US3576625A - Photographic diffusion transfer color processes and film unit for use therein - Google Patents

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

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US3576625A
US3576625A US846442A US3576625DA US3576625A US 3576625 A US3576625 A US 3576625A US 846442 A US846442 A US 846442A US 3576625D A US3576625D A US 3576625DA US 3576625 A US3576625 A US 3576625A
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dye
layer
image
silver halide
film unit
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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
    • G03C8/52—Bases or auxiliary layers; Substances therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42—Structural details
    • G03C8/426—Structures with microcapsules
    • 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

Definitions

  • the present invention relates to a permanently structured composite photographic film unit, adapted to provide a color diffusion transfer image, which includes a first dimensionally stable layer; a photosensitive silver halide layer having associated dye image-forming material which is soluble and diffusible, in alkali, at a first pH,
  • the primary objects of the present invention are to provide photographic products particularly adapted for employment in diffusion transfer color processes; to provide photographic products which comprise a photosensitive composite structure which contains a plurality of essential layers including a first dimensionally stable, liquid impermeable layer, a photosensitive silver halide emulsion layer having a dye image-forming material associated therewith which is soluble and diffusible, in alkaline processing composition, at a first pH, a polymeric layer dyeable by the dye image-forming material, a second dimensionally stable, liquid impermeable layer, transparent to incident radiation and, disposed in an alkaline processing composition permeable layer of the structure, a particulate dispersion of acid material in a concentration effective to reduce a processing composition possessing said first pH to a second pH at which the dye image-forming material is substantially nondiffusible, wherein said acid particles are individually disposed within a polymeric coating permeable to alkaline processing composition at a rate effective to provide contact between said acid and said alkali sufiicient to reduce
  • FIG. 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 FIG. 1, along section line 22, 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;
  • FIGS. 3a and 5a are diagrammatic, still further enlarged cross-sectional views of a functional layer constituting the photosensitive laminate of FIGS. 3 and 5, respectively.
  • 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,
  • 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 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 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 imagereceiving 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-dihydrophenyl 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 imageforming components such as, for example, the previously mentioned dye developers, in diffusion transfer process 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 US. 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 single, 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 bluesensitive 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, magneta 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 cointaining 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 fluid processing composit1on.
  • a coating solution cointaining 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 fluid processing composit1on.
  • 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.
  • 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 becapable 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 cps. at a temperature of approximately 24 C. and preferably in the order of 100,000 cps. to 200,000 cps. at that tempertaure.
  • 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 eifecting the spectral absorption characteristics of the image dye.
  • film units fabricated in accordance with the parameters set forth above specifically require the presence of the stated polymeric acid layer component to effect in situ process adjustment of the film units operational pH range.
  • 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 halfester 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; corbaxymethyl 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 sul
  • free carboxyl groups e.g., cellulose a
  • 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 11 or lower at the end of the imbibition period, and preferably to a pH of about to 8 within a short time after imbibition, thus requiring, of course, that the action of the polymeric acid be accurately so controlled as not to interfere with either development of the negative or image transfer of unoxidized dye developers.
  • the pH of the image layer must be kept at a functional transfer level, for example, 12 to 14 until the dye image has been formed after which the pH is reduced very rapidly to a pH below that at which dye transfer may be accomplished, for example, at least about 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, for example, 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 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 necessaryy or desirable, suitable subcoats are employed to help the various polymeric layers adhere to each other during storage and use.
  • 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 filrm unit of simplified construction and particularly adapted for the Production of dye transfer images of unexpectedly improved stability and other desirable properties by a color diffusion transfer process will be constructed to include a photosensitive element comprising a composite structure possessing, in sequence, as essential layers, a first dimensionally stable layer, a photosensitive silver halide emulsion layer having associated therewith a dye image-forming material which is soluble and diffusible, in alkali, at a first pH, a polymeric layer dyeable by the dye imageforming material, a second dimensionally stable layer transparent to incident actinic radiation, and disposed in an alkaline processing composition permeable layer of the element, a particulate dispersion of acid material in a concentration effective to reduce a processing composition possessing the first pH to a second pH at which the dye image-providing material is substantially nondiffusible, coated with a polymeric coating permeable to alkaline processing composition at a rate effective to provide contact between the acid material and the
  • a rupturable container retaining a processing composition comprising the first pH is fixedly positioned and extends transverse a leading edge of the composite structure whereby to effect, upon application of compressive pressure, discharge of the processing composition intermediate the dyeable polymeric layer and the photosensitive silver halide emulsion next adjacent.
  • polyvinyl alcohols such as cyanoethyl polyvinyl alcohol, hydroxy propyl polyvinyl alcohol, polyvinyl alcohol, etc.
  • polyvinyl acetals such as polyvinyl formyl, polyvinyl acetal, polyvinyl propional, polyvinyl butyral, p-hydroxyphenyl'benzaldehyde acetal of polyvinyl alcohol, B-methoxypropionaldehyde acetal of polyvinyl alcohol, fl-ethoxypropionaldehyde acetal of polyvinyl alcohol
  • cellulose esters such as cellulose acetate, cellulose proprionate, cellulose butyrate, cellulose acetate-propionate, cellulose acetate-butyrate
  • cellulose ethers such as hydroxypropylmethyl cellulose, hydroxypropyl cellulose, etc.
  • the acid material dispersion must remain insulated to a substantial extent from the remainder of the photographic system during storage, exposure and initial processing of the film unit, by means of the polymeric coating, in order to prevent premature pH reduction during processing and, accordingly, the selected acid material must not diffuse out of its encapsulated situs, in a concentration effective to deleteriously effect processing, during the expected life span of the film unit within which it is incorporated.
  • the film unit is specifically adapted to provide for the production of a multicolor dye transfer image and 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 diifusible, in alkali, at a first processnig composition solvent concentration; an alkaline solution permeable polymeric layer dyeable by the dye image-providing materials; 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 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 alkaline solution permeable polymeric interlayers.
  • the selected acid material may be diifusible or nondilfusible, subsequent to substantial transfer image formation, at the election of the operator, and the encapsulating polymeric material may comprise a discontinuous or continuous phase of the layer or layers of which it is a constituent component.
  • 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.
  • 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.
  • 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.
  • FIG. 1 sets forth a perspective view of the film unit, designated 10, and each of FIGS. 2 through 7 illustrate diagrammatic cross-sectional views of film unit 10, along the stated section lines 22,
  • Film unit 10 may comprise rupturable container 11, retaining, prior to processing, aqueous alkaline solution 12 possessing a first pH at which the selected dye developers are soluble and diffusible, and photosensitive laminate 13 including, in order, dimensionally stable, liquid impermeable opaque layer 14, preferably an actinic radiation-opaque vapor permeable flexible sheet material; an alkaline solution permeable cyan dye developer layer 15; an alkaline solution permeable red-sensitive silver halide emulsion layer 16; an alkaline solution permeable interlayer .17; an alkaline solution permeable magenta dye developer layer 18; an alkaline solution permeable greensensitive silver halide emulsion layer 19; an alkaline solution permeable interlayer 20; an alkaline solution permeable yellow dye developer layer 21; an alkaline solution permeable blue-sensitive silver halide emulsion layer 22; an alkaline solution permeable layer 23, which may contain an auxiliary silver halide developing agent; an alkaline
  • Each of alkaline solution permeable layers 15, 16, 17, 18, 19, 20', 21, 22, 23 and 24 possesses a dispersion of particulate acid material 36, the total concentration of which is adapted to effect reduction in the alkalinity of processing solution 12 from the first pH at which the cyan, magenta and yellow dye developers are soluble and diifusible to a second pH at which the dye developers are substantially nondiffusible to image-receiving layer 24, the particles of which comprise polymeric coating 26 permeable by alkaline solution 12 at a rate effective to provide the reduction subsequent to substantial dye transfer image formation in image-receiving layer 24.
  • the structural integrity of laminate 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 solution 12 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 alkaline solution 12 intermediate those layers.
  • the binding member may comprise a pressure-sensitive tape 28 securing and/or maintaining the layers of laminate 13 together at its respective edges. Tape 28 Will also act to maintain processing solution 12 intermediate image-receiving layer 24 and the silver halide emulsion layer next adjacent thereto, upon application of compressive pressure to pod 11 and distribution of its contents intermediate the stated layers. Under such circumstances, binder tape 28 wildl act to prevent leakage of fluid processing composition from the film units laminate during and subsequent to photographic processing.
  • Rupturable container 11 may be of the type shown and described in any of US. Pats. Nos. 2,543,181; 2,634,886; 2,653,732; 2,723,051; 3,056,492; 3,056,491; 3,152,515; and the like.
  • such containers will 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 longitu- '13 dinal and end margins to form a cavity in which processing solution 12 is retained.
  • the longitudinal 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. of the container by the application of compressive pressure to walls 29 of the container.
  • container 11 is fixedly positioned and extends transverse a leading edge of photosensitive laminate 13 whereby to effect unidirectional discharge of the containers contents 12 between image-receiving layer 24 and the stated layer next adjacent thereto, upon application of compressive force to container 11.
  • container 11 as illustrated in FIG. 2, is fixedly positioned and extends transverse a leading edge of laminate 13 with its longitudinal marginal seal 30 directed toward the interface between image-receiving layer 24 and auxiliary layer 23.
  • container 11 is fixedly secured to laminate 13 by extension 32 of tape 28 extending over a portion of one wall 29 of the container, in combination with a separate retaining member such as illustrated retaining tape 33 extending over a portion of the other wall 29 of the container and a portion of laminate 13s surface generally equal in area to about that covered by tape 28.
  • extension flap 32 of tape 28 is preferably of such area and dimensions that upon, for example, manual separation of container 11 and tape 33, subsequent to distribution of processing composition 12, 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 container comprise an aqueous alkaline solution having a pH at which the dye developers are soluble and diifusible and contains an opacifying agent in a quantity sufficient to mask the dye developers associated with the silver halide emulsions subsequent to processing.
  • concentration of opacifying agent or agents selected will be that suflicient 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 solution 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 or the laminate are appropriately protected by incident radiation, at one major surface by the opaque processing composition and at the remaining major surface by the 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 opacifying agent should be one providing a background suitable for viewing the dye developer transfer image formed in the dyeable polymeric layer.
  • an opacifying 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 a background noise signal degrading, or detracting from, the information content of the image.
  • Particularly desirable opacifying 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.
  • opacifying agents examples include barium sulfate, zinc oxide, titanium oxide, barium stearate, silver flake, silicates, alumina, zirconium oxide, zirconium acetyl acetate, sodium zirconium sulfate, kaolin, mica, and the like.
  • a particularly preferred agent comprises titanium dioxide due to its highly effective reflection properties.
  • a processing composition containing about 40- 70 grams of titanium dioxide dispersed in 100 cc. of water will provide a percent reflectance of about -90%.
  • the percent reflectance particularly desired will be in the order of above 85%.
  • a processing composition containing, for example, titanium dioxide or the like, selected predominantly for its radiation reflecting properties, beyond that ordinarily obtained or required to obscure or mask the dye and/ or developed silver associated with the photosensitive silver halide emulsion layers
  • an additional opacifying agent exhibiting more effective filtration of radiation incident on the transparent support layer during processing, such as carbon black, for example, added in a concentration of about one part carbon black to to 500 parts titanium dioxide, in order to further protect the emulsions from physical fog formation during processing.
  • the unit In the performance of a diffusion transfer multi-color 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 container 11 and to effect rupture of longitudinal seal 30 and distribution of alkaline processing composition 12, having a pH and solvent concentration at which the cyan, magenta and yellow dye developers are soluble and diffusible, intermediate dyeable polymeric layer 24 and auxiliary layer 23.
  • Alkaline processing solution 12 permeates 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 nondiffusible oxidized form, thereby providing imagewise distributions of mobile, soluble and ditfusible cyan, magenta and yellow dye developer, as a function of the point-topoint degree of their associated emulsions exposure.
  • 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 units similar to that shown in the drawings may be prepared, for example, by coating, in succession, on a gelatin subbed, 5 mil opaque cellulose triacetate film base, the following layers:
  • the two components thus prepared may then be taped together in laminate form, at their respective edges, by means of a pressure-sensitive binding tape extending around, in contact with, and over the edges of the resultant laminate.
  • 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 a container its contents would be distributed, upon rupture of the containers marginal seal, between layer 9 and the polymeric imagereceiving layer.
  • the processing composition in the preferred embodiment, 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.
  • 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; and cellulose derivatives such as cellulose, acetate, triacetate, nitrate, propionate, butyrate, acetate-propionate, or acetate-butyrate.
  • liquid processing composition employed may contain an auxiliary or accelerating developing agent, such as p-methylaminophenol, 2,4-diaminophenol, p-benzylaminophenyl, 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. Pat. No. 3,039,869, issued June 19, 1962.
  • auxiliary developing agents examples include 1- phenyl-3-pyrazolidone in combination with p-benzylaminophenol and 1-phenyl-3-pyrazolidone in combination with 2,5 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 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 first 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.
  • 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 sufiiciently 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 U.S. Pats. 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, issued Aug.
  • color diffusion transfer processes which employ color cou pling techniques comprising, at least in part, reacting one or 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 U.S. Pat. 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.
  • Optical sensitization of the emulsions silver halide crystals may be accomplished by contact of the emulsion composition with an effective concentration of the se- 19 lected 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. Pats. Nos. 2,271,623; 2,288,226; and 2,334,864; or of the polyethyleneglycol type, as described in U.S. Pat. No. 2,708,162; or of the preceding combination, as described in U.S. Pat. No. 2,886,437; or the thiopolymers, as described in U.S. Pats. Nos. 3,046,129 and 3,046,134.
  • Hardening agents such as inorganic agents providing polyvalent metallic atoms, specifically polyvalent aluminum or chromium ions, for example, potash alum [K Al (SO .24H O] and chrome alum and inorganic 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. Pats. 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.
  • 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. Pats. Nos. 2,322,085 and 2,327, 808; polyacrylamides, as described in U.S. Pat. No. 2,541,- 474; vinyl polymers such as described in U.S. Pats. Nos. 2,253,078; 2,276,322; 2,276,323; 2,281,703; 2,310,223;
  • 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.
  • 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 image-carrying 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 such film unit should be accomplished through an image reversing optical system such a camera possessing an image reversing optical system.
  • 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 essen tial 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.
  • additives such as plasticizers, intermediate essen tial 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.
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxta posed pressure-applying members and which comprises, in combination:
  • a photosensitive element comprising a composite structure containing a plurality of layers including a first dimensionally stable, liquid impermeable layer opaque to incident actinic radiation; an alkaline processing composition permeable photosensitive silver halide emulsion layer having associated therewith a dye image-forming material which is soluble and diffusible, in alkali, at a first pH, as a function of photoexposure of its associated silver halide emulsion layer; an alkaline processing composition permeable polymeric layer dyeable by said dye image-forming material; a second dimensionally stable, liquid impermeable layer transparent to incident actinic radiation; a dispersion of acid material disposed in an alkaline processing composition permeable layer of the composite structure in a concentration eifective to reduce an alkaline processing composition possessing said first pH at which said dye image-forming material is soluble and diifusible to a second pH at which said dye image-forming material is substantially nondiifusible, said acid material particles having associated therewith a poly
  • a rupturable container retaining an alkaline processing solution possessing said first pH and an opacifying agent in a quantity sufiicient to mask said dye imageproviding material fixedly positioned and extending transverse a leading edge of said photosensitive ele ment to effect unidirectional discharge of said containers alkaline processing solution between said dyeable polymeric layer and the photosensitive silver halide emulsion layer next adjacent thereto.
  • said photosensitive element comprises at least two selectively sensitized silver halide emulsion layers each having a dye which dye is a silver halide developing agent of a predetermined color associated therewith, each of said dyes soluble and diffusible, in alkali, at said first pH.
  • each of said selectively sensitized photosensitive s lver halide emulsions has predominant spectral sensitrvrty to separate regions of the spectrum and the dye associated with each of said silver halide emulsion layers possesses a spectral absorption range subsequent to processing substantially complementary to the predominant sensitlvity range of its associated emulsion layer.
  • a photographic film unit as defined in claim 11 which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members and which comprises, in combination, a composite structure containing a plurality of layers including, as essential layers, in sequence, a dimensionally stable, liquid impermeable opaque layer; an alkaline solution permeable polymeric layer containing cyan dye; an alkaline solution permeable red-sensitive silver halide emulsion layer; an alkaline solution permeable polymeric layer containing magenta dye; an alkaline solution permeable green-sensitive silver halide emulsion layer; an alkaline solution permeable polymeric layer containing yellow dye; an alkaline solution permeable blue-sensitive silver halide emulsion layer, each of said cyan, magenta and yellow dyes being silver halide developing agents and being soluble and diffusible, in an aqueous alkaline solution at a first pH; an alkaline solution permeable transparent polymeric layer dyeable by said dyes
  • a rupturable container retaining an aqueous alkaline processing solution possessing said first pH in a quantity suflicient to provide said first concentration of water and an opacifying agent in a quantity sutficient to mask said dyes fixedly positioned and extending transverse a leading edge of said photosensitive element to effect unidirectional discharge of said containers processing solution between said dyeable polymeric layer and said blue-sensitive sliver halide emulsion layer upon application of compressive force to said container.
  • a process as defined in claim 24 including the step of separating said container from said composite structure subsequent to substantial transfer image formation.
  • a photographic film unit which is adapted to be processed by passage through a pair of juxtaposed pressure-applying members and which includes, in combination, a composite structure comprising a first dimensionally stable, liquid impermeable layer opaque to incident actinic radiation; at least two selectively sensitized, alkaline processing solution permeable silver halide emulsion layers, each of said silver halide emulsions having associated therewith a dye, which is a silver halide developing agent, of predetermined color, and is soluble and diffusible, in alkali, at a first pH; an alkaline processing permeable polymeric layer dyeable by said dye; a particulate dispersion of acid material disposed in an alkaline processing solution permeable layer of the composite structure in a concentration eifective to reduce the alkalinity of an alkaline processing solution possessing a first pH at which said dyes are soluble and diifusible to a second pH at which said dyes are substantially nondilfus
  • a rupturable container retaining an alkaline processing solution possessing said first pH and an opacifying agent in a quantity sufficient to mask said dyes fixedly positioned and extending transverse a leading edge of said photosensitive element to effect discharge of said containers processing solution between said dyeable polymeric layer and the photosensitive silver halide emulsion layer next adjacent thereto upon application of compressive force to said container;
  • each of said selectively sensitized silver halide emulsion layers possess predominant spectral sensitivity to a separate region of the spectrum and the dye associated with each of said emulsion layers possesses a spectral absorption range subsequent to processing substantially complementary to the predominant sensitivity range of its associated emulsion.
  • 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 laminate containing a plurality of layers including a dimensionally stable alkaline solution impermeable opaque layer; an alkaline solution permeable red-sensitive silver halide emulsion layer having associated therewith cyan dye; an alkaline solution permeable green-sensitive silver halide emulsion layer having associated therewith magenta dye; an alkaline solution permeable blue-sensitive silver halide emulsion layer having associated therewith yellow dye; each of said cyan, magenta and yellow dyes being silver halide developing agents and soluble and diifusible in aqueous alkaline solution at a first pH; an alkaline solution permeable transparent polymeric layer dyeable by said dyes; a dispersion of particulate acid material disposed in at least one alkaline solution permeable polymeric layer in a concentration

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4201578A (en) * 1977-11-03 1980-05-06 Eastman Kodak Company Blocked competing developers for color transfer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4201578A (en) * 1977-11-03 1980-05-06 Eastman Kodak Company Blocked competing developers for color transfer

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