US3698896A - Diffusion transfer film unit with improved dye image receiving layer comprising a basic polymeric mordant - Google Patents

Diffusion transfer film unit with improved dye image receiving layer comprising a basic polymeric mordant Download PDF

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US3698896A
US3698896A US100486A US3698896DA US3698896A US 3698896 A US3698896 A US 3698896A US 100486 A US100486 A US 100486A US 3698896D A US3698896D A US 3698896DA US 3698896 A US3698896 A US 3698896A
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radical
dye
pat
layer
coupler
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Thomas I Abbott
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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
    • G03C8/56—Mordant layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/142—Dye mordant

Definitions

  • UnitdStates Patent C 3,698,896 DIFFUSION TRANSFER FILM UNIT WITH IM- PROVED DYE IMAGE RECEIVING LAYER COMPRISING A BASIC POLYIVLERIC MORDANT Thomas 1. Abbott, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y. No Drawing. Filed Dec. 21, 1970, Ser. No. 100,486 Int. Cl. G03c 5/54, 5/48, 1/48 US. Cl.
  • a hydrophilic colloidal overcoat layer on a dye imagereceiving element is useful for providing stable dye images of high quality in a color development diffusion transfer system utilizing immobile couplers which form difiusible dyes.
  • This invention relates to the art of photography and more particularly to color diffusion transfer film units and methods for obtaining stable, positive, right-reading diffusion transfer dye images of high quality.
  • Patented Oct. 17, 1972 It is another object of this invention to provide a film unit employing an image-receiving element more resistant to oxidized color developer stain, thereby reducing the minimum or background densities.
  • a photographic film unit according to my 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 image-providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible dye;
  • a dye image-receiving element comprising a support having thereon a dye image-receiving layer comprising a basic polymeric mordant and a hydrophilic colloid layer;
  • a rupturable container containing an alkaline processing composition and which is adapted to be positioned between said photosensitive element and said dye image-receiving element during processing of said film unit so that a compressive force applied to the container by pressure-applying members in a camera will effect a discharge of the containers contents between the image-receiving element and the outermost layer of the photosensitive element
  • the film unit containing an aromatic, primary amino color developing agent, preferably in the rupturable container.
  • the dye image-receiving layer of my film unit is located on a separate support which is adapted to be superposed on the photosensitive element after exposure thereof.
  • the processing composition dif fuses through the film unit thereby initiating imagewise development of the silver halide emulsion layers.
  • Dye images formed as a result of the reaction of oxidized developer with nondiifusible couplers contained in each silver halide emulsion layer or in a layer contiguous thereto, are formed as a function of the imagewise exposure of each said silver halide emulsion layer.
  • At least a portion of the imagewise distributions of diifusible dye diffuses to the image-receiving layer.
  • a positive dye image is viewable upon separation of the image-receiving element from the negative element.
  • the colloid overcoat layer on the dye image-receiving element enhances the maximum density and keeping stability while reducing the minimum density of the transferred dye image.
  • hydrophilic colloids can be employed as dye image-receiving element overcoats in the practice of the invention, e.g., gelatin, casein, starch, dextran, polyvinyl pyrrolidone, gum arabic, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, guargum, gum acacia, e'tc. Gelatin and casein are preferred.
  • the hydrophilic colloid overcoat layer for the dye image-receiving element used in my invention can be employed in any coverage suitable for the intended purpose. Generally, 20-100 mg. per square foot of receiver element can be employed with effective results with a preferred coverage being 30-60 mg. per square foot.
  • the hydrophilic colloidal overcoat on the image-receiving element can also contain ultraviolet absorbing materials to protect the mordanted dye images from fading due to ultraviolet light such as those described in U.S-. Pats. 3,460,942; 3,069,262; 3,330,680; and 3,330,656.
  • Brightening agents such as the stilbenes, coumarins, triazines, oxazoles, etc. can be included in the receiving element, if desired. Best results are obtained if the brightening agent is in a layer under the image-receiving layer.
  • each silver halide emulsion layer of the film assembly of my invention can 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 blue-sensitive silver halide emulsion layer wil lhave 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 can be contained either in the silver halide emulsion layer itself or in a layer contiguous to the silver halide emulsion layer.
  • Spectral sensitizing dyes can be used conveniently to confer additional sensitivity to the light sensitive 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. 2,526,- 632, issued Oct. 24, 1950; Sprague U.S. Pat. 2,503,776, issued Apr. 11, 1950; Brooker et al. U.S. Pat. 2,493,748; and Taber et al. U.S. Pat. 3,384,486.
  • Spectral sensitizers which can be used include the cyanines, merocyanines, complex (tri or tetranuclear) merocyanines, complex (tri or tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines (e.g., enamine hemicyanines), 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 systems either unsubstituted or substituted with halogen, phenyl, alky, 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, alkylamino 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
  • 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 layers for absorbing or filtering blue radiation that may be transmitted through the blue-sensitive layer.
  • the selectively sensitized silver halide emulson 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, ammoni-acal 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.
  • 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. U.S. 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., vol. 12, No. 5, September/October 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 a1. 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 Gofi'e 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 Gofi'e 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. US. Pat.
  • the nondiffusible couplers employed in this invention include those having the formulas:
  • a mercuri radical an oxy radical, an alkylidene radical, a thio radical, a dithio radical or an azoxy radical;
  • COUP is a coupler radical such as a -pyrazolone coupler radical, a pyrazolotriazole coupler radical, a phenolic coupler radical or an open-chain ketomethylene coupler radical, COUP being substituted in the coupling position with LINK;
  • BALL is a photographically inert organic ballasting radical of such molecular size and configuration as to render such coupler nondiifusible during development in the alkaline processing composition
  • SOL is a hydrogen atom or an acidic solubilizing group when the color developing agent contains an acidic solubilizing group, and SOL is an acidic solubilizing group when the color developing agent is free of an acidic solubilizing group;
  • n is an integer of 1 to 2 when LINK is an alkylidene radical, and n is 1 when LINK is an azo radical, a mercuri radical, an oxy radical, a thio radical, a dithio radical or an azoxy radical.
  • the acidic solubilizing radicals attached to the difiusible 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 diifusible dyeproducing coupler compounds described above are not critical as long as they confer nonditfusibility to the coupler compounds.
  • Typical ballast groups include long chain alkyl radicals linked directly or indirectly to the coupler molecules as well as aromatic radicals of the henzene and naphthalene series, etc., linked directly or indirectly to the coupler molecules by a splittable linkage,
  • ballast groups have at least 8 carbon atoms.
  • Typical dye radical sub'stituents 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 With regard to the above-described 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 openchain ketomethylene coupler radicals couple to the carbon atom forming the methylene moiety (e.g.,
  • the cyanproducing coupler has the formula BALLOCYAN- COUP
  • the yellow-producing coupler has the formula BALLOYELLCOUP where- (a) 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;
  • (0) MAGCOUP is a S-pyrazolone coupler radical joined to the -N N moiety of the magenta-producing coupler in the coupling position;
  • YEIJLCOUP is an open-chain ketomethylene coupler radical attached to the --O' moiety of the yellowproducing coupler in the coupling position.
  • nondiifusing 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 nondiifusing 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 nondifiusing materials from which they are derived.
  • Mobile has the same meaning.
  • the connecting radical (LINK) is split and a diifusible 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 (CO'UP) couples with the color developing agent oxidation product to form a dye that is nondiffusible because of the attached ballasting group (BALL) in a noncoupling 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 diifusible image.
  • Couplers having the formula BALLLINK (COUPSOL) as described above are reacted with oxidized color developing agent, the connecting radical (LINK) is split and a diffusible 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. Diifusibility 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 dilfusible dye is determined by the color of the reaction product of color developer oxidation product and the coupler moiety (COiU-P).
  • 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 emulsion layers.
  • the oxidized developing agent then reacts with the nondilfusible coupler present in each silver halide emulsion layer to form imagewise distributions, respectively, of diffusible 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 dilfusible cyan, magenta and yellow dye diffuse to the image-receiving layer to provide a positive dye image upon separation of the receiver from the negative. 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 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 surface-type developer
  • 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, pages 261-297.
  • 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 Ill .0 wavelength preferably 520-554 Ill 1., 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 US. Pat. 3,367,778 and French Pat. 1,520,821.
  • 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 US. Pat. 3,227,552 issued Jan. 4, 1966; hydrazone quaternary salts described in Lincoln and Heseltine application Ser. No. 828,064 filed Apr.
  • the quantity of fogging agent employed can be widely varied depending upon the results desired.
  • 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.
  • 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 Schiif base derivative of an aromatic primary amino color developing agent such as that formed b reacting o-sulfobenzaldehyde and N,N-diethyl-3-methyl-4- aminoaniline. Such incorporated developing agent will be activated by the alkaline processing composition.
  • the incorporated developing agent can be positioned in any layer of the photosensitive element from which it can be readily made available for development upon activation with alkaline processing composition, it is generally either incorporated in the light-sensitive silver halide emulsion layers or in layers contiguous thereto.
  • 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 4-amino-N,N-diethyl-3-methylaniline hydrochloride, N,N-diethyl-p-phenylenediamine, Z-amino-S-diethylamino toluene, N-ethyl-B-methane-sulfonamido-ethyl-3-methyl-4-aminoaniline, 4-amino-N-ethyl-3-methyl-N-(fl-sulfoethyl)aniline, 4-amino-N-ethyl-3 -methoxy-N- (B-sulfoethyl) aniline, 4-amino-N-ethyl-N- (B-hydroxyethyl) aniline, 4-amino-N,N-diethyl-3-hydroxymethyl aniline, 4-
  • the rupturable container employed in this invention can be of the type disclosed in U. S. Pats. Nos. 2,543,181; 2,634,886; 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 the processing composition 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 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 US. Pat. 3,421,892, or any of those disclosed in US. Pats. 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.
  • 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 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 materials.
  • Suitable synthetic polymers include those described, for example, in Nottorf US. Pat. 3,142,568, issued July 28, 1964; White US. Pat. 3,193,386, issued July 6, 1965; Houck et al. US. Pat. 3,062,674, issued Nov. 6, 1962; Houck et al. US. Pat. 3,220,844, issued Nov. 30, 1965; Ream et al. US. Pat. 3,287,289, issued Nov.
  • the dye image-receiving layer in this invention comprises a basic polymeric mordant.
  • Especially preferred basic polymeric mordants are those described and claimed in copending application Ser. No. 709,812, filed Mar. 1, 1968, now abandoned, of my co workers Cohen, King and Minsk and their continuationin-part applications Ser. Nos. 100,487 and 100,491 filed Dec. 21, 1970.
  • the basic polymeric mordants are composed of a polymer having quaternary nitrogen groups and at least two aromatic nuclei for each quaternary nitrogen atom, said polymeric compound being substantially 10 free of carboxy groups.
  • the basic polymeric mordants described in Cohen et al. US. Pat. 3,488,706, issued Jan. 6, 1970 can also be employed with good results.
  • Preferred basic polymeric mordants comprise units of the following formula in copolymerized relationship with units of at least one other ethylenically unsaturated monomer:
  • R and R can each be hydrogen atoms, lower alkyl, e.g., 1-6 carbon atoms such as methyl, ethyl, propyl, n-butyl, t-butyl, and the like; and R can additionally be a group containing at least one aromatic nucleus including substituted aryl, e-.g., phenyl, naphthyl, tolyl, etc.;
  • Q can be a covalent bond, a divalent alkylene, arylene, aralkylene or arylenealkylene radical such as or other radicals including o NHR where R is an alkylene radical typically having 1-4 carbon atoms or R can be taken together with Q to form a or 4-pyridinium and X is an anion, i.e., a monovalent negative-salt form ing radical or atom in ionic relationship with the positive salt-forming radical or polymer cation such as a halide, alkyl, sulf
  • the above-described basic polymeric mordants are water-soluble polymers having a polyhydrocarbon back- 11 bone and are composed of recurring units supplying quaternized nitrogen atoms and preferably having at least two aromatic nuclei, such as aryl groups, per quaternized nitrogen atom.
  • the polymers should be substantially free of carboxy groups for the presence of carboxy groups in the interpolymers interferes with effective dye mordanting.
  • the above-described basic polymer mordants are generally prepared by quaternizing an intermediate polymer having tertiary nitrogen atoms with an alkylating or aralkylation agent.
  • the method of preparation of the intermediate polymer containing the tertiary nitrogen atoms for subsequent quaternization is not critical. Any of the methods known in the art such as mass, solution, or bead polymerization, as well as condensation polymerization, can be used, and the catalyst known to the art such as ultraviolet light, peroxides, azo compounds, e.g., azobisisobutyronitrile, etc. can be employed.
  • the mordanting amount of basic polymeric mordant to be employed in a dye image-receiving layer will vary over a wide range depending upon the amount of dye to be mordanted, the particular polymer employed, the imaging chemistry involved, etc. This amount can easily be determined by one skilled in the art.
  • Typical ethylenically unsaturated monomers which can be used to form ethenic interpolymers comprising the above-described basic polymeric mordants include ethylene, propylene, l-butene, isobutene, 2-methylpentene, 2- methylbutene, 1,1,4,4 tetramethylbutadiene, styrene, alpha-methylstyrene; monoethylenically unsaturated esters of aliphatic acids such as vinyl acetate, isopropenyl acetate, allyl acetate, etc.; esters of ethylenically unsaturated monoor dicarboxylic acids such as methyl acrylate, methyl methacrylate, ethyl acrylate, diethyl methylene malonate, etc.; monoethylenically unsaturated compounds such as acrylonitrile, allyl cyanide, and dienes such as butadiene and isoprene.
  • Basic polymeric mordants included with in the scope of the invention include the following:
  • pH-lowering layer in the dye image-receiving element employed in this invention will increase the stability of the transferred image.
  • the pH-lowering layer 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 US. Pat. 3,362,819 may be employed. Such polymeric acids reduce the pH of the film unit after development to terminate further dye transfer and thus stabilize the dye image.
  • Such polymeric acids comprise polymers containing acid groups, such as carboxylic acid and sulfonic acid groups, which are capable of forming salts with alkali metals, such as sodium or potassium, or with organic bases, particularly quaternary ammonium bases, such as tetramethyl ammonium hydroxide.
  • the polymers can also contain potentially acid-yielding groups such as anhydrides or lactones or other groups which are capable of reacting with bases to capture and retain them.
  • the most useful polymeric acids contain free carboxyl groups, being insoluble in water in the free acid form and which form water-soluble sodium and/or potassium salts.
  • polymeric acids include dibasic acid half-ester derivatives of cellulose which derivatives contain free carboxyl groups, e.g., cellulose acetate hydrogen phthalate, cellulose acetate hydrogen glutarate, cellulose acetate hydrogen succinate, ethyl cellulose hydrogen succinate, ethyl cellulose acetate hydrogen succinate, cellulose acetate succinate hydrogen phthalate; ether and ester derivatives of cellulose modified with sulfoanhydrides, e.g., with ortho-sulfobenzoic anhydride; polystyrene sulfonic acid; carboxymethyl cellulose; polyvinyl hydrogen phthalate; polyvinyl acetate hydrogen phthalate; polyacrylic acid, acetals of polyvinyl alcohol with carboxy or sulfo substituted aldehydes, e.g., 0-, mor p-benzaldehyde sulfonic acid or carboxylic acid; partial esters of ethylene/ maleic
  • solid monomeric acid materials could also be used such as palmitic acid, oxalic acid, se'bacic acid, hydrocinnamic acid, metanilic acid, paratoluenesulfonic acid and benzenedisulfonic acid.
  • Other suitable materials are disclosed in US. Pat. Nos. 3,422,075 and 2,635,048.
  • the pH-lowering layer is usually about 0.3 to about 1.5 mils in thickness and is preferably located in the dye image-receiving element between the support and the dye image-receiving layer.
  • An inert timing or spacer layer coated over the pH- lowering layer may also be used to time or control the pH reduction of the dye image-receiving element as a function of the rate at which the alkali diffuses through the inert spacer layer.
  • 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 irnbibition 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 and may contain a light-reflective material, such as titanium dioxide, if desired.
  • the timing layer comprises a hydrolyzable polymer or a mixture of such polymers which are slowly hydrolyzed by the processing composition.
  • hydrolyza'ble polymers include polyvinyl alcohol, polyvinyl acetate, polyamides, polyvinyl ethers, partial acetals of polyvinyl alcohol, 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.
  • 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 solution is preferred which will impart thereto a viscosity of about 100 cps. to about 200,000 cps.
  • alkaline processing composition used in this invention can be employed in a rupturable container, as described previously, other methods of applying processing composition could also be employed, e.g., bathing the photosensitive element in a processing bath.
  • film units of my invention can be modified so as to be employed in roll form, they are preferably used in cartridges similar to those described in U.S. Pats. 3,080,805; 3,161,118; and 3,161,122; said patents also illustrating typical cameras for performing color diffusion transfer processes of my invention.
  • 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 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.
  • 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 U.S. Pat. 3,133,816; and water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson British Pat. 1,022,878.
  • surfactants such as saponin, anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen U.S. Pat. 2,600,831; amphoteric compounds such as those described in Ben-Ezra U.S. Pat. 3,133,816; and water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson British Pat. 1,022,878.
  • the various layers, including the photographic layers, employed in the practice of this invention can contain light absorbing materials and filter dyes such as those described in Sawdey U.S. Pat. 3,253,921; Gaspar U.S. Pat. 2,274,782; Silverstein et al. U.S. Pat. 2,527,583 and Van Campen U.S. Pat. 2,956,879.
  • the dyes can be mordanted, for example, as described in Milton et al. U.S. Pat. 3,282,699.
  • 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. U.S. Pat. 2,912,- 343; McCrossen et al. U.,S. Pat. 3,342,605; Audran U.S. Pat. 2,996,287 and Johnson et al. U.S. 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 U.S. Pat. 2,681,294. If desired, two or more layers can be coated simultaneously by the procedures described in Russell U.S. 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. U.S. 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,
  • carboxylic and carbonic acid derivatives sulfonated esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, and polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguargum and the like.
  • a multilayer, multicolor photosensitive element is prepared by coating the following layers in the order recited on a cellulose acetate film support:
  • Red-sensitive internal image gelatin-silver chlorobromide emulsion (171 mg. gelatin/ft. and mg. silver/ft.
  • a development modifier 2-(2-octadecyl)-5-sulfohydroquinone potassium salt (1 mg./ft. and a fogging agent formyl-4- methylphenylhydrazine (0.5 mg./ft.
  • Green-sensitive internal image gelatin-silver chlorobromide emulsion 116 mg. gelatin/ft. and 100 mg. silver/ ft. magenta image transfer coupler 1phenyl-3(3,5-dicarboxyanilino) octadecylcarbamylphenylthio) -5 pyrazolone' (79 mg./ft. N-n-b utylacetanilide (40 mg./ft. a development modifier 2-(2-octadecyl)-5-sulfohydroquinone potassium salt (1 mg./ft. and a fogging agent formyl-4-methylphenylhydrazine (0.5 mg./ft.
  • a yellow filter layer comprising l-hydroxy-N-[a- (2,4-ditert-amylphenoxy)butyl]-Z-naphthamide (50 mg./ ft. tri-cresyl phosphate (25 mg./ft. 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 a-pivalyl-a-(4- nitro-3 )-pentadecylphenoxy)-4-sulfamoylacetanilide 100 mg./ft. N-n-butylacetanilide (50 mg./ft. a development modifier 2-(2-octadecyl)-5-sulfohydroquinone potassium salt (1 mg./ft. and a fogging agent formyl-4-methylphnylhydrazine (0.5 mg./ft.
  • a multilayer dye image-receiving element is prepared by coating the following layers in the order recited on a polyethylene coated paper support:
  • a pH lowering layer of poly(methylvinylether/ maleic anhydride) (750 mg./ft. and
  • a dye image-receiving layer of copoly[styrene-N benzyl-N,N-dimethyl-N-( 3 maleimidopropyl)ammonium chloride] (700 mg./ft.
  • the photosensitive element is exposed to a graduated-density multicolor test object.
  • the following processing composition is spread from a pod between the exposed surface of the element and the superposed image-receiving element by passing the transfer sandwich between a pair of juxtaposed pressure rollers:
  • Hydroxyethyl cellulose 30.0 g.
  • the dye image-receiving element After 60 seconds at about 20 C., the dye image-receiving element is peeled apart from the negative. After three weeks keeping at approximately 22 C./50% R.I-I. under fluorescent room light conditions, the minimum densities to red, green and blue light are measured and recorded in Table I.
  • EXAMPLE 3 The procedure as described in Example 2 is followed with the exception that a hydrophilic colloidal overcoat layer of casein is provided over the dye image-receiving layer at the same coverage.
  • EXAMPLE 4 The procedure of Example 2 is repeated with the addition of 25 mg./ft. of the ultraviolet absorber 2(2-hydroxy-3,5-ditert amylphenol)benzotriazole in the overcoat layer. Similar results are obtained.
  • Example 2 The procedure of Example 2 is repeated except that 700 mg./ft. of copoly[styrene-N,N,N-trimethyl-N-(El-maleimidopropyl)ammonium p-toluenesulfonate] is employed as the dye image-receiving layer instead of copoly[styreneN-benzyl N, N-dimethyl-N-(3-maleimidropropyl) ammonium chloride]. Similar results are obtained.
  • 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 non-difi'usible 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 a hydrophilic colloid layer over said dye image-receiving layer, said dye image-receiving layer comprising a basic polymeric mordant.
  • 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 nonditfusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a ditfusible cyan dye, a green-sensitive silver halide emulsion layer having associated therewith a magenta dye image-providing material comprising a nondiffusible 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 nondiflusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diifusible yellow dye.
  • the photographic film unit of claim 1 including a pH-lowering layer between said dye image-receiving layer and its support.
  • said basic polymeric mordant comprises a polymer having at least /3 of the units represented by the following formula in copolymeriezd relationship with units of at least one other ethylenically unsaturated monomer:
  • Lapel L b-l n -i e-n x wherein R and R are hydrogen atoms or lower alkyl groups and R can additionally be a group containing at least one aromatic nucleus; Q can be a covalent bond, a divalent alkylene radical, a divalent arylene radical, a divalent aralkylene radical, a divalent arylenealkylene radical,
  • R is an alkylene radical, or R can be taken together with Q to form a R R and R can be lower alkyl or aryl groups, or R and R and the nitrogen atom to which they are attached can be taken together to represent the atoms and bonds necessary to form a quaternized nitrogen-containing heterocyclic ring which is attached to Q, and X is a monovalent negative salt-forming radical or atom; wherein said polymer is substantially free of carboxy groups.
  • said basic polymeric mordant is copoly[styrene-N-benzyl-N,N dimethyl-N-(3-rnaleimidopropyl)ammonium chloride.
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:
  • a direct-positive, green-sensitive silver halide emulsion layer containnig a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a dilfusible magenta dye;
  • each said nondiffusible coupler having the formula:
  • (l) DYE is 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 radical, 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 non-diffusible 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 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 dithio radical and an azoxy radical;
  • a dye image-receiving element comprising a support having thereon a polymeric acidic material layer and 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 basic polymeric mordant comprises a polymer having at least /3 of the units represented by the following formula in copolymerized relationship with units of at least one other ethylenically unsaturated monomer:
  • R and R are hydrogen atoms or lower alkyl groups and R can additionally be a group containing at least one aromatic nucleus;
  • Q can be a covalent bond, a divalent alkylene radical, a divalent arylene radical, a divlent aralkylene radical, a divalent arylenealkvlene radical wherein R is an alkylene radical, or R can be taken together with Q to form a -o II 0 group;
  • R R and R can be lower alkyl or aryl groups, or R and R and the nitrogen atom to which they are attached can be taken together to represent the atoms and bonds necessary to form a quaternized nitrogen-containing heterocyclic ring which is attached to Q, and
  • X is a monovalent negative salt-forming radical or atom; wherein said polymer is substantially free of carboxy groups and wherein the positive salt-forming radical of said polymer comprises at least two aryl groups for each quaternary nitrogen atom in said polymer and said gelatin layer is present
  • the improvement comprising employing a hydrophilic colloid layer over said dye image-receiving layer, said dye image-receiving layer comprising a basic polymeric mordant.
  • 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 nondifiusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to prolose a difiusible cyan dye, a green-sensitive silver halide emulsion layer having associated therewith a magenta dye image-providing material comprising a nondifiusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a ditfusible magenta dye, and a blue-sensitive silver halide emulsion layer having associated therewith a yellow dye imageproviding material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a ditfusible yellow dye.
  • hydrophilic colloid layer is present at a coverage of 20-100 mg per square foot.
  • hydrophilic colloid layer comprises casein.
  • R and R are hydrogen atoms or lower alkyl groups and R can additionally be a group containing at least one aromatic nucleus:
  • Q can be a covalent bond, a divalent alkylene radical, a divalent arylene radical, a divalent aralkylene radical, a divalent arylenealkylene radical,
  • R is an alkylene radical, or R can be taken together with Q to form a group
  • R R and R can be lower alkyl or aryl groups, or R and R and the nitrogen atom to which they are attached can be taken together to represent the atoms and bonds necessary to form a quaternized nitrogencontaining heterocyclic ring which is attached to Q
  • X is a monovalent negative salt-forming radical or atom; wherein said polymer is substantially free of carboxy groups.
  • said basic polymeric mordant is copoly [styrene-N-benzyl-N,N-dimethyl- N- 3-maleimidopropyl ammonium chloride.
  • each said nondiifusible coupler having the formula:
  • DYELINK-(COUPBALL) n BALLLINK-(COUPSOL) n (1) DYE is 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 radical, 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 non- 21 diffusible 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 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 dithio radical and an azoxy radical;
  • the improvement comprising employing a hydrophilic colloid layer comprising gelatin over said dye image-receiving layer, said dye image-receiving layer comprising a basic polymeric mordant.
  • said basic polymeric mordant comprises a polymer having at least /3 of the units represented by the following formula in copolymerized relationship with units of at least one other ethylenically unsaturated monomer:
  • R and R are hydrogen atoms or lower alkyl groups and R can additionally be a group containing at 22 least one aromatic nucleus;
  • Q can be a covalent bond, a divalent alkylene radical, a divalent arylene radical, a divalent aralkylene radical, a divalent arylenealkylene radical,
  • R is an alkylene radical, or R can be taken together with Q to form a R R and R can be lower alkyl or aryl groups, or R and R and the nitrogen atom to which they are attached can be taken together to represent the atoms and bonds necessary to form a quaternized nitrogen-containing heterocyclic ring which is attached to Q
  • X is a monovalent negative salt-forming radical or atom; wherein said polymer is substantially free of carboXy groups and wherein the positive salt-forming radical of said polymer comprises at least two aryl groups for each quaternary nitrogen atom in said polymer and said gelatin layer is present at a coverage of 20-100 mg. per square foot.

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Cited By (14)

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US3816125A (en) * 1972-06-16 1974-06-11 Polaroid Corp Photographic products and processes
DE2450622A1 (de) * 1973-10-24 1975-04-30 Fuji Photo Film Co Ltd Farbdiffusionsuebertragungselement und verfahren zur bildung von uebertragungsbildern
US3887370A (en) * 1972-01-07 1975-06-03 Mitsubishi Paper Mills Ltd Dye transfer acceleration with polyamine compounds
US4009031A (en) * 1973-11-29 1977-02-22 Polaroid Corporation Diffusion transfer image-receiving element having polyvinylpyridine layer treated with hydrophilic colloid/ammonia solution
US4220700A (en) * 1978-02-03 1980-09-02 Eastman Kodak Company Continuous-tone dyed diazo imaging elements
WO1980002333A1 (en) * 1979-04-24 1980-10-30 Polaroid Corp Color transfer film and process
US4247615A (en) * 1980-03-06 1981-01-27 Eastman Kodak Company Continuous-tone dyed diazo imaging process
US4294907A (en) * 1980-04-24 1981-10-13 Polaroid Corporation Image-receiving elements
US4298674A (en) * 1979-04-24 1981-11-03 Polaroid Corporation Color transfer film and process
US4322489A (en) * 1980-04-22 1982-03-30 Polaroid Corporation Copolymeric mordants and photographic products and processes utilizing same
US4340522A (en) * 1980-04-22 1982-07-20 Polaroid Corporation Process for preparing cationic polymers
US4367277A (en) * 1981-05-26 1983-01-04 Polaroid Corporation Diffusion transfer product and process
US4424326A (en) 1980-04-22 1984-01-03 Polaroid Corporation Copolymeric mordants
US20050195261A1 (en) * 2004-03-05 2005-09-08 Eastman Kodak Company Fuser for ink jet images and ink formulations

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9508596D0 (en) * 1995-04-27 1995-06-14 Conveyor Units Ltd "conveyors"

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3887370A (en) * 1972-01-07 1975-06-03 Mitsubishi Paper Mills Ltd Dye transfer acceleration with polyamine compounds
US3816125A (en) * 1972-06-16 1974-06-11 Polaroid Corp Photographic products and processes
DE2450622A1 (de) * 1973-10-24 1975-04-30 Fuji Photo Film Co Ltd Farbdiffusionsuebertragungselement und verfahren zur bildung von uebertragungsbildern
US4124386A (en) * 1973-10-24 1978-11-07 Fuji Photo Film Co., Ltd. Color diffusion transfer receiving layer comprising polymeric quaternary n-heterocyclic mordant
US4009031A (en) * 1973-11-29 1977-02-22 Polaroid Corporation Diffusion transfer image-receiving element having polyvinylpyridine layer treated with hydrophilic colloid/ammonia solution
US4220700A (en) * 1978-02-03 1980-09-02 Eastman Kodak Company Continuous-tone dyed diazo imaging elements
WO1980002333A1 (en) * 1979-04-24 1980-10-30 Polaroid Corp Color transfer film and process
US4298674A (en) * 1979-04-24 1981-11-03 Polaroid Corporation Color transfer film and process
US4247615A (en) * 1980-03-06 1981-01-27 Eastman Kodak Company Continuous-tone dyed diazo imaging process
US4322489A (en) * 1980-04-22 1982-03-30 Polaroid Corporation Copolymeric mordants and photographic products and processes utilizing same
US4340522A (en) * 1980-04-22 1982-07-20 Polaroid Corporation Process for preparing cationic polymers
US4424326A (en) 1980-04-22 1984-01-03 Polaroid Corporation Copolymeric mordants
US4294907A (en) * 1980-04-24 1981-10-13 Polaroid Corporation Image-receiving elements
US4367277A (en) * 1981-05-26 1983-01-04 Polaroid Corporation Diffusion transfer product and process
US20050195261A1 (en) * 2004-03-05 2005-09-08 Eastman Kodak Company Fuser for ink jet images and ink formulations

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FR2119521A5 (it) 1972-08-04
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NL7117615A (it) 1972-06-23
DE2163261A1 (de) 1972-06-29

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