US3743504A - Developer scavengers for image transfer systems - Google Patents

Developer scavengers for image transfer systems Download PDF

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US3743504A
US3743504A US00148138A US3743504DA US3743504A US 3743504 A US3743504 A US 3743504A US 00148138 A US00148138 A US 00148138A US 3743504D A US3743504D A US 3743504DA US 3743504 A US3743504 A US 3743504A
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layer
dye
pat
image
silver halide
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G Dappen
D Smith
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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
    • G03C8/42—Structural details
    • G03C8/52—Bases or auxiliary layers; Substances therefor
    • 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

Definitions

  • a developer scavenger layer comprising an aldehydebisulfite addition product and a polymeric binder is useful for reducing background stain in a dye image-receiving element of a color diffusion transfer system utilizing immobile couplers which form diffusible dyes.
  • This invention relates to the art of photography, and more particularly to color diffusion transfer film systems, dye image-receiving elements and methods for obtaining positive, right-reading diffusion transfer dye images with reduced color developer stain.
  • US. Pat. 3,445,338 of Beavers et al. describes a receiving sheet for use in a dye diffusion transfer process utilizing aromatic primary arnino color developing agents.
  • the receiving sheet comprises a support having thereon a nondiffusible acid material, an interlayer containing finely divided white pigment and a mordant layer.
  • the acid layer terminates development by lowering the pH of the alkaline developer composition and apparently also functions to salt out residual color developer.
  • the pigmented layer functions to mask the stain formed in the underlying layer.
  • Another object of this invention is to provide timing means in connection with the developer scavenger layer so that development in the photosensitive element is substantially complete before the developer scavenger layer becomes operative.
  • Still another object of this invention is to provide color transfer film units and methods for processing same wherein the dye image-receiving layer is integral with the photosensitive element itself or is provided on a separate support to be superposed on the photosensitive element after exposure thereof.
  • 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, such as would be found in a camera designed for in-camera processing, comprising:
  • a photosensitive element comprising a support having thereon at least one and preferably three, photosensitive silver halide emulsion layers, each silver halide emulsion layer having associated therewith a dye imageproviding material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diifusible dye;
  • the above film unit containing an aromatic primary amino color developing agent, preferably in the rupturable container and an aldehyde-bisulfite addition product in a polymeric binder which is capable of reacting with unused aromatic primary amino color developing agent to form a colorless reaction product.
  • the molecular weight of the polymers and copolymers is at least about 500 and preferably greater than 2000.
  • polymers and copolymers within the scope of Formula III above include homopolymers of acrylaldehyde sodium bisulfite adducts or methacrylaldehyde sodium bisulfite adducts and copolymers of these adducts with vinyl compounds such as unsaturated acids, e.g., acrylic acid and methacrylic acid; acrylic esters, e.g., methyl acrylate and propyl acrylate; methacrylic esters, e.g.
  • acrylamides e.g., acrylamide and isopropyl acrylamide
  • methacrylamides e.g., methacrylamide, and N-methyl-methacrylamide
  • the described developer-scavenging, aldehyde-bisulfite adducts can be employed at any concentration useful for the intended purpose.
  • an effective concentration is from about 250 mg. per square foot of support to about 1500 mg. per square foot of support.
  • Especially good results are obtained at a concentration of from about 500 mg. per square foot of support to about 1250 mg. per square foot of support.
  • the aldehyde-bisulfite addition product of our invention may be dispersed in any polymeric binder suitable for the intended purpose, e.g., gelatin, proteins, cellulose derivatives, polysaccharides, polyvinyl compounds, acrylamide polymers and copolymers, etc.
  • any polymeric binder suitable for the intended purpose e.g., gelatin, proteins, cellulose derivatives, polysaccharides, polyvinyl compounds, acrylamide polymers and copolymers, etc.
  • the developer scavenger material itself is a polymer
  • no additional polymeric binder may be needed, i.e., the polymeric scavenger material can serve as the polymeric binder.
  • the aldehyde-bisulfite adduct functions as a developer scavenger precursor and under the basic conditions of color development reverts to the parent aldehyde compound which in turn reacts with excess unused aromatic primary amino color developing agent to form a colorless product, thereby reducing the yellowish-brown stain which results from the diffusion of unused aromatic primary amino color developing agent into the image-receiving element. Therefore, any aldehydebisulfite addition product which is compatible with the photosensitive and image-receiving elements can be employed in the practice of the invention provided the addition product reverts under alkaline conditions to the parent aldehyde compound which in turn will react with primary amino color developing agent to form a colorless product.
  • the alkali metal bisulfite which is liberated reacts with alkali present thereby lowering the pH of the system, e.g.,
  • the developer scavenger layer of our invention can be used not only in diffusion transfer systems wherein the image-receiving element is located on a separate support from the photosensitive element but also in diffusion transfer systems wherein the image-receiving element is integral with the photosensitive element.
  • the novel dye image-receiving element comprises a support having thereon the following layers:
  • a developer-scavenger layer comprising an aldehydebisulfite adduct in a polymeric binder, and (b) a dye image-receiving layer.
  • a timing layer can also be employed in the invention between the developer-scavenging layer and the dye image-receiving layer which functions to delay the rate of diffusion of aromatic primary ammo color developing agent into the developer-scavengmg layer.
  • the timing layer therefore, ensures the efficient use of the aromatic primary amino color developing agent in the photosensitive element prior to developer-scavenging action by the aldehyde-bisulfite adduct.
  • a pH-lowering material described hereinafter, can also be employed in the dye image-receiving element to increase the stability of the transferred image.
  • a lightreflective layer comprising a white pigment in a binder, described hereinafter, can also be employed in the dye image-receiving element, if desired.
  • the light-reflective layer can be located underneath the dye image-receiving layer or can be combined with the timing layer if one is employed.
  • the above-described dye image-receiving element of the film unit is adapted to be superposed on the photosensitive element after exposure thereof.
  • the development and transfer operations can be effected by bathing either or both the exposed photosensitive element and the dye image-receiving element in a deveolping solution before rolling into contact with each other or a viscous develop ing composition can be placed between the elements for spreading in a predetermined amount across and into contact with the exposed surface of the photosensitive element.
  • the viscous developing composition is desirably utilized in one or more pods attached to the reception sheet or photosensitive element that can be readily ruptured when development is desired as described, for example, in US. Pats. 2,559,643; 2,647,049; 2,661,293; 2,698,- 244; 2,698,798 and 2,774,668.
  • the image dyes formed in the respective blue, green and red-sensitive silver halide emulsion layers diffuse out of the photosensitive element through the viscous developer composition and into the dye image-receiving layer, e.g. into the dye image-receiving element described above, where the dyes are mordanted to form the transferred image.
  • the timing layer if one is present, prevents the dilfusion of color developer into the scavenger layer for the time necessary to ensure the efficient use of the aromatic primary amino color developing agent in the photosensitive element.
  • the unused aromatic primary amino color developing agent diffuses into the developer-scavenger layer where the developer molecules react with the aldehyde compounds which have been liberated from the aldehyde-bisulfite adducts under alkaline conditions of development to form a colorless product.
  • a marked decrease in the yellowish-brown stain caused by the presence of unused color developing agent in color development diffusion transfer image-receiving elements is observed upon utilizing a developer-scavenger layer comprising an aldehyde-bisulfite adduct dispersed in a suitable binder, preferably in the image-receiving element.
  • the developer-scavenger layer can be located in an integral film unit wherein the dye image-receiving layer is 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 described in copending US. application Ser. No. 027,991 of Barr, Bush and Thomas, filed Apr. 13, 1970 and now abandoned.
  • the support for the photosensitive element is transparent and is coated with the dye image-receiving layer, a substantially opaque, light-reflective layer, e.g.
  • TiO a developer scavenger layer comprising an aldehyde-bisulfite adduct dispersed in a suitable binder, and the various layers forming the color-forming units.
  • a rupturable container containing an alkaline processing composition and an opaque process sheet are brought into superposed position.
  • Pressure-applying members in a camera rupture the container and spread processing composition over the photosensitive element as the film unit is Withdrawn from the camera.
  • the processing composition develops the exposed silver halide layers and dye images are formed as a function of development which diffuse to the imagereceiving layer to provide a positive, right-reading image which is viewed through the transparent support on the opaque reflecting layer background.
  • the support for the color diffusion transfer system is transparent and is coated with the image-receiving layer, a substantially opaque, light-reflective layer, e.g. TiO a developer scavenger layer comprising an aldehyde-bisulfite adduct dispersed in a suitable binder, and then the various layers forming the color-forming units 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 between 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 lightinsensitive.
  • the processing composition develops the exposed silver halide layers and dye images are formed as a result of development which diffuse to the image-receiving layer to provide positive, right-reading image which is viewed through the transparent support on the opaque reflecting layer background. Any unused aromatic primary amino color developing agent which may diffuse in the direction of the image-receiving layer is immobilized by the aldehyde-bisulfite adduct present in the developer scavenger layer.
  • each silver halide emulsion layer in the photosensitive element there is associated with each silver halide emulsion layer in the photosensitive element a dye image-providing material comprising a nondifiusible coupler which produces a diffusible dye on reaction with oxidized aromatic primary amino color developing agent in an alkaline processing composition.
  • the nondifiusible couplers employed in this invention include those having formulas:
  • DYE is a dye precursor, e.g., a leuco dye, a shifted dye which shifts hypsochromically or bathochromically when subjected to a different environment such as a change in H, reaction with a material to form a complex, etc.; or a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing radical;
  • (2) LINK is a connecting radical such as an azo radical, a mercuri radical, an oxy radical, an alkylidene radical, a thio radical, a dithio radical or an azoxy radical;
  • n is an integer of l to 2 when LINK is an alkalidene radical, and n is 1 when LINK is an azo radical, a
  • the acidic solubilizing radicals attached to the diffusible dye producing couplers described above can be solubilizing radicals which when attached to the coupler or developer moieties of the dyes, render the dyes diffusible in alkaline processing compositions.
  • Typical of such radicals are carboxylic, sulfonic, ionizable, sulfonamide, and hydroXy-substituted groups that lend to dyes negative charges.
  • ballast groups in the ditfusible dyeproducing coupler compounds described above is not critical as long as they confer nondiffusibility to the coupler compounds.
  • Typical ballast groups include long chain akyl radicals linked directly or indirectly to the coupler molecules as Well as aromatic radicals of the benzene and naphthalene series, etc., linked directly or indirectly to the coupler molecules by a splittable linkage, or by a removable or irremovable but otherwise nonfunctional linkage depending upon the nature of the coupler compound.
  • Useful ballast groups have at least 8 carbon atoms.
  • Typical dye radical substituents include azo, azomethine, indoaniline, indophenol, anthraquinone and related dye radicals well known in the art that exhibit selective absorption in the visible spectrum.
  • the dye radicals contain acidic solubilizing moieties.
  • Coupler radicals (COUP-), the coupling position is well known to those skilled in the photographic art.
  • the S-pyrazolone coupler radicals couple at the carbon atom in the 4-position
  • the phenolic coupler radicals including a-naphthols
  • the open-chain ketomethylene coupler radicals couple to the carbon atom forming the methylene moiety (e.g.,
  • the cyanproducing coupler has the formula BALLO-CYAN- COUP
  • BALL is a photographically inert organic ballasting radical having at least 8 carbon atoms and of such molecular size and configuration as to render the coupler nondiffusible during development in an alkaline processing composition
  • CYANCOUP is a phenolic coupler radical substituted in the 2-position with a fully substituted amido group and attached to the --O- moiety of the cyan-producing coupler in the coupling position;
  • YELLCO'UP is an open-chain ketomethylene coupler radical attached to the O moiety of the yellowproducing coupler in the coupling position;
  • nondilfusing used herein as applied to the couplers has the meaning commonly applied to the term in color photography and denotes materials which for all practical purposes do not migrate or wander through organic colloid layers, such as gelatin, comprising the sensitive elements of the invention. The same meaning is to be attached to the term immobile.
  • diffusible as applied to the dyes formed from the nondiffusing couplers in this invention has the converse meaning and denotes materials having the property of diffusing effectively through the colloid layers of the sensitive elements in the presence of the nondiffusing, materials from which they are derived.
  • Mobile has the same meaning.
  • the connecting radical (LINK) is split and a diffusible preformed dye (DYE) is released which diffuses imagewise to a reception layer.
  • An acidic solubilizing group on the preformed dye lends diffusibility to the dye molecule.
  • the coupling portion of the coupler (COUP) couples which the color developing agent oxidation product to form a dye that is nondiffusible because of the attached ballasting group (BALL) in a nonconpling position.
  • the color of the diffusible dye is determined by the color of the preformed dye moiety (DYE), the color of the reaction product of color developer oxidation product and the coupler moiety (COUP) being unimportant to the color of the diffusible image.
  • the connecting radical (LINK) is split and a dilfusible dye is formed with the color developing agent oxidation product and the coupling portion (COUP) of the coupler which diffuses imagewise to a reception layer. Ditfusibility is imparted to the dye by an acidic solubilizing group attached to a noncoupling position of the coupling portion (COUP) of the coupler or to the color developing agent. The ballasting portion of the coupler remains immobile.
  • the color of the diffusible dye is determined by the color of the reaction product of color developer oxidation product and the coupler moiety (COUP).
  • the production of diifusible dye images is a function of the reduction of developable silver halide images which may involve direct or reversal development of the silver halide emulsions with an aromatic primary amino developing agent.
  • 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 in the receiver portion of the film unit.
  • the nondiffusible coupler can be located in the silver halide emulsion itself.
  • the alkaline processing composition permeates the various layers to initiate development of the exposed photosensitive silver halide emulsion layers.
  • the aromatic primary amino color 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 emulsions layers.
  • the oxidized developing agent then reacts with the nondiffusible coupler present in each silver halide emulsion layer to form imagew-ise distributions, respectively, of dilfusible cyan, magenta and yellow dye 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 cyan, magenta and yellow dye diffuse to the image-receiving layer to provide a positive dye image.
  • Specific examples of such nondiffusing couplers and other details concerning this type of photographic chemistry are found in US. Pats. 3,227,550 and 3,227,552.
  • 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 US. Pat. 2,592,250 issued Apr. 8, 1952, and elsewhere in the literature. Internal image 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 toa 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 surface-type developer
  • the maximum density in Developer A is at least 0.5 density units 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. 261297.
  • Typical methods for the preparation of solarizing emulsions are shown by Groves British Pat. 443,245, Feb. 25, 1936, who subjected emulsions to Roentgen rays until an emulsion layer formed therefrom, when developed without preliminary exposure, is blackened up to the apex of its graduation curve; Szaz British Pat.
  • a suflicient reversal image exposure is employed using minus blue light of from about 500-700 mg wavelength preferably 520-554 mg, to substantially destroy the latent image in the silver halide grains in the region of the image exposure.
  • Particularly useful are the fogged direct positive emulsions of Berriman U.S. Pat. 3,367,778, Illingsworth U.S. Pats. 3,501,305; 3,501,306 and 3,501,507 and combinations thereof.
  • 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; or mixtures thereof.
  • 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.
  • 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. 2,562,632, 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.
  • 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 systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano, or alkoxy groups.
  • the dyes can be symmetrical or unsymmetrical and can contain alkyl, phenyl, enamine or heterocyclic substituents on the methine or polymethine chain.
  • the merocyanine dyes can contain the basic nuclei mentioned above as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones, and malononitrile.
  • These acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups, or heterocyclic nuclei. Combinations of these dyes can be used, if desired.
  • supersensitizing addenda which do not absorb visible light can be included, for instance, ascorbic acid derivatives, azaindenes, cadmium salts, and organic sulfonic acids as described in McF'all et al. U.S. Pat. 2,933,390 and Jones et al. US. Pat. 2,937,089.
  • 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 greensensitive 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 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 coarse or fine grain and can be prepared by any of the well-known procedures, e.g., single jet emulsions, double jet emulsions, such as Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions such as those described in Nietz et al. U.S. Pat. 2,222,264; Illingsworth U.S. Pat. 3,320,069; and McBride U.S. Pat.
  • Emulsions that contain silver halide grains having substantial surface sensitivity can be used, and emulsions that contain silver halide grains having substantial sensitivity inside the grains can be used such as those described in Davey et al. US. Pat. 2,592,250; Porter et al. U.S. Pat. 3,206,313; and Bacon et al. U.S. Pat. 3,447,927.
  • the emulsions can be regular grain emulsions such as the type described in Klein and Moisar, J. Phot. Sci. volume 12, No. 5, Sept/Oct, 1964, pp. 242-251.
  • Negative-type emulsions can be used or direct positive emulsions can be used such as those described in Leermakers U.S. Pat. 2,184,013; Kendall et al. U.S. Pat. 2,541,472; Berriman U.S. Pat. 3,367,778; Schouwenaars British Pat. 723,019; Illingsworth et al. French Pat. 1,520,821; Ives U.S. Pat. 2,563,785; Knott et al. U.S. Pat. 2,456,953 and Land U.S. Pat. 2,861,885.
  • the emulsions used in this invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these. 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 used in 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; Dann et al. U.S. Pat. 3,046,134; Carroll et al. U.S. Pat. 2,944,900; and 'Gotfe U.S. Pat. 3,294,540.
  • 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; Dann et al. U.S. Pat. 3,046,134; Carroll et al. U.S. Pat. 2,944,900; and 'Gotfe U.S. Pat. 3,294,540.
  • 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 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.
  • interlayers are generally employed between the various photosensitive color-forming units to scavenge oxidized developing agent and prevent it from forming an unwanted dye in another color-forming unit.
  • Such interlayers would generally comprise a hydrophilic polymer such as gelatin and an immobilizing coupler, which is capable of reacting with oxidized aromatic primary amino color developing agent to form an immobile product.
  • the aromatic primary amino color developing agent employed in the above-described embodiments is preferably present in. the alkaline processing composition in the rupturable pod.
  • the color developing agent can also be incorporated into the negative portion of the film unit as a separate layer, e.g., by employing a Schiff base derivative of an aromatic primary amino color developing agent such as that formed by reacting o-sulfobenzaldehyde and N,N-diethyl-3-methyl-4-aminoaniline. Such incorporated developing agent will be activated by the alkaline processing composition.
  • aromatic primary amino color developing agents employed in this invention are preferably p-phenylenediamine developing agents. These developing agents are well known to those skilled in the art and include the following compounds and salts thereof:
  • 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 3. 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 imageproviding 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 in addition to those described above, 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 U .3. 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; 3,121,011; and 3,427,158.
  • hydrophilic materials include both naturally-occurring substances such as proteins, 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 mate rials.
  • Suitable synthetic pqlymers include those described, 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; Houc'k et al. U.S. Pat. 3,062,674; issued Nov. 6, 1962; Houck et al. U.S. Pat. 3,220,844, issued Nov.
  • the image-receiving layer in this invention can be employed as the image-receiving layer in this invention as long as the desired function of mordanting or otherwise fixing the dye images will be obtained.
  • the particular material chosen will, of course, depend upon the dye to be mordanted.
  • the image-receiving layer can contain basic mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone such as described in the Minsk U.S. Pat. 2,882,156 granted Apr. 14, 1959 and the polymers disclosed 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-vinyl pyridine metho-p-toluene sulfonate and similar compounds described in Sprague et al. US. Pat. 2,484,430 granted Oct. 111, 1949, and cetyl trimethylammonium bromide, etc.
  • Eifective mordanting compositions are also described in Whitmore U.S. Pat. 3,271,148 and Bush U.S. Pat. 3,271,147.
  • the image-receiving layer can be sufficient 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.
  • the image-receiving layer preferably alkaline solution-permeable, is transparent and about 0.25 to about 0.04 mil in thickness. This thickness, of course, can be modified depending upon the result desired.
  • 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.
  • 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 the invention will usually increase the stability of the transferred image.
  • the pH- lowering material will eifect a reduction in the pH of the image layer from about 13 or 14 to at least 11 and preferably -8 within a short time after imbibition.
  • polymeric acids as disclosed in US. Pat. 3,362,819; or metallic salts, e.g. zinc acetate, zinc sulfate, magnesium acetate, the formates, acetates, propionates, stearates, nitrates or sulfates of zinc, aluminum, iron, maganese, cobalt or nickel, etc.; or solid acids as disclosed in US. Pat.
  • 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.
  • the pH-lowering material can be present as a separate layer between the scavenger layer and the support or it can be contained in the scavenger layer if desired.
  • Timing or spacer layer can be employed in our invention between the developer scavenger layer and the dye image-receiving layer which times or controls the scavenging reaction as a function of the rate at which alkali diffuses through the inert spacer la'yer.
  • timing layers include gelatin, polyvinyl alcohol or any of those disclosed in US. 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 '95 to 100 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 carboxymethyl 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 cps. to about 200,000 cps.
  • 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 may be added to it, 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 effect 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.
  • 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, green and 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 can 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 US. 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.
  • 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 US. 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 sensitizing dyes and other addenda used in the practice of this invention can be added from water solutions or suitable organic solvent solutions can be used.
  • the compounds can be added using various procedures including those described in Collins et al. US. Pat. 2,912,- 343; McCrossen et al. US. Pat. 3,342,605; Audran US. Pat. 2,996,287 and Johnson et al. US. Pat. 3,425,835.
  • the photographic layers used in the practice of this invention can 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 US. Pat. 2,681,294. If desired, two or more layers can be coated simultaneously by the procedures described in Russell US. Pat. 2,761,791 and Wynn British Pat. 837,095. This invention also can be used for silver halide layers coated by vacuum evaporation as described in British Pat. 968,453 and Lu Valle et al. US. Pat. 3,219,451.
  • 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, carbocyclic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguargum and the like.
  • various organic or inorganic hardeners such as the aldehydes, and blocked aldehydes, ketones, carbocyclic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, azirid
  • Potassium hydroxide 35 A multilayer, multicolor photosensitive element 1s prepared by coating the following layers in the order recited 4 N ethyl'N'p'hydroxyethylamhne sulfate 40 on an opaque cellulose acetate film support: f d t 020 (1) Red-sensitive internal image gelatin-silver chloro- 5 g 3 reluc one bromide emulsion (130 mg. gelatin/ft. and 110 mg. i s y gi h e silver/ft.
  • a scavenger interlayer comprising 1-hydroxy-N- blue light are measured both fresh and incubated for 48 [a (2,4-di-tert-amylphenoxy)butyl1-2-naphthamide (45 hours at 60 C./ 70% RH and 4 days at 38 C./ 88% mg./ft. tri-cresyl phosphate (23 mg./ft. and gelatin RH/ 1800 foot-candles of fluorescent light.
  • the following (65 mg./ft. sensitometric results are obtained:
  • Green-sensitive internal image gelatin-silver chlorobromide emulsion 116 mg. gelatin/ft. and 100 mg. silver/ft. magenta image transfer coupler 1-phenyl-3- [(3,5 dicarboxyanilino) octadecylcarbamylphenylthio]- S-pyrazolone (80 mg./ft.
  • diethyl lauramide 40 mg./ ft?) and a fogging agent formyl-4-methy1phenylhydrazine (0.5 g./mole of silver chlorobromide)
  • a scavenger and a yellow filter layer comprising 1 hydroxy N [a (2,4-di-tert-amylphenoxy)butyl]-2- naphthamide (50 mg./ft. tri-cresyl phosphate mg./ ft. yellow Carey Lea silver (15 mg./ft. and gelatin (65 mg./ft.
  • Blue-sensitive internal image gelatin-silver chlorobromoiodide emulsion 126 mg. gelatin/ft. and 100 mg. silVer/ft. yellow image transfer coupler ot-PiV3lY1-oc-[4- (N-methlyl-N-n-octadecylsulfamyl)-phenoxy] 4 sulfo acetanilide, potassium salt (70 mg./ft. and fogging agent formyl-4-methylphenylhydrazine (0.5 g./mole of silver chlorobromide).
  • a multilayer dye image-receiving element is prepared by coating the following layers in the order recited on a paper support:
  • a combined developer-scavenging and pH-lowering layer comprising zinc sulfate (500 mg. /ft. sodium formaldehyde bisulfite adduct (1 00 mg./ft. and terpoly (methyl acrylate/3-acryloyloxypropane-l-sulfonic acid, sodium salt/2-acetoacetoxyethyl methacrylate) (7 :4:0.25) (2000 mg./ft.
  • a control dye image-receiving element is prepared but without the aldehyde bisulfite developer scavenger material.
  • Two samples of the photosensitive element are 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 each superposed dye image-receiving element by passing the transfer sandwich between a pair of puxtaposed pressure rollers:
  • EXAMPLE 2 This example illustrates the use of a light-reflective material in a dye image-receiving element according to our invention.
  • a multilayer dye imagereceiving element is prepared by coating the following layers in the order recited on a paper support:
  • a combined developer-scavenging and pH-lowering layer comprising zinc sulfate (250 mg. ft?) sodium formaldehyde bisulfite adduct (1000 mg./ft. and terpoly (N-isopropylacrylamide/3-acryloyloxypropane-l sulfonic acid, sodium salt/2 acetoacetoxyethyl methacrylate) (7:4:0.25) (2000 mg./ft.
  • a combined light-reflective layer and timing layer comprising 50% hydrolyzed poly(vinyl acetate) (500 mg./ft. and titanium dioxide (1000 mg./ft. and
  • a control dye image-receiving element is prepared but without the aldehyde bisulfite developer scavenger material.
  • Example 1 is repeated except that sodium acetaldehyde bisulfite adduct, bis(sodium succinaldehyde bisulfite)adduct and bis(sodium glutaraldehyde bisulfite) are substituted at the same concentration for sodium formaldehyde bisulfite adduct. Similar results are obtained.
  • EXAMPLE 6 An integral multilayer photosensitive element is prepared by coating the following layers in the order recited on a transparent cellulose acetate film support:
  • Red-sensitive internal image gelatin-silver chlorobromide emulsion 88 mg. gelatin/ft. and 100 mg. silver/ ftfi
  • cyan image transfer coupler 1-hydroxy-4- ⁇ 4-[u-(3- pentadecylphenoxy)butyramido]-phenoxy ⁇ -N-ethyl 3,5- dicarboxy-2naphthanilide 70 mg./ft.
  • Green-sensitive internal image gelatin-silver chlorobromide emulsion (104 mg. gelatin/ft. and 100 mg. silver/ft. magenta image transfer coupler 1-phenyl-3- [(3,5 dicarboxyanilino)octadecylcarbamoylphenylthio]- S-pyrazolone (70 rug/ft?) and fogging agent formyl-4- methylphenylhydrazine (1.0 g./mole of silver chlorobromide).
  • the processing solution is spread from the pod between the exposed surface of the element and an opaque cellulose acetate film support coated with (1) a layer comprising completely hydrolyzed copoly (methylvinyl ether/ maleic anhydride) (1450 mg./ft. acetic anhydride (410 mg./ft. and 1-phenyl-S-mercaptotetrazole (10 mg./ft.), and (2) a cellulose acetate (85 mg./ft. timing layer by passing the transfer sandwich between a pair of juxtaposed pressure rollers. After one minute at about 20 C., a multicolor reproduction of the test object is observed on a white background when viewed through the transparent film support side of the element. After two days, the minimum density of the images to red, green and blue light is measured and recorded in the table.
  • Example 6 is repeated except layer (1) of the opaque process sheet also contains sodium formaldehyde bisulfite adduct (536 mg./ft.
  • Example 6 is repeated except that the opaque process sheet comprises an opaque cellulose acetate film support coated with (1) a layer comprising gelatin 1250 mg./ft. sodium dihydrogen phosphate (1104 mg./ft. and l-phenyl-S-mercaptotetrazole (50 mg./ft. and (2) a cellulose acetate mg./ft. timing layer.
  • the opaque process sheet comprises an opaque cellulose acetate film support coated with (1) a layer comprising gelatin 1250 mg./ft. sodium dihydrogen phosphate (1104 mg./ft. and l-phenyl-S-mercaptotetrazole (50 mg./ft. and (2) a cellulose acetate mg./ft. timing layer.
  • Example 8 is repeated except that layer 1) of the opaque process sheet also contains sodium formaldehyde bisulfite adduct (536 mg./ft.
  • Example 6 As will be seen by comparing the results of Example 6 with Example 7 and Example 8 with Example 9, the use of an aldehyde bisulfite addition product in an integral photosensitive element significantly improves the stability of the transfer image upon keeping.
  • 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 hav ing thereon at least one photosensitive silver halide emulsion layer, each said silver halide emulsion layer having associated therewith a nondifiusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a dilfusible dye;
  • said film unit containing an aromatic primary amino color developing agent; the improvement comprising employing in said film unit a developing agent scavenger layer comprising an aldehyde-bisulfite addition product in a polymeric binder.
  • said photosensitive element comprises a support having thereon a red-sensitive silver halide emulsion layer having associated therewith a cyan dye image-providing material comprising a non-diifusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diifusible cyan dye, a green-sensitive silver halide emulsion layer having associated therewith a magenta dye image-providing material comprising a non-difiusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible magenta dye, and a blue-sensitive silver halide emulsion layer having associated therewith a yellow dye image-providing material comprising a nondiffusible coupler capable of reacting with oxidized amino color developing agent to produce a diffusible yellow dye.
  • said film unit of claim 3 wherein said support is transparent, said film unit also includes a substantially opaque process sheet adapted to be superposed over the layer outermost from the transparent support of said photosensitive element, and said rupturable container is adapted to be positioned during processing of said film unit so that a compressive force applied to said container will efiect a discharge of the containers contents between said process sheet and the outermost layer of said photosensitive element.
  • the film unit of claim 9 which contains a timing layer between said scavenger layer and said dye imagereceiving layer.
  • timing layer also contains a light-reflective material.
  • the film unit of claim 8 which also contains a pH-lowering material.
  • M represents an alkali metal ion.
  • aldehyde bisulfite adduct is soduim formaldehyde bisulfite adduct, sodium acetaldehyde bisulfite adduct, bis(sodium succinaldehyde bisulfite)adduct, bis(sodium glutaraldehyde bisulfite) adduct, or combinations thereof.
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:
  • DYE is a dye precursor or a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group
  • (2) LINK is a connecting radical selected from the group consisting of an azo radical, a mercuri radical, an oxy radical, an alkylidene radicals, a thio radical, a dithio radical and an azoxy radical;
  • COUP is a coupler radical selected from the group consisting of a S-pyrazolone coupler radical, a pyrazolotriazole coupler radical, a phenolic coupler radical and an open-chain ketomethylene coupler radical, said COUP being substituted in the coupling position with said LINK;
  • BALL is a photographically inert organic ballasting radical of such molecular size and configuration as to render said coupler nondigusible during development in said alkaline processing composition
  • SOL is selected from the group consisting of a hydrogen atom and an acidic solubilizing group when said color developing agent contains an acidic solubilizing group, and SOL is an acidic solubilizing group 21 when said color developing agent is free of an acidic solubilizing group;
  • n is an integer of 1 to 2 when said LINK is an alkylidene radical, and n is 1 when said LINK is a radical selected from the group consisting of an azo radical, a mercuri radical, an oxy radical, a thio radical, a thio radical, a dithio radical and an azoxy radical;
  • a dye image-receiving element comprising a support having thereon a dye image receiving layer, said element being adapted to be superposed over said blue-sensitive silver halide emulsion layer after exposure of said photosensitive element;
  • said film unit containing an aromatic primary amino color developing agent; the improvement comprising employing between said dye image-receiving layer and its said support a developing agent scavenger layer comprising an aldehyde-busufite addition product in a polymeric binder.
  • a dye image-receiving element adapted to be superposed on a photosensitive element after exposure thereof comprising a support having thereon the following layers in the order recited:
  • the dye image-receiving element of claim 17 which contains a timing layer between said scavenger layer and said dye-image-receiving layer.
  • timing layer also contains a light-reflective material.
  • the dye image-receiving element of claim 17 which also contains a pH-lowering material.
  • each said silver halide emulsion layer having associated therewith a nonditfusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a ditfusible dye;
  • the improvement comprising employing in said photosensitive element or adjacent to said dye image-receiving layer a developing agent scavenger layer comprising an aldehyde-bisulfite addition product in a polymeric binder.
  • treatment step (B) is effected by (a) superposing over the layer outermost from the support of said photosensitive element said dye imagereceiving layer coated on a support; said scavenger layer being located between said dye image-receiving layer and its said support;

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4069048A (en) * 1975-02-17 1978-01-17 Fuji Photo Film Co., Ltd. Diffusion transfer photographic materials with color developer scavenger
US4105450A (en) * 1973-07-27 1978-08-08 Fuji Photo Film Co., Ltd. Spectrally sensitized positive light-sensitive o-quinone diazide containing composition
US4847179A (en) * 1986-10-30 1989-07-11 Agfa-Gevaert Aktiengessellschaft Photographic dye diffusion transfer process and color photographic recording material suitable for this process
US5288745A (en) * 1992-09-28 1994-02-22 Eastman Kodak Company Image separation system for large volume development
US5322758A (en) * 1992-09-28 1994-06-21 Eastman Kodak Company Integral color diffusion transfer element for large volume development
US5342730A (en) * 1992-09-28 1994-08-30 Eastman Kodak Company Dye releasing couplers for color diffusion transfer elements with dye barrier layers
US5356750A (en) * 1992-12-21 1994-10-18 Eastman Kodak Company Dye releasing couplers for heat image separation systems
US5370967A (en) * 1992-09-28 1994-12-06 Eastman Kodak Company Barrier layer for dye containment in photographic elements
US5455140A (en) * 1994-05-27 1995-10-03 Eastman Kodak Company Methine-dye releasing couplers for heat image separation systems
US5470688A (en) * 1994-05-27 1995-11-28 Eastman Kodak Company Heat development of elements containing methine-dye releasing couplers
US5582957A (en) * 1995-03-28 1996-12-10 Eastman Kodak Company Resuspension optimization for photographic nanosuspensions
US20080073291A1 (en) * 2006-09-22 2008-03-27 Tetra Gmbh Agents and methods for removing chloramine, chlorine, and other active chlorine compounds from water used for keeping water organisms
US20080089955A1 (en) * 2006-09-22 2008-04-17 Tetra Gmbh Preparation and use for reducing the damaging effect of ammonia on organisms living in water

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105450A (en) * 1973-07-27 1978-08-08 Fuji Photo Film Co., Ltd. Spectrally sensitized positive light-sensitive o-quinone diazide containing composition
US4069048A (en) * 1975-02-17 1978-01-17 Fuji Photo Film Co., Ltd. Diffusion transfer photographic materials with color developer scavenger
US4847179A (en) * 1986-10-30 1989-07-11 Agfa-Gevaert Aktiengessellschaft Photographic dye diffusion transfer process and color photographic recording material suitable for this process
US5441854A (en) * 1992-09-28 1995-08-15 Eastman Kodak Company Photographic image forming process utilizing a barrier layer for diffusible dye containment
US5322758A (en) * 1992-09-28 1994-06-21 Eastman Kodak Company Integral color diffusion transfer element for large volume development
US5342730A (en) * 1992-09-28 1994-08-30 Eastman Kodak Company Dye releasing couplers for color diffusion transfer elements with dye barrier layers
US5370967A (en) * 1992-09-28 1994-12-06 Eastman Kodak Company Barrier layer for dye containment in photographic elements
US5288745A (en) * 1992-09-28 1994-02-22 Eastman Kodak Company Image separation system for large volume development
US5356750A (en) * 1992-12-21 1994-10-18 Eastman Kodak Company Dye releasing couplers for heat image separation systems
US5512410A (en) * 1992-12-21 1996-04-30 Eastman Kodak Company Heat image separation with phenolic thermal solvents and dye releasing couplers
US5455140A (en) * 1994-05-27 1995-10-03 Eastman Kodak Company Methine-dye releasing couplers for heat image separation systems
US5470688A (en) * 1994-05-27 1995-11-28 Eastman Kodak Company Heat development of elements containing methine-dye releasing couplers
US5582957A (en) * 1995-03-28 1996-12-10 Eastman Kodak Company Resuspension optimization for photographic nanosuspensions
US20080073291A1 (en) * 2006-09-22 2008-03-27 Tetra Gmbh Agents and methods for removing chloramine, chlorine, and other active chlorine compounds from water used for keeping water organisms
US20080089955A1 (en) * 2006-09-22 2008-04-17 Tetra Gmbh Preparation and use for reducing the damaging effect of ammonia on organisms living in water
US8153165B2 (en) 2006-09-22 2012-04-10 Tetra Gmbh Preparation and use for reducing the damaging effect of ammonia on organisms living in water

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GB1388154A (en) 1975-03-26
IT955931B (it) 1973-09-29

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