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US3888669A - Photographic products and processes with barrier layers for diffusable dyes - Google Patents

Photographic products and processes with barrier layers for diffusable dyes Download PDF

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Publication number
US3888669A
US3888669A US393799A US39379973A US3888669A US 3888669 A US3888669 A US 3888669A US 393799 A US393799 A US 393799A US 39379973 A US39379973 A US 39379973A US 3888669 A US3888669 A US 3888669A
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layer
dye
silver halide
diffusion transfer
film unit
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US393799A
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Paul A Cardone
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Polaroid Corp
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Polaroid Corp
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Priority to US393799A priority Critical patent/US3888669A/en
Priority to DE2441751A priority patent/DE2441751A1/de
Priority to FR7429835A priority patent/FR2242705B1/fr
Priority to GB38353/74A priority patent/GB1482573A/en
Priority to JP10127674A priority patent/JPS5630537B2/ja
Priority to CA208,469A priority patent/CA1036857A/en
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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

Definitions

  • a composite photosensitive structure particularly adapted for reflection type photographic diffusion transfer color process employment, which comprises a plurality of essential layers including, in sequence, a dimensionally stable layer preferably opaque to incident radiation; one or more silver halide emulsion layers having associated therewith a diffusion transfer process dye imageproviding material; a polymeric layer adapted to receive solubilized dye image-providing material diffusing thereto; and a dimensionally stable transparent layer, may be exposed to incident actinic radiation and processed by interposing, intermediate the silver halide emulsion layer and the reception layer, a processing composition and an opacifying agent, which may reflect incident radiation, in a quantity sufficient to mask dye image-providing material associated with the silver halide emulsion.
  • the composite photosensitive structure includes a rupturable container, retaining an alkaline processing composition and the opacifying agent, fixedly positioned extending transverse a leading edge of the composite structure in order to effect, upon application of compressive pressure to the container, discharge of the processing composition intermediate the opposed surfaces of the reception layer and the next adjacent silver halide emulsion.
  • means associated with composite structure are adapted to convert the pH of the film unit from a first processing pH at which dye image'providing material is diffusible as a function of the film units photoexposure to a second pH at which the transfer dye image exhibits increased stability, preferably a sufficient portion of the ions of an alkaline processing composition transfers, by diffusion, to a polymeric neutralizing layer to effect reduction in the alkalinity of the composite film unit from a first alkaline processing pH to the second pH at which dye image-providing material is substantially nondiffusible, and further dye imageproviding material transfer is thereby substantially obviated.
  • the transfer dye image is viewed, as a reflection image, through the dimensionally stable transparent layer against the background provided by the opacifying agent, distributed as a component of the processing composition, intermediate the reception layer and next adjacent silver halide emulsion layer.
  • the thus-formed opacifying stratum effectively masks residual dye image-providing material retained in association with the silver halide emulsion layer subsequent to processing.
  • the dimensionally stable layer of the film unit next adjacent the photosensitive layer or layers is disclosed to be opaque, the opacifying agent is initially disposed in an aqueous alkaline processing composition and the film units pH modulating means are disclosed to comprise a polymeric layer disposed intermediate the dimensionally stable transparent layer and the reception layer and adapted to reduce, subsequent to substantial dye transfer image formation, the pH of an aqueous alkaline processing composition from a first processing pH at which the dye-image-forming material or materials are soluble and diffusible in the composition as a function of the photoexposure of the photosensitive silver halide layer associated therewith to a second pH at which the dye imageforming material or materials are substantially nondiffusible and, as disclosed in U.S.
  • the dimensionally stable layer of the film unit next adjacent the photosensitive silver halide layer or layers is disclosed to be transparent to incident actinic radiation and, as further disclosed in U.S. Pat. No. 3,415,645, in such instance the opacifying agent may be initially disposed in the film unit intermediate the reception layer and next adjacent silver halide layer.
  • the opacifying component of the film unit may optionally be initially disposed as a preformed processing composition permeable layer, intermediate the reception layer and next adjacent silver halide layer, in a concentration which prior to photoexposure is insufficient to prevent transmission therethrough of exposing actinic radiation and which, subsequent to processing, possesses an opacifying capacity effective to mask residual dye image-providing material retained associated with the film units silver halide emulsion layers, and in US. Pat. No. 3,647,435, the opacifying component of the film unit may optionally be initially formed in situ, intermediate the reception layer and next adjacent silver halide layer, during photographic processing of the film unit.
  • the opacifying component is disclosed to optionally comprise a lightabsorbing reagent such as a dye which is present as an absorbing species at the first pH and which may be converted to a substantially non-absorbing species at the second pH, and in U.S. Pat. Nos. 3,473,925; 3,573,042 and 3,576,626, opacifying and reflecting component, respectively, may be individually interposed intermediate the silver halide layer and reception layer by selective distribution from a composite or a plurality of rupturable containers.
  • a lightabsorbing reagent such as a dye which is present as an absorbing species at the first pH and which may be converted to a substantially non-absorbing species at the second pH
  • the polymeric neutralizing layer is disclosed to be optionally disposed intermediate the dimensionally stable opaque layer and next adjacent essential layer, i.e., next adjacent silver halide/dye image-providing material component, to effect the designated modulation of film units environmental pl-l;
  • U.S. Pat. No. 3,576,625 discloses the employment of particulate acid distributed within the film unit to effect the modulation of the environmental pH, and
  • U.S. Pat. No. 3,573,044 discloses the employment of processing composition solvent vapor transmissive dimensionally stable layers to effect process modulation of dye transfer as a function of solvent concentration.
  • the film unit may also be constructed in accordance with the disclosure of U.S. Pat. Nos. 3,594,164; 3,594,165; 3,689,262 and 3,701,656 to comprise a composite photosensitive structure including a transparent dimensionally stable layer carrying a reception layer, a processing composition permeable opaque layer and a photosensitive silver halide layer and the film unit may include a separate dimensionally stable sheet element adapted to be superposed on the surface of the photosensitive structure opposite the dimensionally stable layer and may further include means such as a rupturable container retaining processing composition for distribution of a processing composition intermediate the sheet and photosensitive structure to effect processing.
  • the latter elements may optionally include opacifying component.
  • the dimensionally stable layer referred to may be opaque and in which instance the photosensitive silver halide layer is positioned next adjacent the opaque support layer and the opacifying component of the film units processing composition permeable opaque layer will be disposed in the unit in a concentration insufficient to prevent transmission therethrough of exposing actinic radiation and which, subsequent to processing, possesses an opacifying capacity effective to mask residual dye image-providing material retained associated with the silver halide layer, and as disclosed in U.S. Pat. No. 3,647,434, the opacifying agent may be optionally formed in such film unit, in situ, during processing of the unit.
  • two or more separate diffusion transfer process images may be simultaneously provided by exposure and diffusion transfer processing of a film unit which includes a transfer process image-receiving layer located contiguous one major surface of a silver halide emulsion and an imagereceiving element superposed contiguous the opposite major surface of the emulsion during processing and, subsequent to processing, separating the imagereceiving element from its superposed relationship with the emulsion and, where required, the emulsion from its contiguous relationship with the image-receiving layer for viewing of the respective transfer images.
  • the present invention is directed to novel photographic diffusion transfer color process film units and specifically to integral negative/positive, diffusion transfer process photographic film units adapted to provide, by diffusion transfer processing, photographic color image reproduction as a function of exposure of such film unit to incident actinic radiation.
  • the film units will comprise a plurality of layers including, in relative order, afirst dimensionally stable layer transparent to incident actinic radiation; a diffusion transfer process dye image-forming material impermeable layer permeable to processing composition; one or more photosensitive silver halide layers having associated therewith one or more diffusion transfer process dye image-forming materials; an opaque layer; a second transparent layer adapted to receive dye image-forming material diffusing thereto and a second dimensionally stable layer transparent to incident actinic radiation; means for providing, intermediate the first dimensionally stable layer and next adjacent dye image-forming material impermeable layer, opacifying agent; and means for providing a processing composition in contact with the photosensitive layers, and, in a particularly preferred embodiment, a processing composition possessing a first pH at which the diffusion transfer process dye image-forming material is diffusible during processing and means for modulating the pH of the film unit from the first pH to a second pH at which dye image-forming material is substantially nondiffusible subsequent to substantial dye transfer image formation.
  • a film unit assemblage of the aforementioned general structural parameters will be adapted to be processed, subsequent to photoexposure, in the presence of actinic radiation and may be fabricated to employ, as opacifying agent interposed intermediate the first dimensionally stable layer and next adjacent dye image-forming material impermeable layer subsequent to photoexposure, an inorganic lightreflecting pigment dispersion and the means for interposing the opacifying agent and the processing composition will comprise a rupturable container, retaining the opacifying agent disposed in the processing composition selected, fixedly positioned extending transverse a leading edge of the film unit and adapted, upon application of compressive pressure, to distribute its contents intermediate the first dimensionally stable layer and next adjacent dye image-forming material impermeable layer.
  • FIG. 1 is a fragmentary perspective view of one embodiment of a photographic film unit in accordance with the invention.
  • FIGS. 2, 4 and 6 are diagrammatic enlarged crosssectional views of the film unit of FIG. 1, along section line 2-2, illustrating the association of elements during the three illustrated stages of the performance of a diffusion transfer process, for the production of a multicolor transfer image according to the invention, the thickness of the various materials being exaggerated, and wherein FIG. 2 represents an exposure stage, FIG. 4 represents a processing stage and FIG. 6 represents a product of the process; and
  • FIGS. 3, 5 and 7 are diagrammatic, further enlarged cross-sectional views of the film unit of FIGS. 2, 4 and 6, along section lines 33, 5-5 and 77, respectively, further illustrating, in detail, the arrangement of layers comprising the photosensitive laminate during the three illustrated stages of the transfer process;
  • FIG. 8 is a perspective view of a film pack comprising an assemblage of the film units.
  • FIG. 9 is a longitudinal sectional view taken substantially midway between the sides of the film pack of FIG. 8.
  • diffusion transfer photographic processing in accordance with the present invention may be employed to provide a positive reflection dye image, as a direct function of actinic radiation incident on a film unit assemblage which unit is preferably constructed to comprise a plurality of sequential layers including a first dimensionally stable layer transparent to incident radiation; a first transparent layer permeable to processing composition and impermeable to diffusion transfer process dye image-forming material diffusing thereto; one or more photosensitive silver halide layers having associated therewith one or more diffusion transfer process dye image-forming materials; an opaque layer; a layer adapted to receive dye imageforming material diffusing thereto, a second dimensionally stable layer transparent to incident radiation; means for interposing intermediate the first dimensionally stable layer and the next adjacent dye imageforming material impermeable layer opacifying agent, preferably an inorganic reflecting pigment dispersion, in a concentration effective to provide, subsequent to selective photoexposure of the silver halide layer, protection of the silver halide layer from further exposure to
  • the preferred dye imageforming 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 the last-mentioned preferred structural embodiment, without limitation of the invention to the preferred structure denoted.
  • 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 developing function is a hydroquinonyl group.
  • Other suitable developing functions include ortho-dihydroxy-phenyl and orthoand para-amino substituted hydroxyphenyl groups.
  • the developing function includes a benzenoid developing function, that is, an aromatic developing group which forms quinonoid or quinone substances when oxidized.
  • 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, in a preferred embodiment, or in a separate layer contiguous the respective silver halide stratum.
  • the dye developer may, for example, be in a coating or layer behind or directly disposed in the respective silver halide stratum and such dye developer structure 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.
  • the silver halide strata comprising the multicolor photosensitive laminate preferably possess predominant spectral sensitivity to separate regions of the spectrum and each has associated therewith a dye developer which 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.
  • the film unit is specifically adapted to provide for the production of a multicolor dye transfer image and the photosensitive laminate comprises, in order, at least two selectively sensitized silver halide emulsion strata each having dye image-providing material of predetermined image color subsequent to processing associated therewith which is soluble and diffusible substantially only at a first pH, as a function of the photoexposure of its associated silver halide emulsion stratum.
  • 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 photoexposure or processing a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion.
  • a dye which is a silver halide developing agent and is, most preferably, substantially soluble in the reduced form only at a first pH, possessing subsequent to photoexposure or processing a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion.
  • Specifically preferred dyes comprise dyes which exhibit major spectral absorption outside of the primary regions of the spectrum to which the associated silver halide emulsion is sensitive and a spectral transmission substantially complementary to that absorption, during exposure of the emulsion, and major spectral absorption within the spectral range to which the associated silver halide emulsion is sensitive and a spectral transmission substantially complementary to that absorption, subsequent to exposure or processing of said emulsion, for example, of the type disclosed in U.S. Pat. No. 3,307,947.
  • each of the emulsion strata, and its associated dye may be spaced from the remaining emulsion strata, and their associated dye, by separate alkaline solution permeable polymeric interlayers and the dyeable polymeric layer next adjacent the polymeric acid layer may be separated from that layer by an alkaline solution permeable polymeric spacer layer, most preferably a polymeric spacer layer having decreasing permeability to alkaline solution with increasing temperature.
  • the silver halide emulsion comprises photosensitive silver halide dispersed in gelatin and is about 0.6 to 6 microns in thickness;
  • the dye itself may be dispersed in an aqueous alkaline solution permeable polymeric binder, preferably gelatin, as a separate layer about 1 to 7 microns in thickness;
  • the alkaline solution permeable polymeric interlayers for example, gelatin, may be about 1 to microns in thickness;
  • the alkaline solution permeable and dyeable polymeric layers are transparent and may be about 0.25 to 0.4 mil in thickness;
  • the alkaline solution polymeric spacer layers are transparent and may be about 0.1 to 0.7 mil in thickness;
  • the alkaline solution permeable polymeric acid layers are transparent and may be about 0.3 to 1.5 mils in thickness; and
  • the dimensionally stable transparent layers are alkaline solution impermeable and may be about 2 to 6 mils in thickness.
  • 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 yellow dye developer/blue-sensitive emulsion unit, a cyan dye developer/red-sensitive emulsion unit and a 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.
  • either or both the respec tive yellow and magenta dye developers employed in a preferred tripack configuration which positions the yellow dye developer/blue-sensitive emulsion unti distal the opaque layer dimensionally stable transparent layer and the cyan dye developer/red-sensitive emulsion unit proximal the opaque layer to provide the multicolor transfer image, comprise a dye developer which exhibits major spectral absorption outside of the primary region of the spectrum to which its associated silver halide emulsion is sensitive and a spectral transmission substantially complementary to that absorption, during exposure of the emulsion, then, in many circumstances, it may be advantageous to incorporate filter agents adapted to insure the correct selective exposure of the respective emulsions less proximal the exposure surface of the laminate.
  • a yellow filter agent may advantageously be incorporated intermediate the blue-sensitive emulsion and the remaining greenand red-sensitive emulsions, in order to prevent undesired exposure of the latter emulsions by reason of their inherent sensitivity to actinic radiation within the blue range of the spectrum generally present.
  • magenta filter agent may be advantageously incorporated intermediate the greenand red-sensitive emulsions in instances wherein the red-sensitive emulsion possesses sensitivity to actinic radiation within the green region of the spectrum.
  • 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 crosssectional views of film unit 10, along the stated section lines 2--2, 3-3, 5 -5 and 7-7, during the various depicted stages in the performance of a photographic diffusion transfer process as detailed hereinafter.
  • Film unit 10 comprises rupturable container 11, retaining, prior to processing, aqueous alkaline solution 12, and photosensitive element 13 including, in order, dimensionally stable transparent layer 24a; neutralizing layer 23a; spacer layer 23a; processing composition permeable, dye image-forming material barrier layer 25; blue-sensitive silver halide emulsion layer 15 containing yellow dye developer; interlayer 16; greensensitive silver halide emulsion layer 17 containing magenta dye developer; interlayer 18; red-sensitive silver halide emulsion layer 19 containing cyan dye developer; opaque layer 20; image-receiving layer 21; spacer layer 22b; neutralizing layer 23b; and dimensionally stable transparent layer 24b, both layer 24a and layer 2412 comprising an actinic radiation transparent and processing composition impermeable flexible sheet material.
  • Photosensitive element 13 may be provided with a binding member 26 extending around, for example, the specified edges of the element maintaining the element intact except at the interface between spacer layer 22a and barrier layer 25 during distribution of processing composition 12.
  • the binding member may comprise a pressure-sensitive tape 26 securing the photosensitive elements components together at film unit 10s specified edges. Tape 26 will also act to maintainm processing composition 12 intermediate first spacer layer 22a/barrier layer 25 and upon application of compressive pressure to container 11 and distribution of its contents intermediate stated components 220 and 25. Under such circumstances, binder tape 26 will act to prevent leakage of processing composition from the film unit during and subsequent to photographic processing.
  • binding sheet 26 overlying and secured to the trailing edge sections of transparent layer 24a and transparent layer 24b cooperates with the trailing edge of each of the transparent layers to provide an enclosed chamber or trap area 2 adapted to secure and retain excess processing composition 12, employed to insure adequate processing composition coverage upon distribution.
  • binding member 26 may be provided with one or more air release vents 1 associated with the trailing edge section of the film unit and preferably in direct communication with trap chamber 2 in order to facilitate release of air from the film unit during distribution of processing composition 12.
  • Rupturable container 11 may be of the type shown and described in any of U.S. Pat. Nos. 2,543,181; 2,634,886; 2,653,732; 2,723,051; 3,056,491; 3,056,492; 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 27 which are sealed to one another along their longitudinal and end margins to form a cavity in which processing solution 12 is retained.
  • the longitudinal marginal seal 28 is made weaker than the end seals 29 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 27 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 intermediate first spacer layer 22a and barrier layer 25, 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 28 directed toward the leading edge of the stated interface.
  • container 11 is fixedly secured to laminate 13 by extension 30 of tape 26 extending over a portion of one wall 27 of the container, in combination with a separate retaining member such as illustrated retaining tape 31 extending over a portion of the other wall 27 of the container and a portion of laminate 13s surface generally equal in area to about that covered by tape 26.
  • extension flap 30 of tape 26 may be of such area and dimensions that upon, for example, manual separation of container 11 and leader 31, subsequent to distribution of the composition, from the remainder of film unit 10, flap 30 may be folded over the edge of laminate 13, previously covered by leader 31, 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 24.
  • the film unit will be maintained intact subsequent to processing including retention of the exhausted container, the processing composition in the spacial position assumed during processing.
  • the processing composition employed should possess the requisite adhesive capacity, in both the fluid and dry states, to enhance the integrity and stability of the spacial arrangement assumed.
  • the opacity of processing composition 12 when distributed will be sufficient to prevent further exposure of the film units silver halide emulsion or emulsions, by actinic radiation incident on transparent layer 24a during processing of the unit in the presence of radiation actinic to the emulsion or emulsions.
  • the film unit may be processed, subsequent to exposure, in the presence of such radiation, in view of the fact that the silver halide emulsion or emulsions of the laminate are appropriately protected from incident radiation, at
  • the opaque layer or layers 20 are also opaque, as stated above, edge leakage of actinic radiation incident on the emulsion or emulsions will also be prevented.
  • the selected opaque layer or layers 20, however, should be one providing a background suitable for viewing the respective dye developer transfer image formed in the dyeable polymeric layer.
  • substantially any opaque processing composition and permeable opaque layer may be employed, it is preferred that a processing composition and layer be selected that will not interfere with the color integrity of the dye transfer image carried by the reception layers, as viewed by the observer, and, most preferably, an opaque processing composition and opaque layer which is aesthetically pleasing to the viewer and does not provide a background noise signal degrading, or detracting from, the information content of the dye image.
  • a processing composition and layer be selected that will not interfere with the color integrity of the dye transfer image carried by the reception layers, as viewed by the observer, and, most preferably, an opaque processing composition and opaque layer which is aesthetically pleasing to the viewer and does not provide a background noise signal degrading, or detracting from, the information content of the dye image.
  • Particularly desirable opaque compositions will be those providing a white background, for viewing the transfer image, and specifically those adapted to be employed to provide background for reflection photographic prints and, especially, those layers possessing the optical properties desired for reflectance of incident radiation.
  • the opaque layer may comprise substantially any opacifying agent compatible with the photographic system, such as, for example, barium sulfate, titanium dioxide, barium stearate, silver flake, zirconium oxide, and the like, which may be distributed in a permeable polymeric matrix or binder, such as, for example, gelatin, polyvinyl alcohol, and the like.
  • a particularly preferred opaque layer comprises titanium dioxide due to its highly effective reflection properties.
  • a coating composition for example, hydroxyethylcellulose, containing sufficient titanium dioxide to provide a precent reflectance of about to percent, respectively, will be employed.
  • the percent reflectance desired thus will be in the order of 09 about 85 percent.
  • an additional opacifying agent such as carbon black, for example, in a concentration of about one part carbon black to one hundred to five hundred parts titanium dioxide may be provided to the layer.
  • additional opacifying capacity will be provided by constituting the opacifying layer as a plurality of more or less discrete layers, the layer next adjacent the transparent support comprising a reflection layer and the succeeding layer or layers comprising one or more opacifying agents possessing greater opacifying capacity than that ordi narily obtained from the reflecting agent or agents employed.
  • Such additional opacifying agent may be any of the multiplicity of such agents known in the art such as carbon black, iron oxide, titanium (III) oxide, titanium (III) hydroxide, and the like.
  • the agent or agents should be selected which possess the maximum opacifying capacity per unit weight, is photographically nondeleterious and is substantially nondiffusible throughout the film unit subsequent to distribution.
  • a particularly preferred agent has been found to comprise carbon black employed in a concentration effective, taken together with the selected reflecting agent, to provide the opacity required to prevent undesired physical fogging of the emulsion formulations selected and employed by radiation transmitted through the spread processing composition.
  • the fluid contents of the container preferably comprise an aqueous alkaline solution having a pH and solvent concentration at which the dye developers are so]- uble and diffusible and contains inorganic lightreflecting pigment in a quantity sufficient, upon distribution, to provide a layer exhibiting optical transmission density about six to prevent exposure of photosensitive silver halide emulsion layers 15, 17 and 19 by actinic radiation incident or dimensionally stable transparent layer 24a during processing in the presence of such radiation and to afford immediate viewing of dye image formation in image-receiving layer 21 during and subsequent to dye transfer image formation.
  • the film unit may be processed, subsequent to distribution of the composition, in the presence of such radiation, in view of the fact that the silver halide emulsion or emulsions of film unit are appropriately protected by incident radiation, at one major surface of the opaque processing composition and at the remaining major surface by opaque layer 20. If the illustrated binder tapes are also opaque, edge leakage of actinic radiation incident on the emulsion or emulsions will also be prevented.
  • pigments adapted for employment in processing composition 12 mention may be made of those specifically identified above.
  • a particularly preferred processing composition reflecting agent comprises carbon black due to its highly effective light-absorption properties.
  • the opacifying adjuvants to be employed are those which remain substantially immobile within their respective compositions during and subsequent to photographic processing and particularly those reflecting agents which comprise insoluble and nondiffusible inorganic pigment dispersions within the composition in which they are disposed.
  • opacifying adjuvants constituting layer accordingly may thus be distributed 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, intermediate the image-receiving layer and next adjacent silver halide layer, provided that its distribution and concentration is effective to provide the denoted post processing masking function, and the opacifying agent component of the processing composition may be ultimately disposed within the processing composition residuum located intermediate barrier layer 25 and transparent layer 24a.
  • 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, intermediate the image-receiving layer and next adjacent silver halide layer, provided that its distribution and concentration is effective to
  • 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 by FIG. 2.
  • film unit 10 is processed by being passed through opposed suitable gapped rolls 33 in order to apply compressive pressure to frangible container 1 1 and to effect rupture of longitudinal seal 28 and distribution of processing composition 12, containing opacifying agent and having a pH at which the cyan, magenta and yellow dye developers are soluble and diffusible, intermediate first spacer layer 22a and barrier layer 25 coextensive their respective surfaces.
  • Processing composition 12 permeates through barrier layer 25 and into emulsion layers l5, l7 and 19 to initiate development of the latent images contained in the respective emulsions.
  • the cyan, magenta and yellow dye developers, oflayers 15, 17 and 19 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 point-t0- point degree of their associated emulsions exposure.
  • a sufficient portion of the ions comprising aqueous composition 12 transfer, by diffusion, through permeable spacer layers 22a and 22b and to permeable polymeric acid layers 23a and 23b whereby solution 12 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 thereby provide increases stability to the multicolor dye transfer image.
  • container 11 may be manually dissociated from the remainder of the film unit, as described above.
  • the multicolor dye transfer image is viewable through dimensionally stable transparent layer 24b both during and subsequent to transfer image formation, in the preferred embodiment detailed above.
  • Film units similar to that shown in the drawings may be prepared, for example, by providing, in succession, on a first 4 mil. transparent polyester film base, the following layers:
  • timing layer containing about a 49:1 ratio of a /30/4/6 copolymer of butyacrylate, diacetone acrylamide, styrene and methacrylic acid and polyacrylamide at a coverage of about 500 mgs/ftF;
  • gelatin at a coverage of about 50 mgs/ft 6.
  • a second 4 mil. transparent polyester film base may then be taped to the photosensitive element in laminate form, at their respective lateral and trailing edges, by means of a pressure-sensitive binding tape extending around, in contact with, and over the edges of the resultant laminate.
  • a rupturable container comprising an outer layer of lead foil and an inner liner or layer of polyvinyl chloride retaining an aqueous alkaline processing solution such as, for example, about 0.8 cc. of 0.5 cc. of 1N sodium hydroxide and about 0.8 cc. of water, about 100 cc.
  • the photosensitive composite film units may be exposed through radiation incident on the second transparent polyester film base and processed by passage of the exposed film units through appropriate pressureapplying members, such as suitably gapped, e.g., to mils, opposed rolls, to effect rupture of the container and distribution of its contents. Subsequent to processing, multicolor dye transfer image formation may be viewed through the first transparent polyester layer against a titanium dioxide reflection layer.
  • Film units may be processed in the stated manner, subsequent to exposure through a conventional step wedge, to provide graphic illustration of the characteristic curves of the respective dye transfer images forming the multicolor dye positive images.
  • the detailed characteristic curves may be determined by plotting the density of the respective images to red, green and blue light, as a function of the log exposure of the photosensitive element, e.g., the characteristic cyan, magenta and yellow transfer image dye curves (read to red, green and blue reflected light) of the test film units.
  • image formation in the second image-receiving layer may be immediately viewed upon distribution of the processing composition by reason of the protection against incident radiation afforded the photosensitive silver halide emulsion layers by the compositions optical transmission density of about six density units and against the titanium dioxides effective reflective background afforded by reason of the composition possessing an opti* cal reflection density of about one density units.
  • Processing composition permeable dye impermeable layer 25 of the structure detailed, in accordance with the present invention allows passage of the fluid processing composition including processing adjuvants of a molecular size less than that of the stated yellow, magenta and cyan dye developers simultaneously preventing passage or extraction of processing composition solubilized dye developer from the photosensitive laminate into the processing composition in accordance with differential dye concentration gradients between the laminate and the compositions initial distribution locus and the dye sink capacity of processing compositions generally employed in dye diffusion transfer photographic systems.
  • additional polymeric compositions specifically adapted to provide the required processing composition permeable layer of the present invention impermeable to dye developer for the effective duration of the processing of a film unit constructed as detailed immediately above, mention may be made of, for example, butyl acrylate/diacetone acrylamide/styrene/- methacrylic acid (60/30/4/6) +polyacrylamide at 1 to 2 percent by weight of the tetrapolymer coated at a coverage of about 100 mgs./ft. butyl acrylate/diacetone acrylamide/styrene/methacrylic acid (60/30/4/6) polyvinyl alcohol at a :1 ratio coated at a coverage of about 100 mgs./ft.
  • butyl acrylate/diacetone acrylamide/styrene/- methacrylic acid 60/30/4/6 +polyacrylamide at 1 to 2 percent by weight of the tetrapolymer coated at a coverage of about 100 mgs./
  • Rhoplex E-32, HA12 or HA-l6 trade designation of Rohm and Haas Co., Philadelphia, Pennsylvania, USA, for certain acrylic latices less than 1 percent polyacrylamide; and the like.
  • the pH and solvent concentration of the alkaline H-SO processing solution initially employed will preferably possess a pH above the pKa of the optical filter agents where the latter are employed, that is, the pH at which about fifty percent of the agents are present as the lesser absorbing species and about fifty percent are present as the greater absorbing species, preferably a pKa of about 1 1 and most preferably about 12 and 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 and optical filter agent, or group of dye developers and filter agents, most particularly desirable dye developers are soluble at pHs above 9 and relatively insoluble at pHs below 9, in reduced form, and the system can be readily balanced accordingly for such dye developers.
  • the processing 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.
  • the concentration of solvent, that is, water, etc., comprising the composition be the minimum amount necessary to conduct the desired transfer process, in order not to adversely effect the structural integrity of the laminate and that the layers forming the laminate can readily accommodate and dissipate the solvent throughout during processing and drying without effecting undesirable dimensional changes in the layers forming the laminate.
  • the liquid processing composition referring 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 insert 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 100 cps. at a temperature of approximately 24 C. and preferably in the order of 100,000 cps. to 200,000 cps. at that temperature.
  • Neutralizing means for example, a polymeric acid layer of the type discussed above will be incorporated, as stated, in the film unit of the present invention, to provide reduction of the alkalinity of the processing solution from a pH at which the dyes are soluble as a function of film unit photoexposure and above the pKa of selected optical filter agents where desired to a pH below the pKa of the filter agent selected and at which the dyes are substantially nondiffusible, in order to advantageously further stabilize and optimize reflectivity of the respective dye transfer images.
  • the neutralizing layer may comprise particulate acid reacting reagent disposed within the film unit or a polymeric acid layer, for example, a polymeric acid layer approximately 0.3 to 1.5 mils in thickness, positioned intermediate the first and/or second transparent support and the next adjacent functional layer and the film unit may also contain a polymeric spacer or barrier layer, for example, approximately 0.1 to 0.7 mil in thickness, next adjacent the respective polymeric acid layer or layers, opposite the respective support layer, as previously described.
  • a polymeric spacer or barrier layer for example, approximately 0.1 to 0.7 mil in thickness
  • the film units may employ the presence of a polymeric acid layer such as, for example, of the type set forth in US. Pat. No. 3,362,819 which, most preferably, includes the presence of an inert timing or spacer layer intermediate the polymeric acid layer carried on a support and the image-receiving layer.
  • a polymeric acid layer such as, for example, of the type set forth in US. Pat. No. 3,362,819 which, most preferably, includes the presence of an inert timing or spacer layer intermediate the polymeric acid layer carried on a support and the image-receiving layer.
  • the pH of the processing composition preferably is of the order of about least 12 to 14 and the pKa of the selected optical filter agents will accordingly preferably be in the order of 12 or greater.
  • the 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 ll 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 1 l 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 he 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 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 availability of the acid groups in the polymer layer may be effected by mixing acid polymer with a polymer free of acid groups, or lower in concentration of acid groups, and compatible therewith, as a modulated system, or by using only an acid polymer but selecting one having a predetermined acid group availability rate.
  • the layer containing the polymeric acid may also 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 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.
  • the aforementioned rate at which the cations of the alkaline processing composition, i.e., alkali ions, are available for capture in the polymeric acid layer should be decreased with increasing transfer processing temperatures in order to provide diffusion transfer color processes relatively independent of positive transfer image variations over an extended range of ambient temperatures.
  • the diffusion rate of alkali through a permeable inert polymeric spacer layer increases with increased processing temperature to the extent, for example, that at relatively high transfer processing temperature, 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 temperature that is, transfer processing temperatures above approximately 80 F.
  • 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. 3,148,061, issued Sept. 8, 1964.
  • 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 l-phenyl-3-pyrazolidone in combination with p-benzylaminophenol and l-phenyl- 3-pyrazolidone in combination with 2,5-bisethylenimino-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 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 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 required.
  • components such as restrainers, accelerators, etc.
  • concentration of various components may be varied over a wide range and when desirable adaptable components may be disposed in the photosensitive element, prior to exposure, in a separate permeable layer of the photosensitive element and/or in the photosensitive emulsion.
  • the dimensionally stable layers or sheets referred to may comprise any of various types of conventional transparent rigid or flexible materials, for example, papers and polymeric films of both synthetic types and those derived from naturally occurring products.
  • Suitable materials include alkaline solution impermeable materials such as polymethacrylic acid methyl and ethyl esters; vinyl chloride polymers, polyvinyl acetal; polyamides such as nylon; polyesters such as polymeric films derived from ethylene glycol and terephthalic acid; and cellulose derivatives such as cellulose acetate; triacetate, nitrate, propionate, butyrate, acetatepropionate or acetate-butyrate. It will be recognized that one or more or the designated layers may not be required where the remaining layers of the laminate are such as to provide the functions of these layers in the absence of same, for example, where the remaining layers of the laminate provide the prerequisite dimensional stability and radiation filtering properties.
  • the film unit may also contain ultraviolet absorbing materials to protect the mordanted dye transfer image from fading due to ultraviolet light such as those selected from the general class of benzotriazoles and benzophenones as, for example, the substituted Z-phenyl-benzotriazole agents disclosed in US. Pats. Nos.
  • Tinopal SP, WR, SFG, BV277, 28, GS, NG
  • Leucophor B Leucophor B
  • Calcoflour White MR Blaneofor SC
  • BSP Blaneofor SC
  • l-litamine BSP, N, SOL., 6T6
  • commercially available ultraviolet absorbing agents are distributed under the trade designation Tinuvin and the like.
  • ultraviolet absorbing and optical brightening agents may be employed in concentrations varying over an extended range. Suitable concentrations include those within the range of about 0.2 to mgs./ft. of receptor layer surface area and, preferably, between about 1 to 5 mgs./ft.
  • the agents may be incorporated in any one or more of the layers of the film unit preferably intermediate an opaque layer forming the background against which an image is viewed and the viewing surface in any suitable manner as, for example, a constituent component of the casting and/or coating solution or formulation employed to provide such layer or layers employing an organic solvent or water carrier or as a latex dispersion.
  • the layer may optionally be coated on or carried by an appropriate dimensionally stable support layer of the various types and classes specifically designated hereinbefore or not at the election of the operator.
  • the image receptor stratum when the image receptor stratum comprises a layer carried on a separate dimensionally stable support layer, the receptor stratum will comprise in the order of about 0.1 to 0.4 mil in thickness whereas such stratum employed as a self-sustaining layer will comprise in the order of about 3 to 6 mils in thickness.
  • the preparation of the dye developer and color coupler dispersions may also be obtained by dissolving the dye and/or coupler in an appropriate solvent, or mixture of solvents, and the resultant solution distributed in the polymeric binder, with optional subsequent removal of the solvent, or solvents, employed, as, for example, by vaporization where the selected solvent, or solvents, possesses a sufficiently low boiling point or washing where the selected solvent, or solvents, possesses a sufficiently high differential solubility in the wash medium, for example, water, when measured against the solubility of the remaining composition components, and/or obtained by dissolving both the polymeric binder and dye in a common solvent.
  • 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 to commenceer 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 water-soluble salts by chilling the dispersion, noodling the set dispersion, and washing the noodles with cold water, or alternatively, employing any of the various flocc systems, or procedures, adapted to effect removal of undesired components, for example, the procedures described in US.
  • a 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 emulsionss 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, silver chloroiodobromide 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, silver chloroiodobromide 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 deriva tive, as described in US. Pat. Nos. 2,322,085 and 2,327,808; polyacrylamides, as described in US. Pat. No. 2,541,474; and vinyl polymers such as described in an extensive multiplicity of readily available US. and
  • 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 image-forming material in or behind its respective silver halide emulsion portion.
  • a suitable photosensitive screen may comprise minute red-sensitized emulsion elements, minute green-sensitized emulsion elements and minute bluesensitized emulsion elements arranged in side-by-side relationship in a screen pattern and having associated therewith, respectively, for example, a cyan, a magenta and a yellow dye developer.
  • the present invention also includes the employment of a black dye image-providing material and the use of a mixture of, for example, 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 layers 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 layers will be 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 separatedfrom, 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 separatedfrom, each other, for example, two or more neutralizing layers or the like.
  • sheet 24a illustrated in the figures as transparent and superposed coextensive the exposure surface of the photosensitive laminate in the preferred embodiment, may be adapted to be superposed on the laminate subsequent to photoexposure of the film unit as, for example, by fixedly positioning a leading edge of the sheet extending transverse a leading edge of the photosensitive laminate and adapted to be superposed, subsequent to photoexposure, on and coextensive the exposure surface of the laminate, at least during processing, to facilitate distribution of processing composition upon, for example, rupture of the container and unidirectional discharge of its processing composition contents contiguous the exposure surface of the laminate.
  • the displaceable sheet may be transparent or opaque and the processing composition may or may not retain opacifying agent, at the election of the operator. Subsequent to distribution of the processing composition, the sheet may be manually dissociated from the remainder of the film unit individually and/or in combination with the processing composition employed and/or the expended processing composition rupturable container.
  • the preferred form of the film assemblage for the production of a dye reflection print comprises a photosensitive film unit constructed as described above and specifically adapted to be processed in the presence of ambient radiation and the dye reflection print image to be viewed during and subsequent to processing without separation of film unit components and includes leader means for coupling film units and selectively withdrawing the units sequentially from a film pack or magazine and opacifying agent, preferably disposed in whole or in part in the processing composition, taken together with the opaque layer, adapted to prevent exposure of the first sheet elementss photoresponsive material by radiation actinic thereto incident on the film unit in the processing mode.
  • a preferred form of film pack or magazine embodying the designated film units comprises a plurality of the film assemblies, each adapted to be individually exposed to a camera, enclosed in an initially light-proof container which allows the film units to be sequentially exposed.
  • the container includes a forward wall having a light-transmitting section, e.g., an exposure aperture, therein and an opening in one wall through which film assemblies can be individually withdrawn.
  • the photosensitive film units are positioned together in stacked relationship within the container underlying the exposure aperture with the exposure surface of each film unit uppermost and the rupturable container positioned adjacent the opening through which the film units are withdrawn so that following the exposure of each film unit, the unit is moved, by drawing on the leader of the film unit, and withdrawn from the container through the opening.
  • the film pack is initially provided with a cover element or sheet mounted within the container and extending across the exposure aperture for closing the aperture against the admission of light.
  • the cover element also includes a leader extending from the container through the opening and being removable therethrough.
  • the film pack is employed by being positioned in a camera, including a pair of juxtaposed pressureapplying members, with the opening located adjacent the pressure-applying members and the exposure aperture disposed approximately in the exposure plane of the camera.
  • a leader for the cover element extends from the pack and from the camera where the lastmentioned leader may be grasped for withdrawing the I cover element from the pack through the pressureapplying members and camera to allow'the film units of the pack to be selectively exposed. After each successive film unit is exposed, that film unit is then individually withdrawn from the container and camera between the pressure-applying members by withdrawing the leader of the first film unit and of successive film 27 units from the container and camera.
  • Each film unit 10 includes a leader sheet 31 having a leading end section designated 38 and a trailing end section 40 at which the leader sheet 31 is coupled with the film unit near the leading end thereof.
  • Leader sheet 31 including leading and trailing end sections 38 and 40 is approximately equal in width to the film unit 10 and leading end section 38 of each leader sheet 31 is secured to the trailing end of the next preceding film unit or, in the case of the first film unit, to the cover sheet, preferably near the trailing end section of the preceding element (cover sheet or film unit).
  • leader sheet 31 between its leading edge attachment to one film unit and the trailing edge to the next succeeding film unit is substantially equal to the length of the film units between their leading and trailing edges; and the connected film units and leaders are arranged in zig-zag folded relation.
  • FIGS. 8 and 9 of the drawings A film pack or assemblage of film units 10 embodying the invention is shown in FIGS. 8 and 9 of the drawings.
  • This film pack, designated 44 comprises all of the components and structure including pressure-applying means required to produce a plurality of diffusion transfer process color prints.
  • Film pack 44 comprises a generally parallelepipedshaped container or box 46 for holding and enclosing a plurality of film units 10 arranged in stacked relation.
  • Container 46 is shown as comprising a forward wall 48, side walls 50, a trailing end wall 52, a leading end wall 54, and a rear wall 56 and is preferably formed of plastic material that is at least semi-rigid and adapted to conventional molding techniques.
  • Forward wall 48 is provided with a generally rectangular exposure aperture 58 for transmitting light for exposing the forwardmost of the film units carried in stacked relation within the container.
  • Leading end wall 54 is provided with a generally rectangular withdrawal slot or exit opening 60 the forward edge of which is defined by forward wall 48 and through which film units 10 carried by the container are adapted to be withdrawn one at a time following exposure.
  • restraining means in the form of one or more projections or extensions 62 of end wall 54 may be provided.
  • Projections 62 which as illustrated are integral parts of end wall 54, project forwardly part way across opening 60 to positions whereat they suffuciently obstruct the opening to the extent that they must be deformed in order to permit the passage of the forwardmost film unit in the stack, that is, the film unit positioned for exposure across aperture 58 against forward wall 48.
  • Projections 62 comprise a resilient construction such that as the leading film unit is withdrawn through opening 60, the leading edge of the film unit will engage and deflect projections 62 outward sufficiently to permit the forward film unit only to move through slot 60, while preventing the next succeeding film unit from moving through the slot.
  • the film pack of the invention is initially provided with a dark slide or cover sheet 64 formed of an actinic light-impermeable sheet material for preventing admission of light through exposure aperture 58 prior to loading of the film pack into a camera or attachment of the film pack to the rear of the camera.
  • Cover sheet 64 includes a section at least coextensive in area with forward wall 48 for preventing the admission of light and a leading end section 66 which may be tapered, as
  • a lip 68 is provided on forward wall 48 surrounding opening 58 for cooperating with the camera to properly locate the film pack and exposure opening therein with respect to the exposure systems of the camera and in instances where the film pack is coupled to the rear of the camera rather than being completely enclosed therein, lip 68 also cooperates to form a light-tight seal between the interior of the camera and the interior of the film pack container.
  • the film units 10 are arranged in stacked relation between the forward and rear walls of the film pack with sheets 24a facing forwardly and the exposure areas of the film units aligned with exposure opening 58.
  • Means are provided for resiliently biasing the film units 10 and cover sheet 64 forwardly against the rear surface of forward wall 48 to light-seal the exposure aperture when the cover'sheet is in place and following cover sheet removal, locate the forwardmost film unit in proper position for exposure in the image plane of the camera, i.e., against the rear surface of forward wall 48.
  • a spring and pressure plate assembly designated 70 preferably formed of resilient sheet metal and including a generally rectangular frame 72 for engaging and supporting the rearwardmost film unit and a transverse portion 74 from which extend rearwardly biased spring sections 76 engaged with the rear wall 56 of the film pack for biasing frame 72 and the film units supported thereby, forwardly toward forward wall 48.
  • each film unit 10 includes a leader 31 attached at its trailing end 40 to the forward surface of the film unit near the leading end thereof.
  • the film units and leaders are arranged in the film pack container with the trailing end of each leader 31 folded back upon itself so that the leader extends toward the trailing end of the film unit and pack container between the forward surface of the film unit of which it is a component and the rear surface of the cover sheet 64 (in the case of the forwardmost film unit) or the rear surface of the preceding film unit next adjacent forward wall 48 and exposure aperture 58.
  • the leading end 38 of each leader is folded forwardly upon itself and attached to the rear surface of the component, i.e., cover sheet 64 or film unit 10, located next adjacent the forward wall and is secured to said component near the trailing end thereof.
  • film pack 44 includes means for compressively engaging each film unit as it is withdrawn therefrom following exposure, to rupture container 11 causing the discharge of its liquid

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US393799A 1973-09-04 1973-09-04 Photographic products and processes with barrier layers for diffusable dyes Expired - Lifetime US3888669A (en)

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US393799A US3888669A (en) 1973-09-04 1973-09-04 Photographic products and processes with barrier layers for diffusable dyes
DE2441751A DE2441751A1 (de) 1973-09-04 1974-08-30 Zusammengesetzte filmeinheit fuer das photographische diffusionsuebertragungsverfahren
FR7429835A FR2242705B1 (de) 1973-09-04 1974-09-02
GB38353/74A GB1482573A (en) 1973-09-04 1974-09-03 Photographic diffusion transfer silver halide products and processes
JP10127674A JPS5630537B2 (de) 1973-09-04 1974-09-03
CA208,469A CA1036857A (en) 1973-09-04 1974-09-04 Photographic products and processes

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4190447A (en) * 1978-01-09 1980-02-26 Eastman Kodak Company Cover sheets for integral imaging receiver elements
US4478944A (en) * 1982-11-24 1984-10-23 Eastman Kodak Company Analytical element containing a barrier zone and process employing same
US5254441A (en) * 1991-10-01 1993-10-19 Eastman Kodak Company Development inhibitor reflector layers
US5288745A (en) * 1992-09-28 1994-02-22 Eastman Kodak Company Image separation system for large volume development
US5298376A (en) * 1991-10-01 1994-03-29 Eastman Kodak Company Photographic silver halide material with improved color saturation
US5322758A (en) * 1992-09-28 1994-06-21 Eastman Kodak Company Integral color diffusion transfer element for large volume development
US5342730A (en) * 1992-09-28 1994-08-30 Eastman Kodak Company Dye releasing couplers for color diffusion transfer elements with dye barrier layers
US5370967A (en) * 1992-09-28 1994-12-06 Eastman Kodak Company Barrier layer for dye containment in photographic elements
US5512414A (en) * 1993-09-23 1996-04-30 Eastman Kodak Company Solid particle coupler dispersions for color diffusion transfer elements
US6203970B1 (en) * 1999-12-16 2001-03-20 Eastman Kodak Company Photographic element with porous membrane overcoat

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3701656A (en) * 1968-05-13 1972-10-31 Polaroid Corp Photographic products and processes for color diffusion transfer
US3721562A (en) * 1971-07-29 1973-03-20 Polaroid Corp Integral laminate photographic units comprising developing composition-spreader sheets containing a polymeric acidifying layer
US3765887A (en) * 1968-05-13 1973-10-16 Polaroid Corp Film assemblage for color diffusion transfer
US3785815A (en) * 1972-04-24 1974-01-15 Polaroid Corp Spacer or timing layer in color diffusion transfer film

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE757959A (fr) * 1969-10-24 1971-04-23 Eastman Kodak Co Produit pour la mise en oeuvre d'un procede de photographie en couleurspar diffusion-transfert
DE2032330C3 (de) * 1970-06-30 1974-01-24 International Polaroid Corp., Jersey City, N.J. (V.St.A.) Lichtempfindliches fotografisches Aufzeichnungsmaterial
CA953970A (en) * 1970-07-24 1974-09-03 Walter M. Bush Photosensitive element and film unit for diffusion transfer processing
US3625685A (en) * 1971-02-26 1971-12-07 Polaroid Corp Photographic color diffusion-transfer element comprising aqueous film-forming synthetic polymer suspension layers intermediate its sensitive layers and processes for their use
US3756816A (en) * 1971-12-17 1973-09-04 Polaroid Corp Orming polymer dispersion photographic film units including a layer comprising an aqueous filmf

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3701656A (en) * 1968-05-13 1972-10-31 Polaroid Corp Photographic products and processes for color diffusion transfer
US3765887A (en) * 1968-05-13 1973-10-16 Polaroid Corp Film assemblage for color diffusion transfer
US3721562A (en) * 1971-07-29 1973-03-20 Polaroid Corp Integral laminate photographic units comprising developing composition-spreader sheets containing a polymeric acidifying layer
US3785815A (en) * 1972-04-24 1974-01-15 Polaroid Corp Spacer or timing layer in color diffusion transfer film

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4190447A (en) * 1978-01-09 1980-02-26 Eastman Kodak Company Cover sheets for integral imaging receiver elements
US4478944A (en) * 1982-11-24 1984-10-23 Eastman Kodak Company Analytical element containing a barrier zone and process employing same
US5254441A (en) * 1991-10-01 1993-10-19 Eastman Kodak Company Development inhibitor reflector layers
US5298376A (en) * 1991-10-01 1994-03-29 Eastman Kodak Company Photographic silver halide material with improved color saturation
US5288745A (en) * 1992-09-28 1994-02-22 Eastman Kodak Company Image separation system for large volume development
US5322758A (en) * 1992-09-28 1994-06-21 Eastman Kodak Company Integral color diffusion transfer element for large volume development
US5342730A (en) * 1992-09-28 1994-08-30 Eastman Kodak Company Dye releasing couplers for color diffusion transfer elements with dye barrier layers
US5370967A (en) * 1992-09-28 1994-12-06 Eastman Kodak Company Barrier layer for dye containment in photographic elements
US5441854A (en) * 1992-09-28 1995-08-15 Eastman Kodak Company Photographic image forming process utilizing a barrier layer for diffusible dye containment
US5512414A (en) * 1993-09-23 1996-04-30 Eastman Kodak Company Solid particle coupler dispersions for color diffusion transfer elements
US6203970B1 (en) * 1999-12-16 2001-03-20 Eastman Kodak Company Photographic element with porous membrane overcoat

Also Published As

Publication number Publication date
DE2441751C2 (de) 1988-07-21
DE2441751A1 (de) 1975-03-13
FR2242705B1 (de) 1981-05-08
GB1482573A (en) 1977-08-10
CA1036857A (en) 1978-08-22
FR2242705A1 (de) 1975-03-28
JPS5630537B2 (de) 1981-07-15
JPS5056938A (de) 1975-05-19

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