US3787209A - Color diffusion transfer color process and film with silver precipitating layer - Google Patents

Color diffusion transfer color process and film with silver precipitating layer Download PDF

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US3787209A
US3787209A US00246671A US3787209DA US3787209A US 3787209 A US3787209 A US 3787209A US 00246671 A US00246671 A US 00246671A US 3787209D A US3787209D A US 3787209DA US 3787209 A US3787209 A US 3787209A
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silver halide
image
photographic product
dye
layer
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E Land
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Polaroid Corp
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Polaroid Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
    • G03C8/12—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors characterised by the releasing mechanism
    • G03C8/14—Oxidation of the chromogenic substances
    • G03C8/16—Oxidation of the chromogenic substances initially diffusible in alkaline environment

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  • ABSTRACT Diffusion transfer color processes are disclosed wherein the color image is retained with the developed silver halide emulsion(s) as part of an integral negative-positive reflection print. Provision of a silver precipitating layer between the developed silver halide emulsion layer(s) and a light-reflecting layer substantially reduces discoloration of the color transfer image highlights resulting from undesired transfer of silver ion after formation of the color image.
  • This invention is concerned with photography and, more particularly, with the formation of images in color by diffusion transfer processing.
  • the resulting photograph comprises the developed silver halide emulsions retained with the dye-image carrying layer as part of a permanent laminate.
  • the image-carrying layer is separated from thedeveloped silver halide emulsions in said laminate by a light-reflecting layer, preferably a layer containing titanium dioxide.
  • a light-reflecting layer preferably a layer containing titanium dioxide.
  • the invention accordingly comprises the product possessing the features, properties and relation of components and the process involving the several steps and the relation and order of one or more of such steps with respect to each of the others which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • FIG. 1 is a diagrammatic enlarged schematic illustration of a diffusion transfer dye image formed in accordance with one embodiment of this invention.
  • FIG. 2 is a similar schematic illustration of a diffusion transfer dye image formed in accordance with another embodiment of this invention.
  • this invention is concerned with diffusion transfer processes wherein the layer containing the diffusion transfer dye image, i.e., the imagereceiving layer, is not separated from the developed photosensitive layers after processing but both components are retained together as part of a permanent laminate.
  • Film units particularly adapted to provide such diffusion transfer images have frequently been referred to as integral negative-positive film units.
  • the resulting image may be referred to as an integral negativepositive reflection print and as so used is intended to refer to a reflection print wherein the developed photosensitive layers have not been separated from the image layer, i.e., the layer containing the transfer dye image.
  • a light-reflecting layer between the developed photosensitive layer(s) and the image layer provides a white background for the dye image and masks the developed photosensitive layer(s).
  • These layers are part of a permanent laminate which usually includes dimensionally stable outer or support layers, the transfer dye image being viewable through one of said supports.
  • This invention is concerned with preventing or at least minimizing discoloration of the whites or highlights of such integral negative-positive reflection prints.
  • the present invention is applicable to a wide variety of color diffusion transfer processes and the arrangement and order of the individual layers of the film used in such color processes may vary in many ways as is known in the art, provided the final image is an integral negative-positive reflection print as described above.
  • the more specific description of the invention may be by use of dye developer diffusion transfer color processes and of integral negative-positive film units of the type contemplated in the previously mentioned U. S. Pat. No. 3,415,644.
  • the transfer of unreduced silver complex to the image-receiving element is believed to be a result of the inclusion within the system of a silver halide solvent, such as sodium thiosulfate, to improve the sensitometry of the process, and the continued wet" condition of the laminate.
  • a silver halide solvent such as sodium thiosulfate
  • color transfer images having good highlights and sensitometry may be obtained using a film unit in which the photosensitive and image-receiving layers are maintained as a laminate after processing if a stratum of silver precipitating nuclei is provided, preferably between the silver halide emulsions and the lightreflecting layer.
  • transfer of silver to the stratum of silver precipitating nuclei and reduction to metallic silver is delayed until after the desired image dye density has been obtained.
  • Precipitation of silver behind the light-reflecting layer insures that it will not be visible to the viewer of the color transfer image.
  • This transfer of silver halide and reduction to silver not only insures that any silver halide which may be dissolved by the processing composition will be precipitated in a position not detrimental to transfer image quality but also provides a mechanism by which image dyes undesired in the transfer dye image may be affirmatively excluded from transfer.
  • the more complete development of the silver halide present provides an additional consumption of alkali, thereby providing an additional pH control mechanism.
  • the silver deposited in the silver precipitating stratum is nonimagewise.
  • a sulfur-free second silver halide complexing agent capable of forming a relatively less soluble silver complex e.g., a 6-alkylaminopurine such as 6-benzylamino-purine
  • a sulfur-containing second silver halide complexing agent such as l-phenyl-5-mercaptotetrazole
  • Particularly useful silver halide solvents which are free of sulfur atoms are cyclic imides such as those disclosed in U. S. Pat. No. 2,857,274, issued Oct. 21, 1958 to Edwin H. Land et al. and particularly uracils such as uracil, S-methyl uracil and 6-methyl uracil.
  • the present invention therefore is concerned with providing diffusion transfer color processes for forming integral negative-positive reflection prints which processes may use silver halide solvents, whether or not said solvents contain sulfur atoms, while minimizing photolytically reducible silver complex in the dye image layer.
  • Suitable silver halide solvents include alkali metal and other thiosulfates or thiocyanates as well as the above cyclic imide silver halide solvents and other known silver halide solvents.
  • the silver halide solvent may be used in combination with a second silver halide complexing agent capable of forming a relatively insoluble silver salt or complex,
  • R is an alkyl group, it being understood that alkyl is intended to include aralkyl, such as O CH:
  • alkyl group is a simple alkyl group
  • the alkyl group may be substituted, e.g., by halogen, alkoxy, etc.
  • FIGS. 1 and 2 illustrate in a simplified or schematic form the arrangement of layers in photographic films of the type with which this invention is concerned, the film or film unit being depicted as an integral laminate after processing and image formation. Since the two film units shown have many elements in common, the two figures will be described together.
  • a diffusion transfer image in an image-receiving or image-carrying layer 12 is viewed through a transparent support against a lightreflecting layer 12 which in turn masks the developed I silver halide emulsion(s) 16.
  • an opaque support 18 completes the film unit 10.
  • the light-reflecting layer 14 preferably comprises a white pigment, particularly titanium dioxide.
  • the silver halide emulsion layer 16 may comprise a plurality of silver halide emulsions (blue-, greenand red-sensitive) arranged in overlying coplanar relationship or in a side-by-side or screen-like arrangement as is well known in the art.
  • An image dye-providing material associated with each of the silver halide emulsions in the same layer or in a contiguous layer, provides an image dye or an intermediate for an image dye having a color complementary to the light by which the associated silver halide emulsion is exposable, as is well known in subtractive color processes.
  • a layer 26 of silver precipitant is positioned between the developed silver halide emulsion l6 and the image-receiving layer 12. Soluble silver complex formed in either the exposed or unexposed areas of the silver halide emulsion 16 cannot diffuse to the image-receiving layer 12 for it will be precipitated in the silver precipitant layer 26 where it is masked by the light-reflecting layer 14.
  • Silver precipitating agents useful in this invention may be readily selected from among the many materials taught in the art to be useful in silver transfer processes. Examples of particularly suitable silver precipitating agents are the metallic sulfides and selenides and colloidal metals disclosed in U. S. Pat. No. 2,698,237. As will be readily apparent, suitable precautions should be taken to insure that the silver precipitating agent is confined in its own layer and is not introduced into other layers where it might adversely affect the sensitometry.
  • the elements of the film may be superposed and comprise an integral film unit during photographic exposure, i.e., photoexposure being effected throughthe transparent support 20 as shown, for example, in the aforementioned U. S. Pat. No. 3,415,644.
  • the image-receiving layer 12 and its transparent support 20 may be separated from the photosensitive layers during exposure, the resulting laminate 10 being formed by the superposing of the respective elements with a processing composition containing a light-reflecting pigment distributed therebetween, as described, for example, in the aforementioned U. S. Pat. No. 2,983,606.
  • a particularly useful opacifying system for film units providing integral prints of the type shown in FIG. I and in the aforementioned U. S. Pat. No. 3,415,644 utilizes a color dischargeable reagent, preferably a pII-sensitive optical filter agent or dye, as is described in detail in U. S. Pat. No. 3,647,437 issued Mar. 7, 1972 to Edwin H. Land.
  • a color dischargeable reagent preferably a pII-sensitive optical filter agent or dye
  • photoexposure is effected from the side opposite the side from which the image is viewed, and an appropriate opaque layer 22 is provided over the silver halide emulsion(s) layer 116.
  • This may be done by distributing a processing composition providing an opaque layer 22, e.g., containing carbon black, between the photosensitive layer 16 and the transparent support 24.
  • opaque layer 22 may be omitted and lightprotection provided by an opaque layer (not shown) superposed over the transparent support 24 or directly over the photosensitive layer 16 after exposure.
  • photoexposure is effected through the same transparent support 20 through which the final dye transfer image is viewed.
  • photoexposure is effected through the transparent support 24 and an opaque layer 22 to protect the exposed silver halide from further exposure may be provided by including a light-absorbing opacifying agent, e.g., carbon black, in the processing composition which is distributed between the photosensitive layer 16 and a transparent support 24.
  • a preformed opaque layer e.g., a dispersion of carbon black in a polymer permeable to the processing composition, between a preformed light-reflecting layer 14 and the silver halide emulsion(s) 16.
  • the silver precipitating agent may be positioned in said permeable preformed opaque layer instead of being in a separate layer.
  • the image dye-providing materials which may be employed in such processes generally may be characterized as either (1) initially soluble or diffusible in the processing composition but are selectively rendered non-diffusible in an imagewise pattern as a function of development; or (2) initially insoluble or non-diffusible in the processing composition but which are selectively rendered diffusible or provide a diffusible product in an imagewise pattern as a function of development.
  • These materials may be complete dyes or dye intermediates, e.g., color couplers.
  • the requisite differential in mobility or solubility may, for example, be obtained by a chemical action such as a redox reaction or a coupling reaction.
  • multicolor images are obtained by employing a film unit containing at least two selectively sensitized silver halide layers each having associated therewith an image dye-providing material exhibiting desired spectral absorption characteristics.
  • the most commonly employed elements of this type are the so-called tripack structures employing blue-, a greenand a red-sensitive silver halide layers having associated therewith, respectively, a yellow, a magenta and a cyan image dye-providing material, as disclosed in U. S. Pat. No. 3,345,163 issued Oct. 3, 1967 to Edwin H. Land and Howard G. Rogers.
  • a particulary useful system for forming color images by diffusion transfer is that described in U. S. Pat. No. 2,983,606, employing dye developers (dyes which are also silver halide developing agents) as the image dyeproviding materials.
  • a photosensitive element comprising at least one silver halide layer having a dye developer associated therewith (in the same or in an adjacent layer) is developed by applying an aqueous alkaline processing composition.
  • Exposed and developable silver halide is developed by the dye developer which in turn becomes oxidized to provide an oxidation product which is appreciably less diffusible than the unreacted dye developer, thereby providing an imagewise distribution of diffusible dye developer in terms of unexposed areas of the silver halide layer, which imagewise distribution is then transferred, at least in part, by diffusion, to a dyeable stratum to impart thereto a positive dye transfer image.
  • Multicolor images may be obtained with a photosensitive element having two or more selectively sensitized silver halide layers and associated dye developers, a tripack structure of the type described above in various patents including the aforementioned U. S. Pat. Nos. 2,983,606 and 3,345,163 being especially suitable for accurate color recordation of original subject matter.
  • color transfer images are obtained by exposing a photosensitive element, sometimes referred to as a negative component, comprising' at least a light-sensitive layer, e.g., a gelatino silver halide emulsion layer, having an image dye-providing material associated therewith in the same or in an adjacent layer, to form a developable image; developing this exposed element with a processing composition to form an imagewise distribution of a diffusible image dye-providing material; and transferring this imagewise distribution, at least in part, by diffusion, to a superposed image-receiving layer, sometimes referred to as a positive component, comprising at least a dyeable stratum to provide a color transfer image.
  • a photosensitive element sometimes referred to as a negative component
  • a light-sensitive layer e.g., a gelatino silver halide emulsion layer
  • an image dye-providing material associated therewith in the same or in an adjacent layer
  • the negative and positive components initially may be carried on separate supports which are brought together during processing and thereafter retained together as the final integral negative-positive reflection print, or they may initially comprise a unitary structure, e.g., integral negative-positive film units wherein the negative and positive components are part of a photosensitive laminate or they may otherwise be physically retained together in superposed relationship prior to, during and after image formation.
  • integral negative-positive film units wherein the positive and negative components are temporarily laminated together prior to exposure are described, for example in U. S. Pat. No. 3,652,281 to Albert J. Bachelder and Frederick J. Binda and in U. S. Pat. No. 3,652,282 to Edwin H. Land, both issued Mar.
  • the preferred film units comprise a plurality of essential layers including a negative component comprising at least one light-sensitive silver halide and associated dye imageproviding material and a positive component comprising a dyeable stratum. These components may be laminated together or otherwise secured together in physical juxtaposition as an essentially integral structure. Film units intended to provide multicolor images comprise two or more selectively sensitized silver halide layers each having associated therewith an appropriate image dye-providing material providing an image dye spectral absorption characteristics substantially complementary to the light by which the associated silver halide is exposed.
  • the most commonly employed negative components for forming multicolor images are of the tripack structure and contain blue-, greenand redsensitive silver halide layers each having associated therewith in the same or in a contiguous layer a yellow, a magenta and a cyan image dye-providing material rebe provided between the respective silver halide layers and associated image dye-providing materials or between other layers.
  • such film units further include means for providing a reflecting layer between the dyeable stratum and the negative component in order to mask effectively the silver image or images formed as a function of development of the silver halide layer or layers and also to mask image dye-providing material which is not transferred, thereby providing a background, preferably white, for viewing the color image formed in the dyeable stratum, without separation, by reflected light.
  • This reflecting layer may comprise a preformed layer of a reflecting agent included in the film unit or the reflecting agent may be provided after photoexposure, e.g., by including the reflecting agent in the processing composition. The dye transfer image is then viewable through a dimensionally stable protective layer or support.
  • a dimensionally stable layer or support which may be transparent or opaque, is positioned on the opposed surface of the essential layers so that the aforementioned essential layers are between a pair of dimensionally stable layers or support members, one of which is transparent to permit viewing therethrough of the color transfer image.
  • a rupturable container of known description contains the requisite processing composition and is adapted upon application of pressure torelease its contents for development of the exposed film unit, e.g., by distributing the processing composition in a substantially uniform layer between a pair of predetermined layers.
  • a processing composition containing a white pigment may be distributed between the dyeable stratum and the negative component to provide the light-reflecting layer 14.
  • a preferred opacification system to be contained in the processing composition to effect processing outside of a camera is that described in the above-mentioned U. S. Pat. No. 3,647,437, and comprises a dispersion of an inorganic light-reflecting pigment which also con tains at least one light-absorbing agent, i.e., optical filter agent, at a pH above the pKa of the optical filter agent in a concentration effective when the processing composition is applied, to provide a layer exhibiting optical transmission density than about 6.0 density units with respect to incident radiation actinic to the photosensitive silver halide and optical reflection density than about 1.0 density units with respect to incident visible radiation.
  • an inorganic light-reflecting pigment which also con tains at least one light-absorbing agent, i.e., optical filter agent, at a pH above the pKa of the optical filter agent in a concentration effective when the processing composition is applied, to provide a layer exhibiting optical transmission density than about 6.0 density units with respect to incident radiation actinic to
  • the light-reflecting pigment used to mask the photosensitive strata and to provide the requisite background for viewing the color transfer image formed in the receiving layer may be present initially in whole or in part as a performed layer in the film unit.
  • a preformed layer mention may be made of that disclosed in U. S. Pat. No. 3,615,421 issued Oct. 26, 1971 and in U. S. Pat. No. 3,620,724 issued Nov. 16, 1971, both in the name of Edwin H. Land.
  • the reflecting agent may be generated in situ as is disclosed in U. S. Pat. Nos. 3,647,434 and 3,647,435, both issued Mar. 7, 1972 to Edwin H. Land.
  • the dye developers are preferably selected for their ability to with the development process. Suitable spacer or timing" layers for this purpose are described with particularity in U. S. Pat. Nos. 3,362,819; 3,419,389; provide colors that are useful in carrying out subtractive color photography, that is, the previously mentioned cyan, magenta and yellow. They may be incorporated in the respective silver halide emulsion or, in the preferred embodiment, in a separate layer behind the respective silver halide emulsion.
  • a dye developer may, for example, be in a coating or layer behind the respective silver halide emulsion and such a layer of dye developer may be applied by use of a coating solution containing the respective dye developer distributed, in a concentration calculated to give the desired coverage of dye developer per unit area, in a filmforming natural, or synthethic, polymer, for example, gelatin, polyvinyl alcohol, and the like, adapted to be permeated by the processing composition.
  • Dye developers are compounds which contain the chromophoric system of a dye and also a silver halide developing function.
  • a silver halide developing function is meant a grouping adapted to develop exposed silver halide.
  • a preferred silver halide development function is a hydroquinonyl group.
  • Other suitable developing functions include ortho-dihydroxyphenyl and ortho-and para-amino substituted hydroxyphenyl groups.
  • the development function includes a benzenoid developing function, that is, an aromatic developing group which forms quinonoid or quinone substances when oxidized.
  • the image-receiving layer may comprise one of the materials known in the art, such as polyvinyl alcohol, gelatin, etc. It may contain agents adapted to mordant or otherwise fix the transferred image dye(s).
  • Preferred materials comprise polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine, as disclosed in U. S. Pat. No. 3,148,061, issued Sept. 8, 1964 to Howard C. Haas. If the color of the transferred image dye(s) is affected by changes in pH, the pH of the image layer may be adjusted to provide a pH affording the desired color.
  • polymeric acids may be polymers which contain acid groups, e.g., carboxylic acid and sulfonic acid groups, which are capable of forming salts with alkali metals or with organic bases; or potentially acidyielding groups such as anhydrides or lactones.
  • the'acid polymer contains free carboxyl groups.
  • the acid-reflecting reagent may be in a layer adjacent the silver halide most distant from the image-receiving layer, as disclosed in U. S. Pat. No. 3,573,043 issued Mar. 30, 1971 to Edwin H. Land. Another system for providing an acid-reacting reagent is disclosed in U. S. Pat. No. 3,576,625 issued Apr. 27, 1971 to Edwin H. Land.
  • An inert interlayer or spacer layer may be and is preferably disposed between the polymeric acid layer and the dyeable stratum in order to control or time the pH reduction so that it is not premature and interfere 3,421,893; 3,455,686; and 3,575,701.
  • the acid layer and associated spacer layer are preferably contained in the positive component employed in systems wherein the dyeable stratum and photosensitive strata are contained on separate supports, e.g., between the support for the receiving element and the dyeable stratum; or associated with the dyeable stratum in those integral film units, e.g., on the side of the dyeable stratum opposed from the negative components, they may, if desired, be associated with the photosensitive strata, as is disclosed, for example, in U. S. Pat. Nos. 3,362,821 and 3,573,043. In film units such as those described in the aforementioned U. S. Pat. Nos. 3,594,164 and 3,594,165, they also may be contained on the spreader sheet employed to facilitate application of the processing fluid.
  • the liquid processing composition referred to for effecting multicolor diffusion transfer processes comprises at least an aqueous solution of an alkaline material, for example sodium hydroxide, potassium hydroxide, and the like, and preferably possessing a pH in excess of 12, and most preferably includes a viscosity-increasing compound constituting a film-forming material of the type which, when the composition is spread and dried, forms a relatively firm and relatively stable film.
  • the preferred film-forming materials disclosed comprise high molecular weight polymers such as polymeric, water-soluble ethers which are inert to an alkaline solution such as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.
  • film-forming materials or thickening agents whose ability to increase viscosity is substantially unaffected if left in solution for a long period of time are so disclosed to be capable of utilizat tion.
  • the film-forming material is preferably contained in the processing composition in such suitable quantities as to impart to the composition a viscosity in excess of 100 cps. at a temperature of approximately 24 C. and preferably in the order of 100,000 cps. to 200,000 cps. at that temperature.
  • a blue-sensitive gelatino silver iodobromide emulsion layer including the auxiliary developer 4'- methylphenyl hydroquinone coated at a coverage of about 120 mgs./ft. of silver, about 60 rugs/ft. of gelatin and about 30 mgs/ft. of auxiliary developer; and
  • a very thin coating of zinc sulfide in colloidal silica was applied to the surface of the photosensitive element to provide a silver precipitating layer.
  • a transparent 4 mil. polyethylene teraphthalate film base was coated, in succession, with the following layers to form an image-receiving component:
  • timing layer containing about a 40:1 ratio of a 60-30-4-6 copolymer of butylacrylate, diacetone acrylamide, styrene and methacrylic acid and polyacrylamide at a coverage of about 500 mgs./ft. and
  • the two components thus prepared were then taped together, in laminate form, at their respective edges to provide an integral film unit, with a rupturable container retaining an aqueous alkaline processing solution fixedly mounted on the leading edge of each of the components, by pressure-sensitive tapes, so that, upon application of compressive pressure to the container to rupture the containers marginal seal, its contents were distributed in a layer approximately 0.0026 inches thick between the image-receiving layer and the gelatin overcoat layer of the photosensitive component.
  • the aqueous alkaline processing composition comprised:
  • the photosensitive element was exposed through the transparent support and the layers thereon, the processing composition distributed by passing the film unit between a pair of pressure-applying rolls and into a lighted area.
  • the laminate obtained by distribution of the processing composition was maintained intact to provide an integral negative-positive reflection print which exhibited good color quality and separation. Accelerated ageing of the print showed that darkening of the highlights due to silver ion transferred to the imagereceiving layer was reduced by at least 50 percent.
  • a similarly prepared integral negative-positive reflection print was peeled apart about 5 to 10 minutes after the processing composition was applied.
  • a layer of black silver, substantially nonimagewise, was found to be present between the blue-sensitive silver halide emulsion of the light-reflecting titanium dioxide layer.
  • the concentration of the silver halide solvent and of the other silver halide complexing agent(s) may be varied over a wide range. If the second silver halide complexing agent, e.g., PMT or 6 benzylaminopurine, is initially present in the imagereceiving layer, a higher concentration will be coated therein per unit area than is required if it is initially disposed in the processing composition. It should be noted that the second silver halide complexing agent may be initially present as a component of the processing composition and therefore available for permeation into the silver halide layers as soon as the processing composition is applied.
  • the second silver halide complexing agent e.g., PMT or 6 benzylaminopurine
  • 6-alkylaminopurines gives especially good sensitometric results in dye developer transfer processes over a very wide temperature range.
  • a given concentration of 6- benzylamino-purine will give good sensitometric results over a broader temperature range than will a given concentration of a mercaptan such as PMT.
  • dye transfer images which are neutral or black-and-white instead of multicolor may be obtained by use of a mixture of dyes of the appropriate colors, the transfer of which may be controlled by a single layer of silver halide, in accordance with known techniques. It is also to be understood that direct positive" silver halide emulsions may also be used, depending upon the particular dye imageproviding substances employed and whether a positive or negative color transfer image is desired.
  • the precipitation of silver by the silver precipitating agent could give rise to a reaction product, e.g., an oxidized developing agent, which could react with said image dye-providing material to generate a diffusible image dye or image dye intermediate.
  • a reaction product e.g., an oxidized developing agent
  • Such unwanted dye density in the transfer image may be avoided by positioning a scavenger for such reaction product intermediate the silver precipitating layer and the image dye-providing material.
  • a nondiffusible reducing agent positioned between the silver precipitating layer and the image dye-providing material could be used to reduce the oxidized developing agent before it could enter into the dye release reaction.
  • the layer of silver deposited in the silver precipitating layer may assist in providing the requisite opacification.
  • the opacification provided by the layer of silver thus created may permit discharging the color of an optical filter at a more rapid rate. It is within the scope of this invention to employ as one or both of the support layers polymeric or other materials which transmit water vapor at a rate adapted to dry the laminate rapidly. Suitable supports of this type are described, for example, in U. S. Pat. No. 3,573,044 issued Mar. 30, 1971 to Edwin H. Land.
  • this invention provides a marked reduction in the tendency of diffusion transfer integral negative-positive color reflection prints to exhibit discoloration of the highlights from photolytic degradation of unreduced silver ion present in the dye image layer.
  • a photographic product for forming a diffusion transfer image in dye within a permanent laminate including at least one developed silver halide layer, said photographic product comprising, in combination, an image-receiving layer; at least one silver halide emulsion, each said silver halide emulsion having associated therewith an image dye-providing substance selected from the group consisting of image dyes and image dye intermediates; means providing a light-reflecting layer between said image-receiving layer and said silver halide emulsion(s) to mask said silver halide emulsion(s) after development thereof and to provide a white background for viewing a dye image in said image-receiving layer; a transparent support through which imagereceiving layer may be viewed; a rupturable container releasably retaining a processing composition for developing said silver halide emulsion(s) after photoexposure and for forming a transfer image in at least one dye in said image-receiving layer; said product including a silver
  • each said image dye-providing substance is a dye.
  • each said dye is a dye developer.
  • each said image dye-providing substance is an intermediate for an image dye.
  • a photographic product as defined in claim 1 wherein said silver halide emulsions are a red-sensitive silver halide emulsion, a green-sensitive silver halide emulsion and a blue-sensitive silver halide emulsion, and said silver halide emulsions have associated therewith, respectively, a cyan image dye-providing substance, a magenta image dye-providing substance and a yellow image dye-providing substance.
  • a photographic product as defined in claim 1 comprising a temporary laminate including said layers confined between two dimensionally stable supports, at least one of said supports being transparent, the bond between a predetermined pair of layers being weaker than the bond between other pairs of layers, said rupturable container being so positioned as to distribute said processing composition between said predetermined layers, said processing composition being adpated to provide said permanent laminate following distribution and drying.
  • a photographic product as defined in claim wherein said polyester is polyethylene terephthalate.
  • a photographic product comprising a first support; a red-sensitive silver halide emulsion; a greensensitive silver halide emulsion; and a blue-sensitive silver halide emulsion; said silver halide emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer; an image-receiving layer for receiving image dyes transferred thereto by diffusion as a function of exposure and development of said silver halide emulsion layers; a second support which is transparent and through which said image-receiving layer may be viewed; a rupturable container releasably holding a processing composition adapted, upon distribution between predetermined layers of said film to develop said silver halide emulsions and to effect the formation of a transfer image in dye in said image-receiving layer, said processing composition also being adapted to provide a permanentlaminate including said developed silver halide emulsions and said image-receiving layer; and means
  • a photographic product as defined in claim 18 wherein said means for providing a light-reflecting layer comprises a preformed layer of a white pigment.
  • a photographic product as defined in claim 18 wherein said means for providing a light-reflecting layer comprises a white pigment dispersed in said processing composition.
  • a photographic product as defined in claim 37 wherein said 6-alkylamino-purine is 6-benzylaminopurine.
  • a photographic product as defined in claim 41 wherein said product is a laminate of said layers between said first and said second supports, the bond between a pair of predetermined layers being weaker than the bonds between the other layers, said rupturable container being so positioned as to release said processing composition for distribution between said pair of layers.
  • a photographic product as defined in claim 18 including means to reduce the pH of a layer of said processing composition from a first pH to a second pH.
  • a photographic product as defined in claim 48 wherein said means to reduce the pH comprises a layer of an acid-reacting reagent positioned between said transparent support and said image-receiving layer.
  • a diffusion transfer dye image by developing an exposed silver halide emulsion in the presence of a silver halide solvent, forming a imagewise distribution of a diffusible dye image-providing substance as a function of said development, and transferring at least a portion of said imagewise distribution of diffusible dye image-providing substance to an image-receiving layer in superposed relationship with said silver halide emulsion to provide said dye image, said image-receiving layer and said silver halide emulsion forming a permanent laminate including a lightreflecting layer positioned between said imagereceiving layer and said silver halide emulsion, the improvement wherein soluble silver complex capable of diffusing to said image-receiving layer is precipitated in a layer between said silver halide emulsion and said light-reflecting layer.
  • said dye image is a multicolor image.
  • a photographic product comprising a support carrying a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a bluesensitive silver halide emulsion layer, said red-sensitive silver halide emulsion having associated therewith a cyan image dye-providing substance, said greensensitive silver halide emulsion having associated therewith a magenta image dye-providing substance, and said blue-sensitive silver halide emulsion having associated therewith a yellow image dye-providing substance, each said image dye-providing substance being selected from the group consisting of image dyes and image dye intermediates, the outermost said silver halide emulsion layer carried by said support carrying a silver precipitating layer including a silver precipitating agent.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US00246671A 1972-04-24 1972-04-24 Color diffusion transfer color process and film with silver precipitating layer Expired - Lifetime US3787209A (en)

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US (1) US3787209A (enrdf_load_stackoverflow)
JP (1) JPS5840175B2 (enrdf_load_stackoverflow)
AU (1) AU474442B2 (enrdf_load_stackoverflow)
BE (1) BE798616A (enrdf_load_stackoverflow)
CA (1) CA1007089A (enrdf_load_stackoverflow)
DE (1) DE2319470C2 (enrdf_load_stackoverflow)
FR (1) FR2181912B1 (enrdf_load_stackoverflow)
GB (1) GB1432804A (enrdf_load_stackoverflow)
IT (1) IT980327B (enrdf_load_stackoverflow)
NL (1) NL178724C (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933494A (en) * 1972-11-15 1976-01-20 Minnesota Mining And Manufacturing Company Method for obtaining a color contrast photographic image by color development and silver salt diffusion transfer processing of one photographic element
US4102685A (en) * 1976-08-26 1978-07-25 Polaroid Corporation Photographic uses of polyvinylphenylmercapto-tetrazole:multivalent metal cation combinations
US4134768A (en) * 1976-08-26 1979-01-16 Polaroid Corporation Photographic uses of polyvinyl-phenylmercapto-tetrazoles
US4820608A (en) * 1986-10-23 1989-04-11 Agfa-Gevaert, N.V. Dye diffusion transfer imaging process and image receptor used therein
US5543258A (en) * 1993-06-22 1996-08-06 Fuji Photo Film Co., Ltd. Original forme for electrophotograhic planography

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6029103B2 (ja) * 1976-12-10 1985-07-09 富士写真フイルム株式会社 カラ−拡散転写法用写真要素
CA1132826A (en) * 1979-01-24 1982-10-05 Frans Carael Non-photosensitive receptor material containing an organic compound with a c-linked anionic group and an organic acid-dye mordanting compound
EP0049002B1 (en) * 1980-09-30 1985-09-18 Agfa-Gevaert N.V. Process for the production of a multicolour image by image-wise dye diffusion transfer
JPS60236705A (ja) * 1984-04-20 1985-11-25 久保田コンクリ−ト工業株式会社 トンネル構築用コンクリ−トセグメントの製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415644A (en) * 1967-03-10 1968-12-10 Polaroid Corp Novel photographic products and processes
US3647437A (en) * 1970-12-18 1972-03-07 Polaroid Corp Photographic products, processes and compositions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL126854C (enrdf_load_stackoverflow) * 1960-08-22
DE2049688C3 (de) * 1970-10-09 1981-02-12 Agfa-Gevaert Ag, 5090 Leverkusen Fotografisches Material und Verfahren zur Herstellung farbiger fotografischer Bilder

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415644A (en) * 1967-03-10 1968-12-10 Polaroid Corp Novel photographic products and processes
US3647437A (en) * 1970-12-18 1972-03-07 Polaroid Corp Photographic products, processes and compositions

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933494A (en) * 1972-11-15 1976-01-20 Minnesota Mining And Manufacturing Company Method for obtaining a color contrast photographic image by color development and silver salt diffusion transfer processing of one photographic element
US4102685A (en) * 1976-08-26 1978-07-25 Polaroid Corporation Photographic uses of polyvinylphenylmercapto-tetrazole:multivalent metal cation combinations
US4134768A (en) * 1976-08-26 1979-01-16 Polaroid Corporation Photographic uses of polyvinyl-phenylmercapto-tetrazoles
US4820608A (en) * 1986-10-23 1989-04-11 Agfa-Gevaert, N.V. Dye diffusion transfer imaging process and image receptor used therein
US5543258A (en) * 1993-06-22 1996-08-06 Fuji Photo Film Co., Ltd. Original forme for electrophotograhic planography

Also Published As

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CA1007089A (en) 1977-03-22
IT980327B (it) 1974-09-30
NL178724C (nl) 1986-05-01
AU5445173A (en) 1974-10-17
NL7305701A (enrdf_load_stackoverflow) 1973-10-26
NL178724B (nl) 1985-12-02
FR2181912A1 (enrdf_load_stackoverflow) 1973-12-07
DE2319470A1 (de) 1973-11-15
DE2319470C2 (de) 1984-03-01
JPS4948325A (enrdf_load_stackoverflow) 1974-05-10
BE798616A (fr) 1973-10-24
GB1432804A (en) 1976-04-22
AU474442B2 (en) 1976-07-22
JPS5840175B2 (ja) 1983-09-03
FR2181912B1 (enrdf_load_stackoverflow) 1983-02-18

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