US3635707A - Diffusion transfer products adapted for multiple application of processing composition and/or opacifier and processes for their use - Google Patents

Diffusion transfer products adapted for multiple application of processing composition and/or opacifier and processes for their use Download PDF

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US3635707A
US3635707A US58017A US3635707DA US3635707A US 3635707 A US3635707 A US 3635707A US 58017 A US58017 A US 58017A US 3635707D A US3635707D A US 3635707DA US 3635707 A US3635707 A US 3635707A
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radical
developing agent
layer
coupler
silver halide
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Harold E Cole
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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
    • G03C8/32—Development processes or agents therefor
    • G03C8/34—Containers for the agents
    • 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

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  • the film unit comprises a transparent support coated with an image-receiving layer and having thereon a photosensitive element comprising at least one, and preferably three, silver halide emulsion layers having associated therewith nondiffusible dye image-providing materials capable of reacting with oxidized developing agent to produce diffusible dyes, and a top sheet which can be transparent or opaque.
  • Two rupturable containers or one container with two compartments containing either a processing composition or an opacifier or both are positioned (a) adjacent the top layer of the photosensitive element and sheet and (b) adjacent the image-receiving layer or a contiguous reflective layer and the bottom layer of the photosensitive element.
  • the film unit is placed in a camera, exposed and then passed between a pair of pressure-applying members in the camera as it is being removed therefrom.
  • the pressure-applying members rupture the containers and spread processing composition and/or opacifier over and underneath the photosensitive element to render it light insensitive.
  • the processing composition develops the exposed silver halide layers and diffusible dye images are formed as a result of development which diffuse to the image-receiving layer to provide a positive, rightreading image which is viewed through the transparent support on an opaque reflecting layer background which is present initially in the film unit or formed by opacifier in a rupturable container.
  • Several embodiments of the film unit may be interchangeably employed cameras either with or without an image-reversing optical system.
  • This invention relates to photography and more particularly to an integral, negative-receiver color diffusion transfer film assembly, which can be exposed in a camera and processed outside the camera to yield a right-reading positive image.
  • Prior art U.S. Pat. No. 3,415,644; 3,415,645; and 3,415,646 described film assemblies designed for image transfer in which the receiving layer is not separated from the photosensitive element after processing which takes place out of the camera in room light.
  • these prior art film assemblies require either an image-reversing optical system in the camera or require that an opaque sheet be placed over the top of the assembly after exposure and prior to removing the film assembly from the camera for processing.
  • Another object of my invention is to provide a novel film assembly which does not require an in-camera lamination of an opaque sheet to the film assembly after exposure in order to obtain room light processing capability, thus enabling the camera to be less expensive and less bulky.
  • Another object of my invention is to provide a novel film assembly which can be exposed in a camera, processed outside the camera in room light to yield a right-reading positive image, and which does not require timing of development or any stripping away of the receiving layer from the negative portion of the photosensitive element after processing.
  • Still another object of my invention is to provide new processes for obtaining transfer images employing the novel film assemblies described herein.
  • photographic film unit of my invention which is adapted to be processed by passing the unit between a pair of juxtaposed pressure-applying members and which comprises:
  • a transparent support coated with an image-receiving layer having thereon a photosensitive element comprising at least one photosensitive silver halide emulsion layer, each said silver halide emulsion layer having associated therewith a nondiffusible dye image-providing material capable of reacting with oxidized developing agent to produce a diffusible dye;
  • a first rupturable container being so positioned during processing, preferably transverse a leading edge of the photosensitive element, that a compressive force applied to the first container by the pressure-applying members will effect a discharge of the first containers contents between the top sheet and the outermost layer of the photosensitive element;
  • a second rupturable container being so positioned during processing, preferably transverse a leading edge of the photosensitive element, that a compressive force applied to the second container by the pressure-applying mem bers will effect a discharge of the second containers contents between the image-receiving layer and the innermost layer of the photosensitive element from the transparent support;
  • the film unit containing a developing agent, one of the rupturable containers containing an opacifying agent, and the other rupturable container containing an alkaline processing composition.
  • the top sheet is transparent
  • the first rupturable container contains an alkaline processing composition having therein an opacifying agent
  • the second rupturable container contains an opacifying agent
  • the top sheet is transparent, the first rup'turable container contains an opacifying agent and the second rupturable container contains an alkaline processing composition having therein an opacifying agent.
  • the top sheet is transparent
  • the first rupturable container contains an opacifying agent
  • the second rupturable container contains an alkaline processing composition
  • the film unit contains an opaque reflecting layer intermediate the image-receiving layer and the photosensitive element.
  • the top sheet is opaque, the first rupturable container contains an alkaline processing composition and the second rupturable container contains an opacifying agent.
  • the photosensitive unit is placed in a camera, exposed, and then passed between pressure-applying members in the camera as the unit is being removed therefrom.
  • This compressive force breaks open the rupturable containers and spreads opacifying agent and processing composition into the film unit.
  • the negative portion of the film assembly will then be surrounded by opaque material to render it light insensitive, thus enabling the assembly to be removed from the camera during development.
  • the processing composition diffuses through the film unit to either effect or initiate imagewise development of the silver halide emulsion layers.
  • Exposure and removal of the film assembly of my invention from a camera can be accomplished in. a matter of seconds, thus freeing the camera for use in taking another photograph.
  • prior art film assemblies require relatively expensive, bulky cameras, with obvious disadvantages, for providing within the camera a mechanical film-handling system to manipulate the film after exposure to laminate an opaque sheet over the top prior to removing the film unit from the camera for processing
  • the film assembly of my invention can be employed in a very simple, inexpensive camera in which the only film movement in the camera after exposure occurs when the film unit passes between a pair of pressure'applying rollers as it is being removed from the camera.
  • the film assembly of my invention could be employed in a camera having the film-handling mechanism similar to that illustrated in U.S. Pat. No.
  • FIG. I is a perspective view of a first embodiment of a film unit according to the invention.
  • FIG. 2 and FIG. 3 are diagrammatic cross-sectional views of the film unit of FIG. I along section line 22, illustrating the various elements of a typical film unit before and after rupture of the rupturable containers or pods, the thickness of the various components being exaggerated for purposes of illustration.
  • FIG. 4, FIG. 5, and FIG. 6 are diagrammatic cross-sectional views of a second, third and fourth embodiment, respectively, of typical film units according to my invention.
  • each silver halide emulsion layer of the film assembly of my invention will have associated therewith a dye imageproviding 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 will have a yellow dye image-providing material associated therewith, the green-sensitive silver halide emulsion layer will have a magenta dye image-providing material associated therewith, and the red-sensitive silver halide emulsion layer will have a cyan dye image-providing material associated therewith.
  • the dye image-providing material associated with each silver halide emulsion layer may be contained either in the silver halide emulsion layer itself or in a layer contiguous to the silver halide emulsion layer.
  • 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. No. 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. No. 2,526,632; issued Oct. 24, 1950; Sprague U.S. Pat. No. 2,503,776; issued Apr. 11, 1950; Brooker et al. U.S. Pat. No. 2,493,748; and Taber et al. U.S. Pat. No. 3,384,486.
  • Spectral sensitizers which can be used include the cyanines, merocyanines, complex (trior tetranuclear) merocyanines, complex (trior tetranuclear) cyanines, homopolar 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, alkyl, haloalkyl, cyano, or alkoxy groups.
  • the dyes can be symmetrical or unsymmetrical and can contain alkyl, phenyl, enamine or heterocyclic substituents on the methine or polymethine chain.
  • the merocyanine dyes can contain the basic nuclei mentioned above as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones, and malononitrile.
  • acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, 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
  • ascorbic acid derivatives for instance, ascorbic acid derivatives, azaindenes, cadmium salts, and organic sulfonic acids as described in McFall et al. U.S. Pat. No. 2,933,390 and Jones et al. U.S. Pat. No. 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 as shown in the drawing.
  • a yellow dye layer or a Carey Lea silver layer can be present between the blue-sensitive and green-sensitive silver halide emulsion layer for absorbing or filtering blue radiation that may be transmitted through the blue-sensitive layer.
  • the selectively sensitized silver halide emulsion layers can be disposed in a different order, e.g., the blue-sensitive 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. No. 2,222,264; lllingsworth U.S. Pat. No.
  • 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 as those described in Davey et al. U.S. Pat. No. 2,592,250; Porter et al. U.S. Pat. No. 3,206,313; and Bacon et al. U.S. Pat. No. 3,447,927.
  • the emulsions can be regular grain emulsions such as the type described in Klein and Moisar, J. Phat. Sci., Vol. 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. No. 2,184,013; Kendall et al. U.S. Pat. No. 2,541,472; Berriman U.S. Pat. No. 3,367,778; Schouwenaars British Pat. No. 723,019; lllingsworth et al. French Pat. No. 1,520,821; Ives U.S. Pat. No. 2,563,785 Knott et al. U.S. Pat. No. 2,456,953 and Land U.S. Pat. No. 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. No. 1,623,499; Waller et al. U.S. Pat. No. 2,399,083; McVeigh U.S. Pat. No. 3,297,447; and Dunn U.S. Pat. No. 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. No. 2,886,437; Dann et al. U.S. Pat. No. 3,046,134; Carroll et al. U.S. Pat. No. 2,944,900; and Goffe U.S. Pat. No. 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. No. 2,886,437; Dann et al. U.S. Pat. No. 3,046,134; Carroll et al. U.S. Pat. No. 2,944,900; and Goffe U.S. Pat. No. 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. No. 2,131,038 and Allen et al. U.S. Pat. No. 2,694,716; the azaindenes described in Piper U.S. Pat. No. 2,886,437 and Heimbach et al. U.S. Pat. No. 2,444,605; the mercury salts as described in Allen et al. U.S. Pat. No. 2,728,663; the urazoles described in Anderson et al.
  • the dye image-providing material associated with each silver halide emulsion layer in this invention can be any material which is nondifi'using in alkaline processing compositions and in photographic silver halide emulsions but which produces a diffusible dye on reaction with oxidized silver halide photographic developing agents.
  • the dye image-providing material is a nondiffusible coupler which produces a diffusible dye on reaction with oxidized aromatic primary amino color developing agents such as p-phenylenediamine developing agents.
  • Such nondiffusible couplers may be employed in layer arrangements in a photosensitive element which have advantages over other dye image-providing materials.
  • an initially soluble and diffusible dye image-providing material such as a dye developer
  • the dye developer is chromatically shifted (which is a technically difi'icult task to obtain three such compounds which will not absorb blue, green and red light, respectively, during exposure, and which will form yellow, magenta and cyan dyes, respectively, after transfer)
  • it will usually have to be employed in a layer underneath a contiguous photosensitive silver halide emulsion layer with respect to the exposure side so that exposure and diffusion of unoxidized dye developer take place in opposite directions in order to obtain optimum photographic speed and monitoring of the dye developer layer by the exposed silver halide emulsion layer.
  • a system employing the nondiffusible couplers described herein also has many advantages over systems employing initially diffusible couplers. For example, it is not possible to obtain good color separation in an initially diffusible coupler system unless separate receiving sheets are assembled in register as described in US. Pat. No. 2,647,049 and 2,698,798, column 13, lines 64-85 or unless sequential transfers are made to a single receiver as described in U.S. Pat. No. 2,698,798, column 14, lines l-l2. These such systems, obviously, cannot be employed with a single developing composition and a single receiver as described by the invention herein toprovide a high quality, multicolor, transfer image having good color separa tion and low D,,,,,,. in addition, initially diffusible coupler systems require the use of an oxidizing agent in the receiving layer to oxidize the transferred color developing agent which would tend to degrade the multicolor image or wander into other layers of the integral element causing color contamination.
  • the nondiffusible couplers of this invention include those having formulas:
  • BALLLlNl(-(COUP-SOL), wherein I. DYE is a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing radical;
  • LlNK 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;
  • COUP is a coupler radical such as a S-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 LlNK;
  • BALL is a photographically inert organic ballasting radi' cal of such molecular size and configuration as to render such coupler nohdiffusible 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 l to 2 when L1Nl( 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 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 diffusible dyeproducing coupler compounds described above are not critical as long as they confer nondiffusibility 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 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 eight 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 the coupling position
  • the S-pyrazolone coupler radicals couple at the carbon atom in the 4-position
  • the phenolic coupler radicals including ot-naphthols
  • the open-chain ketomethylene coupler radicals couple to the carbon atom forming the methylene moiety (e.g.,
  • the cyanproducing coupler has the formula BALL-OCYANCOUP
  • the yellow-producing coupler has the formula BALL-O-YELLCOUP wherein:
  • BALL is a photographically inert organic ballasting radical having at least eight 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 at tached to the O moiety of the cyan-producing coupler in the coupling position;
  • YELLCOUP is an open-chain ketomethylene coupler radical attached to the O moiety of the yellowproducing coupler in the coupling position.
  • nondiffusing 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 color of the difiusible 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.
  • Couplers having the formula BALL-LINK- (COUP-SOL), 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. Diffusibility 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 diffusible 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 nondiffusible 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 ditfusible cyan, magenta and yellow dye diffuse to the image-receiving layer to provide a positive dye image viewable through the transparent support.
  • a pH-lowering layer in the film unit lowers the pH of the film unit to stabilize it. Since the receiving layer does not have to be stripped away from the negative portion of the film unit, the composite structure can be maintained intact subsequent to processing. Specific examples of such nondiffusing couplers and other details concerning this type of photographic chemistry are found in U.S. Pat. Nos. 3,227,550 and 3,227,552.
  • Internal image silver halide emulsions useful in the abovedescribed embodiment are direct positive emulsions that form latent images predominantly inside the silver halide grains, as distinguished from silver halide grains that form latent images predominantly on the surface thereof. Such internal image emulsions were described by Davey et al. in U.S. Pat. No. 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 below internal-type
  • Developer 8 described below surfacetype 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. No. 443,245, Feb.
  • Suitable fogging agents include the hydrazines disclosed in Ives U.S. Pat. No. 2,588,982 issued Mar. H, 1952 and No. 2,563,785 issuedAug. 7, i; the hydrazides and hydrazones disclosed in Whitmore U.S. Pat. No. 3,227,552 issued Jan. 4, i966; hydrazone quaternary salts described in Lincoln and l-Ieseltine application Ser. No. 828,064 filed Apr. 28,- l969, now abandoned; or mixtures thereof.
  • the quantity of fogging agent employed can be widely varied depending upon the results desired. Generally, the conccntration of fogging agent is from about I to about 20 mg.
  • the photosensitive portion of the photosensitive element would comprise at least two Color-Forming Units in layers sensitive to different regions of the visible spectrum, separated by a barrier layer comprising a hydrophilic colloid containing a waterinsoluble reactant capable of forming a water insoluble salt with mercaptans, each of the Color-Forming Units comprismg:
  • a developable emulsion layer of a hydrophilic colloid and a water insoluble metal salt which is developable by an aromatic primary amino color developing agent to substantial density without exposure to light, the metal salt having contiguous thereto the nondifiusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to form a diffusible dye;
  • a photosensitive silver halide emulsion layer the silver halide of which has contiguous thereto a nondiffusible development inhibitor-releasing coupler which is capable of reacting with oxidized aromatic primary amino color developing agent to release a diffusible mercaptan development inhibitor which is capable of diffusing imagewise to the adjacent developable emulsion layer to inhibit development therein.
  • the aromatic primary amino color developing agent is preferably a p-phenylenediamine developing agent which is present in the alkaline processing composition and the developable emulsion is preferably an emulsion of a hydrophilic colloid, silver thiocyanate and physical development nuclei that can be developed to substantial density without exposure to light.
  • the developable emulsion can also be made from a metal salt which is made spontaneously developable by incorporating in the emulsion a wide variety of well-known physical development nuclei as disclosed in the above-men tioned U.S. Pat. No. 3,227,551, column 6, lines 63-75 and column 7, lines 1-10.
  • Another method that can be utilized to make the water-insoluble salts spontaneously developable is by prefogging the emulsion with light or with chemical reducing agents such as alkali metal borohydrides and the like in accordance with well-known photographic fogging techniques.
  • BALL is a photographically inert organic ballasting radical of such molecular size and configuration as to render the coupler nondiffusible during development in the alkaline processing composition
  • COUP is a coupler radical such as a S-pyraaolone coupler radical, a phenolic coupler radical or an open-chain ketomethylene coupler radical, COUP being substituted in the coupling position with said LINK;
  • LINK is a connecting radical such as an azo radical, a
  • MERC is a diffusible radical containing a mercapto radical (-Sl-l);
  • RM is a photographically inert, diffusible radical that forms a mercaptan with the monothio connecting or linking radical (-S-);
  • n is an integer of l to 2 when LINK is an alkylidene radical and n is I when LINK is an azo radical, a mercuri radical, an oxy radical, a thio radical, a dithio radical or an azoxy radical; and
  • m is an integer of or I.
  • a wide variety of photographically inert radicals that are diifusible in the layers of the Color-Forming Unit and form mercaptans with the monothio connecting or linkage radical when the connecting is split on development can be used for the RAD substituent of the development inhibitor-releasing couplers.
  • Typical of such radicals are aryl, alkaryl and carboncontaining heterocyclic radicals.
  • the aryl moiety of such radi' cals is preferably phenyl, and includes such substituents as nitro, lower alkyl, lower alkylamido, lower alkoxy, lower alkylsulfoamido, lower alkylcarbamyl, carbon-containing heterocyclic radicals and the like.
  • the carbon-containing heterocyclic radicals which can be attached directly to the monothio linkage radical or as a substituent on the described aryl moieties, generally contain at least one hetero nitrogen, oxygen or sulfur atom, and preferably, one to four hetero nitrogen atoms.
  • the hetero nitrogen atoms in the heterocyclic radicals have no hydrogen atom attached thereto as the RAD radical is photographically inert.
  • Illustrative carbon-containing heterocyclic radicals include l-phenyltetrazolyls, oxazolyls, oxadiazolyls, diazolyls, thiadiazolyls, benzoxazolyls, benzothiazolyls, pyrimidyls, pyridinyls, quinolinyls and the like.
  • MERC is a preformed mercapto development inhibiting moiety.
  • a wide variety of diffusible radicals containing a mercapto radical (-SH) can be used for the MERC substituent of the development inhibitor-releasing couplers.
  • the mercapto radical can be suitably attached to an aryl, alkaryl or a carboncontaining heterocyclic radical such as RAD described above except that it is not necessary that the hetero nitrogen atoms on the heterocyclic radicals be free of hydrogen atoms.
  • ком ⁇ онент-releasing couplers having the formula (BALLCOUP) When development inhibitor-releasing couplers having the formula (BALLCOUP),LINI(MERC are reacted with oxidized color developing agent, the connecting radical (LINK) is split and a mercaptan development inhibitor (MERC) is released that is diffusible in the Color-Forming Unit. A ballasted or immobile dye is formed by reacting the coupler moiety (COUP) at the coupling position with oxidized color developing agent.
  • development inhibitor-releasing couplers are preformed development inhibitors, they are preferably utilized in a layer adjacent to the light-sensitive silver halide emulsion layer of the present Color-Forming Units.
  • a nondiffusible or a nonmordantable dye is formed by reacting the coupler moiety (COUP) at the coupling position with oxidized color developing agent, both the development inhibitor-releasing coupler and the color developing agent being free of acidic solubilizing groups when m is zero and the dye formed is diffusible.
  • the substituent m is preferably one, and such development inhibitor'relcasing couplers can be utilized either in the light-sensitive emulsion or in a layer adjacent thereto in the present Color-Forming Units.
  • ballast groups (BALL) in the development inhibitor-releasing coupler compounds described above is not critical as long as they confer nondiffusibility to the coupler compounds.
  • Typical ballast groups include long-chain alltyl radicals or several short chain alky'l radicals having e.g., 8-22 carbon atoms, 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 splittable linkage, or by a removable or irremovable but otherwise nonfunctional linkage depending upon the nature of the coupler compound.
  • Useful ballast groups generally have at least eight carbon atoms,
  • the Color-Forming Units are sensitive to blue, green and red light and are capable of forming imagewise distributions of diffusible yellow, magenta and cyan dyes.
  • the alkaline processing composition permeates the various layers to initiate development of the latent image contained in each photosensitive silver halide emulsion layer.
  • the aromatic primary amino color developing agent present in the film unit preferably in the alkaline processing composition itself, develops each of the exposed silver halide emulsion layers, thus causing said aromatic primary amino color developing agent to become oxidized imagewise.
  • the oxidized developing agent then reacts with the nondiffusible development inhibitor-releasing coupler contiguous to the silver halide emulsion layer to release a diffusible mercaptan development inhibitor.
  • the mercaptan development inhibitor thereafter diffuses imagewise to each adjacent developable emulsion layer to inhibit development therein corresponding to areas of exposure of the photosensitive silver halide emulsion, the barrier layers preventing the mercaptan development inhibitor formed in one Color-Forming Unit from diffusing to another Color-Forming Unit by forming an insoluble salt with mercaptans diffusing to said barrier layers.
  • each developable emulsion layer wherein development has not been inhibited corresponding to the unexposed areas of the photosensitive silver halide emulsion, are thus developed spontaneously by the developing agent, thus causing the developing agent to become oxidized.
  • the oxidized developing agent then reacts with the nondiffusible coupler contiguous to the metal salt in each developable emulsion layer to form imagewise distributions, respectively, of diffusible cyan, magenta and yellow dye as a function of the imagewise exposure of each silver halide emulsion layer. At least a portion of the imagewise distributions of diffusible cyan, magenta and yellow dye then diffuse to the image-receiving layer to provide a positive dye image viewable through the transparent support.
  • a pl-i-lowering layer in the film unit lowers the pH of the film unit to stabilize it. Since the receiving layer does not have to be stripped away from the negative portion of the film unit, the composite structure can be maintained intact subsequent to processing.
  • the barrier layers referred to above are used between Color'Forming Unit to ensure that the activity of the mercaptan development inhibitor is confined to a single Color-Forming Unitv
  • the barrier layers contain a water-insoluble salt or metal capable of forming a water-insoluble salt with mercaptans, silver halides such as silver chloride, silver bromide, silver iodide, silver bromoiodide, silver chlorobromoiodide, etc., heing'preferably used.
  • colloidal metals such as silver and gold
  • colloidal metal sulfides, selenides and tellurides such as lead sulfide, nickel sulfide, cadmium sulfide, silver sulfide, copper sulfide, zinc sulfide, mercury sulfide, silver selenide, silver telluride and the like.
  • the barrier layers containing light-sensitive silver salts are prepared to be substantially less sensitive to light than the light-sensitive emulsions in the Color-Forming Units. Such barrier layers also serve to prevent oxidized color developing agent from wandering from one Color-Forming Unit to another where it could cause color contamination.
  • Antioxidants such as n-octadecyl hydroquinone and the like phenolic antioxidants, and nondiffusible photographic color couplers that form nondiffusible dyes on coupling with oxidized aromatic primary amino color developing agents can be utilized in the barrier layers to prevent wandering of such oxidized color developing agent.
  • Still another embodiment of the invention employing the nondiffusible couplers described above to produce a diffusible dye image-providing material is to employ them in combination with physical development nuclei in a nuclei layer contiguous to each photosensitive silver halide emulsion layer.
  • the film unit contains a silver halide solvent, preferably in a rupturable container with the alkaline processing composition, and each photosensitive silver halide emulsion layer contains an immobilizing coupler, e.g., a coupler with a ballast group, which is capable of reacting with oxidized aromatic primary amino color developing agent to form an immobile product.
  • Each photosensitive silver halide emulsion layer and its contiguous nuclei layer are separated from the other silver halide emulsions and their contiguous nuclei layers in the film unit by means of an alkaline solution-permeable barrier layer for retaining silver complexes.
  • the alkaline processing composition permeates the various layers to initiate development of the latent image contained in each photosensitive silver halide emulsion layer.
  • the aromatic primary amino color developing agent present in the film unit develops each of the exposed silver halide emulsion layers, thus causing the aromatic primary amino color developing agent to become oxidized imagewise.
  • the oxidized developing agent then reacts with the immobilizing coupler present in each said photosensitive silver halide emulsion layer to form an immobile product.
  • the remaining silver halide in each silver halide emulsion layer corresponding to unexposed and thus underdeveloped areas forms a soluble silver ion complex with the silver halide solvent present in or activated by the processing composition and migrates to each adjacent nuclei layer.
  • the transferred silver complex is reduced or physically developed in the nuclei layer, thus causing the developing agent to become oxidized.
  • the oxidized developing agent then reacts with the nondiffusible coupler present in each nuclei layer to form imagewise distributions, respectively, of diffusible cyan, magenta and yellow dye as a function of the imagewise exposure of each said silver halide emulsion layer.
  • the diffusible dye can be formed by the reaction of the ox idized developing agent with the nondiffusible coupler or a preformed dye can be released by the reaction of the oxidized developing agent with the nondiffusible coupler, as described above. At least a portion of said imagewise distributions of diffusible cyan, magenta and yellow dyes then diffuse to the image-receiving layer to provide a positive dye image viewable through the transparent support.
  • a pH-lowering layer in the film unit lowers the pH of the film unit to stabilize it. Since the receiving layer does not have to be stripped away from the negative portion of the film unit, the composite structure can be maintained intact subsequent to processing.
  • the aromatic primary amino color developing agent is preferably a p-phenylenediamine developing agent which is present in the alkaline processing composition.
  • the physical development nuclei can be any of those well known to those in the art such as colloidal metals, e.g., colloidal silver, gold, platinum, palladium, colloidal metal sulfides, e.g., colloidal silver sulfide, zinc sulfide, etc, Materials which form physical development nuclei may also be used such as reducing agents and labile sulfur compounds.
  • the nuclei layer can also be split into two layers, one on each side of the photosensitive silver halide emulsion layer, if desired.
  • the silver halide solvent employed can be any of those well known to those skilled in the art, such as alkali metal and ammonium thiosulfates and thiocyanates, e.g., sodium thiosulfate, ammonium thiosulfate, ammonium thiocyanate, potassium thiocyanate, etc., and may be incorporated in a separate layer, if desired, either in the photosensitive element or in the opaque process sheet.
  • Spacer layers comprising gelatin are preferably employed between the nuclei layers and the photosensitive silver halide emulsion layers to prevent undesirable mixing of the two layers upon coating.
  • the spacer layers may also contain nuclei and nondiffusible coupler capable of reacting with oxidized color developing agent to form an immobile product in order to increase its efficiency.
  • nuclei and nondiffusible coupler capable of reacting with oxidized color developing agent to form an immobile product in order to increase its efficiency.
  • 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, as described above, which is capable of reacting with oxidized aromatic primary amino color developing agent to form an immobile product.
  • Such interlayers may also scavenge other materials such as soluble silver ion complexes or mercaptans in the described systems to prevent such materials from contaminating other Color-Forming Units.
  • a developer scavenging interlayer may also be employed in the above-described embodiments adjacent to the support carrying the photosensitive layers to prevent excess color developing agent from staining the image-receiving layer.
  • a layer may comprise for exam ple, a fogged silver halide emulsion, or a spontaneously developable silver halide emulsion, physical development nuclei, and a nondiffusible coupler capable of reacting with oxidized color developing agent to form an immobile product.
  • the developer scavenger interlayer may also contain a waterinsoluble reactant capable of forming a water-insoluble salt with mercaptans, etc.
  • the developer scavenger interlayer may also be coated with a polymeric timing layer, e.g., gelatin, if desired, to allow for complete development before the developer scavenger interlayer becomes operative.
  • 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-methyI-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-S-methyl aniline hydrochloride N,N-diethyl-p-phenylenediamine, 2amino-5- diethylamino toluene, N-ethyl-/3-methane-sulfonamido-ethyl- 3-methyl-4-aminoaniline, 4-amino-N-ethyl-3-methyl-N-(B- sulfoethyl)aniline, 4-amino-N-ethyl-3-methoxyN-(B-sulfoethyl)aniline, 4-amino-N-ethyl-N-(B-hydroxyethyl)aniline, 4-amino-N,l-l-diethyl-S-hydroxymethyl aniline, 4amino-N- methyl-N-(B-carboxyethyl)aniline, 4-amino
  • rupturable containers II and I3 are positioned transverse a leading edge of the photosensitive laminate and are held in place by binding means 30, which can be a pressure-sensitive tape, which encloses that edge of the laminate.
  • binding means 30 can be a pressure-sensitive tape, which encloses that edge of the laminate.
  • the other edges of the photosensitive laminate are similarly enclosed with binding means 3K, 32 and 33 which enhance the structural integrity of the laminate and prevent leakage of processing solution during and after photographic processing when rupturable containers Ill and 13 are broken open by pressure-applying members 36 to discharge their contents into the photosensitive laminate.
  • film unit It comprises a first rupturable container Ill containing, prior to passing between pressure-applying members 36, an alkaline processing composition containing an opacifying agent, rupturable container 13 containing an opacifying composition, and a photosensitive laminate comprising top transparent sheet 29 coated with polymeric acid layer 23 and polymeric timing layer 27 and a photosensitive element comprising transparent support layer coated with an image-receiving layer 16, permeable support 118, cyan dye image-providing layer 19, red-sensitive silver halide emulsion layer 20, barrier interlayer 2i, magenta dye image-providing layer 22, green-sensitive silver halide emulsion layer 23, barrier interlayer 24, yellow dye image-providing layer 25 and blue-sensitive silver halide emulsion lay-er 26. Exposure of the film unit takes place through the top transparent sheet 29 which is preferably an actinic radiation transmissive flexible sheet material.
  • the film unit of FIG. 2 has: been passed between pressure-applying members 36 such as would be found in a camera, thus causing rupturable containers 11 and I3 to collapse.
  • the alkaline processing composition containing an opacifying agent is discharged from container Ill between the polymeric timing layer 27 and the blue-sensitive silver halide emulsion layer 26 while the opacifying composition is discharged between the permeable support 18 and the imagereceiving layer 16.
  • a positive, right-reading image may be viewed through transparent support 115.
  • FIG. 4, FIG. 5 and FIG. 6 illustrate other embodiments of the film unit of my invention.
  • the embodiment of FIG. 4i is similar to the embodiment of FIG. 2 with the exception that the alkaline processing composition is contained in the second or lower rupturable container and the photosensitive layer arrangement has been reversed to facilitate exposure from the bottom rather than the top side of the film unit.
  • FIG. 5 is similar to the embodiment shown in FIG. 2 with the exception that it contains opaque reflective layer 17 between the permeable support I8 and image-receiving layer 16 and the first or upper rupturable container contains an opacifying composition while the second or lower rupturable container contains the alkaline processing composition.
  • exposure in FIG. 5 takes place from the top side and the transferred positive image is viewed from the bottom side.
  • FIG. 6 illustrates still another embodiment similar to FIG. 2 with the exception that the top transparent sheet is replaced by opaque layer 36, the first or upper rupturable container does not contain any opacifying agent and the photosensitive layer arrangement has been reversed to facilitate exposure from the bottom rather than the top side of the film unit.
  • FIGS. 2-6 indicate that the two rupturable containers are separated from each other, this is done merely for purposes of illustration. Since the layers in the film unit are actually very thin, the two rupturable containers in actual practice are superimposed on each other.
  • one processing container with two compartments such as that shown in FIG. 2 of US. Pat. No. 3,473,925, may be employed in my invention. In that case, each compartment would serve as a rupturable container and this feature is within the scope of my invention.
  • the film unit of my invention can be interchangeably employed in cameras with different optical systems which is not feasible with other types of image-providing materials.
  • the photosensitive layers in either FIG. 2 or FIG. 4 are replaced by a pan-sensitized silver halide emulsion having a dye image'providing material associated therewith as described previously or having three such dye image-providing materials associated therewith as described in copending U.S. application Ser. No. 58,195 of Walter M. Bush filed of even date herewith for black-and-white reproduction, the film unit could be exposed from either the top side or the bottom side to provide a transferred positive image.
  • Such a film unit could thus be employed in a camera similar to that illustrated in U.S. Pat. No. 3,447,437 with an imagereversing optical system (exposure from the bottom side) or in a similar camera without the image-reversing optical system (exposure from the top side) to provide a rightreading, positive image in the image-receiving layer which would be viewable through the transparent support.
  • FIG. 4 and FIG. 6 could be employed in a camera similar to that illustrated in U.S. Pat. No. 3,447,437 with an image-reversing optical system to provide a right-reading, positive image in the image-receiving layer.
  • the same type of chemistry can be employed in film units for usein a camera similar to that illustrated in U.S. Pat. No. 3,447,437 but without an imagereversing optical system to also provide a right-reading, positive image in the image-receiving layer.
  • the opacifying composition in one container is separated from the alkaline processing composition which is present in the other container.
  • These embodiments are particularly useful when it is desired to keep these two components separated from each other, e.g., when the opacifier is present in an unusually high concentration which might interfere with the diffusion of the alkaline processing composition or when the components might react with each other, etc.
  • the film unit of my invention may be constructed by assembling the various parts in an atmosphere maintained at a pressure lower than atmospheric pressure and by sealing the top sheet and image-receiving element to the photosensitive element along their edges in order to prevent the admission of air between them.
  • the exclusion of air between the various sheets and the photosensitive element is desirable in order to prevent air bubbles from being entrained in the processing composition which would form discontinuities in the positive image. Details of this method of assembly and other methods for assuring a uniform distribution of processing composition between two sheets are described in Belgian Pat. No. 71 1,897.
  • the film unit of my invention can also contain a liquid trap at the opposite end in which the processing compositions are introduced in order to trap any excess processing composition and keep it from being expelled from the film unit.
  • the liquid trap may also function to let air escape, if any is present.
  • Such liquid traps are disclosed, for example, in Belgian Pat. No. 71 1,899.
  • Rupturable containers 11. and 13 can be of the type disclosed in U.S. Pat. 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 airimpervious 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 composition is contained
  • the longitudinal marginal seals are made weaker than the end margin seals so as to become unsealed in response to the hydraulic pressure generated within the fluid contents of the containers by the application of a compressive force to the outside walls of the containers.
  • containers 11 and 13 are fixedly positioned and extend transverse a leading edge of the photosensitive laminate so that a compressive force applied to said containers will effect a unidirectional discharge of the containers contents into the film unit.
  • the weak longitudinal marginal seals 35 are directed towards the interfaces between layers 27 and 26 and between layers 16 and 18 to facilitate this operation.
  • the unit In the performance of a multicolor diffusion transfer process employing the film unit of FIG. 2, the unit is exposed to radiation incident on the photosensitive laminates upper surface through transparent sheet 29. Subsequent to exposure, the film unit 10 is processed by passing it between pressureapplying members 36 in order to apply compressive pressure to frangible containers II and 13 and to effect rupture of Iongitudinal seals 35 and distribution of alkaline processing composition containing an opacifying agent between layers 27 and 26 and distribution of opacifying composition between layers 16 and 18 of the film unit 10.
  • the alkaline processing composition permeates the silver halide emulsion layers 26, 23 and 20 to initiate development of the latent images contained therein.
  • Diffusible yellow, magenta and cyan dye images are formed from material in layers 25, 22 and 19 as a function of the imagewise exposure of their associated emulsions. At least part of the imagewise distributions of mobile yellow, magenta and cyan dyes transfer, by diffusion, to the image-receiving layer 16 to provide a positive dye image therein. This positive, right-reading image can then be viewed through transparent support layer 15 on the opacifying composition background. Since the receiving layer does not have to be stripped away from the negative portion of the film unit, the composite structure can be maintained intact subsequent to said processing.
  • 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 U.S. Pat. No. 3,421,892 or any of those disclosed in U.S. Pat. Nos. 2,992,104; 3,043,692; 3,044,873; 3,061,428; 3,069,263; 3,069,264; 3,121,01 1;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 I to 7 microns in thickness; and the alkaline solution-permeable polymeric interlayers, e.g., gelatin, are about 1 to 5 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 U.S. Pat. No. 3,142,568, issued July 28, 1964; White U.S. Pat. No. 3,193,386, issued July 6, 1965; Houck et al. U.S. Pat. No.
  • 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 imagereceiving layer can contain basic polymeric mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone such as described in the Minsk U.S. Pat. No. 2,882,156 granted Apr. 14, 1959.
  • Other mordants useful in our invention include poly-4-vinylpyridine, the 2-vinylpyridine polymer metho-p-toluene sulfonate and similar compounds described in Sprague et al. U.S. Pat.
  • the mordant ing compositions described in the Bush patent comprise at least one hydrophilic organic colloid containing a finely divided, uniform dispersion of particles of a salt of an organic acidic composition containing free acid moieties and at cationic, nonpolymeric organic dye-mordanting compound for acid dyes.
  • Useful cationic or basic organic dye-mordanting compounds for dyes include quaternary ammonium and phosphonium, and ternary sulfonium compounds in which there is linked to the N, P, or S onium atom at least one hydrophobic ballast group such as long-chain alkyl or substituted alkyl groups.
  • 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 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 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 imagereceiving layer can also contain ultraviolet absorbing materials to protect the mordanted dye images from fading due to ultraviolet
  • plH-lowering layer in the film unit of the invention will usually increase the stability of the transferred image.
  • the pll-l-lowering layer will effect a reduction in the pH of the image layer from about 13 to 14 or to at least 1 l and preferably -8 within a short time after imbibition.
  • polymeric acids as disclosed in U.S. Pat. No. 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 salt 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 lid 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., O-, lVlor p-benzaldehyde sulfonic acid orcarboxylic acid; partial esters of
  • solid monomeric acid materials could also be used such as palmitic acid, oxalic acid, sebacic acid, hydrocinnamic acid, metanilic acid, paratoluenesulfonic acid and benzenedisulfonic acid.
  • Other suitable materials are disclosed in U.S. Pat. No. 3,422,075, and 2,635,048.
  • the pH-lowering layer is usually about 0.3 to about 1.5 mils in thickness.
  • the pH-lowering layer is usually located in the receiver portion of the film unit between the support and the image-receiving layer, it can actually be located anywhere within the film unit as long as the desired function is obtained.
  • a polymeric acid layer could be located in the negative portion of the film unit, as disclosed in US. Pat. No. 3,362,821, with the polymeric acid encapsulated in a polymeric material and dispersed in an alkaline solutionpermeable binder. In this instance, the processing solution would quickly diffuse through the element to permeate the silver halide emulsion layers.
  • the pH of the film unit would then decrease, thus stabilizing the film unit as a whole.
  • the pH-lowering layer could also be located on the top sheet which is superposed over the photosensitive element of the film unit of the invention.
  • the alkaline processing composition which is discharged from a rupturable container would diffuse upward to contact the pH-lowering layer, become acidic and then diffuse downward into the negative portion of the photosensitive element, thus lowering the pH of the film unit as a whole after development and imagewise diffusion of the various dyes have taken place.
  • An inert timing or spacer layer coated over the pH-lowering layer can also be used to time" or control the pH reduction of the film unit 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 dis closed in US. Pat. No. 3,455,686.
  • the timing layer is also effective in evening out the various reaction rates over a wide range of temperatures, e.g., premature pH reduction is prevented when imbibition is effected at temperatures above room temperature, for example, at to F.
  • the timing layer is usually about 0.1 to about 0.7 mil in thickness.
  • the timing layer comprises a hydrolyzable polymer or a mixture of such polymers which are slowly hydrolyzed by the processing composition.
  • hydrolyzable polymers include polyvinyl acetate, polyamides, polyvinyl ethers, partial acetate 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 concen tration of viscosity-increasing compound of about 1 to about 5 those disclosed in U.S. Pat. No.
  • auxiliary or accelerating developing agents can be employed either in the liquid processing composition or may be contained, at least in part, in any layer or layers of the film unit such as the silver halide emulsion layers, the dye image-providing material layers, interlayers, image-receiving layer, etc.
  • the alkaline processing composition employed in this invention can also contain a desensitizing agent such as methylene blue, nitro-substituted heterocyclic compounds, 4,4-bi-pyridinium salts, etc., to insure that the photosensitive element is not further exposed after it is removed from the camera for processing.
  • a desensitizing agent such as methylene blue, nitro-substituted heterocyclic compounds, 4,4-bi-pyridinium salts, etc.
  • alkaline processing composition and opacifying composition used in this invention can be employed in rupturable containers, as described previously, to conveniently facilitate the introduction of the compositions, into the film unit, other methods of inserting these compositions into the film unit could also be employed, e.g., interjecting such compositions with communicating members similar to hypodermic syringes which are attached either to a camera or camera cartridge.
  • any opacifying agent can be employed in the alkaline processing composition or as a separate opacifying composition in my invention as long as it provides the desired opacity to light.
  • opacifying agents include carbon black, barium sulfate, zinc oxide, barium stearate, silver flake, silicates, alumina, zirconium oxide, zirconium acetyl acetate, sodium zirconium sulfate, kaolin, mica, titanium dioxide, organic dyes such as the nigrosines, or mixtures thereof in widely varying amounts depending upon the degree of opacity desired.
  • the concentration of opacifying agent should be sufficient to prevent further exposure of the film units silver halide emulsion or emulsions by ambient actinic radiation transversing through the film unit subsequent to distribution of the processing composition and various opacifying agents into the film unit.
  • carbon black or titanium dioxide will provide sufficient opacity when they are present in the alkaline processing composition or in a separate opacifying composition in an amount of from about 5 to 40 percent by weight.
  • the opacifying agent can either be employed in the alkaline processing composition or in a separate opacifying composition.
  • a separate opacifying composition it can be employed by itself but is preferably dispersed in a film-forming binder, e.g., an alkaline solution-permeable polymeric binder such as polyvinyl alcohol, gelatin. etc.
  • the alkaline solution-permeable, substantially opaque, light-reflective layer 17 of FIG. 5 can generally comprise any opacifier dispersed in a binder as long as it has the desired properties. Particularly desirable are white light-reflective layers since they would be esthetically pleasing backgrounds on which to view a transferred dye image and would also possess the optical properties desired for reflection of incident radiation.
  • 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 can 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.
  • Another technique to increase the opacifying capacity of the light-reflective layer is to employ a separate opaque layer underneath it comprising, e.g., carbon black, nigrosine dyes, etc., dispersed in an alkaline solution-permeable polymeric matrix such as, for example, gelatin, polyvinyl alcohol, and the like.
  • Such an opaque layer would generally have a density of at least 4 and preferably greater than 7 and would be substantially opaque to actinic radiation.
  • the opaque layer may also be combined with a developer scavenger layer if one is present.
  • the light-reflective and opaque layers are generally I to 6 mils in thickness although they can be varied depending upon the opacifying agent employed, the degree of opacity desired, etc.
  • the opaque layer 36 of FIG. 6 can comprise any opacifying agent described above dispersed in a binder so long as it has the desired opacity.
  • the opaque layer of FIG. 6 is similar to the opaque layer of FIG. 5 with the exception that the binding agent does not have to be alkaline solution permeable, i.e., it can be any film-forming polymeric material such as polyesters, cellulose esters, polycarbonates, etc.
  • the transparent sheet in several embodiments of the film assembly of my invention can be any transparent material as long as it does not deleteriously effect the photographic properties of the film unit and is dimensionally stable.
  • Typical actinic radiation transmissive flexible sheet materials include cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate, poly(vinyl acetal) film, polystyrene film, poly(ethyleneterephthalate) film, polycarbonate film, poly-aolefins such as polyethylene and polypropylene film, and related films or resinous materials as well as glass.
  • the transparent sheet is usually about 2 to 6 mils in thickness. If desired, an adhesive layer activatable by the processing composition may be present on the transparent sheet in order to increase its adhesion to the photosensitive element after processing.
  • 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. No. 2,600,831; amphoteric compounds such as those described in Ben-Ezra U.S. Pat. No. 3,133,816; and water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson British Pat. No. 1,022,878.
  • surfactants such as saponin, anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen U.S. Pat. No. 2,600,831; amphoteric compounds such as those described in Ben-Ezra U.S. Pat. No. 3,133,816; and water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson British Pat. No. 1,02
  • 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. No. 3,253,921; Gasper U.S. Pat. No. 2,274,782; Silverstein et al. U.S. Pat. No. 2,527,583 and Van Campen U.S. Pat. No. 2,956,879.
  • the dyes can be mordanted, for example, as described in Milton et al. U.S. Pat. No. 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. No. 2,912,343; McCrossen et a1. U.S. Pat. No. 3,342,605; Audran U.S. Pat. No. 2,996,287 and Johnson et al. U.S. Pat. No. 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 No. 2,681,294. If desired, two or more layers can be coated simultaneously by the procedures described in Russell U.S. Pat. No. 2,761,791 and Wynn British Pat. No. 837,095. This invention also can be used for silver halide layers coated by vacuum evaporation as described in British Pat. No. 968,453
  • 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, ltetones, carbocylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl esters, 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, ltetones, carbocylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl esters, active halogen compounds
  • a photosensitive element is prepared by coating the following layers in the order recited on an alkaline solution-permeable polyvinyl alcohol film support:
  • Red-sensitive gelatin-silver bromide emulsion 110 mg. gelatin/ft. and 70 mg. silver/ft.
  • 1-hydroxy-N-[ct-(2,4-ditert-amylphenoxy)butyl]-2-naphthamide 87 mg./ft. and di n-butylphthalate (44 mg./ft.
  • Green-sensitive gelatin-silver bromide emulsion (1 mg. gelatin/ft and 70 mg. silver/ft. 1-hydroxy-N-[a-( 2,4-di-tertamylphenoxy)butyl]-2-naphthamide (87 mgjft?) and di-nbutylphthalate (44 mg./ft.
  • Nuclei layer of yellow image transfer coupler a-Pivalyla-(3-octadecylcarbamylphenylthio)-4-sulfoacetanilide potassium salt (60 mg./ft. colloidal palladium (0.24 mgJftf) and gelatin (50 mgJftF) l4. Spacer layer ofgelatin (100 rug/ft?) 15. Blue-sensitive gelatin-silver bromide emulsion (1 10 mg. gelatin/ft. and 70 mg. silver/ftF), l-hydroxy-N-[a-(2,4-ditert-amylphenoxy)butyl]-2-naphthamide (87 mg./ft. and di n-butylphthalate (44 mg./ft.
  • Nuclei layer of yellow image transfer coupler a-Pivalyla-(3-octadecylcarbamylphenylthio-4-sulfoacetanilide potassium salt (60 mg./ft. colloidal palladium (0.24 mg./ft. and gelatin (50 mg./ft.
  • the photosensitive emulsions listed above are negativetype, developing out emulsions.
  • the following processing composition is employed in the first processing pod:
  • a transparent sheet of cellulose acetate film base is then superposed over the top layer 17 of the element with the first processing pod placed in between the film base and the element.
  • the second processing pod and the image-receiving layer are positioned on the other side of the photosensitive element with the pod in between the image-receiving layer and the photosensitive element.
  • the element is then exposed through the transparent sheet to a graduated-density multicolor test object.
  • the processing compositions are spread from the pods into the film unit by passing the transfer sandwich between a pair of juxtaposed pressure rollers. After about 3 minutes at 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 unit.
  • EXAMPLE 2 (FIG. 4 EMBODlMENT) A photosensitive element is prepared by coating the follow ing layers in the order recited on an alkaline solution-permeable polyvinyl alcohol film support:
  • Blue-sensitive gelatin-silver bromide emulsion 10 gelatin/ft. and 70 mg. silver/ft. l-hydroxyN-[a-(2,4-ditert-amylphenoxy)butyl]-2-naphthamide (87 mgjft?) and din-butylphthalate (44 mg./ft.
  • Green-sensitive gelatin-silver bromide emulsion (l 10 mg. gelatin/ft. and 70 mg. silver/fe l-hydroxy-N-[a-(2,4-ditert-amylphenoxy)butyll-2'naphthamide (87 mgjft?) and din-butylphthalate (44 mg./ft.
  • Red-sensitive gelatin-silver bromide emulsion 110 mg. gelatin/ft. and 70 mg. silver/ft
  • l-hydroxy-N-[a-(2,4-ditert-amylphenoxy)butyll-2-naphthamide 87 mg./ft. and din-butylphthalate (44 mg./ft.
  • the photosensitive emulsions listed above are negative-type, developing-out emulsions.
  • An image-receiving layer similar to that of example 1 is coated on a transparent cellulose acetate film support.
  • First and second processing pods are prepared containing the processing compositions listed in example 1.
  • a transparent sheet of cellulose acetate film base is then superposed over the top layer 11 of the element with the second processing pod, i.e., the one containing water, hydroxyethylcellulose and titanium dioxide, placed in between the film base and the element.
  • the first processing pod and the image-receiving layer are positioned on the other side of the photosensitive element with the pod in between the imagereceiving layer and the photosensitive element.
  • the element is then exposed through the imagereceiving layer to a graduated-density multicolor test object.
  • the film unit is then processed as in example 1 to obtain a multicolor reproduction of the test object on a white background when viewed through the transparent film support side of the unit.
  • a photosensitive element is prepared by coating the following layers in the order recited on an alkaline solution-permeable polyvinyl alcohol film support:
  • Red-sensitive gelatin-silver bromide emulsion 100 mg. gelatin/ft. and 150 mg. silver/ft?) and developer inhibitor releasing coupler l-hydroxy-4-( l-phenyl-5-tetrazolylthio)-2- (2'-n-tetradecyloxy)naphthanilide (60 mg./ft.
  • Green-sensitive gelatin-silver bromide emulsion 100 mg. gelatin/ft. and 75 mg. silver/ft?) and developer inhibitor releasing coupler l-hydr0xy-4-( l-phenyl-5-tetrazolylthio)-2- (2-n-tetradecyloxy)naphthanilide (60 mg./ft.
  • the following processing composition is employed in the first processing pod.
  • a transparent sheet of cellulose acetate film base is then superposed over the top layer 8 of the element with the first processing pod placed between the film base and the element.
  • the second processing pod and the image-receiving element as positioned on the other side of the photosensitive element with the pod in between the image-receiving element and the photosensitive element.
  • the element is then exposed through the transparent sheet to a graduated-density multicolor test object.
  • the processing compositions are spread from the pods into the film unit by passing the transfer sandwich" between a pair of juxtaposed pressure rollers. After about three minutes at 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 unit.
  • a photosensitive element is prepared by coating the following layers in the order recited on an alkaline solution-permeable polyvinyl alcohol film support:
  • Red-sensitive gelatin-silver chlorobromide emulsion 120 mg. gelatin/ft. and 100 mg. silver/ft
  • the photosensitive emulsions listed above are internal image emulsions having high internal sensitive and lower surface sensitivity a d are'prepared by the procedure described in Davey et al. US. Pat. No. 2,592,250, issued Apr. 8, 1952.
  • An imagereceiving layer similar to that of example 1 is coated on a transparent cellulose acetate film support.
  • the following processing composition is employed in the first processing pod:
  • An opaque sheet of poly(ethyleneterephthalate) is then coated with a pl-l-lowering layer of polyacrylic acid and timing layer of polyvinyl acetate.
  • the coated opaque sheet is then superposed over the top layer 5 of the element with the first processing pod placed between the coated opaque sheet and the element.
  • the second processing pod and the imagereceiving layer are positioned on the other side of the photosensitive element with the pod in between the imagereceiving layer and the photosensitive element.
  • the element is then exposed through the image-receiving layer to a graduated-density multicolor test object.
  • the film unit is then processed as in example 3 to obtain a multicolor reproduction of the test object on a white background when viewed through the transparent film support side of the unit.
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:
  • a transparent support coated with an image-receiving layer having thereon a photosensitive element comprising at least one photosensitive silver halide emulsion layer, each said silver halide emulsion layer having associated therewith a nondiffusible dye image-providing material capable of reacting with oxidized developing agent to produce a diffusible dye;
  • the photographic film unit of claim 3 including a pH- lowering layer which is capable of lowering the pH of the film unit subsequent to diffusion therethrough by said alkaline processing composition.
  • each said nondiffusible coupler is contained in a layer contiguous to each said silver halide emulsion layer.
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:
  • a transparent support coated with an image-receiving layer having thereon a photosensitive element comprising an alkaline solution-permeable support having thereon the following layers in the order recited:
  • each said nondiffusible coupler having the formula:
  • 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 nondiffusible 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;
  • a first rupturable container being positioned transverse at least a portion of a leading edge of said photosensitive element so that a compressive force applied to said first container by said pressure-applying members will effect a discharge of said first containers contents between said transparent sheet and said underlying blue-sensitive silver halide emulsion layer of said photosensitive element adjacent thereto;
  • a second rupturable container being positioned transverse at least a portion of a leading edge of said photosensitive element so that a compressive force applied to said second container by said pressureapplying members will effect a discharge of said second containers contents between said alkaline solution-permeable support of said photosensitive element and said image-receiving layer;
  • said film unit containing an aromatic primary amino color developing agent; one of said rupturable containers containing an opacifying agent and the other said rupturable container containing an alkaline processing composition.
  • said aromatic primary amino color developing agent is a p-phenylenediamine developing agent which is present in said alkaline processing composition
  • said transparent sheet is coated with, successively, a pH-lowering layer and an alkaline solution-permeable polymeric timing layer on the side thereof which is closest to said photosensitive element, said pH-lowering layer being capable of lowering the pH of the film unit subsequent to diffusion therethrough by said alkaline processing composition
  • each said direct positive silver halide emulsion is an internal image emulsion wherein the silver halide forms latent images predominantly inside the silver halide rains.
  • said first rupturable container contains an alkaline processing composition having therein an opacifying agent and said second rupturable container contains an opacifying agent.
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:
  • a transparent support coated with an image-receiving layer having thereon a photosensitive element comprising an alkaline solution-permeable support having thereon the following layers in the order recited:
  • each said nondiffusible coupler having the formula:
  • DYE is a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group
  • 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 LlNK;
  • BALL is a photographically inert organic ballasting radical of such molecular size and configuration as to render said coupler nondiffusible 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;
  • a is an integer of l 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 first rupturable container being positioned transverse at least a portion of a leading edge of said photosensitive element so that a compressive force applied to said first container by said pressure-applying members will effect a discharge of said first containers contents between said top sheet and said underlying red-sensitive silver halide emulsion layer of said photosensitive element adjacent thereto;
  • a second rupturable container being positioned transverse at least a portion of a leading edge of said photosensitive element so that a compressive force applied to said second container by said pressure-applying members will effect a discharge of said second containers contents between said alkaline solution-permeable support of said photosensitive element and said image-receiving layer; said film unit containing an aromatic primary amino color developing agent; one of said rupturable containers containing an opacifying agent and the other said rupturable container containing an alkaline processing composition.
  • said aromatic primary amino color developing agent is a p-phenylenediamine developing agent which is present in said alkaline processing composition
  • said top sheet is coated with, successively, a pH-lowering layer and an alkaline solutionpermeable polymeric timing layer on the side thereof which is closest to said photosensitive element, said pH-lowering layer being capable of lowering the pH of the film unit subsequent to diffusion therethrough by said alkaline processing composition
  • each said direct positive silver halide emulsion is an internal image emulsion wherein the silver halide forms latent images predominantly inside the silver halide grains.
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:
  • a transparent support coated with an image-receiving layer having thereon a photosensitive element comprising an alkaline solution-permeable support having thereon the following layers in the order recited:
  • a Color-Forming Unit comprising:
  • a developable emulsion layer of a hydrophilic colloid and a water-insoluble metal salt which is developable by an aromatic primary amino color developing agent to substantial density without exposure to light, said metal salt having contiguous thereto a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible cyan dye;
  • a red-sensitive silver halide emulsion layer the silver halide of which has contiguous thereto a nondiffusible development inhibitor-releasing coupler which is capable of reacting with oxidized aromatic primary amino color developing agent to release a diffusible mercaptan development inhibitor which is capable of diffusing imagewise to said adjacent developable emulsion layer to inhibit development therein;
  • an alkaline solution-permeable barrier layer comprising a hydrophilic colloid containing a water-insoluble reactant capable of forming a water-insoluble salt with mercaptans;
  • a Color Forming Unit comprising:
  • a developable emulsion layer of a hydrophilic colloid and a wateninsoluble metal salt which is developable by an aromatic primary amino color developing agent to substantial density without exposure to light, said metal salt having contiguous thereto a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible magenta dye;
  • a green-sensitive silver halide emulsion layer the silver halide of which has contiguous thereto a nondiffusible development inhibitor-releasing coupler which is capable of reacting with oxidized aromatic primary amino color developing agent to release a diffusible mercaptan development inhibitor which is capable of diffusing imagewise to said adjacent developable emulsion layer to inhibit development therein;
  • an alkaline solution-permeable barrier layer comprising a hydrophilic colloid containing a water-insoluble reactant capable of forming a water-insoluble salt with mercaptans;
  • a Color-Forming Unit comprising:
  • a developable emulsion layer of a hydrophilic colloid and a water-insoluble metal salt which is developable by an aromatic primary amino color developing agent to substantial density without exposure to light, said metal salt having contiguous thereto a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible yellow dye;
  • a blue-sensitive silver halide emulsion layer the silver halide of which has contiguous thereto a nondiffusible development inhibitor-releasing coupler which is capable of reacting with oxidized aromatic primary amino color developing agent. to release a diffusible mercaptan development inhibitor which is capable of diffusing imagewise to said adjacent developable emulsion layer to inhibit development therein;
  • each said nondiffusible coupler having the formula:
  • DYE is a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group
  • 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 nondiffusible 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 l 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 first rupturable container being positioned transverse at least a portion of a leading edge of said photosensitive element so that a compressive force applied to said first container by said pressure-applying members will effect a discharge of said first containers contents between said transparent sheet and said underlying blue-sensitive silver halide emulsion layer of said photosensitive element adjacent thereto;
  • a second rupturable container being positioned transverse at least a portion of a leading edge of said photosensitive element so that a compressive force applied to said second container by said pressure-applying members will effect a discharge of said second containers contents between said alkaline solution-permeable support of said photosensitive element and said image-receiving layer; said film unit containing an aromatic primary amino color developing agent; one of said rupturable containers containing an opacifying agent and the other said rupturable container containing an alkaline processing composition.
  • said aromatic primary amino color developing agent is a p-phenylenediamine developing agent which is present in said al' kaline processing composition
  • said developable emulsion is an emulsion of a hydrophilic colloid, silver thiocyanate and physical development nuclei that can be developed to substantial density without exposure to light
  • said transparent sheet is coated with, successively, a pI-I-lowering layer and an alkaline solution-permeable polymeric timing on the side thereof which is closest to said photosensitive element, said pH-lowering layer being capable of lowering the pH of the film unit subsequent to diffusion therethrough by said alkaline processing composition.
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:
  • a transparent support coated with an image-receiving layer having thereon a photosensitive element comprising an alkaline solution-permeable support having thereon the following layers in the order recited:
  • a Color-Forming Unit comprising:
  • a developable emulsion layer of a hydrophilic colloid and a water-insoluble metal salt which is developable by an aromatic primary amino color developing agent to substantial density without exposure to light, said metal salt having contiguous thereto a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible yellow dye;
  • an alkaline solution-permeable barrier layer comprising a hydrophilic colloid containing a water-insoluble reactant capable of forming a water-insoluble salt with mercaptans;
  • a Color-Forming Unit comprising:
  • a developable emulsion layer of a hydrophilic colloid and a water-insoluble metal salt which is developable by an aromatic primary amino color developing agent to substantial density without exposure to light, said metal salt having contiguous thereto a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a dilTusible magenta dye;
  • an alkaline solution-permeable barrier layer comprising a hydrophilic colloid containing a water-insoluble reactant capable of forming a water-insoluble salt with mercaptans;
  • a Color-Forming Unit comprising:
  • a red-sensitive silver halide emulsion layer the silver halide of which has contiguous thereto a nondiffusible development inhibitor-releasing coupler which is capable of reacting with oxidized aromatic primary amino color developing agent to release a diffusible mercaptan development inhibitor which is capable of diffusing imagewise to said adjacent developable emulsion layer to inhibit development therein;
  • a developable emulsion layer of a hydrophilic colloid and a water-insoluble metal salt which is developable by an aromatic primary amino color developing agent to substantial density without exposure to light, said metal salt having contiguous thereto a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible cyan dye; each said nondiffusible coupler having the formula:
  • DYE is a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group
  • 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 nondiffusible 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 solu bilizing group;
  • n is an integer of l 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 first rupturable container being positioned transverse at least a portion of a leading edge of said photosensitive element so that a compressive force applied to said first container by said pressure-applying members will effect a discharge of said first containers contents between said top sheet and the underlying outermost layer of said photosensitive element adjacent thereto;
  • a second rupturable container being positioned transverse at least a portion of a leading edge of said photosensitive element so that a compressive force applied to said second container by said pressure-applying members will effect a discharge of said second containers contents between said alkaline solution-permeable support of said photosensitive element and said image-receiving layer;
  • said film unit containing an aromatic primary amino color developing agent; one of said rupturable containers containing an opacifying agent and the other said rupturable container containing an alkaline processing composition.
  • said aromatic primary amino color developing agent is a p-phenylenediamine developing agent which is present in said alkaline processing composition
  • said developable emulsion is an emulsion of a hydrophilic colloid, silver thiocyanate and physical development nuclei that can be developed to substantial density without exposure to light
  • said top sheet is coated with, successively, a pH-lowering layer and an alkaline solution-permeable polymeric timing layer on the side thereof which is closest to said photosensitive element, said plHl-lowering layer being capable of lowering the pH of the film unit subsequent to diffusion therethrough by said alkaline processing composition.
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising a transparent support coated with an image-receiving layer having thereon a photosensitive element comprising an alkaline solutionperrneable support having thereon the following layers in the order recited:
  • a spacer layer comprising a hydrophilic polymer
  • nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a difiusible magenta dye
  • a spacer layer comprising a hydrophilic polymer
  • nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible yellow dye
  • DYE is a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group
  • 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 nondiffusible 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 l 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 first rupturable container being positioned transverse at least a portion of a leading edge of said photosensitive element so that a compressive force applied to said first container by said pressure-applying members will effect a discharge of said first containers contents between said transparent sheet and said underlying blue-sensitive silver halide emulsion layer of said photosensitive element adjacent thereto;
  • a second rupturable container being positioned transverse at least a portion of a leading edge of said photosensitive element so that a compressive force applied to said second container by said pressure-applying members will effect a discharge of said second containers contents between said alkaline solution-permeable support of said photosensitive element and said image-receiving layer; said film unit containing an aromatic primary amino color developing agent and a silver halide solvent; one of said rupturable containers containing an opacifying agent and the other said rupturable container containing an alkaline processing composition.

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* Cited by examiner, † Cited by third party
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US4028103A (en) * 1976-04-12 1977-06-07 Eastman Kodak Company Processing compositions for color transfer processes comprising alkali metal fluorides and oxalates
US4030920A (en) * 1976-04-12 1977-06-21 Eastman Kodak Company Processing compositions containing glycols for color transfer processes comprising direct positive silver halide developement
US4052214A (en) * 1974-08-26 1977-10-04 Fuji Photo Film Co., Ltd. Color diffusion transfer photographic light-sensitive material for forming both positive transfer dye images and negative dye images
US4060417A (en) * 1974-04-30 1977-11-29 Polaroid Corporation Diffusion transfer elements comprising color-providing compounds capable of cleavage upon reaction with silver ions and silver ion barrier layers
US4154610A (en) * 1974-10-31 1979-05-15 Fuji Photo Film Co., Ltd. Photographic method and film unit
US4183749A (en) * 1977-02-10 1980-01-15 Fuji Photo Film Co., Ltd. Photographic film with polyethylene terephthalate-polyalkylene glycol copolymer support
US4190447A (en) * 1978-01-09 1980-02-26 Eastman Kodak Company Cover sheets for integral imaging receiver elements
US4205987A (en) * 1978-11-15 1980-06-03 Eastman Kodak Company Sulfonamido phenol scavenger compounds
US4272594A (en) * 1978-12-04 1981-06-09 Polaroid Corporation Photographic product including a light-reflecting layer with carbon coated with reflecting material
US4288522A (en) * 1979-01-24 1981-09-08 Agfa-Gevaert N.V. Non-photosensitive receptor material suited for producing black-and-white silver images and dye images and a process for the production of such images therewith
JPS6175348A (ja) * 1984-09-20 1986-04-17 Konishiroku Photo Ind Co Ltd カラ−拡散転写法用感光要素
US6114080A (en) * 1993-12-21 2000-09-05 Eastman Kodak Company Chromogenic black and white imaging for heat image separation

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US2607685A (en) * 1946-10-03 1952-08-19 Polaroid Corp Photographic product comprising a plurality of rupturable containers, each carrying a liquid for processing said product

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* Cited by examiner, † Cited by third party
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US2607685A (en) * 1946-10-03 1952-08-19 Polaroid Corp Photographic product comprising a plurality of rupturable containers, each carrying a liquid for processing said product

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4060417A (en) * 1974-04-30 1977-11-29 Polaroid Corporation Diffusion transfer elements comprising color-providing compounds capable of cleavage upon reaction with silver ions and silver ion barrier layers
US4052214A (en) * 1974-08-26 1977-10-04 Fuji Photo Film Co., Ltd. Color diffusion transfer photographic light-sensitive material for forming both positive transfer dye images and negative dye images
US4154610A (en) * 1974-10-31 1979-05-15 Fuji Photo Film Co., Ltd. Photographic method and film unit
US4028103A (en) * 1976-04-12 1977-06-07 Eastman Kodak Company Processing compositions for color transfer processes comprising alkali metal fluorides and oxalates
US4030920A (en) * 1976-04-12 1977-06-21 Eastman Kodak Company Processing compositions containing glycols for color transfer processes comprising direct positive silver halide developement
USRE29942E (en) * 1976-04-12 1979-03-20 Eastman Kodak Company Processing compositions for color transfer processes comprising alkali metal fluorides
US4183749A (en) * 1977-02-10 1980-01-15 Fuji Photo Film Co., Ltd. Photographic film with polyethylene terephthalate-polyalkylene glycol copolymer support
US4190447A (en) * 1978-01-09 1980-02-26 Eastman Kodak Company Cover sheets for integral imaging receiver elements
US4205987A (en) * 1978-11-15 1980-06-03 Eastman Kodak Company Sulfonamido phenol scavenger compounds
US4272594A (en) * 1978-12-04 1981-06-09 Polaroid Corporation Photographic product including a light-reflecting layer with carbon coated with reflecting material
US4288522A (en) * 1979-01-24 1981-09-08 Agfa-Gevaert N.V. Non-photosensitive receptor material suited for producing black-and-white silver images and dye images and a process for the production of such images therewith
JPS6175348A (ja) * 1984-09-20 1986-04-17 Konishiroku Photo Ind Co Ltd カラ−拡散転写法用感光要素
US6114080A (en) * 1993-12-21 2000-09-05 Eastman Kodak Company Chromogenic black and white imaging for heat image separation

Also Published As

Publication number Publication date
GB1345071A (enrdf_load_stackoverflow) 1974-01-30
DE2136994B2 (enrdf_load_stackoverflow) 1974-03-14
NL7110236A (enrdf_load_stackoverflow) 1972-01-26
CA956831A (en) 1974-10-29
BE770455A (fr) 1971-12-01
AU3160571A (en) 1973-01-25
DE2136994A1 (de) 1972-01-27
FR2103212A5 (enrdf_load_stackoverflow) 1972-04-07

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