethine chain.
  • the merocyanine dyes can contain the basic nuclei mentioned above as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones, and malononitrile.
  • acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylarnino groups, or heterocyclic nuclei. Combinations of these dyes can be used, if desired.
  • supersensitizing addenda which do not absorb visible light
  • addenda which do not absorb visible light
  • ascorbic acid derivatives for instance, ascorbic acid derivatives, azaindenes, cadimum salts, and organic sulfonic acids as described in McFall et al., U.S. Pat. 2,933,390 issued Apr. 19, 1960 and Jones et al., U.S. Pat. 2,937,089 issued May 17, 1960.
  • the various silver halide emulsion layers of a color film assembly 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 red-sensitive 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 12 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 layer first with respect to the exposure side, followed by the red-sensitive and green-sensitive layers.
  • the silver halide emulsions used in this invention can 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. LXXIX, May 1939 (pp.
  • doublejet 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. 3,271,157 issued Sept. 6, 1966.
  • Surface-image emulsions can be used or internal-image emulsions can be used such as those described in Davey et al., U.S. Pat. 2,592,250 issued May 8, 1952; Porter et al., U.S. Pat.
  • the emulsions may be regular-grain emulsions such as the type described in Klein and Moisar, J. Phot. Sci., vol. 12, No. 5, September/ October, 1964, (pp. 242-251).
  • Negative-type emulsions may be used or direct-positive emulsions may be used 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.
  • the emulsions used with this invention may 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 Jan. 10, 1967.
  • the silver halide emulsions used with this invention may contain speed increasing compounds such as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper, U.S. Pat. 2,886,437 issued May 12, 1959; Damn et al., U.S. Pat. 3,046,134 issued July 24, 1962; Carroll et al., U.S. Pat. 2,944,900 issued July 12, 1960; and Goife, U.S. Pat. 3,294,540 issued Dec. 27, 1966.
  • speed increasing compounds such as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper, U.S. Pat. 2,886,437 issued May 12, 1959; Damn et al., U.S. Pat. 3,046,134 issued July 24, 1962; Carroll et al., U.S. Pat. 2,944,900 issued July 12, 1960; and Goife, U.S. Pat. 3,294,540 issued Dec. 27, 1966.
  • the silver halide emulsions used in the practice of this invention can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping.
  • Suitable antifoggants and stabilizers each used alone or in combination include thiazolium salts described in Brooker et al., U.S. Pat. 2,131,038 issued Sept. 27, 1938; and Allen et al., U.S. Pat. 2,694,716 issued Nov. 16, 1954; 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 described in Allen et al., U.S. Pat.
  • the rupturable container employed in this invention can be of the type disclosed in U.S. Pat. Nos. 2,543,181; 2,643,886; 2,653,732; 2,723,051; 3,056,492; 3,056,491 and 3,152,,515.
  • such containers comprise a rectangular sheet of fluid and air-impervious material folded longitudinally upon itself to form two walls which are sealed to one another along their longitudinal and end margins to form a cavity in which processing solution is contained.
  • each silver halide emulsion layer containing a dye image-providing material or having the dye image-providing material present in a contiguous layer may be separated from the other silver halide emulsion layers in the negative portion of the film unit by materials including gelatin, calcium alginate, or any of those disclosed in U.S. Pat. No. 3,384,483, polymeric materials such as polyvinylamides as disclosed in US. Pat. 3,421,892, or any of those disclosed in French Pat. 2,028,236 or U.S. Pat. Nos. 2,992,104; 3,043,692; 3,044,873; 3,061,428; 3,069,263; 3,069,264; 3,121,001; and 3,427,158.
  • the silver halide emulsion layers in the invention comprise photosensitive silver halide dispersed in gelatin and are about 0.6 to 6 microns in thickness; the dye image-providing materials are dispersed in an aqueous alkaline solution-permeable polymeric binder, such as gelatin, as a separate layer about 1 to 7 microns in thickness; and the alkaline solution-permeable polymeric interlayers, e.g., gelatin, are about 1 to microns in thickness.
  • these thicknesses are approximate only and can be modified according to the product desired.
  • hydrophilic materials which can be employed include both naturally-occurring substances such as proteins, e.g., 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 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 de scribed for example, in Nottorf, 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., US. Pat.
  • the image-receiving layer can contain basic polymeric mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone such as described in Minsk, U.S. Pat. 2,882,156 issued Apr. 14, 1959, and basic polymeric mordants such as described in copending U.S. application Ser. No. 100,491 of Cohen et al. filed Dec. 21, 1970.
  • mordants useful in our invention include poly-4-vinylpyridine, the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in Sprague et al., U.S. Pat. 2,484,430 issued Oct. 11, 1949, and cetyl trimethylammonium bromide, etc. Effective mordanting compositions are also described in Whitmore, U.S. Pat. 3,271,148 and Bush, U.S. Pat. 3,271,147, both issued Sept. 6, 1966.
  • the image-receiving layer can be suflicient by itself to mordant the dye as in the case of use of an alkaline solution-permeable polymeric layer such as N-methoxymethyl polyhexylmethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plasticizers; cellulose acetate; gelatin; and other materials of a similar nature.
  • an alkaline solution-permeable polymeric layer such as N-methoxymethyl polyhexylmethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plasticizers; cellulose acetate; gelatin; and other materials of a similar nature.
  • an alkaline solution-permeable polymeric layer such as N-methoxymethyl polyhexylmethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plasticizers; cellulose acetate; gelatin; and other materials of
  • the image-receiving layer can also contain ultraviolet absorbing materials to protect the mordanted dye images from fading due to ultraviolet light, brightening agents such as the stilbenes, coumarins, triazines, oxazoles, dye stabilizers such as the chromanols, alkylphenols, etc.
  • pH-lowering material in the dye image-receiving element of a film unit according to the invention will usually increase the stability of the transferred image.
  • the pH-lowering material will effect a reduction in the pH of the image layer from about 13 or 14 to at least 11 and preferably 5-8 within a short time after imbibition.
  • polymeric acids as disclosed in U.S. Pat. 3,362,819 or solid acids or metallic salts, e.g., zinc acetate, zinc sulfate, magnesium acetate, etc., as disclosed in U.S. Pat. 2,584,030 may be employed with good results.
  • Such pH-lowering materials reduce the pH of the film unit after development to terminate development and substantially reduce further dye transfer and thus stabilize the dye image.
  • An inert timing or spacer layer can be employed in the practice of our invention over the pH-lowering layer which times or controls the pH reduction as a function of the rate at which alkali diffuses through the inert spacer layer.
  • examples of such timing layers include gelatin, polyvinyl alcohol or any of those disclosed in U.S. Pat. 3,455,686.
  • the timing layer is also effective in evening out the various reaction rates over a wide range of temperatures, e.g., premature pH reduction is prevented when imbibition is effected at temperatures above room temperature, for example, at to F.
  • the timing layer is usually about 0.1 to about 0.7 mil in thickness.
  • the timing layer comprises a hydrolyzable polymer or a mixture of such polymers which are slowly hydrolyzed by the processing composition.
  • hydrolyzable polymers include polyvinyl acetate, polyamides, cellulose esters, etc.
  • the alkaline processing composition employed in this invention is the conventional aqueous solution of an alkaline material, e.g., sodium hydroxide, sodium carbonate or an amine such as diethylamine, preferably possessing a pH in excess of 12, and preferably containing a developing agent as described previously.
  • the solution also preferably contains a viscosity-increasing compound such as a high molecular-weight polymer, e.g., a water-soluble ether inert to alkaline solutions such as hydroxyethyl cellulose or alkali metal salts of carboxymethyl cellulose such as sodium carboxymethy cellulose.
  • a concentration of viscosity-increasing compound of about 1 to about 5% by weight of the processing composition is preferred which will impart thereto a viscosity of about 100 c.p.s. to about 200,000 c.p.s.
  • an opacifying agent e.g., TiO carbon black, etc., may be added to the processing composition.
  • alkaline processing composition used in this invention can be employed in a rupturable container, as described previously, to conveniently facilitate the introduction of processing composition into the film unit, other methods of inserting processing composition into the film unit could also be employed, e.g., interjecting processing solution with communicating members similar to hypodermic syringes which are attached either to a camera. or camera cartridge.
  • the alkaline solution-permeable, substantially opaque, light-reflective layer employed in certain embodiments of photographic film units of our invention can generally comprise any opacifier dispersed in a binder as long as it has the desired properties.
  • Suitable opacifying agents include titanium dioxide, barium sulfate, zinc oxide, barium stearate, silver flake, silicates, alumina, zirconium oxide, zirconium acetyl acetate, sodium zirconium sulfate, kaolin, mica, or mixtures thereof in widely varying amounts depending upon the degree of opacity desired.
  • the opacifying agents may be dispersed in any binder such as an alkaline solution-permeable polymeric matrix such as, for example, gelatin, polyvinyl alcohol, and the like. Brightening agents such as the stilbenes, coumarins, triazines and oxazoles can also be added to the light-reflective layer, if desired.
  • dark-colored opacifying agents e.g., carbon black, nigrosine dyes, etc.
  • carbon black e.g., carbon black, nigrosine dyes, etc.
  • the supports for the photographic elements of this invention can be any material as long as it does not deleteriously affect the photographic properties of the film unit and is dimensionally stable.
  • Typical flexible sheet materials include 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 as well as glass, paper, metal, etc.
  • the support is usually about 2 to 6 mils in thickness.
  • dotwise coating such as would be obtained using a gravure printing technique, could also be employed.
  • small dots of blue-, greenand red-sensitive emulsions have associated therewith, respectively, dots of yellow, magenta and cyan color-providing substances. After development, the transferred dyes would tend to fuse together into a continuous tone.
  • the 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 issued June 17, 1952; amphoteric compounds such as those described in Ben-Ezra, U.S. Pat. 3,133,816 issued May 10, 1964; and water-soluble adducts of glycidal and an alkyl phenol such as those described in Olin Mathieson, British Pat. 1,022,878 issued Mar. 16, 1966; and Knox, U.S. Pat. 3,514,293 issued May 26, 1970.
  • surfactants such as saponin
  • anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen, U.S. Pat. 2,600,831 issued June 17, 1952
  • amphoteric compounds such as those described in Ben-Ezra, U.S. Pat. 3,133,816 issued May 10, 1964
  • 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 issued May 31, 1966; Gaspar, U.S. Pat. 2,274,782 issued Mar. 3, 1942; Silberstein et a1.
  • the sensitizing dyes and other addenda used in the practice of this invention can be added from water solutions or suitable organic solvent solutions may be used.
  • the compounds can be added during various procedures including those described in Collins et al., U.S. Pat. 2,912,343 issued 16 Nov. 10, 1959; McCrossen eta1., U.S. Pat. 3,342,605 issued Sept. 19, 1967; Audran, U.S. Pat. 2,996,287 issued Aug. 15, 1961 and Johnson et al., U.S. Pat. 3,425,835 issued 'Feb. 4, 1969.
  • the photographic layers used in the practice of this invention may be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in Beguin, U.S. Pat. 2,681,294 issued June 25, 1954. If desired, two or more layers may be coated simultaneously by the procedures described in Russell, U.S. Pat. 2,761,- 791 issued Sept. 4, 1956; Hughes, U.S. Pat. 3,508,947 issued Apr. 18, 1970; and Wynn, British Pat. 837,095 issued June 9, 1960.
  • This invention also can be used for silver halide layers coated by vacuum evaporation as described in British Pat. 968,453 issued Sept. 2, 1964, and LuValle et al., U.S. Pat. 3,219,451 issued Nov. 23, 1965.
  • 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 as described in Allen et al., U.S. Pat. 3,232,764 issued Feb. 1, 1966; ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers as described in Burness et al., U.S. Pat. 3,539,644 issued Nov.
  • active halogen compounds such as oxidized polysaccharides like dialdehyde starch and oxyguargum and the like.
  • Compound D (0.5 g.) is hydrolyzed under nitrogen in a mixture of 15 ml. ethanol, 50 ml. H 0 and 1 g. of 50% NaOH. After 35 minutes at 65 C., it is acidified with acetic acid, collected and recrystallized from ethanol to yield 0.25 g. of Compound IV, M.P. 159-1 63 C.
  • CONHCHa ()C O 0 CH2C5H5 isHai S0z NHCOCaHs (5H JZONH
  • a S-g. portion of Compound E in 10 ml. of thionyl chloride and 30 ml. of chloroform is refluxed for 1 hour and the solvents removed in vacuo.
  • the resulting gum (Compound F) is dissolved in 30 ml. dry dioxane and then 5 g. of 2-benzamido-S-aminophenol and 4 g. of quinoline are added. The mixture is stirred at ambient temperature for 1 hour and then heated in the steam bath for 15 minutes.
  • EXAMPLE 7 A single-layer, light-sensitive element is prepared by dissolving 0.3 g. of Compound I in 0.6 ml. of diethyl lauramide and 3.0 ml. of 2-methyltetrahydrofuran. The solution is dispersed in 15.5 ml. of aqueous gelatin with a colloid mill. One ml. of tri-isopropyl naphthalene sulfomate as a 5% solution is added to aid in dispersion. To this is added 3 ml. of a gelatin-silver bromide emulsion and 1.0 ml. of a 7 /2% solution of the spreading agent saponin.
  • the volume of the mixture is adjusted with water and 10% CISHH NHC O C' -H gelatin and coated on a support such that about 32x 10- moles/ft. of silver is present and there are 6 moles of silver coated for every 1 mole of Compound I.
  • a sample of the photosensitive element is exposed to a graduated-density multicolor test object.
  • a processing composition comprising Phenidone (0.25 g./l.), NaOH (1 normal), Na SO (25 g./1.) and hydroxyethylcellulose (3O g./l.) is employed in a pod and is spread between the exposed surface of the photosensitive element and a superposed dye image-receiving element comprising a support coated with 700 mg./ft. of gelatin and mg./ft. of the mordant N-n-octadecyl-tri-butylammonium bromide, by passing the transfer sandwich between a pair of juxtaposed pressure rollers.
  • the film unit After 60 seconds at about 24 C., the film unit is separated. A negative yellow dye image is observed on the dye image-receiving sheet.
  • a photosensitive element is prepared by coating on an opaque cellulose acetate film support a negative-working gelatin-silver chlorobromide emulsion (150 mg. gelatin/ ft. and 60 mg. silver/ft?) andmagenta cleavable Compound IV, 3-[4-(1-hydroxy-4-isopropoxy-Z-naphthylazo) phenylsulfonyl]-5-pentadecylhydroquinone (60 mg./ft.
  • a dye image-receiving element is prepared by coating an N-n-hexadecyl-N-morpholinium ethosulfate/methyl-trin-dodecylammonium p-toluenesulfonate coacervate mordant dispersion of the type described in US. Pat. 3,271,- 147 of Bush issued Sept. 6, 1966, on an opaque support.
  • a sample of the photosensitive element is exposed to a graduated-density multicolor test object.
  • the following processing composition is employed in a pod and is spread between the exposed surface of the photosensitive element and the superposed dye image-receiving element by passing the transfer sandwich between a pair of juxtaposed pressure rollers:
  • the dye image-receiving element After 60 seconds at about 25 C., the dye image-receiving element is separated from the negative element. A negative, magenta dye image is observed on the dye imagereceiving element.
  • EXAMPLE 9 The procedure of Example 8 is repeated except that the processing composition does not contain Phenidone. No visible dye image in the receiving element is obtained and no visible silver development takes place in the negative element. This example illustrates that the cleavable compounds of our invention are incapable of development themselves and require a separate silver halide developing agent in the system.
  • a photosensitive element is prepared by coating on an opaque cellulose acetate film support a negative-working gelatin-silver chlorobromide emulsion (150 mg. gelatin/ ft. and 87 mg. silver/ft?) and yellow cleavable Compound V, 3-[4-(1-phenyl-3-methylcarbamoyl-4-pyrazolin- 5 ony1azo)phenylsulfonyl] 5 pentadecylhydroquinone (93.5 mg./ft.
  • This element is exposed and processed as in Example 8 to obtain a negative, yellow dye image on the dye image-receiving element.
  • EXAMPLE 11 The procedure of Example 10 is repeated except that the processing composition does not contain Phenidone. No visible dye image in the receiving element is obtained and no visible silver development takes place in the negative element. This example illustrates that the cleavable 23 compounds of our invention are incapable of development themselves and require a separate silver halide developing agent in the system.
  • EXAMPLE 12 A multilayer, multicolor photosensitive element is prepared by coating the following layers in the order recited on an opaque cellulose acetate film support:
  • a sample of the photosensitive element is exposed to a graduated-density, multicolor test object.
  • the following processing composition is employed in a pod and is spread between the exposed surface of the photosensitive element and a superposed dye image-receiving element similar to that of Example 8 by passing the transfer sandwich between a pair of juxtaposed pressure rollers:
  • the dye imagereceiving element After 60 seconds at about 25 C., the dye imagereceiving element is separated from the negative element. A well-defined, negative, two-color magenta-yellow reproduction of the test object is observed on the dye image-receiving element.
  • a photosensitive element is prepared by coating on an opaque cellulose acetate film support: (1) a negativeworking gelatin-silver bromide emulsion (300 mg. gelatin/ft? and 100 mg. silver/ft?) and cyan dye-providing Compound VII (90 mg./ft. (this compound is colorless in this state) and (2) gelatin overcoat (80 mg./ft.
  • a dye image-receiving element is prepared as in Example 8.
  • a sample of the photosensitive element is exposed and processed as in Example 8 employing the following processing composition: NaOH (1 normal), Na SO g./l.), hydroxyethylcellulose g./l.) and N-methyl-paminophenol (0.9 g./l.).
  • the film unit After 60 seconds at 24 C., the film unit is separated. A negative cyan dye image is observed on the dye imagereceiving sheet.
  • a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, each said silver halide emulsion layer having 24 associated therewith a compound which is cleavable upon oxidation in an alkaline medium having the formula:
  • each R represents hydrogen or a hydrolyzable moiety
  • Ballast is a photographically inert organic ballasting radical of such molecular size and configuration as to render said cleavable compound nondiffusible during development in an alkaline processing composition
  • Dye is a dye or dye precursor
  • n is an integer of 1 to 3;
  • m is an integer of 1 to 3.
  • a photosensitive element comprising a support having thereon a red-sensitive silver halide emulsion layer having associated therewith a cyan dye image-providing material, a green-sensitive silver halide emulsion layer having associated therewith a magenta dye image-providing material, and a blue-sensitive silver halide emulsion layer having associated therewith a yellow dye imageproviding material, at least one of said dye image-providmg materials being a compound which is cleavable upoln oxldation in an alkaline medium having the formu a:
  • each R represents hydrogen or a hydrolyzable moiety
  • Ballast is a photographically inert organic ballasting radical of such molecular size and configuration as to render said cleavable compound nondiifusible during development in an alkaline processing composition
  • Dye is a dye or dye precursor
  • n is an integer of 1 to 3;
  • m is an integer of l to 3.
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:
  • a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, each said silver halide emulsion layer having associated therewith a compound which is cleavable upon oxidation in an alkaline medium having the formula:
  • each R represent hydrogen or a hydrolyzable moiety
  • Ballast is a photographically inert organic ballasting radical of such molecular size and configuration as to render said cleavable compound nondiffusible during development in an alkaline processing composition
  • Dye is a dye or dye precursor
  • n is an integer of l to 3;
  • m is an integer of 1 to 3;
  • a rupturable container containing an alkaline processing composition said container being adapted to be positioned during processing of said film unit so that a compressive force applied to said container by said pressure-applying members will effect a discharge of the containers contents within said film unit;
  • said film unit containing a silver halide developing agent. 7.
  • R is H, n is 1 and m is 1.
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:
  • a photosensitive element comprising a support having thereon a red-sensitive silver halide emulsion layer having associated therewith a cyan dye imageproviding material, a green-sensitive sliver halide emulsion layer having associated therewith a magenta dye image-providing material, and a blue-sensitive silver halide emulsion layer having associated therewith a yellow dye image-providing material;
  • each R represents hydrogen or a hydrolyzable moiety
  • Ballast is a photographically inert organic ballasting radical of such molecular size and configuration as to render said cleavable compound nondiffusible during development in an alkaline processing composition
  • Dye is a dye or dye precursor
  • n is an integer of 1 to 3;
  • m is an integer of 1 to 3.
  • a process for producing a photographic transfer image in color comprising:
  • each R represents hydrogen or a hydrolyzable moiety
  • Ballast is a photographically inert organic ballasting radical of such molecular size and configuration as to render said cleavable compound nondiffusible during development in an alkaline processing composition
  • Dye is a dye or dye precursor
  • n is an integer of 1 to 3;
  • m is an integer of 1 to 3;
  • a process for producing a photographic transfer image in color comprising:
  • each R represents hydrogen or a hydrolyzable entity
  • Ballast is a photographically inert organic ballasting radical of such molecular size and configuration as to render said cleavable compound nondifiusible during development in an alkaline processing composition
  • Dye is a dye or dye precursor
  • n is an integer of 1 to 3;
  • m is an integer of 1 to 3;
  • a process for producing a photographic transfer image in color comprising:
  • said dye image-providing materials comprising a compound which is cleavable upon oxidation in an alkaline medium having the formula:
  • each R represents hydrogen or a hydrolyzable entity
  • Ballast is a photographically inert organic ballasting radical of such molecular size and configuration as to render said cleavable compound nonditlfusible during development in an alkaline processing composition
  • Dye represents a dye or dye precursor
  • n is an integer of 1 to 3;
  • m is an integer of 1 to 3;

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Cited By (23)

* Cited by examiner, † Cited by third party
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US3854945A (en) * 1972-02-17 1974-12-17 Eastman Kodak Co Shifted indophenol dye developers
US3868252A (en) * 1973-11-02 1975-02-25 Eastman Kodak Co Photographic elements containing polymeric oxidants
US3880658A (en) * 1971-12-10 1975-04-29 Eastman Kodak Co Photographic elements containing oxichromic compounds with reduced azomethine linkages
US3923510A (en) * 1973-12-06 1975-12-02 Eastman Kodak Co Process for producing color images by bleaching redox diffusible dye releasers
US3928043A (en) * 1973-11-16 1975-12-23 Eastman Kodak Co Photographic elements containing iodoso or iodoxy oxidants
US3930863A (en) * 1973-04-13 1976-01-06 Fuji Photo Film Co., Ltd. Color photographic sensitive material
US3935262A (en) * 1971-12-10 1976-01-27 Eastman Kodak Company Oxichromic compounds, stabilized oxichromic compounds and processes for preparing same
US3942987A (en) * 1973-02-12 1976-03-09 Eastman Kodak Company Photographic materials with ballasted, alkali cleavable azo dyes
US3954476A (en) * 1974-02-05 1976-05-04 Eastman Kodak Company Diffusable dye-releasing compounds which are cleavable upon oxidation
US3993638A (en) * 1975-04-16 1976-11-23 Eastman Kodak Company Ballasted p-sulfonamidophenols capable of releasing a non-heterocyclic azo dye
US3998637A (en) * 1974-07-10 1976-12-21 Eastman Kodak Company Process for producing positive color diffusion transfer images using redox dye releasers
US3998640A (en) * 1973-06-05 1976-12-21 Eastman Kodak Company Photographic elements containing N-oxide oxidants
US4009029A (en) * 1973-06-05 1977-02-22 Eastman Kodak Company Cyanoethyl-containing blocked development restrainers
US4030920A (en) * 1976-04-12 1977-06-21 Eastman Kodak Company Processing compositions containing glycols for color transfer processes comprising direct positive silver halide developement
US4053312A (en) * 1974-09-04 1977-10-11 Eastman Kodak Company O-sulfonamidonaphthol diffusible dye image providing compounds
US4088488A (en) * 1973-06-05 1978-05-09 Eastman Kodak Company Photographic elements containing nitroxyl radical oxidants
US4152153A (en) * 1971-08-31 1979-05-01 Eastman Kodak Company Sulfonamido dye releasing compounds in photographic elements
FR2427212A1 (cs) * 1978-05-31 1979-12-28 Eastman Kodak Co
US4199355A (en) * 1975-06-24 1980-04-22 Eastman Kodak Company Positive-working immobile photographic compounds and photographic elements containing same
US4268606A (en) * 1974-02-05 1981-05-19 Eastman Kodak Company Azo dye compounds and photographic materials
US4345016A (en) * 1980-07-04 1982-08-17 Fuji Photo Film Co., Ltd. Color photographic sensitive material
EP0149260A1 (en) * 1984-01-12 1985-07-24 Agfa-Gevaert N.V. Compounds for use in a dye diffusion transfer process and photographic elements incorporating them
EP0345839A1 (en) * 1988-06-07 1989-12-13 Agfa-Gevaert N.V. Magenta dye-releasing compounds

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4152153A (en) * 1971-08-31 1979-05-01 Eastman Kodak Company Sulfonamido dye releasing compounds in photographic elements
US3935262A (en) * 1971-12-10 1976-01-27 Eastman Kodak Company Oxichromic compounds, stabilized oxichromic compounds and processes for preparing same
US3880658A (en) * 1971-12-10 1975-04-29 Eastman Kodak Co Photographic elements containing oxichromic compounds with reduced azomethine linkages
US3854945A (en) * 1972-02-17 1974-12-17 Eastman Kodak Co Shifted indophenol dye developers
US3942987A (en) * 1973-02-12 1976-03-09 Eastman Kodak Company Photographic materials with ballasted, alkali cleavable azo dyes
US3930863A (en) * 1973-04-13 1976-01-06 Fuji Photo Film Co., Ltd. Color photographic sensitive material
US4088488A (en) * 1973-06-05 1978-05-09 Eastman Kodak Company Photographic elements containing nitroxyl radical oxidants
US3998640A (en) * 1973-06-05 1976-12-21 Eastman Kodak Company Photographic elements containing N-oxide oxidants
US4009029A (en) * 1973-06-05 1977-02-22 Eastman Kodak Company Cyanoethyl-containing blocked development restrainers
US3868252A (en) * 1973-11-02 1975-02-25 Eastman Kodak Co Photographic elements containing polymeric oxidants
US3928043A (en) * 1973-11-16 1975-12-23 Eastman Kodak Co Photographic elements containing iodoso or iodoxy oxidants
US3923510A (en) * 1973-12-06 1975-12-02 Eastman Kodak Co Process for producing color images by bleaching redox diffusible dye releasers
US3954476A (en) * 1974-02-05 1976-05-04 Eastman Kodak Company Diffusable dye-releasing compounds which are cleavable upon oxidation
US4268606A (en) * 1974-02-05 1981-05-19 Eastman Kodak Company Azo dye compounds and photographic materials
US3998637A (en) * 1974-07-10 1976-12-21 Eastman Kodak Company Process for producing positive color diffusion transfer images using redox dye releasers
US4053312A (en) * 1974-09-04 1977-10-11 Eastman Kodak Company O-sulfonamidonaphthol diffusible dye image providing compounds
US3993638A (en) * 1975-04-16 1976-11-23 Eastman Kodak Company Ballasted p-sulfonamidophenols capable of releasing a non-heterocyclic azo dye
US4199355A (en) * 1975-06-24 1980-04-22 Eastman Kodak Company Positive-working immobile photographic compounds and photographic elements containing same
US4030920A (en) * 1976-04-12 1977-06-21 Eastman Kodak Company Processing compositions containing glycols for color transfer processes comprising direct positive silver halide developement
FR2427212A1 (cs) * 1978-05-31 1979-12-28 Eastman Kodak Co
US4345016A (en) * 1980-07-04 1982-08-17 Fuji Photo Film Co., Ltd. Color photographic sensitive material
EP0149260A1 (en) * 1984-01-12 1985-07-24 Agfa-Gevaert N.V. Compounds for use in a dye diffusion transfer process and photographic elements incorporating them
EP0345839A1 (en) * 1988-06-07 1989-12-13 Agfa-Gevaert N.V. Magenta dye-releasing compounds

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GB1397964A (en) 1975-06-18

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