US3345165A - Photographic product and process of using same - Google Patents

Photographic product and process of using same Download PDF

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Publication number
US3345165A
US3345165A US298967A US29896763A US3345165A US 3345165 A US3345165 A US 3345165A US 298967 A US298967 A US 298967A US 29896763 A US29896763 A US 29896763A US 3345165 A US3345165 A US 3345165A
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United States
Prior art keywords
image
liquid
layer
sheet
outer layer
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US298967A
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English (en)
Inventor
Edwin H Land
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Polaroid Corp
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Polaroid Corp
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Publication date
Priority to NL131882D priority Critical patent/NL131882C/xx
Application filed by Polaroid Corp filed Critical Polaroid Corp
Priority to US298967A priority patent/US3345165A/en
Priority to CH968364A priority patent/CH508227A/de
Priority to FR983341A priority patent/FR1405601A/fr
Priority to BE651209D priority patent/BE651209A/xx
Priority to DEJ26306A priority patent/DE1208190B/de
Priority to NL6408787A priority patent/NL6408787A/xx
Priority to GB31557/64A priority patent/GB1081165A/en
Application granted granted Critical
Publication of US3345165A publication Critical patent/US3345165A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B17/00—Details of cameras or camera bodies; Accessories therefor
    • G03B17/48—Details of cameras or camera bodies; Accessories therefor adapted for combination with other photographic or optical apparatus
    • G03B17/50—Details of cameras or camera bodies; Accessories therefor adapted for combination with other photographic or optical apparatus with both developing and finishing apparatus
    • G03B17/52—Details of cameras or camera bodies; Accessories therefor adapted for combination with other photographic or optical apparatus with both developing and finishing apparatus of the Land type
    • 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
    • G03C8/24—Photosensitive materials characterised by the image-receiving section
    • G03C8/26—Image-receiving layers
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/142—Dye mordant

Definitions

  • Diffusion transfer processes for forming transfer images in a camera are now well known. In general, these processes have involved exposing a succession of areas of a photosensitive image-recording sheet, superposing each exposed area with an area of a second sheet and distributing a processing liquid between the superposed sheets in order to produce a positive transfer print in an imagereceiving layer on the second sheet by a diffusion-transfer process.
  • the materials employed comprise an imagerecording sheet including an image-forming material such as a heavy metal salt .(e.g., silver halide), a second or image-receiving sheet for supporting an image-receiving layer containing a diffusion-transfer image, and a processing liquid providing a developing agent for the photosensitive material and including an alkali for rendering the developing agent reactive. It has been proposed to incorporate all of the materials for producing a transfer print including the photosensitive image-recording material, image-receiving material, developing agent, alkali, transferable image-forming substances, and/ or agents capable of forming transferable image-forming substances and even water, in layers or strata comprising the image-recording and second sheets.
  • an image-forming material such as a heavy metal salt .(e.g., silver halide)
  • a second or image-receiving sheet for supporting an image-receiving layer containing a diffusion-transfer image
  • a processing liquid providing a developing agent for the photosensitive material
  • a principal object of this invention is to provide novel photographic elements which include an image-receiving layer and which are impregnated with an aqueous alkaline liquid.
  • Another object .of the invention is to provide novel and improved diffusion transfer processes wherein successive areas of an image-recording sheet including a photosensitive image-forming material, are exposed, said image-recording sheet preferably also including a developing agent therefor, and processing each exposed area by pressing the image-recording sheet into contact with an area of a second sheet impregnated with an aqueous alkaline liquid.
  • a further object of the invention is to provide a novel and improved photographic product in the form of a film assemblage comprising an image-recording sheet including an image-forming material and a developing agent therefor, and a second sheet including an image-receptive stratum carrying an aqueous alkaline liquid, said second sheet being impregnated with a liquid having a very high pH, i.e., at least 12.
  • the invention accordingly comprises the process comprising the several steps and the relation and order of one 3,345,165 Patented Oct. 3, 1967 or more of said steps with respect to each of the others, and the product possessing the features, properties and the relation of components whiich are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • FIGURE 1 is a sectional view of one embodiment of an image-receiving element embodying the invention.
  • FIG. 2 is a sectional view of the camera taken substantially midway between the upper and lower sides thereof and showing a film assemblage within the camera.
  • This invention is particularly concerned with producing multicolor photographic transfer prints according to the process disclosed in US. Patent No. 2,983,606 issued May 9, 1961, to Howard G. Rogers; and utilizing integral multilayer negatives incorporating dye developers such as are disclosed therein and in the copending US. application of Edwin H. Land and Howard G. Rogers, Ser. No. 565,135, filed Feb. 13, 1956.
  • the multilayer negative (sheet) is exposed and superposed with a second sheet including a receiving layer for image-forming dyes transferred by diffusion from the negative sheet; and a liquid reagent is distributed between the two sheets for permeation into the layers of the negative containing the photosensitive materials and dye developers and the image-receiving layer.
  • the liquid reagent is alkaline in nature and serves to render the other reagents, particularly the developers, reactive to develop the exposed silver halide, thereby immobilizing image-forming dyes in areas where image development occurs and causing image-forming dyes in unexposed areas to transfer by diffusion to the image (dye)-receiving layer.
  • the process performed in this invention and the novel products useful therein differ from known processes and products basically in the manner in which the liquid is supplied for permeation into the negative layers.
  • this has been accomplished by providing a quantity of the liquid including a thickening agent in a layer between the two sheets and spreading the thickened (viscous) liquid in a thin layer over each exposed area by moving the sheets in superposition relative to and between a pair of pressure-applying members.
  • the aqueous alkaline liquid required for processing is carried by the imagereceiving layer itself.
  • This makes possible a very simple film assemblage essentially comprising two sheets and a container for the image-receiving sheet and liquid; as compared with existing film assemblages including such components as masks, containers, liquid-trapping devices, indexing members and the like, requiring careful and precise fabrication and assembly to insure proper operation, registration and location of the various components during processing.
  • the processing components of the camera for use in practicing this invention are correspondingly simple
  • the liquid, examples of which are given hereinafter, carried by the image-receiving layer is highly alkaline, this alkalinity being achieved by the inclusion in the liquid of an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, preferably in sufficient quantity to achieve a pH of at least 12.
  • an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide
  • suitable precautions must be taken to prevent pH reduction resulting from absorption of carbon dioxide in the processing liquid.
  • One technique for excluding carbon dioxide, such as is found in the atmosphere, from the liquid is to include within the camera a container and/ or a container closure for protecting the liquid-carrying, image-receiving sheet from the atmosphere while allowing successive areas of the image-receiving sheet to be withdrawn from a container (gas impermeable) in the camera and pressed into superposition with successive exposed areas of the image-recording sheet, as disclosed in the aforementioned copending applications.
  • the container and container closure may comprise components of the camera or cooperating components of both the camera and film assemblage employed therein, while achieving a primary object in providing the simplest and least expensive (expendable) film assemblage capable of being processed in the least complicated and expensive camera.
  • a typical multilayer negative for producing multicolor transfer prints includes blue-sensitive, green-sensitive and red-sensitive silver iodobromide emulsion layers having positioned behind them, respectively, a yellow dye developer, a magenta dye developer and a cyan dye developer; gelatin interlayers positioned between the yellow dye developer layer and the green-sensitive emulsion and between the magenta dye developer layer and the red-sensitive emulsion; and a support for the emulsion layers, dye developer layers, and gelatin inner layers.
  • Multilayer negatives of this type are disclosed, for example, in FIG. 9 of the aforementioned US. Patent No. 2,983,606. Multicolor negatives of the type used in Type 48 Polaroid Polacolor film are particularly useful.
  • the image-receiving element or sheet comprises a support, preferably of a material which is chemically inert to, is insoluble in and impermeable to aqueous alkaline liquids, and an image-receiving layer of a material receptive to the aforementioned dye developers, securely adhered to the support and s constituted, by virtue of its composition and thickness, as to retain an amount of liquid sufiicient to process the negative. It has been found that where the image-receiving layer is water-permeable and alkali-permeable, unexpectedly good shelf life with an adequate amount of high pH processing composition present may be obtained by positioning intermediate said support and image-receiving layer at least one layer which is partially permeable to water and alkali.
  • the aqueous alkaline liquid-permeable layer thus has a graded permeability ranging from an impermeable material on a support such as paper, to a highly permeable material swollen by the aqueous alkaline liquid, and comprises a combination of strata of different composition and permeability bonded to one another and the support with the degree of swelling increasing progressively outward from the support.
  • the image-receiving elements of this inven-. tion thus may be described as comprising a hydrophilic outer or image-receiving layer, intermediate layers of graded progressively decreasing hydrophilic character, and a hydrophobic base layer.
  • the water-impermeable and alkali-impermeable base layer may be coated on a support, such as paper or a plastic, or it may constitute the support.
  • a support such as paper or a plastic
  • the surface or a thin surface portion of the base layer may be chemically converted to a form providing desired physical properties, e.g., good wet adhesion to the layers subsequently coated thereon.
  • the base layer is cellulose acetate
  • the surface thereof may be hydrolyzed or regenerated to cellulose. Techniques and procedures for effecting such surface conversions, e.g., alkaline hydrolysis, are well known and therefore they need not be described here.
  • the various layers of the image-receiving element are composed of materials, preferably polymeric, which are chemically stable to the aqueous alkaline processing solutions.
  • materials preferably polymeric, which are chemically stable to the aqueous alkaline processing solutions.
  • gelatin is not contemplated since gelatin will hydroyze in alkali over a period of time, giving products unsuitable for use in this invention.
  • partially hydrolyzed polyvinyl acetate may be employed in certain locations since the fully hydrolyzed product, i.e., polyvinyl alcohol, has the requisite alkali stability.
  • the graded permeability of hydrophilic character may be obtained by using a hydrophobic polyvinyl butyral base, i.e., it has sufiicient butyral content to be non-swellable, and intermediate layers of partial polyvinyl butyrals in which the proportion of butyral to hydroxyl groups increases outward from the hydrophobic base layer.
  • a particularly useful image-receiving layer comprises a mixture of polyvinyl alcohol and poly-4-vinylpyridine.
  • particular useful in- 0 termediate layers comprise mixtures of poly-4-vinylpyridine and polyvinyl alcohol, the proportion of polyvinyl alcohol increasing progressively outward from the support, as will be indicated in more detail in the examples below.
  • FIG. 1 A cross-sectional view of one embodiment of the novel image-receiving element is shown in FIG. 1, wherein an alkali-impermeable and water-impermeable base 1 carries a plurality of intermediate layers 3a, 3b, 3c and 3d which exhibit progressively increased alkali-permeable outward from said base 1, over which is coated a water-permeable and alkali-permeable image-receiving layer 5.
  • the aqueous alkaline processing solution is impregnated into all of the alkali-permeable layers.
  • the distribution of the processing composition in these layers follows the alkali-permeability, with the maximum amount of solution per unit area being present in the image-receiving layer 5. This method of distributing the processing composition also helps to insure a supply of processing solution adequate to process the exposed negative without having excess solution collect on the surface of the image-receiving layer.
  • the surface of the image-receiving layer is substantially dry, i.e., there is not moisture or free liquid visible on the surface and the surface is substantially dry to the touch.
  • FIG. 2 A camera suitable for use with the novel image-receiving elements of this invention (and disclosed and claimed in the aforementioned application of Edwin H. Land, Ser. No. 298,968, filed concurrently herewith) is shown in FIG. 2.
  • a camera designated 10
  • Such a camera, designated 10 comprises a housing including three relatively movable sections designated a forward section 12, a rear section 14 and an end section 16.
  • the forward section of the camera housing comprises a forward wall 18 having a generally rectangular opening therein including a recessed section defined by an upper side wall (not shown), a lower side wall 22, end walls 24 and 26 and a rear wall 28 provided with a rectangular exposure aperture 30.
  • the camera is of the folding type and includes a conventional lens and shutter assembly 32 coupled with rear wall 28 by a bellows 34 which is collapsible (the usual erecting mechanism is not shown) to permit the bellows and the lens and shutter assembly to be contained within the recess in the forward housing section.
  • a bellows 34 which is collapsible (the usual erecting mechanism is not shown) to permit the bellows and the lens and shutter assembly to be contained within the recess in the forward housing section.
  • the rear housing section includes a rear wall 36 having a curved end section 3-8 (at the left in the drawings) at which the rear housing section is pivotally secured to the forward housing section by a hinge 40.
  • the forward and rear housing sections, specifically forward wall 18, upper side wall, lower side wall 22, wall 24 and end section 38 of rear wall 36 cooperate to provide a storage chamber 42 for mounting and enclosing a roll of a photosensitive image-recording sheet 44 of the type described.
  • the rear housing section also includes a portion designated 46 located at the end of rear wall 36 opposite end section 38 which projects rearwardly from rear wall 36 and includes a wall 48 having an L-shaped cross section and upper and lower side walls 50 which are disposed above and below the upper and lower side walls.
  • the rear housing section is pivotable between the closed or operative position in which the forward and rear housing section cooperate to provide closed storage chamber 42; and an open position at which access is provided to chamber 42 for loading a roll of image-recording sheet 44 into the storage chamber and threading the sheet or a leader attached thereto through the camera between rear walls 28 and 36 across exposure aperture 30'.
  • the rear surface of rear wall 28 and the forward surface of rear wall 36 are located generally at the focal surface of the lens of assembly 32 and cooperate to locate successive areas of the image-recording sheet in position for exposure to light transmitted by the lens through aperture 30.
  • the forward housing section 12 includes an end wall designated 60 spaced from end wall 26 and cooperating with the latter, forward wall 18 and upper wall (not shown) and lower wall 22 to provide another chamber 62 for enclosing components of the apparatus.
  • End wall 60 also functions to provide a wall for a sealed container (to be described hereinafter).
  • End walls 26 and 60 extend rearwardly to join rear wall 36 at the end of the forward housing section 12 furthest from chamber 42.
  • the inner, upper and lower walls (not shown) of end section 16, forward wall 64, end wall 66, and rear wall 68 cooperate to provide an open storage chamber 82 for a supply of the image-recording sheet designated 84.
  • End section 16 is coupled with forward housing section 12 by a hinge 86 constructed to provide for limited linear movement of the end section relative to the forward section as well as pivotal movement of the two sections with respect to one another.
  • Hinge 86 is secured to forward walls 18 and 64 of, respectively, the forward and end housing sections and permits the end section to be pivoted with respect to the forward section between the operative or closed position and the open or inoperative position.
  • end wall 60 of the forward section cooperates with the end section to provide a closure for storage chamber 82, whereas in the open position of the end section, chamber 82 is open to permit loading of a supply of an imagereceiving sheet 84 into chamber 82.
  • End section 16 of the housing includes a rearwardly projecting portion 88 comprising upper and lower walls joined by an L-shaped wall 92 extending rearwardly from rear wall 68 and then parallel with the rear wall and co- 6 operating with said upper and lower walls to provide a chamber 94 for enclosing components of the apparatus.
  • the camera includes means for retaining the housing sections in the closed or operative position shown in FIG. 2. These means comprise extensions 96 on the upper and lower portions of L-shaped wall 92 which extend, in the closed position of the housing, outside of wall 48 of portion 46 of rear housing section 14.
  • Latch means are provided for retaining end housing section 16 in its closed position and may comprise a pair of generally L-shaped latching arms each having a hook on its inner end.
  • slots 114 In the operative position of the housing sections, walls 48, 92 and extensions 96 of wall 92 cooperate to define a slot 114 connecting with chamber 94 defined by portions 46 and 88 of the rear and end housing sections. Slot 114 is dimensioned to permit withdrawal of the image-recording and image-receiving sheets in superposition from the camera housing and a cutting bar having a sharpened, serrated edge is provided within slot 114 on wall 48 for facilitating the severance of sheet materials extending from the camera housing through the slot.
  • Photosensitive image-recording sheet 44 is supplied in a coiled condition in the usual manner, e.g., on a spool, is housed in chamber 42 and is threaded from the chamber across opening 30 between rear walls 28 and 36 into chamber 94.
  • the liquid impregnated image-receiving sheet 84 is supplied in a coiled condition in a container which is substantially impermeable to the processing liquid, water vapor and gases, particularly carbon dioxide (and oxygen where a silver halide developing agent is present in the processing liquid).
  • a typical container for the liq uid impregnated image-receiving sheet is illustrated in FIG. 2.
  • This container, designated 118 includes a generally cylindrical peripheral wall and two circular end walls.
  • Wall 120 is provided with an axial slot defined by a pair of overlapping outer and inner lips designated, respectively, 124 and 126.
  • the edge portion of the outer lip is thickened and the inner lip is provided with a rib to stifien the two lips and retain them in a closed position in engagement with a portion of image-receiving sheet 84 extending from the container through the passage between the lips.
  • the edge of inner lip 126 closest the outer lip is provided with a sharpened corner designed to function as a squeegee for removing any liquid from a surface of image-receiving sheet 84.
  • Container 118 may be formed of any suitable material particularly organic plastics, such as polyethylene, which are air and water vapor impervious and are compatible with aqueous alkaline liquids.
  • the image-receiving sheet is supplied in a coiled condition in container 118 with a leading end portion of the sheet extending from the container through the passage between lips 124 and 126.
  • Additional means may be provided for sealing the passage against the admission of air and the leakage of water or water vapor and in the form shown these sealing means may comprise a seal of some material, such as wax, which may be introduced in a softened or molten condition into the passage between the lips 124 and 126 in surrounding relation to the sheet to fill the passage and form a rupturable bond between the sheet and container to prevent the passage of air and water between the lips.
  • Receiving sheet 84 may be coiled with the liquid impregnated image-receiving layer facing inwardly or outwardly and is shown in FIG. 2 with the liquid impregnated layer facing outwardly. Since the container must be opened to permit the withdrawal of the image-receiving sheet and thus possibly permit escape of water vapor and/ or admission of air, it may be desirable to provide a reservoir of excess processing liquid within the container together with means for gettering carbon dioxide so that any carbon dioxide gaining admission to the container does not react with the hydroxide in the processing liquid to reduce the pH thereof.
  • the image-receiving sheet is preferably coiled tightly upon itself to help prevent contact between the liquid impregnated image-receiving layer and the atmosphere of the container.
  • the atmosphere of the container is preferably maintained saturated with water vapor by the provision of a reservoir of water or processing liquid.
  • This reservoir of excess processing liquid or water may comprise the image-receiving layer itself which may be impregnated with excess liquid which could be removed by squeegeeing during withdrawal of the receiving sheet from the container.
  • squeegees would be provided on both lips 124 and 126 for removing liquid from both surfaces of the image-receiving sheet so that the sheet, upon withdrawal from the container, is substantially dry to the touch with all the liquid required for processing being retained within the image-receiving layer.
  • water or processing liquid may be provided in a reservoir apart from the image-receiving sheet.
  • a reservoir may comprise, for example, a liquid impregnated absorbent material shown wrapped around the outside of the coiled image-receiving sheet, but in an alternative embodiment could be disposed within the coiled receiving sheet.
  • hydroxides particularly the hydroxides comprising the processing liquid are highly reactive with carbon dioxide, such a getter may also comprise a hydroxide contained, for example, within the reservoir of liquid which provides for the water vapor saturated atmosphere within the container.
  • Alkaline earth metal hydroxides particularly are suggested for use as getters and include hydroxides which combine with carbon dioxide to form carbonates which are less soluble than the carbonates formed by the alkali metal hydroxide in the processing liquid.
  • potassium hydroxide when potassium hydroxide is used in the processing liquid, calcium hydroxide may be provided for reacting with carbon dioxide in order to prevent reaction of the potassium hydroxide with carbon dioxide within the container.
  • Barium hydroxide is also suggested as a getter when potassium hydroxide is employed in the processing liquid.
  • Sodium hydroxide may be incorporated in the processing liquid instead of potassium hydroxide to provide for the high pH thereof, in which case any of potassium hydroxide, barium hydroxide and calcium hydroxide may be incorporated in the container as a getter for carbon dioxide.
  • Container 118 in which liquid impregnated sheet 84 is supplied is unsealed at the commencement of withdrawal of the image-receiving sheet therefrom and in the form shown remains unsealed thereafter.
  • the camera in which the container is employed includes either: means for sealing the container against the escape of water vapor and the admission of carbon dioxide, or a container for holding container 118 and which may be sealed against the escape of water vapor and the admission of carbon dioxide, between times when the image-receiving sheet is being withdrawn from container 118 and/or the container within the camera.
  • This container includes a container which is substantially impervious to water vapor and carbon dioxide and which may be sealed against the admission or escape of water vapor and carbon dioxide and may be opened to permit the withdrawal movement of the imagereceiving sheet therefrom.
  • This container comprises storage chamber 32 and is defined by end wall 60, inner upper wall (not shown), inner lower wall (not shown) and end wall 66.
  • Means are provided for sealing stor- 8 age chamber 82 and preferably comprise in the form shown a pair of seals formed of an elastomeric material which is compatible with or unaffected by hydroxide, is substantially impervious to water vapor and carbon dioxide, and is highly resistant to assuming a permanent set.
  • each of rolls 164 and 166 is shown as comprising a metal shaft covered by an elastomeric material such that the rolls are slightly compressible and, in fact, the resiliency of the elastomeric material may be employed to apply the necessary pressure to the two sheets.
  • Roll 164 is pivotally mounted on rear housing section 14 between upper and lower side walls 50 for movement into juxtaposition with roll 166 which is also mounted within chamber 94 of the inner upper and inner lower walls.
  • image-receiving sheet 84 extends from chamber 82 into superposition with image-recording sheet 44 between rolls 164 and 166.
  • the rolls are rotated in engagement with the superposed sheets in order to superpose an exposed area of the photosensitive sheet with an area of receiving sheet and simultaneously advance the sandwich thus formed from the camera through slot 114 and advance the next succeeding area of the image-recording sheet into position for exposure in alignment with aperture 30.
  • Suitable gear means may be provided rolls, preferably with a gear ratio such that one complete revolution of a crank rotates roll 164 sufliciently to advance an exposed area of the image-recording sheet into superposition with the image-receiving sheet and from the camera.
  • roll 164 is located as close as possible to the end edge of exposure aperture 30 and the opening into chamber 82 so as to minimize the length of sheet materials constituting waste between successive exposed areas of the photosensitive sheet and the length of the image-recording sheet superposed therewith.
  • FIG. 2 The camera shown in FIG. 2 is described in more detail in the aforementioned copending applications filed herewith.
  • the film assemblage including the sheet materials employed in the camera shown and described, is supplied with a leading end portion thereof, or leader attached thereto, extending from container 118 and coupled with a leader or the leading end of the image-recording sheet.
  • the coil of image-recording sheet is introduced into chamber 42; the rear housing section is pivoted into closed position; the container of imagereceiving sheet is loaded into chamber 82; end housing section 16 is then pivoted into closed position, and latching arms are pivoted in a counterclockwise direction to retain the camera in closed position.
  • the camera housing sections are thus closed with the coupled leaders extending between rolls 164 and 166 through slot 114.
  • An area of the image-recording sheet is then advanced into position for exposure, e.g., by pulling on the coupled leaders or by rotating suitable gear means.
  • the coupled leaders are again advanced, thereby processing each exposed area of the image-recording sheet by pressing it into superposition with an area of the image-receiving sheet to form a sandwich and advancing the sandwich from the camera through slot 114.
  • the superposed areas of the two sheets comprising the sandwich may be severed from portions of the sheets remaining within the camera housing by drawing the sandwich against a cutting bar (not shown).
  • the sheets are retained in superposition during a processing period of predetermined duration at the end of which the sheets are separated to reveal a transfer print on the image-receiving sheet.
  • the image-receiving sheet 84 may also be supplied in a coiled condition in a container in the form of a bag.
  • the sheet material comprising the bag may be a multiply material formed, for example, of paper and/ or metal foil with an inner ply of a polymeric material, preferably one which is thermoplastic and can be bonded to itself and other materials by application of heat and pressure.
  • the completed container is formed with a pair of lips releasably secured to the image-receiving sheet and defining a mouth through which the image-receiving sheet may be withdrawn.
  • a clip or other means may be provided for holding the lips in a closed position prior to loading of the container into a camera.
  • a reservoir for excess water or processing liquid and a getter for carbon dioxide may take the'form of a sheet of an absorbent material impregnated with the desired liquid disposed in surrounding relation to the coiled image-receiving sheet.
  • the film assemblage described herein together with the camera are intended for intermittent frame by frame exposure and processing, with the film assemblage itself being substantially simplified, as compared to existing self-developing roll film assemblages, in that its essential elements are limited to an image-recording sheet, a liquid impregnated image-receiving sheet and a container for the latter.
  • Masks, fluid collecting and retaining devices, indexing references and the like, heretofore associated with this type of roll film assemblage have been made unnecessary and the camera itself is simplified particularly with regard to the mechanism for pressing the two sheets together and distributing the processing liquid between the sheets.
  • the camera may be modified to provide for withdrawal of the sheets by manually engaging and pulling on the sheets.
  • an indexing system may be provided in association with the rolls, and manual-1y operable means would be provided for at least opening the container to permit withdrawal of the image-receiving sheet.
  • the sandwich comprising the two superposed sheets may be advanced directly from the camera in which exposure and processing is accomplished and accordingly,
  • the photosensitive and image-receiving sheets are each formed of a material or provided with a layer which is opaque to actinic light.
  • Each of the aforesaid 3:1, 2:1 and 1:1 mixtures was diluted by an equal quantity of water before application. All of the layers were applied by a conventional reverse roll coating technique in which a doctor was employed spaced from the coating roll by a .003 inch gap; and the six layers comprising the image-receiving layer were found after drying to have an aggregate thickness of about .0007 inch.
  • the image-receiving sheet thus prepared was immersed for 5 minutes in an aqueous alkaline processing composition comprising:
  • the processing liquid required for treating the photosensitive sheet is contained entirely within the swollen, imagereceiving layer so that this layer too may appear to and, in any event, no free liquid remainedv on the surface of the imagereceiving layer following the squeegeeing operation.
  • the exposed photosensitive sheet and the impregnated imagereceiving element were passed between soft rubber rolls. The tension on the rubber rolls was so set that there was no real squeezing action but a good surface contact was effected. Just enough liquid was squeezed out to insure a good wet contact between the superposed sheets. The pressure was less than would be required to squeeze out a major portion of the liquid.
  • the image-receiving element was separated and contained a positive multicolor transfer image.
  • the surface of the separated imagereceiving element was very slightly damp (apparently because the photosensitive element did not absorb all of the liquid initially present in the image-receiving element) but dried completely within a minute or two.
  • EXAMPLE 2 The procedure described in Example 1 was repeated except that the polyvinyl butyral-coated baryt-a paper was replaced by a cast sheet of polyvinyl butyral film.
  • Example 3 The procedure describedin Example 1 was repeated except that the polyvinyl butyral back coat was replaced by ethyl cellulose.
  • EXAMPLE 5 The procedure described in Example 1 was repeated except that the polyvinyl butyral-coated baryta paper was replaced'by a paper-like sheet of polyethylene fibers.
  • the image-receiving element was immersed in the liquid processing composition for about minutes; it was found that longer soaking times did not result in appreciably more liquid being absorbed.
  • This immersion time may be varied, depending upon the particular composition of the image-receiving element. The minimum time necessary to absorb the desired amount of liquid thus may be readily determined by one skilled in the art.
  • the base for the image-receiving element contains a stratum or core which is permeable to the processing solution
  • paper bases be impregnated with a plastic which minimizes or prevents such edge absorption of liquid.
  • ethanol is retained by polyvinyl butyral and acts as a plasticizer therefor; the ethanol is not readily given up by the polyvinyl butyral, even on baking.
  • Such retention of coating solvent may result in variations in properties of the liquid impregnated image-receiving element over a period of time.
  • the liquid impregnated image-receiving element preferably is not passed over sharp edges, since this may cause delamination.
  • liquid-impregnated imagereceiving elements of this invention cannot contain a pH control layer of the type disclosed and claimed in the copending application of Edwin H. Land, Ser. No. 234,864, filed Nov. 1, 1962.
  • These liquid-impregnated image-receiving elements are particularly useful with photosensitive elements containing a polymeric acid layer adjacent the support, such as those disclosed and claimed in the copending application of Edwin H. Land, Ser. No. 277,209, filed May 1, 1963.
  • the following example of the preparation of such a photosensitive element is given for purposes of illustration only.
  • EXAMPLE 9 300 g. of high viscosity poly-(ethylene/maleic anhydride) [commercially available from Monsanto Chemical Co., St. Louis, Mo., under the trade name DX-840-31 Resin] was dissolved in 1500 cc. of acetone. 150 g. of n- 12 butyl alcohol and 1 cc. of phosphoric acid were added and the mixture was refluxed for 14 hours. The resulting solution of a polymer containing recurring segments of the formula:
  • liquid-impregnated image-receiving elements also are very useful in continuous processing applications, such as photofinishing processing of color print copies.
  • liquid-impregnated image-receiving elements of this invention provides a number of advantages.
  • One important advantage which may be mentioned is the elimination of excess processing composition; because of the high pH, such compositions are potentially harmful to skin tissues.
  • the manner of supplying the liquid processing composition and the distribution thereof maybe more uniform than if a conventional rupturable container were used.
  • Examination of the transfer images prepared in the above examples also has given indications of improved color separation. Because of the intimate contact between the two sheets and the absence of a layer of viscous reagent therebetween, lateral diffusion of transferring dyes is minimized.
  • the image-receiving layer serves two functions: (1) it releasably retains over a period of time the liquid necessary to process a photosensitive element, and (2) it gives up that liquid in exchange for the image dyes transferred by diffusion to the image-receiving layer through that liquid.
  • a sheet-like element releasa-bly retaining an aqueous alkaline composition and adapted to be used in processing an exposed photosensitive silver halide stratum, said element comprising:
  • each said intermediate layer being at least partially permeable to water and alkali
  • aqueous alkaline composition includes a quaternary ammonium compound.
  • an image-receiving element releasably retaining an aqueous alkaline solution and adapted to be used in processing an exposed photosensitive silver halide element containing at least one dye developer, said element comprising:
  • a water-permeable and alkali-permeable outer layer comprising a mixture of polyvinyl alcohol and poly-4-viny1pyridine.
  • each said intermediate layer being at least partially permeable to water and alkali and composed of a mixture of polyvinyl alcohol and poly-4-vinylpyridine, the relative amount of said poly- 4-vinylpyridine progressively increasing in each intermediate layer inwardly from said outer layer,
  • said aqueous alkaline solution being present in an amount sufiicient to process said exposed photosensitive element.
  • a photographic product comprising a roll of a photosensitive silver halide element, a roll of an image-receiving element as defined in claim 1, a leading portion of said photosensitive element being so attached to a leading por tion of said image-receiving element that the outer layer of said image-receiving element is in contact with the outer photosensitive surface of said photosensitive element.
  • a diffusion transfer process comprising the steps of exposing a photosensitive silver halide element, bringing said exposed photosensitive element into contact with the liquid-impregnated outer layer of the image-receiving element defined in claim 1, said contact being efiected under pressure sufficient to obtain surface-to-surface wet contact but insuflicient to squeeze a major portion of said liquid out of said image-receiving element, whereby said liquid is absorbed by said photosensitive element and develops the exposed areas thereof, and an imagewise distribution of diffusible image-forming components is transferred by diffusion to said image-receiving element to form a postive transfer image.
  • said photosensitive element includes a layer of a polymeric acid between the support and the photosensitive layer, whereby the pH of the surface of the image-receiving layer is reduced prior to separation of said photosensitive element and said image-receiving element.
  • a photographic product comprising a hydrophobic base layer, a hydrophilic outer layer containing a mordant for a dye developer adapted to receive a dye image during photographic use, at least two layers intermediate said base layer and said outer layer, said intermediate layers being of progressively increasing hydrophilic character outward from said base layer, said hydrophilic layers releasably containing an aqueous alkaline solution in sufficient volume to process a photosensitive element of the same area.
  • a water-permeable and alkali-permeable outer layer comprising a mixture of polyvinyl alcohol and poly-4-vinylpyridine,
  • each said intermediate layer being at least partially permeable to water and alkali and composed of a mixture of polyvinyl alcohol and poly-4-vinylpyridine, the relative amount of said poly-4-vinylpyridine progressively increasing in each intermediate layer inwardly from said outer layer, and
  • said outer and intermediate layers being swellable by an aqueous alkaline solution, said outer layer being appreciably swellable and said intermediate layers inward from said outer layer being progressively less swellable than said outer layer.

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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)
US298967A 1963-07-31 1963-07-31 Photographic product and process of using same Expired - Lifetime US3345165A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
NL131882D NL131882C (de) 1963-07-31
US298967A US3345165A (en) 1963-07-31 1963-07-31 Photographic product and process of using same
CH968364A CH508227A (de) 1963-07-31 1964-07-23 Mehrschichtiges Bildempfangselement und Verwendung desselben
FR983341A FR1405601A (fr) 1963-07-31 1964-07-28 Produit photographique et procédé dans lequel on utilise ce produit photographique
BE651209D BE651209A (de) 1963-07-31 1964-07-30
DEJ26306A DE1208190B (de) 1963-07-31 1964-07-30 Fuer photographische Diffusionsuebertragungs-verfahren geeignetes Bildempfangsmaterial
NL6408787A NL6408787A (de) 1963-07-31 1964-07-31
GB31557/64A GB1081165A (en) 1963-07-31 1964-08-04 Photographic diffusion transfer receptor

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BE (1) BE651209A (de)
CH (1) CH508227A (de)
DE (1) DE1208190B (de)
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NL (2) NL6408787A (de)

Cited By (13)

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US3415645A (en) * 1967-03-10 1968-12-10 Polaroid Corp Opaque permeable polymeric layer in photo-sensitive element
US3419389A (en) * 1967-05-26 1968-12-31 Polaroid Corp Cyanoethylated polyvinyl spacer layers for image-receiving element
US3421893A (en) * 1967-05-26 1969-01-14 Polaroid Corp Acrylic polymer spacer layers for photographic elements
US3607269A (en) * 1968-04-01 1971-09-21 Polaroid Corp Image-receiving elements and photographic processes employing same
US3709687A (en) * 1970-04-06 1973-01-09 Polaroid Corp Diffusion transfer receiving element with varing concentration of precipitating nuclei
US3772025A (en) * 1967-10-16 1973-11-13 Polaroid Corp Diffusion transfer receiving sheets
US3907563A (en) * 1973-12-13 1975-09-23 Polaroid Corp Diffusion transfer process using processing composition impregnated image-receiving element
US4379828A (en) * 1980-05-16 1983-04-12 Agfa-Gevaert Aktiengesellschaft Image receptor element for the dye diffusion transfer process
US4443530A (en) * 1982-10-22 1984-04-17 Polaroid Corporation Self-processing film unit with liquid applicator
US4523825A (en) * 1984-06-14 1985-06-18 Polaroid Corporation Film processing apparatus and system
US4605608A (en) * 1985-09-23 1986-08-12 Polaroid Corporation Image-receiving element with crosslinked hydrophilic polymer containing processing composition
US5970271A (en) * 1997-03-11 1999-10-19 Polaroid Corporation Spool caddy for use with dry optical image processing of roll film
US5993080A (en) * 1997-03-11 1999-11-30 Polaroid Corporation System for optical dry processing of spooled photographic film

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US2543181A (en) * 1947-01-15 1951-02-27 Polaroid Corp Photographic product comprising a rupturable container carrying a photographic processing liquid
CA576537A (en) * 1959-05-26 Polaroid Corporation Processes of forming photographic images
CA623390A (en) * 1961-07-04 Polaroid Corporation Photographic compositions
US3003872A (en) * 1957-12-03 1961-10-10 Polaroid Corp Photographic products and processes
US3148061A (en) * 1960-08-22 1964-09-08 Polaroid Corp Photographic diffusion transfer processes employing image receiving layers containing poly-4-vinylpyridine
US3179517A (en) * 1959-08-24 1965-04-20 Eastman Kodak Co Web processing method and composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA576537A (en) * 1959-05-26 Polaroid Corporation Processes of forming photographic images
CA623390A (en) * 1961-07-04 Polaroid Corporation Photographic compositions
US2543181A (en) * 1947-01-15 1951-02-27 Polaroid Corp Photographic product comprising a rupturable container carrying a photographic processing liquid
US3003872A (en) * 1957-12-03 1961-10-10 Polaroid Corp Photographic products and processes
US3179517A (en) * 1959-08-24 1965-04-20 Eastman Kodak Co Web processing method and composition
US3148061A (en) * 1960-08-22 1964-09-08 Polaroid Corp Photographic diffusion transfer processes employing image receiving layers containing poly-4-vinylpyridine

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415645A (en) * 1967-03-10 1968-12-10 Polaroid Corp Opaque permeable polymeric layer in photo-sensitive element
US3419389A (en) * 1967-05-26 1968-12-31 Polaroid Corp Cyanoethylated polyvinyl spacer layers for image-receiving element
US3421893A (en) * 1967-05-26 1969-01-14 Polaroid Corp Acrylic polymer spacer layers for photographic elements
US3772025A (en) * 1967-10-16 1973-11-13 Polaroid Corp Diffusion transfer receiving sheets
US3607269A (en) * 1968-04-01 1971-09-21 Polaroid Corp Image-receiving elements and photographic processes employing same
US3709687A (en) * 1970-04-06 1973-01-09 Polaroid Corp Diffusion transfer receiving element with varing concentration of precipitating nuclei
US3907563A (en) * 1973-12-13 1975-09-23 Polaroid Corp Diffusion transfer process using processing composition impregnated image-receiving element
US4379828A (en) * 1980-05-16 1983-04-12 Agfa-Gevaert Aktiengesellschaft Image receptor element for the dye diffusion transfer process
US4443530A (en) * 1982-10-22 1984-04-17 Polaroid Corporation Self-processing film unit with liquid applicator
US4523825A (en) * 1984-06-14 1985-06-18 Polaroid Corporation Film processing apparatus and system
US4605608A (en) * 1985-09-23 1986-08-12 Polaroid Corporation Image-receiving element with crosslinked hydrophilic polymer containing processing composition
US5970271A (en) * 1997-03-11 1999-10-19 Polaroid Corporation Spool caddy for use with dry optical image processing of roll film
US5993080A (en) * 1997-03-11 1999-11-30 Polaroid Corporation System for optical dry processing of spooled photographic film
US6000863A (en) * 1997-03-11 1999-12-14 Polaroid Corporation Photographic processing method

Also Published As

Publication number Publication date
CH508227A (de) 1971-05-31
BE651209A (de) 1965-02-01
NL131882C (de)
DE1208190B (de) 1965-12-30
NL6408787A (de) 1965-02-01
GB1081165A (en) 1967-08-31

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