US2977226A - Photographic process, product and apparatus - Google Patents

Photographic process, product and apparatus Download PDF

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Publication number
US2977226A
US2977226A US614983A US61498356A US2977226A US 2977226 A US2977226 A US 2977226A US 614983 A US614983 A US 614983A US 61498356 A US61498356 A US 61498356A US 2977226 A US2977226 A US 2977226A
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Prior art keywords
sheets
layers
fluid
photosensitive
image
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US614983A
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English (en)
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Land Edwin
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Polaroid Corp
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Polaroid Corp
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Priority to NL104746D priority Critical patent/NL104746C/xx
Priority to NL221363D priority patent/NL221363A/xx
Priority to BE561463D priority patent/BE561463A/xx
Application filed by Polaroid Corp filed Critical Polaroid Corp
Priority to US614983A priority patent/US2977226A/en
Priority to GB29931/57A priority patent/GB853877A/en
Priority to FR1192238D priority patent/FR1192238A/fr
Priority to DEJ13831A priority patent/DE1240401B/de
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Publication of US2977226A publication Critical patent/US2977226A/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
    • G03C8/52—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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03D—APPARATUS FOR PROCESSING EXPOSED PHOTOGRAPHIC MATERIALS; ACCESSORIES THEREFOR
    • G03D9/00—Diffusion development apparatus
    • G03D9/02—Diffusion development apparatus using rupturable ampoules of liquid
    • G03D9/025—Diffusion development apparatus using rupturable ampoules of liquid for colour films

Definitions

  • This invention relates to photography and, more particularly, to improved methods for treating photosensitive materials with fluid processing reagents and to film units and apparatus for use inthe performance of said methods.
  • Objects of the present invention are: to provide a novel method for simultaneously treating at least two superposed photosensitive material layers' with at least two fluid processing reagents, which method is characterized by the fact that one of the fluid reagents is spread in a layer on one of the photosensitive layers simultaneuosly with the spreading of the other reagent on the other photosensitivelayer and the photosensitive layers and reagents are isolated from one another during spreading and during the processing reactions instituted thereby, to pro.- vide a novel method of the foregoing type wherein spreading of the fluid reagents is eflected by movement of the photosensitive layers in superposed relation between a pair of pressure-applying members and whereby an accurate control may be had over the thickness of each layer of fluid reagent spread on one of the photosensitive layers; and to provide a novel method of the foregoing type wherein at least two layers of fluid are spread on opposite sides of a substantially rigid sheetlike element located between and in superposition with a pair of photosensitive layers located on flexible support sheets.
  • the methodof the present invention finds particular application in a number of photographic processes, such as color processes involving the formation of two or i more positive images, wherein it is desirable to simultaneously expose at least two different photosensitive layers while the photosensitive layers are maintained in intimate face-to face contact, to separate the photosensitive layers during treatment, which results in the production of positive images in separate layers, and'thereaftersuperposing the image-carrying layers in face-to-face contact with the images in registrationwhereby theimages maybe viewed in conjunction with one another.
  • a further object of the invention is to provide photographic products and apparatus adapted to be employed in the foregoing methods.
  • Figure 1 is a schematic enlarged sectional view of a photographic assemblage adaptedto be employed in the Fig.- 5 is a schematic enlarged elevational view, par-v tially in section, illustrating? one stage in carrying out the process of the invention; and i Fig. 6 is an enlarged schematic elevational view, partially in section, illustrating another embodiment of the invention and showing one stage in carrying out the process of the invention.
  • vention find utility in the treatment of photosensitive sheet materials, and particularly materials comprising a layer of light-sensitive material, such as a silver halide emulsion, carried on a flexible'support sheet, for example of paper, organic plastic material and the like. Processing of the photosensitive material is effected by a fluid reagentdis:
  • the second sheet may serve merely to aid in the spreading of theprocessing agent or it may serve other functions; for example, it may be provided with additional reagents which participate in a processing reaction or it mayserve as a support for image-forming substances transferred from the photosensitive material duringprocessing,
  • the fluid processing reagent maybe provided and distributed between'the sheets in a number of ways, shown and described, for example, in Patent No. 2,647,056, issued July 28, 1953, to Edwin H. Land.
  • the fluid agent is provided in a rupturable podlike container located between the photosensitive and second sheets adjacent an edge of the area of the photosensitive sheet over which the fluid is to be distributed so that, as the two sheets are moved between the pressure-applying members, the container is first to be subjected to compressive forces for causing its fluid contents to be discharged between the sheets. Continued movement of the sheets between the pressure-applying members is then effective to distribute the fluid in a thin layer between adjacent surfaces of the two sheets. To permit a more uni.- form and controlled spreading of the fluid in the container, there is provided in the fluid a material which imparts thereto a predetermined high viscosity. A further control may be had over the uniformity and thickness of the layer of fluid, as described in Patent No.
  • processes may be performed which require at least two photosensitive materials arranged in separate layers and located in superposed relation, although not necessarily in contact with one another. It may be desirable to process each of these two layers with a separate fluid reagent while maintaining the layers in superposed relation and to effect the spreading of the two fluid reagents on the photosensitive layers simuitaneously. Hithertofore this has been accomplished by superposing each photosensitive layer or sheet with the surface of a second sheet, which surfaces may be the opposite surfaces of .the'same sheet, and moving the sheets in superposition between a pair of pressure-applying members. This arrangement, while essentially satisfactory, is not, howeveryconducive to ac ra e con rol o er the.
  • the present invention comprehends a method whereby at l st two fl i proc g r g may b spr d simultaneously in two separate and distinct layers of accu; rately predetermined uniform thickness on and between adjacent and coextensive areas of two flexible photosensia tive sheet materials by movement of said sheet materials in superposed relation between a pair of pressure-applying members.
  • a substantially rigid flat sheetlike element or plate between the two superposed photosensitive sheets and moving the sheets and intervening plate in superposition between a pair of pressure-applying members each having cooperating portions for engaging the margins of the sheets and maintaining the fluid-spreading surfaces of the pressure-applying members spaced apart by an amount predeterminedly exceeding the combined thickness of the margins of the photosensitive sheets and intervening rigid element.
  • Each surface of the intervening plate functions in the nature of one of a pair of fluidspreading surfaces and cooperates with the fluid-spreading surface of one of the pressure-applying members for insuring an even, controlled spread of fluid in a layer between the surface of the plate and a superposed photosensitive sheet.
  • the plate is sufliciently rigid and inflexible so that it cannot be readily deformed due to hydraulic pressure generated in the layers of processing fluid, with the result that the pressures exerted on each layer of fluid and generated therein are substantially equal to the pressures exerted on and generated in the other layer, and the gaps or spaces between the surfaces of the rigid plate and the photosensitive elements are accurately and uniformly controlled and maintained.
  • each of the pressure-applying members includes cooperating portions for engaging one of the superposed photosensitive sheets adjacent the opposite edges thereof and the pressure-applying members include fluid-spreading portions located be tween the edge-engaging portions having cooperating converging fluid-spreading surfaces at least one of which is preferably convexedly curved.
  • At least one of the pressure-applying members is movably mountedfor movement toward and away from the other member and means are provided for resiliently urging the movably mounted member toward the other member under a force greater than the force produced by the pressure generated in the fluids during spreading thereof.
  • the edge-engaging portions are so related to the members as to space the converging fluid-spreading surfaces apart a predetermined distance greater than the spacing existing between said edge-engaging portions when the latter are operatively associated. These latter portions are operative to move the movable pressure-applying member to cause the ,spac ing of the fluid-spreading surfaces to increase upon any increase in the thickness of the photosensitive sheets or intervening plate, and allows said resilient means to move 1 said member to decrease the spacing of said surfaces upon any decrease in thickness of said sheets.
  • This ar-v rangement of the portions of the pressure-applying members permits separation of the two sheets and intervening plate as they are advanced between the fluid-spreading surfaces which are independent of the thicknesses of the sheets and plate.
  • the sheet-engaging portions of the pressure-applying members preferably constitute a pair of shoulders on eachmember cooperating with corresponding shoulders on the opposite member.
  • the shoulders extend beyond the-fluid-spreading surface of each member toward the other member to engage marginal superposed edges of the two sheets and the intervening plate as the sheets and plate pass'between the fluidspreading surfaces. and thus predeterminedly space the fluid-spreading surfaces apart from one another a predetermined amount greater than the combined edge thickness of said sheets and said plate, and space each of said fluid-spreading surfaces apart from the surface of the intervening plate a predetermined amount greater than the edge thickness of the photosensitive sheet located between said member and said plate.
  • edge-engaging shoulders may .beprovided on either or both surfacesof the intervening plate fo pacing he fluidspreading surface of a pressure-applying member apart from the surfaceot the plate a pre S determined amount greater than the edge thickness of the photosensitive sheet located therebetween.
  • Photographic assemblagesor film units adapted to use in this process generally comprise two.
  • the two sheets are attached to one another with the photosensitive layers in face-to-face contact and remain fastened togetherthroughout the process, being fastened in such a manner that the areas thereof adapted to be exposed and treated with fluid reagents may be spaced apart from one another during treatment and topermit the separation of the emulsion layers fromthe imagereceiving layers while assuring accurate registration of the images in the image-receivinglayers when the latter are superposed with one another.
  • the photographic assemblage designated 10
  • the photographic assemblage comprises a pair of sheetlike elements 12 and 22 each comprising a multiplicity of layers or strata carried on a flexible sup port sheet.
  • Sheets 12 and 22 comprise, respectively, support sheets 14 and 24 formed of a transparent and substantially flexible material of the type generally used as a base for photographic film, such as cellulose acetate, cellulose triacetate or other organic plastic materials.
  • Support sheets 14 and 24 carry, respectively, image receiving layers 16v and 26, stripping layers 18 and 28, and photosensitive emulsion layers 20 and 30, stripping layers 18 and 28 being located between the image-receiving layers and the emulsion layersto provide for the separation of the emulsion layers from the image-receiving layers which are adapted to remain on the support sheets in the finished print. If the finished print is to be of the type adapted to be viewed in reflected light, rather than a transparency, one of support sheets 14 and 24 (here sheet 24) could be of an opaque material such as paper or the like so, long as the other support sheet registered with one another even though the sheets are spaced apart during processing.
  • this last-mentioned means for fastening sheets 12 and 22 together comprises a hinge 32 secured to one edge of the sheets, permitting the areas thereof which are exposed and treated to be spaced apart, yet prohibiting lateral movement of the sheets relative to one another. Fastening of the sheets together in this manner, it will be noted, also permits them to be spaced apart, if desired, during exposure while retaining the advantages of predetermined registration.
  • Other conventional fastening means useful for securing sheets together are suitable for the purposes for this invention and include, for example, staples, rivets stitching, cementing and the like.
  • support sheets 14 and 24 could comprise sections of a single sheet folded intermediate its ends.
  • Sheets 12 and 22 are superposed with one another with the emulsion layers 20 and 30 in intimate face-to-face contact so that the two emulsion layers can be exposed simultaneously, one through the other, while both layers are maintained in intimate contact.
  • the two emulsion layers include generally coextensive areas adapted to be exposed and. the two sheets .12 and 22 are fastened together adjacent one edge of these areas in such a manner that the images formed in the two sheets may be easily 20 and 30 are in superposition with opposite surfaces of the plate.
  • Plate 34 is substantially rigid, as compared to sheets 12 and 22, and is at least sufficiently inflexible to resist deformation due to differences in hydraulic pressure generated within the layers of fluids as they are spread on opposite sides of the plate.
  • plate 34 may be considerably thicker in section than sheets 12 and 22' and is formed, for example, of sheet metal or organic plastic materials having substantial structural strength and rigidity.
  • One end of plate 34 may be tapered, as shown, to facilitate introduction of the plate between the sheets and the other end may be suitably formed so as to aid in trapping any excess of the fluid reagents.
  • the pressure-applying members comprise a pair of elongated rolls 36 and 38 having intermediate cylindrical portions defining fluid-spreading surfaces.
  • Roll 38 is mounted for rotation on a pair of stubshafts 40 located at its ends journaled in a suitable support or frame 42 which may comprise a portion of veinapparatus, such as a camera. its ends mounted for rotation on a pair of movable support members 46 so that roll 36 is movable'towa-rd and away from roll 38.
  • Resilient means in the forrriof springs 48 are provided for urgingroll '36 toward roll 38.
  • the pressure-applying members have been shown as comprisinga pair of rotatably mounted, cylindrical rolls, other formsof the invention contemplate theuse of nonrotatable pressure-applying members having convergent fluid-spreading surfaces.
  • substantially rigid members having fluid-spreading surfaces which converge toward one another and are straight in the direction of their elongation. The fluid-spreading surfaces of the presrolls shown.
  • the preferred form of the invention the
  • pressure-applying members are held stationary while the sheets are moved therebetween. However, it is possible to spread the fluid by holding the sheets stationary and moving the pressure-applying members.
  • the aforementioned edge-engaging portions of the pressure-applying rolls comprise a pair of steps or raised shoulders on the ends of each roll having a diameter greater thauthe intermediate portions of the roll.
  • These steps on the ends of rolls 36 and 38 are'designated 37 and '39, respectively, and are positioned to engage theedges of sheets '12 and 22 and plate 34 superposed therebetween for spacing the fluid-spreading surfaces of the rolls apart by an'amount predeterminedly Figs. 2 through 5 of the drawings wherein there is illustrated a preferred method
  • Roll 36 includes a pair of stub shafts 44 at if greater than the combined thickness of the edge portions of the sheets and plate.
  • the height of the shoulders on each roll or the difference between the radius of the shoulders and the fluid-spreading surfaces therebetween approximates the thickness of a layer of fluid to be spread thereby between one of the sheets and a surface of plate 34.
  • the height ofeach pair of shoulders ranges between two and six thousandths of an inch and controls the spacing between the fluid-spreading surface of a roll and a surface of plate 34, so that it remains greater than the edge thickness of the sheet located therebetween by a constant amount which is substantially equal to the height of the shoulders, this amount remaining substantially constant despite variations in the thicknesses of the sheets and plate.
  • Plate 34 located between sheets 12 and 22, functions in the nature of a pressure-applying member in that each surface of the plate acts as one of a pair of fluid-spreading surfaces, the other of the pair of surfaces comprising one of the rolls.
  • Plate 34 being substantially rigid, is not easily deformed due to hydraulic pressure generated in the fluid layers so that the thickness of each layer is a function of the height of the shoulders on one of the rolls. Accordingly, by providing rolls with shoulders of different heights, it is possible to spread two fluids simultaneously in layers of different thickness and and the thicknesses of said layers can be accurately predetermined and maintained uniform. Another feature of having shoulders on the rolls is that the shoulders exert increased pressure at the margins of the sheets, tending to confine the fluids between the sheets and prevent their escaping from between the margins of the sheets as the fluids are being spread.
  • the fluid reagents may be provided between the sheets in a'variety of ways and, in a preferred form of the invention, are provided in a pair of elongated rupturablc containers t adapted to rupture and discharge their fluid contents in one direction when subjected to compressive pressure during advancement between a pair of pressureapplying mernlbers.
  • Containers of the preferred type may be formed, for example, by taking a single sheet of fluidimpervious multilayer material and folding the same medially, and thereafter securing the end marginal portions and the longitudinal portions of the two folded faces to one another, providing a central cavity for containing the fluid reagent. The longitudinal.
  • seal between the marginal portions is preferably such that, upon application of a predetermined force to the walls of the container, there may be created within the container a sufficient hydraulic pressure to separate the marginal portions throughout substantially their entire length.
  • con tainers 50 each carrying a quantity of fluid indicated at 52, are secured to opposite sides of plate 34- adjacent the tapered end thereof adapted to be introduced between sheets 12 and 22. This arrangement is preferable to securing the containers between the sheets since, in this arrangement, the containers do not interfere with the registration of the two sheets when they are superposed.
  • treatment of the photosensitive layers with fluid reagents is effected by introducing a plate 34, carrying a pair of fluid-filled containers 5%, between sheets 12 and 22 with the containers located adjacent hinge 32 substantially in the manner shown in Fig. 2. Thereafter, the sheets and plate are moved in superposition between rolls 36 and 38, commencing at the end adjacent the containers, for spreading each of'fiuids 52 in a layer 54 between one of the sheets and-a surface of plate 34 toform a sandv lich.
  • the plate being rigid, may be employed to advantage for I pushing the assemblage between the rolls or the assemblage maybe drawn between the rolls or advanced therebetween in response to rotation of the rolls. Following spreadingof the fluids, the sheets are allowed to remain in superposed relation during a predetermined processing period, at the end of which each of the sheets may be stripped from the plate, the plate withdrawn from between the sheets and the two sheets superposed again in their original position.
  • the containers are preferably attached to the plate so that they remain with the plate when it is withdrawn from between the sheets.
  • emulsion layers 26 and 30 are intended to be stripped from image-receiving layers 16 and 26 and this may be accomplished by causing the emulsion layers to adhere to the plate as the sheets are stripped therefrom.
  • the cooperating portions which act to space apart the fluid-spreading surface of each roll and the surface of the rigid plate, may be provided on the plate itself as marginal shoulders or strips on either or both surfaces of the plate.
  • the three layers of fluid designated 61, 63 and 65, are spread, respectively, on three sheets 60, 62 and 64 with the aid of two rigid plates 66 and 68 and a pair of pressure-applying rolls 70 and 72.
  • Each of rolls 70 and 72 includes a pair of raised shoulders, designated respectively 71 and 73, at its ends substantially as shown and previously described and one of the plates, here plate 6 8, is provided with a pair of raised shoulders 69 at its lateral edges.
  • the sheets 60, 62 and 64 may be of any desired nature and composition and, for example, sheets 68 and 62 may be similar to sheets 12 and 22 and adapted to record two portions of the spectrum while sheet 64 may be adapted to record a third portion of the spectrum so that the as semblage of the three sheets may be used in the production of an image in terms of three colors or dyes.
  • 'Plate 66 is substantially flat and without shoulders and is located between sheets 6d and 62. Shoulders 71 on roll 70 cooperate with plate as to control the thickness of layer 61 of fluid spread between sheet 6ft and the surface of plate 66.
  • Plate 625 is located between sheets 62 and 64 with shoulders 69 in contact with sheet 62 so that they cooperate, with plate 66 to control the thickness of the layer 63 of fluid spread between the other surface of plate 66 and sheet 62.
  • the surface ofplate 63 located adjacent sheet 64 is plane and shoulders 73 on roll 72 cooperate with plate 63 to control the thickness of the spread of fluid in layer 65 between sheet 64 andplate 68.
  • the three sheets 6%, 62 and 4 may be fastened together and exposed while in superposition, although it is apparent that only two of the photosensitive layers (on sheets 69 and 62) would be in contact with one another.
  • the plates would be provided with containers of fluid, one of the plates mounting two containers and the other plate mounting one container. The two plates would be introduced between the sheets to commence the treatment of the sheets and would be withdrawn'frorn between the sheets at the end of the treatment, at which time the photosensitive layers could be stripped from the sheets, for example, by adhering them to the plates.
  • the three sheets each preferably carrying an image, could then be superposed with two of the image-carrying layers in contact with one another and with the third layer spaced from the other two by the thickness of one of the sheets whereby the three images could be viewed in conjunction with one another.
  • fluid processing reagents useful in the performance of the invention include a fihn-forming material which is preferably a high molecular weight polymer and which imparts to the fluid agent a predetermined high viscosity.
  • a high viscosity for the fluid processing agent is very desirable since it makes possible the relatively uni form spreading of the fluid agent and insures a complete coverage of the desired area by said agent.
  • the fihnforming material is preferably contained in thefiuid agent in suitable quantities to impart thereto a viscosity in excess of lOOOcentipoises at a temperature of 24 C. and pref 9 erably of the order of 1000 to 200,000 centipoises at said temperature.
  • the film-forming material is preferably of such character as to retain its viscosity-imparting and film-forming properties in an aqueous alkaline solution so that the fluid agent, once its ingredients have been mixed 'and have attained an equilibrium, remains uniformly viscous for any given temperature for long periods of time.
  • the film-forming material is. preferably one of the class of high molecular weight polymers which include, in their chemical structure, such groups as, for example, the ether, alkyl, hydroxyl, carboxyl and acetyl groups that are stable to alkalies and .which contain chemical groups, such as the ester and acid chloride groups, that are stable to alkalies.
  • the polymers also contain groups, such as the hydroxyl and/or carboxyl groups, which tend to solubilize the polymer in aqueous alkaline solution.
  • groups such as the hydroxyl and/or carboxyl groups, which tend to solubilize the polymer in aqueous alkaline solution.
  • Suitable examples of such polymers are the alkali-inert and water-soluble cellulose derivatives such as sodium carboxymethyl cellulose and hydroxyethyl cellulose and the alkali-inert and water-soluble polyalkane derivatives such as polyvinyl alcohol and the sodium salts of polymethacrylic and polyacrylic acid.
  • Fluid processing compositions adapted to be spread 'in a thin layer between an exposed silver halide emulsion layer and a rigid plate to effect the formation of a dye image in an image-receiving layer underlying 'the emulsion layer preferably contain color-providing substances.
  • the expressioncolor-providing substances, as used herein, is intended to include all types of substances or reagents which may be utilized to produce a positive image in terms of a dye.
  • the chromophoric system imparting the desired color properties to the positive image dye may be initially contained in such colorproviding substances or such chrornophoric system may be formed as a result of a reaction after transfer, such as oxidation and/or coupling.
  • Thecolor-providing substance initially may be of the same color as the inrage dye to be produced thereby or may be of a different color or a :neutral color.
  • Such color-providing substances do not form a part of the inventive subject matter, .of this application and therefore are not given in 'detail.' For purposes of illustration, however, Jmention may be made of the following types of color-providing substances which may be utilized in employing the inventive concepts of this invention.
  • Self cou'pling developers e.g., a silverihalide developing agent, capable ,of 'coup1ing with itself, iwhen oxidized, to form a dye; see for examplejthe above mentioned Patent'No. 2,698,244.
  • Leuco dyes that is, dyes utilized in their leucopr reduced form and'which possess a silver; halide developing functionfbut which must be"oxid ized after transfer the imageireceiving material; see for example-the cop'endingf applicationiof Howard G. Roger'sfserial No. x
  • Coupling dyes i.e.,' acomplete dye which is halide emulsion layer containing a latent color record image is processed by a fluid reagent to obtain an imagewise distribution of diffusible color-providing substances.
  • the imagewise distribution of difiusible color-providing substances results from immobilization or trapping of color-providing substances in exposed areas in situ with the developed silver as a result of the development of the latent image.
  • a positive image may be obtained by the transfer of such diifusible nonimmobilized color-providing substances by imbibition from the developed photosensitive layer to a superposed image-receiving layer.
  • the desired image is then revealed by stripping the developed photosensitive layer from the image-receiving layer after a suitable imbibition period.
  • the preferred color-providing substances are dye developers and the desired imagewise distribution of diffusible dye developer results from the immobilization of the dye developer oxidized in developing the latent image.
  • an aqueous fluid processing composition including a dye developer as the color-providing substance is given, by weight, as follows:
  • support sheet 24 may comprise one of the 'opaque sheetmaterials generally used as abase for positive prints, such as baryta paper.
  • Theimage-receiving layers 16 and 26 are of a material substantive to'the dyes employed in the fluid reagent.
  • DuPont-Type 8 ,lslylon (trade name ,for. N-me'thoxy methyl .polyhexam e y ene a pami e).
  • ay at this m terial may be M f 1,4 bis 3-(2,5'-dihydroxyphenyl)-propylamino]- .formediby coating a solution using "ethyl alcohol "'as *a SO'lVeBt.
  • the silver halide emulsion layers are intended to be stripped from the :imageqeceiv- 'ing layers when treatment is complete.
  • T o facilitate'stripplug of photosensitive emulsion layers and 30, there are provided stripping layers 18 and ZS'betWeen the emulsion layers and the image-receiving layers.
  • Stripping layers 18 and 28 are of a material which is soluble in, or atleast softened by, thefiuid reagents, such materials as hydroxyiethyl cellulose and cellulose acetate hydrogen phthalate being suitable'for this purpose.
  • Stripping layers 18 and 28 may be prepared by coating an aqueous solution comprising, by weight, 2% hydroxyethyl cellulose and 2% sugar on the image-receiving layers.
  • the film-forming materials in the layers of fluid reagents tendto solidify as the'fluid is absorbed into the sheets or evaporates fromthe layers and, as the materialsolidifies, causes'the photosensitive emulsion layers to be adhered to the rigid plate.
  • photosensitive layers are adhered to the plate with a greater afiinity than to the image-receiving layers when the stripping layers have been dissolved or softened, with the result that, as the sheets and plate are stripped apart,
  • the plate may be provided with a coating of a material which is substantially nonsubstantive to the dyes employed and, for the purposesof the present invention, is preferably polyvinyl alcohol.
  • the color-providing sub-stances may be provided other than in the fluid reagent; for example, they may be'provided in one of the layers comprising each of'the sheets or as layers on the surfaces of the rigid plate. It is possible to'apply the dye developers to the surfaces of the rigid plate by coating the plate with gelatin and applying each developer to the gelatin in a solution of 4%, by Weight cellulose acetate hydrogen phthalate in 50-50 by volume of ace tone and tetrahydrofuran.
  • one of the photosensitive elements may include a screen type of sturcture for producing two or more subtractive, color records :as described in my copending application Serial No. .448,44'l, filed August 9, 1954, now US. Patent 2,968,554, issued January 17,1961, while the other photosensitive element is so constituted as to produce a monochrome accord in a'third color substantially as described.
  • one of the photosensitive elements may be constructed and processed in accordance'with my copending joint application with Howard G. Rogers, Serial No. 565,135, filed February 13, 1956, wherein there is described the structure of a photosensitive elementtcomprising two or more differently sensitized emulsion layers superposed with one another, each emulsion layer being sensitized preferably for one of the primary colors and containing a color-providing substance for providing an image in terms of a dye of the complementary color.
  • the photosensitive layers have been shown and described as preferably comprisingsilver halide emulsions and-the fluid reagents as comprising materials fo'r'p'roduc- :jngpositive images in terms of dyes, the 'pre'sent'int/ention may'find' equal utility in the performance of photographic processes employing other photosensitive materials and/ or reagents.
  • the fluid processing reagents may 1 2 be -adapte'cl-to the production off-positivesilver images by diffusion transfer-reversal and may comprise 'a silver halide developer such as hydroquinone, a silver halide solvent such as sodium thiosulfa'teyand 'an alkali.
  • Fluid reagents ofthis type are adapted to developth'e exposed isilver halide to'silver and to form from unexposed silve'r halide a'soluble silver complex whichmay be transferred by-imbibition to the image-receiving layer where it is reduced to silver to form a positive print.
  • the image-receiving layers preferably contain certain materials whose presence during a silver halide diffusion transfer-reversal process have a desirable effect on the amount and character ofthe silver precipitated during print formation.
  • This layer which preferably provides a vigorous silver precipitating environment, contains silver precipitating nuclei of the type described Patents Nos. "2,698,237 and 2,698,245, both issued to Edwin H. Land on December 28, 1954, dispersed i-n a'macroscopically continuous vehicle including Water-impermeable, inorganic, preferably siliceous material.
  • This layer may-contain, for example, one of the absorbent siliceous materials such as oxides of silicon like silica aerogel, mica and talc, and one of the'metallic sulfides and selenides, thiooxalates, thioacetamides, and colloidal metals, specifically colloidal silver.
  • the absorbent siliceous materials such as oxides of silicon like silica aerogel, mica and talc
  • the absorbent siliceous materials such as oxides of silicon like silica aerogel, mica and talc
  • the photosensitive layers may comprise photosensitive ferric salts which, when photoexposed, are capable of being reduced to ferrous salts.
  • Suitable photosensitive ferric salts include ferric chloride and ferric salts of organic acids, such as ferric oxalate, ferric tartrate and ferric citrate.
  • the fluid processing reagents would preferably include couplers which differentiate between ferric and ferrous salts to form visibly distinguishable reduction products with one or the other.
  • couplers examples include potassium ferricyanide, potassium ferrocyanide, the tannins, B-naphthoquinone sulfonic acid, silver salts, platinum and palladium salts, and various colloid materials such as gelatin andfgu'm arabic.
  • the photosensitive layers may include photosensitive 'diazomum compounds
  • the fluid reagents may include couplers capable of combining with exposed or unexposed :diazonium compounds to form visibly distinguishable dyes; or the couplers may be provided in the photosensitive layers or otherlayers associated therewith, while the fluids merely provide environments in which the coupling reactionsv may occur.
  • Suitable photosensitive drazomum compounds for example, may be prepared by treating aromatic amines with nitrous acid'at low temperature and, as suitable couplers, mention may be made of phenols, naphthols and amino compounds.
  • Qth'er materials which may find utility in the photosensrtrve layer include materials which are differentially 'solubi'lized by exposure t'o'light and include, for example, dichromated gelatin and the like;
  • the emulsionlaye'r'sjw and- 30 of sheets '12 and 22, respectivelyf may be coextensive with the entire inner Surface of each "ofthe sheet' sfia's shown in Fig. 2)
  • n that the emulsion layer is also'present in the region where 'no processinguoccur's, that is, in the region of containers -50.
  • "l'n'jthis case the portions ofthe emulsion layersiii this region may 'not be stri ped fm g image r eb;iving layers and may remain 'betweenthe two sheets.
  • the sheets may be provided without photosensitive layers in the region of the containers'where no processing occurs so that the finished product, after processing is complete and the processed emulsion layers have been stripped therefrom, may contain no emulsion layer substantially as shown in Fig. 4.
  • a method of simultaneously treating at least two exposed photosensitive material layers arranged in facing relation and each including a latent photographic image and each comprising at least a portion of a substantially flexible sheet, with at least two fluid processing agents to produce two visible photographic images comprising introducing a substantially inflexible sheetlike element between said flexible sheets in superposition with said exposed photosensitive layers, the latter being dis-,
  • said element be-.
  • the last-mentioned photosensitive layer comprises a silver halide emulsion
  • the last-mentioned fluid processing agent includes a substance selected from the class consisting of the silver halide developers and a substance selected from the class consisting of the silver halide solvents.
  • a method of simultaneously producing two visible photographic images in registration with one another comprises superposing two sheets, each 14 including a photosensitive layer, with said photosensitive?- layers in face-to-face contact with one'another and simul-' taneously exposing said photosensitive layers to produce latent photographic images in said photosensitive layers; introducing between said sheets a sheetlike element which is substantially less flexible than said sheets and has attached to its opposite surfaces at least two rupturable containers each holding a quantity of a fluid composition 'capable, when permeated into one of said photosensitive layers, of developing the latent image in said one photosensitive layer and producing, as a result of development of said latent image therein, an imagewise distribution of transferable image-forming substances; superposing each of said photosensitive layers with one of said surfaces of said element; moving said sheets and said element in superposition together with said containers relative to and between a pair of pressure-applying members, each having a fluid-spreading surface portion juxtaposed with the other and cooperating portions on opposite sides of said fluid
  • compositions are spread; thereafter maintaining said sheets and said element in superposition with said layers of fluid located between said sheets on opposite sides of said element for a processing period of predetermined duration said processing period developing said latent images, forming imagewise distributions of transferable image-forming substances and transferring said image-forming substances by diffusion from each of said photosentitive layers to an imagereceiving layer comprising the same sheet as saideach photosentitive layer to form a visible transfer image in said image-receiving layer; during said image-receiving layers being located exterior of the sandwich comprising said element and said photosentitive layers; at the end of said period, withdrawing said element from between said sheets, removing said photosensitive layers from said image-receiving layers and superposing said sheets and said image-receiving layers with said visible transfer images in registration with one another.
  • said photosensitive layers comprise silver halide emulsions having different color sensitivities
  • said visible images comprise dyes
  • said fluid compositions include substances selected from the class consisting of the silver halide developers and said image-forming substances produced by said fluid compositions as a result of development of said latent images comprise color-providing substances selected from the glass consisting of said dyes and intermediates for said yes. 1
  • a method .of forming at least two photographic images comprising two sheets fastened to one another and each including superposed photosensitive and image-receiving layers, said sheets being arranged with said photosensitivelayers in face-to-face contact; while maintaining said sheets'secured together and while holding said photosensitive layers in intimate face-to-face contact, simultaneously exposing said photosensitive layers to produce therein at least two different latent images of a subject; separating said exposed photosensitive layers from one another and while maintaining said photosensitive layers separated from one another, providing quantities of fluid sides of an'intervening layer, said fluid agents 'being' capable, when permeated into each of said photosensitive layers, of developing the latent image therein and forming, as a result of said development, an imagewise.
  • At least one of said photosensitive layers comprises at least two photosensitive silver halide emulsions each having a peak sensitivity within a dilferent portion of the visible Wavelength range and the other of said photosensitive layers comprises a photosensitive silver halide emulsion having a peak sensitivity within a portion of said Wavelength range difierent from the peak sensitivity of the first-mentioned silver halide emulsions;
  • said images comprise dyes;
  • said transferable image-forming substances comprise colorproviding substances initially incorporated in each of said emulsions, the color-providing substance incorporated in each of said emulsions comprising a material selected from the class consisting of said dyes and intermediates for said dyes, the colorof each of said dyes being thesubstantial complement of the color for which the parsaid photosensitive layers and the surfaces of said ele-:
  • said photosensitive layers are caused by said layers of fluid agents to be adhered to the surfaces of said element with a greater afiinity than to the imagereceiving layers with which said photosensitive layers are superposed during withdrawal of said element from between said sheets, whereby said photosensitive layers are stripped from said image-receiving layers by withdrawal of said element.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Color Printing (AREA)
US614983A 1956-10-09 1956-10-09 Photographic process, product and apparatus Expired - Lifetime US2977226A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL104746D NL104746C (fr) 1956-10-09
NL221363D NL221363A (fr) 1956-10-09
BE561463D BE561463A (fr) 1956-10-09
US614983A US2977226A (en) 1956-10-09 1956-10-09 Photographic process, product and apparatus
GB29931/57A GB853877A (en) 1956-10-09 1957-09-24 Photographic method and assemblage
FR1192238D FR1192238A (fr) 1956-10-09 1957-10-07 Perfectionnements à la photographie
DEJ13831A DE1240401B (de) 1956-10-09 1957-10-08 Verfahren zum gleichzeitigen Entwickeln bzw. Farbentwickeln von mindestens zwei belichteten lichtempfindlichen Schichten

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US614983A US2977226A (en) 1956-10-09 1956-10-09 Photographic process, product and apparatus

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US2977226A true US2977226A (en) 1961-03-28

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US (1) US2977226A (fr)
BE (1) BE561463A (fr)
DE (1) DE1240401B (fr)
FR (1) FR1192238A (fr)
GB (1) GB853877A (fr)
NL (2) NL104746C (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3269839A (en) * 1963-01-04 1966-08-30 Altman Gerald Photographic product for direct viewing and directive imaging
US3473925A (en) * 1968-05-23 1969-10-21 Polaroid Corp Photographic diffusion transfer color process and film unit for use therein
US3620731A (en) * 1969-09-29 1971-11-16 Polaroid Corp Novel processes for forming two negative color transfer images
US3836365A (en) * 1973-03-23 1974-09-17 Polaroid Corp Novel photographic products and processes
US3930864A (en) * 1974-04-15 1976-01-06 Eastman Kodak Company Auxiliary mordant layer for excess dye formed in integral color transfer assemblage
US4192640A (en) * 1975-08-06 1980-03-11 Winter Park Associates Multiple transfer process and article resulting therefrom
US6317561B1 (en) 2000-01-31 2001-11-13 Polaroid Corporation Processing fluid spread system for a detachable electronic photographic printer and camera
US6330397B1 (en) 2000-01-31 2001-12-11 Polaroid Corporation Film unit drive assembly for an electronic photographic printer and camera and related method thereof
US6342331B2 (en) * 1999-12-07 2002-01-29 Fuji Photo Film Co., Ltd. Diffusion transfer film units with two receiving layers
US6417911B1 (en) 2000-01-31 2002-07-09 Polaroid Corporation Processing fluid spread system for an electronic photographic printer and camera and related method thereof
US6795114B1 (en) 2000-01-31 2004-09-21 Polaroid Corporation Film unit drive assembly for a detachable electronic photographic printer and camera

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US3625129A (en) * 1970-06-30 1971-12-07 Polaroid Corp Photographic fluid-spreading apparatus
US3625130A (en) * 1970-06-30 1971-12-07 Polaroid Corp Stepped photographic processing fluid-spreading apparatus
CA1132826A (fr) * 1979-01-24 1982-10-05 Frans Carael Produit recepteur non photosensible, contenant un compose organique avec un groupe anionique lie au c, et un compose organique mordant pour colorant acide
EP0261280B1 (fr) * 1986-09-23 1990-06-06 Agfa-Gevaert N.V. Méthode de production d'images par diffusion-transfert et feuille réceptrice pour la production de document d'identification personnelle

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US2565378A (en) * 1950-09-19 1951-08-21 Polaroid Corp Photographic product
US2647049A (en) * 1947-02-25 1953-07-28 Polaroid Corp Photographic element for color photography and a process of producing multicolor pictures
US2686716A (en) * 1949-04-16 1954-08-17 Polaroid Corp Photographic product comprising a sheet support and means for collecting liquid spread upon said support in excess of that required to cover a predetermined area of the support
US2740341A (en) * 1952-09-27 1956-04-03 Polaroid Corp Photographic apparatus

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US2500421A (en) * 1944-11-03 1950-03-14 Polaroid Corp Photographic silver halide transfer process
US2543181A (en) * 1947-01-15 1951-02-27 Polaroid Corp Photographic product comprising a rupturable container carrying a photographic processing liquid
FR965191A (fr) * 1947-02-08 1950-09-05
US2662822A (en) * 1949-04-21 1953-12-15 Polaroid Corp Photographic transfer processes and compositions for the practice of said processes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2647049A (en) * 1947-02-25 1953-07-28 Polaroid Corp Photographic element for color photography and a process of producing multicolor pictures
US2686716A (en) * 1949-04-16 1954-08-17 Polaroid Corp Photographic product comprising a sheet support and means for collecting liquid spread upon said support in excess of that required to cover a predetermined area of the support
US2565378A (en) * 1950-09-19 1951-08-21 Polaroid Corp Photographic product
US2740341A (en) * 1952-09-27 1956-04-03 Polaroid Corp Photographic apparatus

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3269839A (en) * 1963-01-04 1966-08-30 Altman Gerald Photographic product for direct viewing and directive imaging
US3473925A (en) * 1968-05-23 1969-10-21 Polaroid Corp Photographic diffusion transfer color process and film unit for use therein
US3620731A (en) * 1969-09-29 1971-11-16 Polaroid Corp Novel processes for forming two negative color transfer images
US3836365A (en) * 1973-03-23 1974-09-17 Polaroid Corp Novel photographic products and processes
US3930864A (en) * 1974-04-15 1976-01-06 Eastman Kodak Company Auxiliary mordant layer for excess dye formed in integral color transfer assemblage
US4192640A (en) * 1975-08-06 1980-03-11 Winter Park Associates Multiple transfer process and article resulting therefrom
US6342331B2 (en) * 1999-12-07 2002-01-29 Fuji Photo Film Co., Ltd. Diffusion transfer film units with two receiving layers
US6317561B1 (en) 2000-01-31 2001-11-13 Polaroid Corporation Processing fluid spread system for a detachable electronic photographic printer and camera
US6330397B1 (en) 2000-01-31 2001-12-11 Polaroid Corporation Film unit drive assembly for an electronic photographic printer and camera and related method thereof
US6417911B1 (en) 2000-01-31 2002-07-09 Polaroid Corporation Processing fluid spread system for an electronic photographic printer and camera and related method thereof
US6795114B1 (en) 2000-01-31 2004-09-21 Polaroid Corporation Film unit drive assembly for a detachable electronic photographic printer and camera

Also Published As

Publication number Publication date
NL221363A (fr)
FR1192238A (fr) 1959-10-23
GB853877A (en) 1960-11-09
DE1240401B (de) 1967-05-11
BE561463A (fr)
NL104746C (fr)

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