US3647434A - Integral negative/positive color diffusion transfer process film unit employing in situ generated visible light-reflecting agent - Google Patents

Integral negative/positive color diffusion transfer process film unit employing in situ generated visible light-reflecting agent Download PDF

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US3647434A
US3647434A US43741A US3647434DA US3647434A US 3647434 A US3647434 A US 3647434A US 43741 A US43741 A US 43741A US 3647434D A US3647434D A US 3647434DA US 3647434 A US3647434 A US 3647434A
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layer
silver halide
laminate
dye
halide emulsion
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Edwin H Land
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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
    • G03C8/42—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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  • photographic products particularly adapted for employment W in diffusion transfer color processes; to provide photographic products which comprise a photosensitive laminate which contains a plurality of layers including a dimensionally stable common support carrying on one surface a dyeable polymeric layer and a photosensitive silver halide emulsion layer having a dye image-forming material which is processing composition diffusible, as a function of the point-to-point degree of the emulsions exposure to actinic radiation, and a layer permeable to processing composition solubilized dye image-forming material comprising visible light-reflecting agent precursor in a concentration sufficient to mask dye image-forming material associated with the photosensitive silver halide emulsion layer subsequent to and as a function of processing, positioned intermediate the dyeable polymeric layer and the photo
  • 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 following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • FIGS. I, 2 and 3 are diagrammatic enlarged cross-sectional views of one embodiment of the photographic film unit of the present invention illustrating the association of elements during the three illustrated stages of the performance of a difiusion 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. 1, represents an exposure stage, FIG. 2 represents a processing stage and FIG. 3 represents a product of the process;
  • FIG. 4 is a perspective view of a second embodiment of the photographic film unit of the present invention.
  • FIGS. 5, 7 and 9 are diagrammatic enlarged cross-sectional views of a first film unit of FIG. 4, along section line AA, illustrating the association of elements during the three illustrated stages of the performance of a multicolor diffusion transfer process according to the invention, the thickness of the various materials being exaggerated, and wherein FIG. 5 represents an exposure stage, FIG. 7 represents a processing stage and FIG. 9 represents a product of the process;
  • FIGS. 6, 8 and 10 are diagrammatic, further enlarged crosssectional views of the film unit of FIGS. 5, 7 and 9; along section lines 6-6, 88 and I0l0, respectively, further illustrating, in detail, the arrangement of layers comprising the photosensitive composite structure during the three illustrated stages of the transfer process;
  • FIGS. ll, 13 and 15 are diagrammatic enlarged cross-sectional views of a second film unit of FIG. 4, along section line A-A, illustrating the association of elements during the three illustrated stages of the performance of a multicolor diffusion transfer process according to the invention, and wherein FIG. 11 represents an exposure stage, FIG. I3 represents a processing stage and FIG. 15 represents a product of the process; and
  • FIGS. 12, 14 and 16 are diagrammatic, further enlarged cross-sectional views of the film unit of FIGS. 11, I3 and 15 along section lines 12-12, l4I4 and 16-16, respectively, further illustrating, in detail, the arrangement of layers comprising the photosensitive composite structure 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 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 imagereceiving 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 imagereceiving 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 may be 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 para-amino 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 image-fon'ning 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 developers by employment of an integral multilayer photosensitive element, such as is disclosed in the aforementioned U.S. Pat. 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 sin gle, common image-receiving layer.
  • a suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum 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 thesilver 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 percent, 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 fluid processing composition.
  • a coating solution containing about 0.5 to 8 percent, 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 fluid processing composition.
  • solution dyeable polymers such as nylon 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. Pat. No. 3,148,06l, 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 film-forming 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.
  • 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 I00 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 processing composition layer opaque is spread between the image-receiving layer and the silver halide emulsion or emulsions.
  • 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 diffusion will 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 of unexpectedly improved stability and other properties, by a color diffusion transfer process will be constructed, for example, in accordance with aforementioned U.S. Pat. No. 3,415,644, to include a photosensitive element comprising a laminate having, in sequence, as essential layers, a dimensionally stable opaque layer; a photosensitive silver halide emulsion layer having associated therewith dye image-providing material which is soluble and diffusible, in alkali, at a first pH; an alkaline solution permeable polymeric layer dyeable by the dye image-providing material; a polymeric acid layer containing sufficient 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 insoluble and nondiffusible; and a dimensionally stable transparent layer.
  • a rupturable container retaining an aqueous alkaline processing composition having the first pH and containing an opacifying agent, in a quantity sufficient to mask the dye image-providing material, is fixedly positioned and extends transverse a leading edge of the laminate whereby to effect unidirectional discharge of the containers contents between the alkaline solution permeable and dyeable polymeric layer and the photosensitive silver halide emulsion layer next adjacent thereto, upon application of compressive force to the container.
  • the dimensionally stable polymeric support layer next adjacent the photosensitive silver halide emulsion layer or layers may be transparent, as disclosed in aforementioned U.S. Pat. No. 3,415,646, and that in such instance the opacifying agent may be initially dispersed in the composite film unit intermediate the dyeable polymeric layer and the silver halide emulsion layer next adjacent, as disclosed in aforementioned U.S. Pat. No. 3,415,645.
  • Film units fabricated in accordance with the parameters set forth above specifically disclose the presence of the stated polymeric acid component to effect in situ process adjustment of the film units operational pH range.
  • the film units require the presence of a polymeric acid layer such as, for example, of the type set forth in U.S. Pat. No. 3,362,819 which, most preferably, includes the presence of an inert timing or spacer layer intermediate the acid containing layer carried on a support and the imagereceiving layer.
  • a polymeric acid layer such as, for example, of the type set forth in U.S. Pat. No. 3,362,819 which, most preferably, includes the presence of an inert timing or spacer layer intermediate the acid containing layer carried on a support and the imagereceiving layer.
  • the polymeric acid layer comprises polymers which contains acid materials, such as integral 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-reacting group is, of course, restrained from the acid polymer layer.
  • 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 watersoluble sodium and/or potassium salts.
  • dibasic acid halfester derivatives of cellulose which derivatives contain frec 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 acid
  • the pH of the processing composition preferably is of the order of at least 12 to 14.
  • 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 12 to 14 to a pH of at least 1 l 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, thus requiring, of course, that the action of the neutralizing acid be accurately so controlled as not to interfere with either development of the negative or image transfer of unoxidized dye developers.
  • 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 material in the acid polymer layer may be effected by mixing an 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,
  • These embodiments are illustrated, respectively, in the cited copending application, by (a)'a mixture of cellulose acetate and cellulose acetate hydrogen phthalate and (b) a cellulose acetate hydrogen phthalate polymer having a much lower percentage of phthalyl groups than the first-mew tioned cellulose acetate hydrogen phthalate.
  • 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 are employed to help the various polymeric-layers adhere to each other during storage and use.
  • the acid polymeric layer may be disposed within the photosensitive element of the film unit intermediate that elements support and next adjacent photosensitive silver halide emulsion layer and associated dye image-providing material, with the optional presence of a spacer or timing layer intermediate the acid layer and next adjacent silver halide emulsion layer.
  • the inert spacer layer of the last-mentioned patent 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 is there 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.
  • an integral photographic film unit of simplified construction and particularly adapted for the production of dye transfer images of desirable properties by a color diffusion transfer process will be constructed to include a photosensitive element comprising a laminate structure possessing, as essential layers: a dimensionally stable common support carrying on one surface a photosensitive silver halide emulsion layer having associated therewith a dye image-forming material which is soluble and diffusible in processing composition as a function of the point-to-point degree of exposure of the photosensitive silver halide emulsion layer to incident actinic radiation; a layer permeable to processing composition diffusible dye image-forming material which comprises a reflecting agent precursor present in a concentration sufficient to mask dye image-forming material associated with the photosensitive silver halide emulsion layer subsequent to and as a function of processing; and a polymeric layer dyeable by the dye imageforming material.
  • the dimensionally stable common support is opaque and the photosensitive silver halide emulsion layer is positioned intermediate the support and the dyeable polymeric layer and the transfer image is viewed at the surface of the laminate opposite the opaque support subsequent to processing of the film unit.
  • the dimensionally stable common support is transparent and the dyeable polymeric layer is positioned intermediate the support and the photosenstive silver halide emulsion layer, where it is intended that the dye transfer image be viewed through the support and/or the image residing in the photosensitive silver halide emulsion layer be viewed at the surface of the laminate opposite the support, subsequent to processing, or the photosensitive silver halide emulsion layer is positioned intermediate the support and the dyeable polymeric layer, where it is intended that the dye transfer image be viewed at the surface of the laminate and/or the image residing in the photosensitive silver halide emulsion layer, subsequent to processing, be viewed through the support.
  • the film unit is specifically adapted to provide for the production of a multicolor dye transfer image and the photosensitive laminate comprises, as essential layers, at least two selectively sensitized silver halide emulsion strata each having dye imageproviding materials of predetermined color associated therewith which are soluble and diffusible in processing composition as a function of the point-to-point degree of exposure of the respective associated silver halide emulsion strata; a polymeric layer permeable by processing composition solubilized dye image-providing materials which contains a reflecting agent precursor in a quantity sufficient to mask the dyeimageproviding materials associated with the sensitized silver halide emulsion strata subsequent to and as a function of processing; a polymeric layer dyeable by the dye image-providing material; and the dimensionally stable common support layer.
  • the preferred dye image-providing materials comprise dyes which are silver halide developing agents, as stated above, for purposes of simplicity and clarity, the present invention will be further described hereinafter in terms of such dyes, without limitation of the invention to the illustrative dyes denoted, and, in addition the photographic film unit structure will be detailed hereinafter employing preferred structural embodiments, without limitation of the invention to the preferred structures denoted.
  • 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 a first pH possessing, subsequent to processing, 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 processing solution permeable polymeric interlayers.
  • 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 processing solution permeable polymeric binder, preferably gelatin, as a separate layer about 1 to 7 microns in thickness; the processing solution permeable polymeric interlayers, preferably gelatin, are about 1 to 5 microns in thickness; the processing solution permeable reflecting agent precursor containing layer is about 0.05 to 0.25 micron in thickness; the processing solution permeable and dyeable polymeric layer is transparent and about 0.25 to 0.4 mil in thickness; and the dimensionally stable' support layer is processing solution impermeable and about 2 to 6 mils in thickness.
  • 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 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/redsensitive emulsion unit distal the laminates exposure surface, the yellow dye developer/blue-sensitive emulsion unit proximal the exposure surface and the magenta dye developer/greensensitive emulsion unit intermediate those units, recognizing that the relative order of such units may be varied in accordance with the desires of the operator.
  • FIGS. 1 through 16 of the drawings wherein there is illustrated preferred film units of the present invention and wherein like numbers, appearing in the various figures, refer to like components.
  • FIGS. I through 3 illustrate diagrammatic cross-sectional views of a preferred film unit of the present invention during the various depicted stages in the performance of a photographic diffusion transfer process as detailed hereinafter.
  • the film unit detailed comprises, prior to processing, a photosensitive laminate including, in order, dimensionally stable opaque support layer 10, preferably an actinic radiation-opaque flexible sheet material; cyan dye developer layer ll; red-sensitive silver halide emulsion layer 12; interlayer I3; magenta dye developer layer 14; green-sensitive silver halide emulsion layer I; interlayer I6; yellow dye developer layer 17; blue-sensitive silver halide emulsion layer 18; reflecting agent precursor layer 19; imagereceiving layer 20; and stripping layer 21.
  • a photosensitive laminate including, in order, dimensionally stable opaque support layer 10, preferably an actinic radiation-opaque flexible sheet material; cyan dye developer layer ll; red-sensitive silver halide emulsion layer 12; interlayer I3; magenta dye developer layer 14; green-sensitive silver halide emulsion layer I; interlayer I6; yellow dye developer layer 17; blue-sensitive silver halide emulsion layer 18; reflecting agent precursor layer 19;
  • the unit In the performance of a diffusion transfer multicolor process employing the film unit, the unit is exposed to radiation, actinic to photosensitive laminate l3, incident on the laminates exposure surface, as illustrated in FIG. 1.
  • the film unit is processed by distribution of processing composition 22 from applicator 23, on the surface of the laminate opposite opaque support layer 10, possessing a pH and solvent concentration at which the cyan, magenta and yellow dye developers are soluble and diffusible as a function of the point-to-point degree of exposure of red-sensitive silver halide emulsion layer 12, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer 18, respectively.
  • Processing solution 22 penneates emulsion layers l2, l5 and 18 to initiate development of the latent images contained in the respective emulsions.
  • the cyan, magenta and yellow dye developers, of layers 11, 14 and 17, 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 nondiffusible oxidized form, thereby providing imagewise distributions of mobile, soluble and diffusible cyan, magenta and yellow dye developer, as a function of the pointto-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 dyeable polymeric layer to provide a multicolor dye transfer image to that layer which is viewable against the background provided by the in situ process generation of reflecting agent in layer 47 which effects masking of yellow, magenta and cyan dye developer remaining associated with blue-sensitive emulsion layer 18, green-sensitive emulsion layer 15 and red-sensitive emulsion layer 12.
  • layer 22 of the processing solution optionally may be manually dissociated from the remainder of the film unit, which may be facilitated by stripping layer 21, as described above, to provide the product illustrated in FIG. 3.
  • FIG. 4 sets forth a perspective view of the therein specified film units of the present invention, designated 30, and each of FIGS. 5 through 16 illustrate the therein detailed diagrammatic cross-sectional views of such film units, along the stated section line A-A, during the various depicted stages in the performance of the photographic diffusion transfer process as detailed hereinafter.
  • film unit 30 comprises rupturable container 31, retaining, prior to processing, aqueous processing solution 22, photosensitive laminate 32 including, in order, image-receiving layer 20; reflecting agent precursor layer 19; blue-sensitive silver halide emulsion layer 18; yellow dye developer layer 17; interlayer l6; green-sensitive silver halide emulsion layer 15; magenta dye developer layer 14; interlayer l3; red-sensitive silver halide emulsion layer 12; cyan dye developer layer 11; spacer layer 29; neutralizing layer 28; and dimensionally stable opaque support layer I0; and, superposed coextensive the surface of the laminate opposite opaque support layer 10, dimensionally stable transparent sheet 24; both support layer 10 and sheet 24 preferably comprising processing composition impermeable flexible sheet material.
  • Rupturable container 31 may be of the type shown and described in any of U.S. Pat. Nos. 2,543,I8l; 2,634,886; 3,653,732; 2,723,051; 3,056,492; 3,056,491; 3,l52,5l5; and the like.
  • such containers will comprise a rectangular blank of fluidand air-impervious sheet material folded longitudinally upon itself to form two walls 41 which are sealed to one another along their longitudinal and end margins to form a cavity in which processing solution 26 is retained.
  • the longitudinal marginal seal 42 is made weaker than the end seals 43 so as to become unsealed in response to the hydraulic pressure generated within the fluid contents 26 of the container by the application of compressive pressure to walls 41 of the container.
  • container 3 is fixedly positioned and extends transverse a leading edge of the photosensitive laminate whereby to effect unidirectional discharge of the containers contents 26 between the laminate and next adjacent sheet, upon application of compressive force to container 31.
  • container 31, as illustrated in FIGS. 5 and I1 is fixedly positioned and extends transverse a leading edge of the laminate with its longitudinal marginal seal 42 directed toward the interface between the laminate and halide emulsion layer; and that reflecting agent may be in part generated within the image-receiving and/or next adjacent silver halide emulsion strata of the film unit.
  • a particularly preferred embodiment of the present invention employs a metathetical reaction between selected precursor salts, the respective exchange of cations or anions of which provide for the simultaneous generation of two separate reflecting agents such as, for example, the metathetical generation of both barium sulfate and zinc sulfide white, inorganic salt pigments by the in situ reaction of substantially colorless barium sulfide and zinc sulfate precursor salts.
  • Such preferred embodiments provide for the in process generation of an increased quantity of reflecting agent per unit volume of precursor salts employed.
  • a particularly preferred reflecting agent comprises barium sulfate due to its highly effective reflection properties.
  • the reflecting agent precursor selected will, as previously denoted, comprise a precursor specifically adapted to provide a substantially white inorganic pigment which reflects visible light and, in particularly preferred embodiments, will be coated at a coverage effective to provide 200 to 1,000 mgs./ft. reflecting agent, as a result of processing, which coverage is generally sufficient, subsequent to processing, to mask opacifying agent distributed in the processing composition and any residual dye developer present intermediate the image-receiving layer and the dimensionally stable opaque layer.
  • reflecting agent precursor or precursors may be distributed in whole or in part within a processing composition permeable polymeric matrix such as gelatin and/or any other such polymeric matrixes as are specifically denoted throughout the specification as suitable for employment as a matrix binder and may be distributed in one or more of the film unit layers which may be separated or contiguous and should be intermediate the image-receiving layerand dimensionally stable opaque layer, provided that its distribution and concentration is effective to provide the denoted post procesing masking function, and that in whole or in part the resultant generated reflecting agent may be ultimately disposed within the processing composition residuum located intermediate the image-receiving layer and next adjacent silver halide emulsion strata and associated dye image-forming material.
  • a processing composition permeable polymeric matrix such as gelatin and/or any other such polymeric matrixes as are specifically denoted throughout the specification as suitable for employment as a matrix binder and may be distributed in one or more of the film unit layers which may be separated or contiguous and should be intermediate the image-
  • 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.
  • 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.
  • Alkaline processing solutionvl2 permeates emulsion layers 16, 19 and 22 to initiate development of the latent images contained in the respective emulsions and reflecting agent precursor layer 25 to initiate generation of reflecting agent.
  • the cyan, magenta and yellow dye developers, of layers l5, l8 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 nondiffusible oxidized form, thereby providing irnagewise distributions of mobile, soluble and diffusible cyan, magenta and yellow dye developer, as a function of the point-to-point degree of their associated emulsions exposure.
  • At least part of the irnagewise distributions of mobile cyan, magenta and yellow dye developer transfers, by diffusion, to dyeable polymeric layer 24 to provide a multicolor dye transfer image to that layer which is viewable against the background provided by the in situ generated reflecting agent layer 26 which layer effects masking of opacifying agent present in processing composition residuum l2 and cyan, magenta and yellow dye developer remaining associated with blue-sensitive emulsion layer 22, green-sensitive emulsion layer 19 and red-sensitive emulsion layer 16.
  • container 11 may be manually dissociated from the remainder of the film unit, as described above, to provide the product illustrated in FIG. 6.
  • Film unit similar to that shown in the drawings may be prepared, for example, by coating, in succession, on a gelatin subbed, 4 mil. opaque polyethylene terephthalate film base, the following layers:
  • cyan, magenta and yellow dye developer transfers, by diffusion, to aqueous alkaline solution permeable and dyeable polymeric layer 20 to provide a multicolor dye transfer image to that layer which is viewable against the background provided by the in situ generation of reflecting agent in layer 49 which effects masking of yellow, magenta and cyan dye developer associated with the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer subsequent to processing.
  • a sufficient portion of the ions comprising aqueous alkaline solution 26 transfers, by diffusion, through permeable polymeric spacer layer 29 and to permeable polymeric acid layer 28 whereby alkaline solution 26 decreases in pH, as a function of neutralization, to a pH at which the cyan, magenta and yellow dye developers, in the reduced form, are substantially insoluble and nondiffusible, to provide thereby a stable multicolor dye transfer image viewable through dimensionally stable transparent layer 24.
  • container 31 may be manually dissociated from the remainder of the film unit, as described above.
  • the multicolor dye transfer image of laminate 32 is viewable through dimensionally stable transparent sheet 24 and that of laminate 33 is viewable through dimensionally stable transparent layer 39 subsequent to transfer image formation, in the preferred embodiments detailed above.
  • the dimensionally stable sheet may comprise a flexible sheet material displaced from contact with the surface of laminate 32 and/or 33 during photoexposure and brought into superposed relationship with such surface subsequent to exposure contemporaneous with, or preceding, distribution of processing composition 26 intermediate such sheet and the photoexposed laminate.
  • the superposed dimensionally stable sheet may be stripped from the remainder of the film unit alone or in accompaniment with the processing composition where desired.
  • the flexible sheet material when superposed on the surface of the laminate subsequent to photoexposure of laminate 32 may comprise an opaque sheet material and/or the processing composition may retain opacifying agent or agents and either and/or both taken together may possess sufficient opacifying capacity to insure protection of the laminate from actinic radiation incident on that surface of the laminate through which photoexposure was accomplished, which, in combina tion with opaque support layer 10 of the laminate, provides a structure adapted to be processed in the presence of actinic radiation.
  • the superposed dimensionally stable sheet may be stripped from the remainder of the film unit, where desired or opaque, alone or in accompaniment with the processing composition, where desired or opaque, to reveal the dye transfer image carried by the laminate.
  • Displacement of the flexible sheet may be manually effected alone or together with processing composition residuum where desired by selective adhesion to, or release of the processing composition from, the manually displaced sheet element.
  • substitution of a dimensionally stable transparent support layer in replacement for the opaque support layer 10 of laminate 32, exposes to viewing the dye image present in the photosensitive silver halide emulsion and associated dye developer layers which is negative with respect to the dye transfer image carried by imagereceiving layer 20 and may be viewed against reflecting layer 45 which masks the dye transfer image from observation through such transparent support layer.
  • the dimensionally stable sheet may be stripped from the remainder of the film unit alone or in combination with the processing composition and especially where either the sheet and/or the processing composition is opaque and it is desired to view the aforementioned negative dye image.
  • Film units similar to that set forth in the drawings may be prepared, for example, by coating, in succession, on an opaque, 4-mil polyethylene terephthalate film base:
  • magenta dye developer 4-isopropoxy-2'l p- (B-hydroquinonyl ethyl) phenylazol-naphthalene-lethoxy acetate dispersed in gelatin and coated at a coverage of about 70 mgs./ft. of dye and about 100 mgs./ft. of gelatin;
  • l 1. a 2:1 mixture, by weight, of polyvinyl alcohol and poly- 4-vinylpyridine, at a coverage of approximately 600 mgs./ft. to provide a polymeric image-receiving layer approximately 0.40 mil thick.
  • Transparent polyethylene terephthalate sheet may then be superposed on the external surface of coating No. l 1 and the two components then taped together, in composite form, at their respective edges by means of pressure-sensitive binding tape extending around, in contact with, and over the edges of the resultant film unit.
  • a rupturable container comprising an outer layer of paper, an intermediate layer of lead foil and an inner liner or layer of polyvinyl chloride retaining an aqueous alkaline processing solution comprising:
  • the photosensitive laminates may be exposed through step wedges to selectively filtered radiation incident on the transparent polyethylene terephthalate sheet and processed by passage of the exposed film unit through suitably gapped opposed rolls, to effect rupture of the container and distribution of the containers contents between the photosensitive element and the sheet element.
  • a multicolor dye transfer image formation may be viewed through the transparent polyethylene terephthalate sheet and such image formation is found to be substantially completed and exhibiting the required color brilliance, hues, saturation and isolation within a period of about 1 to 3 minutes.
  • the barium chloride precursor of layer immediately above may be replaced with a dispersion of barium sulfide in gelatin coated, as above, at an average of approximately 725 mgs./ft. barium sulfide and of approximately 150 mgs./ft. gelatin and the sodium sulfate precursor of the processing composition may be replaced with 12.2 grams of zinc sulfate to effectively provide the simultaneous in situ generation of both barium sulfate and zinc sulfide reflecting agent pigments, intermediate the image-receiving layer of the film unit and auxiliary layer 9, during processing of a photoexposed film unit.
  • the pH of the alkaline processing solution initially employed must be a pH at which the dye developers employed are soluble and diffusible.
  • 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 pH s 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 composition in the preferred embodiments detailed, will include the stated film-forming viscosity-increasing agent or agents, to facilitate spreading of the composition and to provide maintenance of the spread composition as a structurally stable layer 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 to adversely effect the structural integrity of the laminate and that the layers forming the laminate can readily accommodate and dissipate the solvent throughout during film unit of the present invention, to provide reduction of the alkalinity of the film unit from a pH at which the dyes are soluble to a pH at which the dyes are substantially nondiffusible, in order to advantageously stabilize the dye transfer image.
  • a polymeric acid layer such as that obtained by coating the polyethylene terephthalate film base with the partial butyl ester of polyethylene/maleic anhydride copolymer prepared by refluxing, for 14 hours, about 300 grams of high viscosity poly-(ethylene/maleic anhydride), about 140 grams of n-butyl, alcohol and about 1 cc. of percent phosphoric acid to provide a polymeric acid layer approximately 0.75 mil thick preferably in turn overcoated with a 2:1 solution of hydroxypropyl cellulose and polyvinyl alcohol in water to provide a polymeric spacer layer approximately 0.25 mil thick, will be positioned intermediate the common support and next adjacent essential layer, as previously described.
  • 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 of 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 1,000, preferably of about 1,000 to 50,000, possessing a degree of acetalation within about to 30 percent, 10 to 30 percent, 20 to 80 percent, and 10 to 40 percent, of the polyvinyl alcohols theoretical polymeric hydroxy 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.
  • multicolor transfer images may be provided 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.
  • the dimensionally stable support layers referred to may comprise any of the various type of conventional opaque and transparent rigid or flexible materials possessing the support and optional characteristics denoted above, and may comprise polymeric films of both synthetic types and those derived from naturally occurring products.
  • Particularly suitable materials include aqueous alkaline solution impermeable, water vapor permeable, flexible polymeric materials such as vapor permeable polymeric films derived from ethylene glycol terephthalic acid, vinyl chloride polymers; polyvinyl acetate; polyamides; polymethacrylic acid methyl and ethyl esters; cellulose derivatives such as cellulose, acetate, triacetate, nitrate, propionate, butyrate, acetate-propionate, or acetate-butyrate; alkaline solution impermeable, water vapor permeable papers; crosslinked polyvinyl alcohol; regenerated cellulose; and the like.
  • liquid processing composition employed may contain an auxiliary or accelerating developing agent, such as p-methylaminophenol, 2,4-diaminophenol, pbenzylaminophenyl, 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 benzcnoid developing agent, as disclosed in U.S. Pat. No. 3,039,869, issued June 19, 1962. As examples of suitable combinations of auxiliary developing agents, mention may be made of l-phenyl-3-pyrazolidone.
  • 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 image-receiving 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 energytransfer 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 energytransfer 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 composition 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 composition is initially at the pH and solvent concentration 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.
  • nitrocarboxymethyl cellulose as disclosed in U.S. Pat. No. 2,992,104
  • an acylamidobenzene sulfo ester of a partial sulfobenzal of polyvinyl alcohol as disclosed in U.S. Pat. No. 3,043,692
  • polymers of N-alkyl-a,B-unsaturated carboxamides and copolymers of N- alkyl-a, B-carboxamides with N-hydroxyalkyl-a,B-unsaturated carboxamides as disclosed in U.S. Pat. No.
  • copolymers of vinylphthalimide and a,B-unsaturated carboxylic acids as disclosed in U.S. Pat. No. 3,061,428; copolymers of N-vinylpyrrolidones and a,B-unsaturated carboxylic acids and terepolymers of N-vinyl pyrrolidones, a,B-unsaturated carboxylic acids and alkyl esters of a,B-unsaturated carboxylic acids, as disclosed in U.S. Pat. No.
  • the silver halide crystals may be prepared by reacting a water-soluble 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 or undesired components, for example, the procedures described in US.
  • a water-soluble 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 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. Pat. Nos. 2,322,085 and 2,327,808; polyacrylamides, as described in US. Pat. No. 2,541,474; vinyl polymers such as described in an extensive multiplicity of readily available US. and foreign patents.
  • 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 associatedtherewith, 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 ele ments 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 imagecarrying layer as being reversed, in the positive-negative sense, with respect to the image in the photosensitive emulsion layers.
  • positive image assume that the photosensitive element is exposed to actinic light through a negative transparency. ln 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 image-carrying layer.
  • 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.
  • 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.
  • a photographic film unit which comprises a photosensitive laminate containing, as essential layers, a dimensionally stable common support carrying on one surface, a dyeable polymeric layer and a photosensitive silver halide emulsion layer having associated therewith a dye image-forming material which is processing composition diffusible, as a function of the point-to-point degree of the emulsions exposure to actinic radiation
  • the improvement which comprises a layer permeable to processing composition solubilized dye image-forming material comprising light-reflecting agent precursor which comprises, upon contact with a processing composition, first ionic species adapted to interact with second ionic species to provide a substantially white, inorganic visible light-reflecting agent intermediate said dyeable polymeric layer and said photosensitive silver halide emulsion layer in a quantity effective to mask said dye image-forming material associated with said photosensitive silver halide emulsion layer subsequent to processing.
  • a photographic film unit as defined in claim 2 including a processing composition permeable polymeric spacer layer positioned intermediate said acidic layer and said next adjacent essential layer. 7
  • a photographic film unit as defined in claim 5 which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members, including a transparent dimensionally stable sheet superposed substantially coextensive the surface of said laminate opposite said dimensionally stable opaque support and a rupturable container retaining a processing composition fixedly positioned and extending transverse a leading edge of said photosensitive laminate and adapted to effect unidirectional discharge of said containers contents intermediate said sheet and said laminate.
  • a photographic film unit as defined in claim 7 which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members, including a dimensionally stable sheet superposed substantially coextensive the surface of said laminate opposite said dimensionally stable transparent common support and a rupturable container retaining a processing composition fixedly positioned and extending transverse a leading edge of said photosensitive laminate and adapted to effect unidirectional discharge of said containers contents intermediate said sheet and said laminate.
  • a photographic film unit as defined in claim I which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members, including a separate dimensionally stable sheet having a leading edge fixedly positioned extending transverse a leading edge of said laminate and adapted to be superposed subsequent to photoexposure of said laminate substantially coextensive the surface of said laminate opposite said dimensionally stable common support and a rupturable container retaining a processing composition and extending transverse said leading edge of said photosensitive laminate intermediate said sheet and said laminate and adapted to effect unidirectional distribution of said containers contents intermediate said sheet and said laminate upon superpositioning of said sheet on said surface of said laminate.
  • a photosensitive laminate containing, as essential layers, 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 diffusible, in alkali, at a first pH, as a function of exposure of its associated silver halide emulsion layer, an alkaline solution permeable transparent polymeric layer dyeable by said dyes, a dimensionally stable alkaline solution impermeable support layer, and an alkaline solution permeable transparent acidic layer containing sufficient acidifying groups to effect reduction of the processing solution having said first pH to a second pH at which said dyes are insoluble and nondiffusible positioned intermediate said dimensionally stable support layer and the essential layer next adjacent thereto; the improvement which comprises a layer, permeable to solubilized dye and positioned inter-

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US3765885A (en) * 1972-01-03 1973-10-16 Polaroid Corp Neutralizing layer for color diffusion transfer film

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US4356250A (en) * 1981-01-12 1982-10-26 Eastman Kodak Company Use of zinc salts to increase dye stability

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US3765885A (en) * 1972-01-03 1973-10-16 Polaroid Corp Neutralizing layer for color diffusion transfer film

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