US3473925A - Photographic diffusion transfer color process and film unit for use therein - Google Patents

Photographic diffusion transfer color process and film unit for use therein Download PDF

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US3473925A
US3473925A US731399A US3473925DA US3473925A US 3473925 A US3473925 A US 3473925A US 731399 A US731399 A US 731399A US 3473925D A US3473925D A US 3473925DA US 3473925 A US3473925 A US 3473925A
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layer
dye
image
polymeric
silver halide
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Terry W Milligan
Richard W Young
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Polaroid Corp
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Polaroid Corp
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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
    • G03C8/42—Structural details
    • G03C8/44—Integral units, i.e. the image-forming section not being separated from the image-receiving section
    • G03C8/48—Integral units, i.e. the image-forming section not being separated from the image-receiving section characterised by substances used for masking the image-forming section

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  • the present invention relates to photography and, more particularly, to photographic products particularly adapted for employment in photographic diffusion transfer color processes.
  • the primary objects of the present invention are to provide photographic products particularly adapted for employment in diffusion transfer photographic color proccsses; to provide photographic products which comprise a hotosensitive composite structure or laminate which contains a plurality of essential layers including a dimensionally stable layer preferably opaque to actinic radiation, a photosensitive silver halide emulsion layer having a dye image-forming material associated therewith which is soluble and diifusible, in alkali, at a first pH, a permeable polymeric layer dyeable by the dye image-forming material, a polymeric acid layer containing sufficient acidifying groups to effect reduction of a selected processing solution having the first pH to a second pH at which the dye image-forming material is substantially insoluble and nondifiusible, and a dimensionally stable transparent layer; to provide photographic diffusion transfer products comprising a film unit including a photosensitive laminate, of the last-identified type, in combination with rupturable container means separately retaining a first aqueous processing composition containing dispersed therein an opacifying agent and
  • the invention accordingly comprises the product possessing the features, properties and the relation of components and the process involving the several steps and the relation and order of one or more of such steps with respect to each of the others which are exemplified in the States Patent following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • FIGURE 1 is a perspective view of a photographic film unit embodying the invention
  • FIGS. 2, 4 and 6 are diagrammatic enlarged cross-sectional views of the film unit of FIGURE 1, along section line 2-2, illustrating the association of elements during the three illustrated stages of the performance of a diffusion transfer process, for the production of a multicolor transfer image according to the invention, the thickness of the various materials being exaggerated, and wherein FIG. 2 represents an exposure stage, FIG. 4 represents a processing stage and FIG. 6 represents a product of the process; and
  • FIGS. 3, S and 7 are diagrammatic, further enlarged cross-sectional views of the film unit of FIGS. 2, 4 and 6, along section lines 3-3, 55 and 77, respectively, further illustrating, in detail, the arrangement of layers comprising the photosensitive laminate during the three illustrated stages of the transfer process.
  • a photosensitive element containing a dye developer that is, a dye which is a silver halide developing agent, and a silver halide emulsion may be exposed and wetted by a liquid processing composition, for example, by immersion, coating, spraying, flowing, etc., in the dark, and the exposed photosensitive element is superposed prior to, during, or after Wetting, on a sheetlike support element which may be utilized as an image-receiving element.
  • the liquid processing composition is applied to the photosensitive element in a substantially uniform layer as the photosensitive element is brought into superposed relationship with the image-receiving layer.
  • the liquid processing composition positioned intermediate the photosensitive element and the image-receiving layer, permeates the emulsion to initiate development of the latent image contained therein.
  • the dye developer is immobilized or precipitated in exposed areas as a consequence of the development of the latent image. This immobilization is apparently, at least in part, due to a change in the solubility characteristics of the dye developer upon oxidation and especially as regards its solubility in alkaline solutions. It may also be due in part to a tanning effect on the emulsion by oxidized developing agent, and in part to a localized exhaustion of alkali as a result of development.
  • the dye developer In unexposed and partially exposed areas of the emulsion, the dye developer is unreacted and diffusible and thus provides an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition, as a function of the point-to-point degree of exposure of the silver halide emulsion. At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer or element, said transfer substantially excluding oxidized dye developer.
  • the image-receiving element receives a depthwise diffusion, from the developed emulsion, of unoxidized dye developer without appreciably disturbing the imagewise distribution thereof to provide the reversed or positive color image of the developed image.
  • the image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer. If the color of the transferred dye developer is affected by changes in the pH of the image-receiving element, this pH maybe adjusted in accordance with well-known techniques to provide a pH affording the desired color.
  • the desired positive image is revealed by stripping the image-receiving layer from the photosensitive element at the end of a suitable imbibition period.
  • the dye developers are compounds which contain, in the same molecule, both the chromophoric system of a dye and also a silver halide developing function.
  • a silver halide developing function is meant a grouping adapted to develop exposed silver halide.
  • a preferred silver halide development function is a hydroquinonyl group.
  • Other suitable developing functions include ortho-dihydroxyphenyl and orthoand paraamino substituted hydroxyphenyl groups.
  • the development function includes a benzenoid developing function, that is, an aromatic developing group which forms quinonoid or quinone substances when oxidized.
  • Multicolor images may be obtained using color imageforming components such as, for example, the previously mentioned dye developers, in diffusion transfer processes by several techniques.
  • One such technique contemplates obtaining multicolor transfer images utilizing dye devel opers by employment of an integral multilayer photosensitive element, such as is disclosed in the aforementioned U.S. Patent No. 2,983,606, and particularly with reference to FIG. 9 of the patents drawing, wherein at least two selectively sensitized photosensitive strata, superposed on a single support, are processed, simultaneously and without separation, with a single, common imagereceiving layer.
  • a suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stra turn and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, for example, a cyan dye developer, a magenta dye developer and a yellow dye developer.
  • the dye developer may be utilized in the silver halide emulsion layer, for example, in the form of particles, or it may be employed as a layer behind the appropriate silver halide emulsion strata.
  • Each set of silver halide emulsion and associated dye developer strata are disclosed to be optionally separated from other sets by suitable interlayers, for example, by a layer of gelatin or polyvinyl alcohol.
  • suitable interlayers for example, by a layer of gelatin or polyvinyl alcohol.
  • a yellow dye developer of the appropriate spectral characteristics and present in a state capable of functioning as a yellow filter may 'be employed. In such instances, a separate yellow filter may be omitted.
  • the dye developers are preferably selected for their ability to provide colors that are useful in carrying out subtractive color photography, that is, the previously mentioned cyan, magenta and yellow.
  • the dye developers employed may be incorporated in the respective silver halide emulsion or, in the preferred embodiment, in a separate layer behind the respective silver halide emulsion.
  • the dye developer may, for example, be in a coating or layer behind the respective silver halide emulsion and such a layer of dye developer may be applied by use of a coating solution containing about 0.5 to 8%, by weight, of the respective dye developer distributed in a film-forming natural, or synthetic, polymer, for example, gelatin, polyvinyl alcohol, and the like, adapted to be permeated by the chosen diffusion transfer fiuid processing composition.
  • a coating solution containing about 0.5 to 8%, by weight, of the respective dye developer distributed in a film-forming natural, or synthetic, polymer, for example, gelatin, polyvinyl alcohol, and the like, adapted to be permeated by the chosen diffusion transfer fiuid processing composition.
  • imagereceiving elements particularly adapted for employment in diffusion transfer processes of the type disclosed in aforementioned U.S. Patent No. 2,983,606, wherein the imagereceiving elements are separated from contact with a superposed photosensitive element, subsequent to substantial transfer image formation, preferably comprise a support layer possessing on one surface thereof, in sequence, a polymeric acid layer and an image-receiving layer adapted to provide a visible image upon transfer to said layer of diffusible dye image-forming substance, and most preferably include an inert timing or spacer layer intermediate the polymeric acid layer and the image-receiving layer.
  • the polymeric acid layer comprises polymers which contain acid groups, such as carboxylic acid and sulfonic acid groups, which are capable of forming salts with alkali metals, such as sodium potassium etc., or with organic bases, particularly quaternary ammonium bases. such as tetramethyl ammonium hydroxide, or 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 acid polymer contains free carboxyl groups and the transfer processing composition employed contains a large concentration of sodium and/or potassium ions.
  • the acid polymers stated to be most useful are characterized by containing free carboxyl groups, being insoluble in water in the free acid form, and by forming water-soluble sodium and/ or potassium salts.
  • 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 hydrogen succinate hydrogen phthalate; ether and ester derivatives or cellulose modified with sulfoanhydrides, e.g., with ortho-sulfobenzoic anhydride; polystyrene sulfonic acid; carboxymethyl cellulose; polyvinyl hydrogen phthalate; polyvinyl acetate hydrogen phthalate; polyacrylic acid; acetals of polyvinyl alcohol with carboxy or sulfo substituted aldehydes, e.g., 0-, m-, or p-benzaldehyde sulfonic
  • the acid polymer layer is disclosed to contain at least sufficient acid groups to effect a reduction in the pH of the image layer from a pH of about 13 to 14 to a pH of at least 11 or lower at the end of the imbibition period, and preferably to a pH of about 5 to 8 within a short time after imbibition.
  • the pH of the processing composition preferably is of the order of at least 13 to 14.
  • the pH of the image layer is kept as a level of pH 12 to 14 until the dye image has been formed after which the pH is reduced very rapidly to at least about pH 11, and preferably about pH 9 to 10.
  • Unoxidized dye developers containing hydroquinonyl developing radicals diffuse from the negative to the positive as the sodium or other alkali salt.
  • the diffusion rate of such dye image-forming components thus is at least partly a function of the alkali concentration, and it is necessary that the pH of the image layer remain on the order of 12 to 14 until transfer of the necessary quantity of dye has been accomplished.
  • the subsequent pH reduction in addition to its desirable effect upon image light stability, serves a highly valuable photographic function by substantially terminating further dye transfer.
  • the processing technique thus effectively minimizes changes in color balance as a result of longer imbibition times in multicolor transfer processes using multilayer negatives.
  • the acid groups are disclosed to be so distributed in the acid polymer layer that the rate of their availability to the alkali is controllable, e.g., as a function of the rate of swelling of the polymer layer which rate in turn has a direct relationship to the diffusion rate of the alkali ions.
  • the desired distribution of the acid groups in the acid polymer layer may be effected by mixing the acid polymer with a polymer free of acid groups, or lower in concentration of acid groups, and compatible therewith, or by using only the acid polymer but selecting one having a relatively lower proportion of acid groups.
  • the layer containing the polymeric acid may contain a water-insoluble polymer, preferably a cellulose ester, which acts to control or modulate the rate at which the alkali salt of the polymer acid is formed.
  • a water-insoluble polymer preferably a cellulose ester
  • cellulose esters contemplated for use mention is made of cellulose acetate, cellulose acetate butyrate, etc.
  • the particular polymers and combinations of polymers employed in any given embodiment are, of course, selected so as to have adequate wet and dry strength and when necessary or desirable, suitable subcoats may be employed to help the various polymeric layers adhere to each other during storage and use.
  • the inert spacer layer of aforementioned U.S. Patent No. 3,362,819 acts to time control the pH reduction by the polymeric acid layer. This timing is disclosed to be a function of the rate at which the alkali diffuses through the inert spacer layer, It was stated to have been found that the pH does not drop until the alkali has passed through the spacer layer, i.e., the pH is not reduced to any significant extent by the mere diffusion into the interlayer, but the pH drops quite rapidly once the alkali diffuses through the spacer layer.
  • the aforementioned rate at which the cations of the alkaline processing composition, i.e., alkali ions, are available for capture in the polymeric acid layer should be decreased for capture in the polymeric acid layer should be decreased with increasing transfer processing temperatures in order to provide diffusion transfer color processes relatively independent of positive transfer image variations over an extended range of ambient temperatures.
  • the diffusion rate of alkali through a permeable inert polymeric spacer layer increases with increased processing temperature to the extent, for example, that at relatively high transfer processing temperatures, that is, transfer processing temperatures above approximately 80 F, a premature decrease in the pH of the transfer processing composition occurs due, at least in part, to the rapid diffusion of alkali from the dye transfer environment and its subsequent neutralization upon contact with the polymeric acid layer.
  • transfer processing temperatures that is, transfer processing temperatures above approximately 80 F
  • the last-mentioned inert spacer layer was disclosed to provide an effective diffusion barrier timewise preventing effective traverse 0f the inert spacer layer by alkali having temperature depressed diffusion rates and to result in maintenance of the transfer processing environments high pH for such an extended time interval as to facilitate formation of transfer image stain and its resultant degradation of the positive transfer images color definition.
  • acetals of polyvinyl were stated to generally comprise saturated aliphatic hydrocarbon chains of a molecular weight of at least 1000, preferably of about 1000, to 50,000, possessing a degree of acetalation within about 10 to 30%, 10 to 30%, 20 to and 10 to 40%, of the polyvinyl alcohols theoretical polymeric hydroxyl groups, respectively, and including mixed acetals where desired.
  • a mixture of the polymers is to be employed, for example, a mixture of hydroxypropyl methyl cellulose and partial polyvinyl butyral.
  • solution dyeable polymers such as nylons as, for example, N-methoxymethyl polyhexamethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plasticizers; cellulose acetate with filler as, for example, one-half cellulose acetate and one-half oleic acid; gelatin; and other materials of a similar nature.
  • Preferred materials comprise polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine, as disclosed in U.S. Patent No. 3,148,061, issued Sept. 8, 1964.
  • the liquid processing composition referred to for effecting multicolor diffusion transfer processes comprises at least an aqueous solution of an alkaline material, for example, diethylamine, sodium hydroxide or sodium carbonate and the like, and preferably possessing a pH in excess of 12, and most preferably includes a viscosity-increasing compound constituting a film-forming material of the type which, when the composition is spread and dried, forms a relatively firm and relatively stable film.
  • the preferred filmforming materials disclosed comprise high molecular weight polymers such as polymeric, water-soluble ethers which are inert to an alkaline solution such as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose. Additionally, film-forming materials or thickening agents whose ability to increase viscosity is substantially unaffected if left in solution for a long period of time are also disclosed to be capable of utilization.
  • the film-forming material is preferably contained in the processing composition in such suitable quantities as to impart to the composition a viscosity in excess of 100 cps. at a temperature of approximately 24 C. and preferably in the order of 100,000 cps. to 200,000 cps. at that temperature.
  • an image-receiving layer of the type disclosed in that patent need not be separated from its superposed contact with the photosensitive element, subsequent to transfer image formation, if the image-receiving element is transparent and a processing composition containing a substance rendering the dried processing composition layer opaque is spread between the image-receiving layer and the silver halide emulsion or emulsions.
  • the image-receiving element is maintained in contact with the photosensitive element, subsequent to dye developer transfer image formation, and includes the presence of an alkaline processing composition, necessarily having a pH at which dye developer, for example, in reduced form, diffuses to form the dye transfer image, intermediate the elements, the transfer image thus formed is unstable over an extended period of time.
  • the dye image instability is due, at least in part to the presence of What is, in general, a relatively high pH alkaline composition in intimate contact with the dye or dyes forming the image. This contact itself provides instability to the molecular structure of dye by, for example, catalyzing degradation and undesirable structural shifts effecting the spectral absorption characteristics of the image dye.
  • an alkaline composition possessing a pH at which the dye, for example, in reduced form, diffuses
  • an integral dynamic system wherein oxidized dye, immobilized in areas of the photosensitive element, as a function of its development, with the passage of time attempts to generate, in such areas, an equilibrium between oxidized and reduced dye.
  • the pH of the dynamic system is such that diffusion of the reduced form of the dye will occur, such reduced dye will, at least in part, transfer to the image-receiving layer and the resultant dilfusion mill imbalance the equilibrium, in such areas of the photosensitive element, in favor of additional formation of reduced dye.
  • the ultimate result is substantially the same overall image distortion as occurs when the image-receiving layer acts as a dye sink, with the exception that the dye is more extensively distributed throughout the film unit and the ultimate overall dyeing of the image-receiving layer itself is of lower saturation.
  • an integral photographic film unit particularly adapted for the production of a dye transfer image or unexpectedly improved stability and other properties, by a color diffusion transfer process described hereinafter will be constructed to include a photosensitive element comprising a composite structure or laminate having, in sequence as essential layers, a dimensionally stable layer preferably opaque to actinic radiation; a photosensitive silver halide emulsion layer having associated therewith dye image-providing material which is soluble and dilfusible, in alkali, at a first pH; an alkaline solution permeable polymeric layer dyeable by the dye imageproviding material; an alkaline solution permeable polymeric acid layer containing sufiicient acidifying groups to effect reduction, subsequent to substantial transfer dye image formation, of a selected processing solution having the first pH to a second pH at which said dye image-providing material is substantially insoluble and nondilfusible; and a dimensionally stable transparent layer.
  • rupturable container means separately retaining a first aqueous processing composition containing an opacifying agent and a second processing composition containing a reflecting agent, which compositions, taken together, possess the first pH and concentration of opacifying and reflecting agents in a quantity sufficient, upon distribution.
  • a processing composition permeable polymeric sheet transparent in at least those embodiments wherein the first-mentioned dimensionally stable layer is opaque to actinic radiation, is positioned intermediate the dyeable polymeric layer and silver halide emulsion next adjacent, and the container means is specifically adapted to distribute the first processing composition intermediate the silver halide emulsion and polymeric sheet and the second composition intermediate the dyeable polymeric layer and the polymeric sheet.
  • the preferred construction facilitates the substantially simultaneous distribution of the respective processing compositions as substantially separate, individual layers, in the order designated layerwise and specifically required for the practice of the present invention.
  • the preferred construction provides maximum flexibility in terms of processing composition selection, and distribution conditions, in view of the resultant independence of the selected compositions from consideration of the effect of their rheological characteristics upon turbulent intermixing generated in any selected system requiring substantially contemporaneous contiguous distribution.
  • the photosensitive laminate comprises, in order of essential layers, the dimensionally stable opaque layer; at least two selectively sensitized silver halide emulsion strata each having dye image-providing materials of predetermined color associated therewith which are soluble and diffusible, in alkali, at a first pH; the alkaline solution permeable polymeric layer dyeable by the dye image-providing materials; the alkaline solution permeable polymeric acid layer containing sulficient acidifying groups to effect reduction, subsequent to substantial multicolor transfer dye image formation, of a processing composition having the first pH to a second pH, at which the dye imageproviding material is substantially insoluble and nondiffusible; and the dimensionally stable transparent layer.
  • the silver halide emulsions comprising the multicolor photosensitive laminate preferably possess predominant spectral sensitivity to separate regions of the spectrum and each has associated therewith a dye, which is a silver halide developing agent and is, most preferably, substantially soluble in the reduced form only at the first pH, possessing a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion.
  • a dye which is a silver halide developing agent and is, most preferably, substantially soluble in the reduced form only at the first pH, possessing a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion.
  • each of the emulsion strata, and its associated dye is separated from the remaining emulsion strata, and their associated dye, by separate alkaline solution permeable polymeric interlayers and the dyeable polymeric layer is separated from the polymeric acid layer by an alkaline solution permeable polymeric spacer layer, most preferably a polymeric spacer layer having decreasing permeability to alkaline solution with increasing temperature.
  • the silver halide emulsion comprises photosensitive silver halide dispersed in gelatin and is about 0.6 to 6 microns in thickness; the dye itself is dispersed in an aqueous alkaline solution polymeric binder, preferably gelatin, as a separate layer about 1 to 7 microns in thickness; the alkaline solution permeable polymeric interlayers, preferably gelatin, are about 1 to microns in thickness; the alkaline solution permeable and dyeable polymeric layer is transparent and about 0.25 to 0.4 mil. in thickness; the alkaline solution polymeric spacer layer intermediate the dyeable polymeric layer and the polymeric acid layer is transparent and about 0.1 to 0.7 mil.
  • the alkaline solution permeable polymeric acid layer is transparent and about 0.3 to 1.5 mils. in thickness; and each of the dimensionally stable opaque and transparent layers are alkaline solution impermeable and about 2 to 6 mils. in thickness. It will be specifically recognized that the relative dimensions recited above may be appropriately modified, in accordance with the desires of the operator, with respect to the specific product to be ultimately prepared.
  • the preferred dye imageproviding materials comprise dyes which are silver halide developing agents, as stated above, the present invention will be further described hereinafter in terms of such dyes without limitation of the invention to the illustrative dyes.
  • the respective layers comprising the composite structure are secured in fixed relationship which, in whole or in part, may be readily and simply achieved by retaining means such as, for example, a pressure-sensitive tape binding member extending around the edges of the com- 1'9 posite structure securing or maintaining the layers of the composite together at their respective edges.
  • retaining means such as, for example, a pressure-sensitive tape binding member extending around the edges of the com- 1'9 posite structure securing or maintaining the layers of the composite together at their respective edges.
  • the respective silver halide/dye developer units of the photosensitive element will be in the form of a tripack configuration which will ordinarily comprise a cyan dye developer/red-sensitive emulsion unit contiguous the dimensionally stable opaque layer, the yellow dye developer/blue-sensitive emulsion unit most distant from the opaque layer and the magenta dye developer/ green-sensitive emulsion unit intermediate those units, recognizing, that the relative order of such units may be varied in accordance with the desires of the operator.
  • the dimensionally stable polymeric support layer next adjacent the photosensitive silver halide emulsion layer or layers may be transparent and in such instance the photosensitive emulsions may be selectively optimized for exposure by actinic radiation incident on the selected transparent polymeric support layer.
  • Such film units preferably will additionally contain an opaque sheet fixedly positioned, for example, extending transverse a leading edge of the unit, adapted to be superposed on and coextensive with the surface of the transparent support layer opposite the silver halide emulsion layer next adjacent.
  • multicolor transfer images may be provided by processing in the presence of actinic radiation over an extended processing temperature range which exhibit desired maximum and minimum dye transfer image densities; yellow, magenta and cyan dye saturation; red, green and blue hues; and color separation.
  • FIGS. 1 through 7 of the drawings wherein there is illustrated a preferred film unit of the present invention and wherein like numbers, appearing in the various figures, refer to like components.
  • FIGURE 1 sets forth a perspective view of the film unit, designated 10, and each of FIGS. 2 through 7 illustrate diagrammatic crosssectional views of film unit 10, along the stated section lines 22, 3-3, 55 and 7-7, during the various depicted stages in the performance of a photographic diffusion transfer process as detailed hereinafter.
  • Film unit 10 comprises rupturable containers 11 and 11a retaining, prior to processing, aqueous alkaline solutions 12 and 12a, and photosensitive laminate 13 including, in order, dimensionally stable opaque layer 14, preferably an actinic radiation-opaque flexible sheet material; cyan dye developer layer 15; red-sensitive silver halide emulsion layer 16; interlayer 17; magenta dye developer layer 18; green-sensitive silver halide emulsion layer 1?; interlayer 20; yellow dye developer layer 21; blue-sensitive silver halide emulsion layer 22; auxiliary layer 23, which may contain an auxiliary silver halide developing agent; image-receiving layer 24; spacer layer 25; neutralizing layer 26; and dimensionally stable transparent layer 27, preferably an actinic radiation transmissive flexible sheet material.
  • opaque layer 14 preferably an actinic radiation-opaque flexible sheet material
  • cyan dye developer layer 15 red-sensitive silver halide emulsion layer 16; interlayer 17; magenta dye developer layer 18; green-sensitive silver
  • the structural integrity of composite 13 may be maintained, at least in part, by the adhesive capacity exhibited between the various layers comprising the laminate at their opposed surfaces.
  • the adhesive capacity exhibited at an interface intermediate image-receiving layer 24 and the silver halide emulsion layer next adjacent thereto, for example, intermediate image-receiving layer 24 and auxiliary layer 23 as illustrated in FIGS. 2 through 7, should be less than that exhibited at the interface between the opposed surfaces of the remainder of the layers forming the laminate, in order to facilitate distribution of processing solutions 12 and 12a intermediate the stated image-receiving layer 24 and the silver halide emulsion layer next adjacent thereto.
  • the laminates structural integrity may also be enhanced or provided, in whole or in part, by providing a binding member extending around, for example, the edges of laminate 13, and maintaining the layers comprising the laminate intact, except at the interface between layers 23 and 24 during distribution of solutions 12 and 12a intermediate those layers.
  • the binding member may comprise a pressure-sensitive tape 28 securing and/ or maintaining the layers of composite 13 together at its respective edges. Tape 28 will also act to maintain processing solutions 12 and 12a intermediate image-receiving layer 24 and the silver halide emulsion layer next adjacent thereto, upon application of compressive pressure to pods 11 and 11a and distribution of their contents, intermediate the stated layers. Under such circumstances, binder tape 28 will act to prevent leakage of processing composition from the film units laminate during and subsequent to photographic processing.
  • Rupturable containers 11 and 11a may be of any suitable configuration adapted to retain and distribute the processing composition and may comprise, for example, the types shown and described in any of U.S. Patents Nos. 2,543,181; 2,607,685; 2,634,886; 2,653,732; 2,674,- 532; 2,702,146; 2,723,051; 2,750,075; 2,903,829; 2,992,- 102; 3,056,491; 3,056,492; 3,152,515; 3,173,580; 3,221,- 942; and the like.
  • such containers may comprise a rectangular blank of fluidand air-impervious sheet material folded longitudinally upon itself to form two walls 29 which are sealed to one another along their longitudinal and end margins to form a cavity in which 2 processing solutions 12 and 12a are retained.
  • the 1ongitudinal marginal seal 30 is made weaker than the end seals 31 so as to become unsealed in response to the hydraulic pressure generated within the fluid contents 12 and 12a of the containers by the application of compressive pressure to walls 29 of the containers.
  • fluid containers particularly adapted to retain photographic processing compositions may be formed of a plurality of layers including, respectively, an outer layer, for example, kraft paper; a layer of metallic foil, for example, lead foil; and an inner lining, or layer, of a thermoplastic resin, for example, a polyvinyl acetal such as polyvinyl butyral, polyvinyl chloride and the like.
  • the rupturable container means may comprise a single compartmented rupturable container separately retaining the designated processing solutions such as, for example, compartmented rupturable containers of the type set forth in FIG. 8 of US. Patent No. 2,992,102 or the like.
  • Such compartmented rupturable containers may simply employ a polymeric separator sheet effectively separating a rupturable containers single chamber into two separate container chambers sufliciently insulating the opacifying and reflecting agents from admixture and which sheet may extend intermediate and beyond, if transparent and permeable, longitudinal marginal seal to facilitate simultaneous distribution of eacn compartments fluid contents as a functionally separate medium.
  • containers 11 and 11a are fixedly positioned and extend transverse a leading edge of photosensitive laminate 13 whereby to erfect unidirectional discharge of the respective containers contents 12 and 12a, in order, layerwise, between imagereceiving layer 24 and the stated layer next adjacent thereto, upon application of compressive force to containers 11 and 11a.
  • containers 11 and 11a are fixedly positioned and extend transverse a leading edge of laminate 13 with their longitudinal marginal seals 30 and 30a directed towards the interface between image-receiving layer 24 and auxiliary layer 23.
  • container 11a is fixedly secured to laminate 13 by extension 32 of tape 28, extending over a portion of one wall 29 of container 110, and to transparent, processing composition and image dye permeable sheet 36 extending intermediate containers 11 and 11a.
  • Container 11 is, in turn, fixedly secured to laminate 13 by a separate retaining member such as illustrated retaining tape 33, extending over a portion of wall 29 of container 11 and a portion of laminate 13s surface generally equal, in area, to about that covered by tape 28, and to sheet 36 extending intermediate containers 11 and 1101.
  • a separate retaining member such as illustrated retaining tape 33
  • retaining tape 33 extending over a portion of wall 29 of container 11 and a portion of laminate 13s surface generally equal, in area, to about that covered by tape 28, and to sheet 36 extending intermediate containers 11 and 1101.
  • extension flap 32 of tape 28 is preferably of such area and dimensions that upon, for example, manual separation of containers 11 and 11a and tape 33, subsequent to distribution of processing compositions 12 and 12a, from the remainder of film unit 10, flap 32 may be folded over the edge of laminate 13. previously covered by tape 33, in order to facilitate maintenance of the laminates structural integrity, for example. during the flexations inevitable in storage and use of the processed film unit, and to provide a suitable mask or frame, for viewing of the transfer image through the picture viewing area of transparent layer 27.
  • the fluid contents of the containers taken together. comprise an aqueous solution having a pH at which the dye developers are soluble and ditfusible and processing composition 12 contains an opacifying and processrng solution 12a a reflecting agent, taken together. in a quantity suflicient to mask the dye developers associated with the silver halide emulsions subsequent to processing to prevent further exposure of the film units silver halide emulsion or emulsions, by actinic radiation traversing through the dimensionally stable transparent layer, subsequent to distribution of the processing solutions intermediate the dyeable polymeric layer and the stated layer next adjacent thereto.
  • the film unit may be processed, subsequent to distribution of the composition, in the presence of such radiation, in view of the fact that the silver halide emulsion or emulsions of the laminate are appropriately protected by incident radiation, at one major surface by the opaque processing composition and at the remaining major surface by a dimensionally stable opaque layer. If the illustrated binder tapes are also opaque, edge leakage of actinic radiation incident on the emulsion or emulsions will also be prevented.
  • the selected reflecting agent should be one providing a background suitable for viewing the dye developer transfer image formed in the dyeable polymeric layer.
  • a reflecting agent be selected that will not interfere with the color integrity of the dye transfer image, as viewed by the observer, and, most preferably, an agent which is aesthetically pleasing to the viewer and does not provide .t background noise signal degrading, or detracting from,
  • Particularly desirable reflecting agents will be those providing a white background, for viewing the transfer image, and specifically those conventionally employed to provide background for reflection photographic prints and, especially those agents possessing the optical properties desired for reflection of incident radiation.
  • reflecting agents adapted for employment in the practice of the present invention, mention may be made of barium sulfate, zinc oxide, titanium dioxide, barium stearate, silver flake, silicates, alumina, zirconium oxide, zirconium acetyl acetate, sodium zirconium sulfate, kaolin, mica, and the like.
  • a particularly preferred reflecting agent comprises titanium dioxide due to its highly effective reflection properties.
  • a processing composition containing about 40-50 grams of titanium dioxide dispersed in 100 cc. of water will provide a percent refiectance of incident actinic radiation of about 85-90%, respectively.
  • Transparent separator sheet 36 may comprise any of various types of alkaline processing composition permeable rigid or flexible materials includmg polymeric film or sheet, continuous or mesh, planar or corrugated, of both the synthetic type and those derived from naturally occurring products, including specifically polyamides such as nylon, vinyl polymers, for example, polyvinyl alcohol, partially acetylated polyvinyl alcohol, cellulosic polymers, for example, methyl cellulose, hydroxyethyl cellulose, carboxyethyl cellulose, cellulose sulfate, hydroxypropyl cellulose, and the like, which are generally employed in a thickness of about 0.05 to 1.0 mil.
  • polyamides such as nylon
  • vinyl polymers for example, polyvinyl alcohol, partially acetylated polyvinyl alcohol, cellulosic polymers, for example, methyl cellulose, hydroxyethyl cellulose, carboxyethyl cellulose, cellulose sulfate, hydroxypropyl cellulose, and the like
  • Preferred opacifying agent or agents will possess the maximum opacifying capacity per unit weight, be photographically nondeleterious and substantially nondiffusrble during and subsequent to distribution of the processing composition containing same.
  • a particularly preferred opacifying agent has been found to comprise carbon black due to its highly efllcient absorption characteristics.
  • a processing composition particularly desired for employment in the practice of the present invention will contain carbon black in a concentration effective, e.g., about 3 to 6 grams of carbon black dispersed in 100 cc. of water, to prevent transmission, through the distributed stratum comprising the composition, of in excess of 95% of the actinic radiation incident on the stratum.
  • preferred agents are those which remain immobile within their respective compositions during and subsequent to photographic processing and particularly those which comprise insoluble and nondiffusible pigment dispersions within their respective processing solutions.
  • the unit In the performance of a diffusion transfer multicolor process employing film unit 10, the unit is exposed to radiation, actinic to photosensitive laminate 13, incident on the laminates exposure surface 34, as illustrated in FIG. 2.
  • film unit 10 is processed by being passed through opposed suitably gapped rolls 35 in order to apply compressive pressure to frangible containers 11 and 11a and to effect rupture of longitudinal seals 30 and 30a and distribution of alkaline processing compositions 12 and 12a, having a pH at which the cyan, magenta and yellow dye developers are soluble and diflusible, intermediate dyeable polymeric layer 24 and auxiliary layer 23.
  • Alkaline processing solutions 12 and 12a permeate emulsion layers 16, 19 and 22 to initiate development of the latent images contained in the respective emulsions.
  • the cyan, magenta and yellow dye developers, of layers 15, 18 and 21, are immobilized as a function of the development of their respective associated silver halide emulsions, preferably substantially as a result of their conversion from the reduced form to their relatively insoluble and nondiifusible oxidized form, thereby providing imagewise distributions of mobile, soluble and diffusible cyan, magenta and yellow dye developed, as a function of the point-to-point degree of their associated emulsions exposure.
  • At least part of the imagewise distributions of mobile cyan, magenta and yellow dye developer transfers, by diffusion, to aqueous alkaline solution permeable polymeric layer 24 to provide a multicolor dye transfer image to that layer.
  • a sufiicient portions of the ions comprising aqueous alkaline solution 12 transfers, by diffusion, through permeable polymeric layer 24, permeable spacer layer 25 and to permeable polymeric acid layer 26 whereby alkaline solutions 12 and 12a decrease in pH, as a function of neutralization, to a pH at which the cyan, magenta and yellow dye developers, in the reduced form, are insoluble and nondiflusible, to provide thereby a stable multicolor dye transfer image.
  • containers 11 and 11a may be manually dissociated from the remainder of the film unit, as described above, to provide the product illustrated in FIG. 6.
  • processing solution 12 is distributed intermediate sheet 36 and auxiliary layer 23
  • processing solution 12a is distributed intermediate sheet 36 and dyeable polymeric layer 24.
  • processing compositions may be employed possessing rheological properties adapted to maintain substantial integrity of the separate solutions during and subsequent to distribution within the film unit laminate. Specifically, it is desirable that the opacifying agent or agents employed not substantially diffuse into and contaminate the optical effciency of the layer comprising the elected re fleeting agent.
  • Film units similar to that shown in the drawing may be prepared, for example, by coating, in succession, on a gelatin subbed, opaque cellulose triacetate film base, the following layers:
  • a transparent cellulose triacetate film base may be coated, in succession, with the following illustrative layers:
  • the two components thus prepared may then be taped together in laminate form, at their respective edges, with an intermediate sheet of methyl cellulose 0.05 to 1.0 mils. thick, by means of a pressure-sensitive binding tape extending around, in contact with, and over the edges of the resultant laminate.
  • Two separate rupturable containers comprising an outer layer of paper, an intermediate layer of lead foil and an inner liner or layer of polyvinyl chloride and retaining, respectively, an aqueous alkaline processing composition
  • an aqueous alkaline processing composition comprising:
  • each of the laminates may then be fixedly mounted on the leading edge, of each of the laminates, by pressure-sensitive tapes interconnecting the respective containers and laminates, such that upon application of compressive pressure to the containers their contents would be distributed, upon rupture of the respective containers marginal seal, in order, between the 4'-methylphenyl hydroquinone containing layer and the polymeric image-receiving layer, the first solution denoted distributed between the hydroquinone containing 1% layer and the methyl cellulose sheet and the second solution denoted distributed between the image-receiving layer and the methyl cellulose sheet.
  • the photosensitive laminates may then be exposed through step' wedges to selectively filtered radiation in cident on the transparent cellulose triacetate layer and processed, in the presence of actinic radiation, subsequent to passage of the exposed film unit through suitable gapped opposed rolls, to effect rupture of the containers and distribution of their contents.
  • the multicolor dye transfer image formation may be viewed through the transparent cellulose triacetate film base and such image formation is found to be substantially completed and exhibiting the required color brilliance, hues, saturation, and isolation, within a period of approximately 1-2 minutes.
  • the pH of the processing solutions taken together initially employed must be an alkaline pH at which the dye developers employed are soluble and difiusible.
  • the specific pH to be employed may be readily determined empirically for any dye developer, or group of dye developers, most particularly desirable dye developers are soluble at pHs above 9 and relatively insoluble at pHs below 9, in reduced form. and the system can be readily balanced accordingly for such dye developers.
  • the processing compositions, in the preferred embodirnent will include the stated film-forming viscosityincreasing agent, or agents, to facilitate spreading of the compositions and to provide maintenance of the spread compositions as structurally stable layers of the laminate. subsequent to distribution, it is not necessary that such agent be employed as a component of the composition.
  • the concentration of solvent, that is, water etc., comprising the composition be the minimum amount necessary to conduct the desired transfer process, in order not to adversely effect the structural integrity of the laminate and that the layers forming the laminate can readily accom modate and dissipate the solvent throughout during processing and drying without effecting undesirable dimensional changes in the layers forming the laminate.
  • liquid processing composition employed may contain an auxiliary or accelerating developing agent, such as p-methylaminophenol, 2,4-diaminophenol, p-benzylaminophenol, hydroquinone, toluhydroquinone, phenylhydroquinone, 4'-methylphenylhydroquinone, etc. It is also contemplated to employ a plurality of auxiliary or accelerating developing agents, such as a 3-pyrazolidone developing agent and a benzenoid developing agent, as disclosed in U.S. Patent No. 3,039,869, issued June 19, 1962.
  • auxiliary developing agents examples include l-phenyl-3-pyrazolidone in combination with p-benzylaminophenol and 1-phenyl3-pyrazolidone in combination with 2,S-bis-ethylenimino-hydroquinone.
  • auxiliary developing agents may be employed in the liquid processing composition or they may be initially incorporated, at least in part, in any one or more of the silver halide emulsion strata, the strata containing the dye developers, the interlayers, the overcoat layer, the imagereceiving layer, or in any other auxiliary layer, or layers. of the film unit.
  • the dye developer oxidized during development may be oxidized and immobilized as a result of a reaction, e.g., an energy-transfer reaction, with the oxidation product of an oxidized auxiliary developing agent, the latter developing agent being oxidized by the development of exposed silver halide.
  • a reaction e.g., an energy-transfer reaction
  • Such a reaction of oxidized developing agent with unoxidized dye developer would regenerate the auxiliary developing agent for further reaction with the exposed silver halide.
  • the relative proportions of the agents of the diffusion transfer processing compositions may be altered to suit the requirements of the operator.
  • modify the herein described developing compositions by the substitution of preservatives, alkalies, etc., other than those specifically mentioned, provided that the pH of the compositions taken together is initially at the first pH required.
  • components such as restrainers, accelerators, etc.
  • concentration of various components may be varied over a Wide range and when desirable adaptable components may be disposed in the photosensitive element, prior to exposure, in a separate permeable layer of the photosensitive element and/or in the photosensitive emulsion.
  • the dimensionally stable layers referred to may comprise any of various types of conventional opaque and transparent rigid or flexible materials, for example, glass, paper, metal, and polymeric films of both synthetic types and those derived from naturally occurring products.
  • Suitable materiols include alkaline solution impermeable materials such as polymethacrylic acid, methyl and ethyl esters; vinyl chloride polymers; polyvinyl acetal; polyamides such as nylon; polyesters such as polymeric films derived from ethylene glycol terephthalic acid; and cellulose derivatives such as cellulose acetate, triacetate, nitrate, propionate, butyrate, acetate-propionate, or acetatebutyrate.
  • one or more of the designated layers may not be required where the remaining layers of the laminate are such as to provide the functions of these layers in the absence of same, for example, where the remaining layers of the laminate provide the requisite dimensional stability and radiation filtering properties.
  • nitrocarboxyrnethyl cellulose as disclosed in US. Patent No. 2,992,104
  • an acylamidobenzene sulfo ester of a partial sulfobenzal of polyvinyl alcohol as disclosed in US. Patent No. 3,043,692
  • polymers of N-alkyl-oz,fiunsaturated carboxamides and copolymers of N-alkyl-u,,8-carboxamides with N-hydroxyalkyl-c p-unsaturated carboxamides as disclosed in US. Patent No.
  • the preparation of the dye developer dispersion may also be obtained by dissolving the dye in an appropriate solvent, or mixture of solvents, and the resultant solution distributed in the polymeric binder, with optional subsequent removal of the solvent, or solvents, employed, as, for example, by vaporization where the selected solvent, or solvents, possesses a sufficiently low boiling point or washing where the selected solvent, or solvents, possesses a sufficiently high differential solubility in the wash medium, for example, water, when measured against the solubility of the remaining composition components, and/ or obtained by dissolving both the polymeric binder and dye in a common solvent.
  • dye image-providing materials Although the invention has been discussed in detail throughout employing dye developers, the preferred dye image-providing materials, it will be readily recognized that other, less preferred, dye image-providing materials may be substituted in replacement of the preferred dye developers in the practice of the invention.
  • dye image-forming materials such as those disclosed in US. Patents Nos. 2,647,049; issued July 28, 1953; 2,661,293, issued Dec. 1, 1953; 2,698,244, issued Dec. 28, 1954; 2,698,798, issued Jan. 4, 1955; and 2,802,735; issed Aug.
  • color diffusion transfer processes which employ color coupling techniques comprising, at least in part, reacting one or more more color developing agents and one or more color formers or couplers to provide a dye transfer image to a superposed image-receiving layer and those disclosed in US. Patent No. 2,774,668, issued Dec. 18, 1956, wherein color diffusion transfer processes are described which employ the imagewise differential transfer of complete dyes by the mechanisms therein described to provide a transfer dye image to a contiguous image-receiving layer.
  • the silver halide crystals may be prepared by reacting a Watersoluble silver salt, such as silver nitrate, with at least one water-soluble halide, such as ammonium, potassium or sodium bromide, preferably together with a corresponding iodide, in an aqueous solution of a peptizing agent such as a colloidal gelatin solution; digesting the dispersion at an elevated temperature, to provide increased crystal growth; washing the resultant dispersion to remove undesirable reaction products and residual water-soluble salts by chilling the dispersion, noodling the set dispersion, and washing the noodles with cold water, or alternatively, employing any of the various flocc systems, or procedures, adapted to effect removal of undesired components, for example, the procedures described in US.
  • a Watersoluble silver salt such as silver nitrate
  • water-soluble halide such as ammonium, potassium or sodium bromide
  • a peptizing agent such as a colloidal gelatin solution
  • Optical sensitization of the emulsions silver halide crystals may be accomplished by contact of the emulsion composition with an effective concentration of the selected optical sensitizing dyes dissolved in an appropriate dispersing solvent such as methanol, ethanol, acetone, water, and the like; all according to the traditional procedures of the art, as described in Hammer, F.M., The Cyanine Dyes and Related Compounds.
  • an appropriate dispersing solvent such as methanol, ethanol, acetone, water, and the like
  • Additional optional additives such as coating aids, hardeners, viscosity-increasing agents, stabilizers, preservatives, and the like, for example, those set forth hereinafter, also may be incorporated in the emulsion formulation, according to the conventional procedures known in the photographic emulsion manufacturing art.
  • the photoresponsive material of the photographic emulsion will, as previously described, preferably comprise a crystal of silver, for example, one or more of the silver halides such as silver chloride, silver iodide, silver bromide, or mixed silver halides such as silver chlorobromide or silver iodobromide, of varying halide ratios and varying silver concentrations.
  • the silver halides such as silver chloride, silver iodide, silver bromide, or mixed silver halides such as silver chlorobromide or silver iodobromide, of varying halide ratios and varying silver concentrations.
  • the emulsions may include the various adjuncts, or addenda, according to the techniques disclosed in the art, such as speed-increasing compounds of the quaternary ammonium type, as described in U.S. Patents Nos. 2,271,- 623; 2,288,226; and 2,334,864; or of the polyethyleneglycol type, as described in U.S. Patent No. 2,708,162; or of the preceding combination, as described in U.S. Patent No. 2,886,437; or the thiopolymers, as described in U.S. Patents Nos. 3,046,129 and 3,046,134.
  • the emulsions may also be stabilized with the salts of the noble metals such as ruthenium, rhodium, palladium, iridium and platinum, as described in U.S. Patents Nos. 2,566,245 and 2,566,263; the mercury compounds of U.S. Patents Nos. 2,728,663; 2,728,664 and 2,728,665; the triazoles of U.S. Patent No. 2,444,608; the azaindines of U.S. Patents NOS.
  • the noble metals such as ruthenium, rhodium, palladium, iridium and platinum
  • Hardening agents such as inorganic agents providing polyvalent metallic atoms, specifically polyvalent aluminum or chromium ions, for example, potash alum and chrome alum [K Cr (SO -24H O] and organic agents of the aldehyde type, such as formaldehyde, glyoxal, mucochloric, etc.; the ketone type such as diacetyl; the quinone type; and the specific agents described in U.S. Patents Nos. 2,080,019; 2,725,294; 2,725,295; 2,725,305; 2,726,162; 2,732,316; 2,950,197; and 2,870,013, may be incorporated, where desired and compatible, in the selected coating solution compositions.
  • inorganic agents providing polyvalent metallic atoms specifically polyvalent aluminum or chromium ions
  • organic agents of the aldehyde type such as formaldehyde, glyoxal, mucochloric, etc.
  • the ketone type
  • Coating solution compositions employed to fabricate the respective strata of the film unit may contain one or more coating aids, where desired and compatible, such as saponin; a polyethyleneglycol of U.S. Patent No. 2,831,- 766; a polyethyleneglycol ether of U.S. Patent No. 2,- 719,087, a taurine of U.S. Patent No. 2,739,891; a maleopimarate of U.S. Patent No. 2,823,123; and amino acid of U.S. Patent No. 3,038,804; a sulfosuccinamate of U.S. Patent No. 2,992,108; or a polyether of U.S. Patent No.
  • coating aids such as saponin; a polyethyleneglycol of U.S. Patent No. 2,831,- 766; a polyethyleneglycol ether of U.S. Patent No. 2,- 719,087, a taurine of U.S. Patent No. 2,739,891;
  • the aforementioned gelatin may be, in whole or in part, replaced with some other colloidal material such as albumin; casein; or zein; or resins such as a cellulose derivative, as described in U.S. Patents Nos. 2,322,085 and 2,327,808; polyacrylamides, as described in U.S. Patent No. 2,541,- 474; vinyl polymers such as described in U.S. Patents 20 Nos.
  • some other colloidal material such as albumin; casein; or zein
  • resins such as a cellulose derivative, as described in U.S. Patents Nos. 2,322,085 and 2,327,808; polyacrylamides, as described in U.S. Patent No. 2,541,- 474; vinyl polymers such as described in U.S. Patents 20 Nos.
  • the photosensitive component of the film unit may comprise at least two sets of selectively sensitized minute photosensitive elements arranged in the form of a photosensitive screen wherein each of the minute photosensitive elements has associated therewith, for example, an appropriate dye developer in or behind its respective silver halide emulsion portion.
  • a suitable photosensitive screen will comprise minute red-sensitized emulsion elements, minute green-sensitized emulsion elements and minute blue-sensitized emulsion elements arranged in side-by-side relationship in a screen pattern and having associated therewith, respectively, a cyan, a magenta and a yellow dye developer.
  • the present invention also includes the employment of a black dye developer and the use of a mixture of dye developers adapted to provide a black and white transfer image, for example, the employment of dye developers of the three subtractive colors in an appropriate mixture in which the quantities of the dye developers are proportioned such that the colors combine to provide black.
  • the expression positive image has been used, this expression should not be interpreted in a restrictive sense since it is used primarily for purposes of illustration, in that it defines the image produced on the image-carrying layer as being reversed, in the positive-negative sense, with respect to the image in the photosensitive emulsion layers.
  • the expression positive image assume that the photosensitive element is exposed to actinic light through a negative transparency. In this case, the latent image in the photosensitive emulsion layers will be a positive and the dye image produced on the image-carrying layer will be a negative.
  • the expression positive image is intended to cover such an image produced on the imagecarrying layer.
  • the transfer image formed upon direct exposure of the film unit to a selected subject and processing will be a geometrically reversed image of the subject. Accordingly, to provide transfer image formation geometrically nonreversed, exposure of the film unit should be accomplished through an image reversing optical system such as a camera possessing image reversing optics.
  • the film unit may also contain one or more subcoats or layers, which, in turn, may contain one or more additives such as plasticizers, intermediate essential layers for the purpose, for example, of improving adhesion, and that any one or more of the described layers may comprise a composite of two or more strata of the same, or different, components and which may be contiguous, or separated from, each other, for example, two or more neutralizing layers or the like, one of which may be disposed intermediate the cyan dye image-forming component retaining layer and the dimensionally stable opaque layer.
  • additives such as plasticizers, intermediate essential layers for the purpose, for example, of improving adhesion
  • any one or more of the described layers may comprise a composite of two or more strata of the same, or different, components and which may be contiguous, or separated from, each other, for example, two or more neutralizing layers or the like, one of which may be disposed intermediate the cyan dye image-forming component retaining layer and the dimensionally stable opaque layer.
  • a photographic film unit which is adapted to be processed by passing said unit between a pair or" juxtaposed pressure-applying members and which includes, in combination:
  • a photosensitve element comprising a compo-site structure containing, as essential layers, in sequence, a first dimensionally stable support layer, a photosensitive silver halide emulsion layer having associated therewith a dye image-providing material which is soluble and diflusible, in alkali, at a first pH, an alkaline solution permeable polymeric layer dyeable by said dye image-providing material, an alkaline solution permeable polymeric acid layer containing suflicient acidifying groups to effect reduction of a processing composition having said first pH to a second pH at which said dye image-providing material is substantially insoluble and nondiffusible, a second dimensionally stable support layer, transparent to ctinic radiation and means securing said layers in fixed relationship, and
  • rupturable container means separately retaining first and second aqueous processing compositions, said first composition containing dispersed therein an opacifying agent and said second composition containing dispersed therein a reflecting agent, fixedly positioned and extending transverse a leading edge of said photosensitive element to effect unidirectional discharge of said first and second compositions, in order, layerwise, intermediate the emulsion layer and dyeable polymeric layer next adjacent said first and second compositions, taken together, possessing said first pH and said opacifying and reflecting agents, taken together, present in a quantity sufficient, upon distribution, to mask dye image-providing material associated with said emulsion layer and to prevent exposure of said emulsion layer during processing in the presence of radiation actinic thereto and incident on said second support layer.
  • a photographic film unit as defined in claim 1 including an alkaline solution permeable polymeric sheet extending intermediate said dyeable polymeric layer and said photosensitive silver halide emulsion layer next adjacent and said rupturable container means mounted to eliect unidirectional discharge of said first composition intermediate said polymeric sheet and the photosensitive silver halide emulsion layer next adjacent and said second composition intermediate said polymeric sheet and the dyeable polymeric layer next adjacent.
  • a photographic film unit as defined in claim 9 wherein said film-forming polymeric material is hydroxyethyl cellulose.
  • a photographic film unit as defined in claim 2, which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members and which includes, in combination:
  • a photosensitive element comprising a composite structure containing, as essential layers, in sequence, a dimensionally stable alkaline solution impermeable opaque layer, at least two selectively sensitized silver halide emulsion layers each having a dye, which dye is a silver halide developing agent, of predetermined color associated therewith, each of said dyes soluble and diflusible, in alkali, at a first pH, an alkaline solution permeable transparent polymeric sheet, an alkaline solution permeable transparent polymeric layer dyeable by said dyes, an alkaline solution permeable transparent polymeric acid layer containing suflicient acidifying groups to effect reduction of a processing solution having said first pH to a second pH at which said dyes are substantially insoluble and nondii fusible, a dimensionally stable alkaline solution impermeable transparent layer, and means securing said layers in fixed relationship, and
  • rupturable container means separately retaining first and second aqueous processing compositions, said first composition containing dispersed therein a substantially nondiflusible opacifying agent and said second composition containing dispersed therein a substantially nondifiusible reflecting agent, fixedly positioned and extending transverse a leading edge of said photosensitive element to effect unidirectional discharge of said first composition intermediate said photosensitive emulsion layer and transparent polymeric sheet and said second composition intermediate said dyeable polymeric layer and said transparent polymeric sheet, said first and second compositions, taken together, possessing said first pH and said opacifying and reflecting agents, taken together, present in a concentration sufficient, upon distribution, to mask dye material associated with said emulsion layer and to prevent exposure of said emulsion layer during processing in the presence of radiation actinic thereto and incident on said dimensionally stable transparent layer.
  • each of said selectively sensitized photosensitive silver halide emulsion layers has predominant spectral sensitivity to separate regions of the spectrum and the dye associated with each of said silver halide emulsion layers possesses a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion layer.
  • each of said silver halide emulsion layers and its associated dye is separated from the next adjacent silver halide emulsion layer and its associated dye by an alkaline solution permeable polymeric interlayer.
  • a photographic film unit as defined in claim 12, which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members and which comprises, in combination:
  • a photosensitive element including a composite structure containing, as essential layers, in sequence, a dimensionally stable alkaline solution impermeable opaque layer, an alkaline solution permeable polymeric layer containing cyan dye, a red-sensitive silver halide emulsion layer, an alkaline solution permeable polymeric layer containing magenta dye, a green-sensitive silver halide emulsion layer, an alkaline solution permeable polymeric layer containing yellow dye, a blue-sensitive silver halide emulsion layer, each of said cyan, magenta and yellow dyes being silver halide developing agents and being soluble and difiusible, in alkali, at a first pH, an alkaline solution permeable transparent polymeric sheet, an alkaline solution permeable transparent polymeric layer dyeable by said dyes, an alkaline solution permeable transparent polymeric acid layer containing suflicient acidifying groups to effect reduction of a processing solution having said first pH to a second pH at which said dyes are substantially
  • rupturable container means separately retaining first and second aqueous processing compositions, said first composition containing dispersed therein an opacifying agent and said second composition containing dispersed therein a reflecting agent, adapted to eflect unidirectional discharge of said first composition intermediate said blue-sensitive silver halide emulsion layer and said transparent polymeric sheet and said second composition intermediate said dyeable polymeric layer and said polymeric sheet, said first and second compositions, taken together, present in a quantity sufiicient upon distribution to mask said dyes associated with said emulsion layers and to prevent exposure of said emulsion layers during processing in the presence of radiation actinic thereto and incident on said dimensionally stable transparent layer.
  • a process of forming transfer images in color which comprises, in combination, the steps of:
  • sential layers in sequence, a dimensionally stable layer, a photosensitive silver halide emulsion layer having associated therewith dye image-providing material which is soluble and diifusible, in alkali, at a first pH, an alkaline solution permeable polymeric layer dyeable by said image-providing material, an alkaline solution permeable polymeric acid layer containing sufiicient acidifying groups to eifect reduction of a processing solution having said first pH to said second pH at which said dye imageproviding material is substantially insoluble and nondiflusible, a dimensionally stable transparent layer, and means securing said layers in fixed relationship, and
  • rupturable container means separately retaining first and second aqueous processing compositions, said first composition containing dispersed therein an opacifying agent and said second composition containing dispersed therein a reflecting agent, fixedly positioned and extending transverse a leading edge of said photosensitive element to effect unidirectional discharge of said first and second compositions, in order, layerwise, intermediate the emulsion layer and adjacent dyeable polymeric layer, said first and second compositions, taken together, possessing said first pH and said opacifying and reflecting agents, taken together, present in a concentration effective, upon distribution, to mask dye imageforming material associated with said emulsion layer and to prevent exposure of said emulsion layer during processing in the presence of radiation actinic thereto and incident on said dimensionally stable transparent layer;
  • a process as defined in claim 19 including the step of separating said container means from said composite structure subsequent to substantial transfer image formation.
  • said dye image-providing material is a dye which is a silver halide developing agent.
  • a process of forming transfer images, in color, as defined in claim 19 which comprises, in combination, the steps of:
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members and which includes, in combination, a photosensitive element comprising a composite structure containing, as essential layers, in sequence, a dimensionally stable opaque layer, at least two selectively sensitized silver halide emulsion layers, each of said sllver halide emulsions having associated therewith a dye,
  • rupturable container means separately retaining first and second aqueous processing compositions, said first composition containing dispersed therein an opacifying agent and said second composition containing dispersed therein a reflected agent, fixedly positioned and extending transverse a leading edge of said photosensitive element to effect unidirectional discharge of said first composition intermediate the emulsion layer and adjacent transparent polymeric sheet and said second composition intermediate the dyeable polymeric layer and the transparent polymeric sheet, said first and second compositions, taken together, possessing said first pH and said opacifying and reflecting agents taken together, present in a concentration effective upon distribution to mask dye image-forming material associated with said emulsion layer and to further exposure of said emulsion layer during processing in the presence of radiation actinic thereto and incident on said dimensionally stable transparent layer;
  • each of said selectively sensitized silver halide emulsion strata has predominant spectral sensitvity to a separate region of the spectrum and the dye associated with each of said emulsion strata has a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion.
  • a process of forming transfer images in color which comprises, in combination, the steps of:
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members and which includes, in combination, a photosensitive element comprising a composite structure containing, as essential layers, in sequence, a dimensionally stable alkaline solution impermeable opaque layer, an alkaline solution permeable polymeric layer containing cyan dye, a red-sensitive silver halide emulsion layer, an alkaline solution permeable polymeric layer containing magenta dye, a green-sensitive silver halide emulsion layer, an alkaline solution permeable polymeric layer containing yellow dye, a blue-sensitive silver halide emulsion layer, each of said cyan, magenta and yellow dyes being silver halide developing agents and being soluble and difiusible, in alkali, at a first pH, an alkaline solution permeable transparent polymeric sheet, an alkaline solution permeable transparent polymeric layer dyeable by each of said dyes, an alkaline solution per
  • rupturable container means separately retaining first and second aqueous processing compositions, said first composition containing dispersed therein an opacifying agent and said second composition containing dispersed therein a reflecting agent, fixedly positioned and extending transverse a leading edge of said photosensitive element to effect unidirectional discharge of said first composition intermediate said emulsion layer and said transparent polymeric sheet and said second composition intermediate said dyeable polymeric layer and said transparent polymeric sheet, said first and second compositions, taken together, possessing said first pH and said opacifying and reflecting agents, taken together, present in a concentration effective, upon distribution, to mask dye image-forming material associated with said emulsion layer and to prevent exposure of said emulsion layer during processing in the presence of radiation actinic thereto and incident on said dimensionally stable transparent layer;

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US731399A 1968-05-23 1968-05-23 Photographic diffusion transfer color process and film unit for use therein Expired - Lifetime US3473925A (en)

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Application Number Title Priority Date Filing Date
US731399A Expired - Lifetime US3473925A (en) 1968-05-23 1968-05-23 Photographic diffusion transfer color process and film unit for use therein

Country Status (7)

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US (1) US3473925A (enrdf_load_stackoverflow)
JP (1) JPS4839734B1 (enrdf_load_stackoverflow)
BE (1) BE733539A (enrdf_load_stackoverflow)
DE (1) DE1926549C3 (enrdf_load_stackoverflow)
FR (1) FR2009217A1 (enrdf_load_stackoverflow)
GB (1) GB1234532A (enrdf_load_stackoverflow)
NL (1) NL165305C (enrdf_load_stackoverflow)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647441A (en) * 1969-03-06 1972-03-07 Polaroid Corp Photographic apparatus and method
US3652281A (en) * 1968-07-15 1972-03-28 Polaroid Corp Photographic film unit
US3661585A (en) * 1970-01-19 1972-05-09 Polaroid Corp Photographic diffusion transfer color process and film unit for use therein
DE2222235A1 (de) * 1971-05-05 1972-11-16 Polaroid Corp Verfahren zum Herstellen photographischer Selbstentwicklerfilmverbaende
JPS4845226A (enrdf_load_stackoverflow) * 1971-03-15 1973-06-28
JPS5063926A (enrdf_load_stackoverflow) * 1972-11-03 1975-05-30
JPS5542373B1 (enrdf_load_stackoverflow) * 1970-06-18 1980-10-30
US6565271B1 (en) * 2002-09-20 2003-05-20 Polaroid Corporation Self-developing film assemblages
US6671032B2 (en) 2000-07-07 2003-12-30 Polaroid Corporation Simplified self-developing film assemblages and methods of making the same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3778271A (en) * 1971-10-22 1973-12-11 Polaroid Corp Photographic products comprising an opacifying agent in association with a reflecting agent
JPS5729630U (enrdf_load_stackoverflow) * 1980-07-25 1982-02-16

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2647049A (en) * 1947-02-25 1953-07-28 Polaroid Corp Photographic element for color photography and a process of producing multicolor pictures
US2977226A (en) * 1956-10-09 1961-03-28 Polaroid Corp Photographic process, product and apparatus

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2647049A (en) * 1947-02-25 1953-07-28 Polaroid Corp Photographic element for color photography and a process of producing multicolor pictures
US2977226A (en) * 1956-10-09 1961-03-28 Polaroid Corp Photographic process, product and apparatus

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3652281A (en) * 1968-07-15 1972-03-28 Polaroid Corp Photographic film unit
US3647441A (en) * 1969-03-06 1972-03-07 Polaroid Corp Photographic apparatus and method
US3661585A (en) * 1970-01-19 1972-05-09 Polaroid Corp Photographic diffusion transfer color process and film unit for use therein
JPS5542373B1 (enrdf_load_stackoverflow) * 1970-06-18 1980-10-30
JPS4845226A (enrdf_load_stackoverflow) * 1971-03-15 1973-06-28
DE2222235A1 (de) * 1971-05-05 1972-11-16 Polaroid Corp Verfahren zum Herstellen photographischer Selbstentwicklerfilmverbaende
JPS5063926A (enrdf_load_stackoverflow) * 1972-11-03 1975-05-30
US6671032B2 (en) 2000-07-07 2003-12-30 Polaroid Corporation Simplified self-developing film assemblages and methods of making the same
US6565271B1 (en) * 2002-09-20 2003-05-20 Polaroid Corporation Self-developing film assemblages

Also Published As

Publication number Publication date
JPS4839734B1 (enrdf_load_stackoverflow) 1973-11-27
NL6907943A (enrdf_load_stackoverflow) 1969-11-25
DE1926549C3 (de) 1973-10-18
DE1926549B2 (de) 1973-04-05
NL165305C (nl) 1981-03-16
BE733539A (enrdf_load_stackoverflow) 1969-11-24
DE1926549A1 (de) 1970-06-11
GB1234532A (enrdf_load_stackoverflow) 1971-06-03
FR2009217A1 (enrdf_load_stackoverflow) 1970-01-30
NL165305B (nl) 1980-10-15

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