US3856521A - Diffusion transfer color film and process - Google Patents

Diffusion transfer color film and process Download PDF

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US3856521A
US3856521A US00247022A US24702272A US3856521A US 3856521 A US3856521 A US 3856521A US 00247022 A US00247022 A US 00247022A US 24702272 A US24702272 A US 24702272A US 3856521 A US3856521 A US 3856521A
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silver halide
image
dye
processing composition
layer
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R Bilofsky
H Rogers
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Polaroid Corp
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Polaroid Corp
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Priority to US00247022A priority Critical patent/US3856521A/en
Priority to AU54449/73A priority patent/AU464590B2/en
Priority to GB1813873A priority patent/GB1425835A/en
Priority to DE2319469A priority patent/DE2319469C2/de
Priority to FR7314294A priority patent/FR2181915B1/fr
Priority to CA169,196A priority patent/CA1012817A/en
Priority to JP7344985A priority patent/JPS539738B2/ja
Priority to IT49645/73A priority patent/IT980343B/it
Priority to BE130335A priority patent/BE798619A/xx
Priority to NLAANVRAGE7305705,A priority patent/NL179236C/xx
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Publication of US3856521A publication Critical patent/US3856521A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes

Definitions

  • 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 the developed 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.
  • Yet another object of this invention is to provide color diffusion transferprocesses wherein a metal chelating agent is provided to increase the resistance to discoloration of diffusion transfer dye images containing a light-reflecting pigment.
  • 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.
  • 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 arrange ment and order of the individual layersof 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 developed diffusion transfer color processes and of integral negative-positive film units of this type contemplated in the previously mentioned U.S. Pat. No. 3,415,644
  • the various layers comprising the laminate tend to remain wet for a period of time much longer than the processing time, i.e., the time required simply to develop the exposed silver halide and to form the transfer image.
  • This extended wet condition thus may permit reactions to occur which will adversely affect the color transfer image; These further reactions are most readily evidenced by changes in the highlights or whites of the color image.
  • reagents used in the process include functional groups which are capable of forming colored metal complexes.
  • the optical filter agent OH on ooon nooo CHHUO-K contains two acid -type groups.
  • Ethylene diamine tetraacetic acid and related compounds are known to have a buffering action at certain pH levels. Careful study has shown that the beneficial uracil, with a o-alkylaminopurine of the formula:
  • R is an alkyl group, it being understood that alkyl is intended to include aralkyl, such as I OCHJ effect of ethylene diamine tetraacetic acid is not due to a buffer action, as other compounds known to buffer at the same or similar pH levels do not prevent the formation of this stain.
  • the beneficial effect of the addition of other metal ions, such as aluminum ions, is considered to be strong-additional evidence that a buffer action is not to be credited.
  • an acid reacting reagent is generally present to reduce the pH by neutralizing the alkaline system, the final pH within the integral negative-positive print is likely to be below the pH at which ethylene diamine tetraacetic acid is a buffer.
  • the beneficial effects of the metal chelating agent are particularly useful in dye developer diffusion transfer processes wherein development is effected in the presence of a sulfur-free silver halide solvent and a second sulfurfree silver halide complexing agent which forms a relatively less soluble silver complex.
  • Particu larly useful are combinations of a cyclic imide, preferably a uracil such as uracil, S-methyl uracil or 6-methyl
  • a cyclic imide preferably a uracil such as uracil, S-methyl uracil or 6-methyl
  • the alkyl group is a simple alkyl group, better results are generally obtained when the alkyl group contains more than one or two carbons.
  • the alkyl group may be substi-v tuted, 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 20 against a lightreflecting layer 12 which in turn masks the developed 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.
  • the elements of the film may be superposed and comprise an integral film unit during photographic exposure, i.e., photoexposure being effected through the transparent support 20 as shown, for example, in the aforementioned U.S. Pat. No. 3,426,644.
  • the image-receiving layer 12 and its transparent support 2.0 may be separated from the photosensitive layers during exposure, the resulting laminate 110 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 US. Pat. No. 2,983,606.
  • a particularly useful opacifying system for film units providing integral prints of the type shown in FIG. 1 and in the aforementioned US. Pat. No. 3,426,644 utilizes a color dischargeable reagent, preferably a pH-sensitive optical filter agent or dye, as is described in detail in US. Pat. No. 3,647,437 issued Mar. 7, 1972 to Edwin H. Land.
  • a color dischargeable reagent preferably a pH-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 photo sensitive 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 image dyeproviding 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 cou plers.
  • the requisite differential in mobility or solubility may, for example, be obtained by achemical action such as a redox reaction or a coupling reaction.
  • multicolor images are ob tained 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 dyeproviding material, as disclosed in U.S. Pat. No. 3,345,163 issued Oct. 3, 1967 to Edwin H. Land and Howard G. Rogers.
  • a particularly useful system for forming color images by diffusion transfer is that described in US. 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 oxi dation 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 dyeab'le stratum to inpart 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 tripaclt structure of the type described above in various patents including the aforementioned US. Pat. Nos. 2,983,606 and 3,345,163 being especially suitable for accurate color recordation oforiginal subject matter.
  • color transfer images are obtained by exposing a photosensitive element, sometimes referred to as a negative compoto 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 compoto a superposed image-receiving layer, sometimes referred to as a positive component, comprising at least a dyeable stratum to provide a color transfer image.
  • 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,
  • integral negative-positive film units wherein the negative and positive components are part of a photosensitive laminate or they may otherwise by physically retained together in superposed relationship prior to, during and after image formation.
  • Processdures for forming such 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. 28, 1972.
  • the positive component is not removed from the negative component for viewing purposes.
  • 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.
  • 'Filmunits 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 respectively.
  • lnterlayers or spacer layers may, if desired, be 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 to release 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. 1n film units providing an integral negative-positive reflection print of the type illustrated in FIG. 1, a processing composition containing a white pigment may be distributed between the dyeable stratum and the negative component to providethe 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 contains 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 about 6.0 density units with respect to incident radiation actinic to the photosensitive silver halide and optical reflection density about 1.0 density units with respect to incident visible radiation.
  • an inorganic light-reflecting pigment which also contains 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 about 6.0 density units with respect to incident radiation actinic to the photosensitive silver hal
  • 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.
  • the dye developers are preferably selected for their ability to provide colors that are useful in carrying out subtractive color photography, that is, the previously mentioned cyan, magenta and yellow. 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 synthetic, 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.
  • 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. 1f 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 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; 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 3,573,043.1n film units such as those described in the aforementioned US. 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 include 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.
  • filmforming 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 utilization.
  • the film-forming material is preferably contained in the processing composition in such suitable quantities as to impart to the composition a viscosity in excess of cps. at a temperature of approximately 24C. 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 mgs./ft. of gelatin and about 30 mgs./ft. of auxiliary developer; and
  • a transparent 4 mil. polyethylene teraphthalate film base was coated, in succession, with the following layers to form an image-receiving component:
  • 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 alkalineprocessing composition comprised:
  • N-benzyl-a-picolinium bromide (50% solution in water) 1 1.3 g.
  • dodium carboxyrnethyl cellulose (Hercules Type 7H4F providing a viscosity of 3000 cps at 1% in water at 25C.) 0 .59 9'.
  • Titanium dioxide 44.9 g.
  • Colloidal silica aqueous dispersion (30% SiO 1.96 g.
  • 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 essentially no yellow stain which was observed in the absence of the ethylene diamine tetraacetic acid.
  • colloidal silica in the processing composition is the subject of the copending application of Edwin H. Land, Ser, No. 247,025, filed concurrently herewith (now U.S. Pat. No. 3,776,726 issued Dec. 3, 1973).
  • polyethylene glycol in the processing composition is the subject of the copending application of Edwin H. Land, Ser. No. 247,023, filed concurrently herewith (now U.S. Pat. No. 3,793,023 issued Feb. 19, I974) as a continuation-in-part of application Ser. No. 209,754, filed Dec. 20, 1971, now abandoned.
  • the ethylene diamine tetraacetic acid was added as the dipotassium salt; if it is added as the free acid, additional alkali may be added to cmpensate for the alkali consumed by the acid.
  • ethylene glycine diamino-cyclohexane tetraacetic acid may vary, ofcourse, with the particular metal complexing agent and may be readily determined by routine testing.
  • Other metal complexing agents which are use ful maybe readily determined by a simple screening test wherein the pigment (or other source of metal ions) and the reagent which itself is colorless in acid but which with such metal ions can form a reaction product which would be colored at the final pH of the transfer image are allowed to contact under strong alkaline conditions before being neutralized to a pH of about 7, and preferably a pH of about 5.
  • a thin layer of the resulting mixture preferably confined between two transparent polyester supports, may be heated at 120F. for 18 hours in the dark.
  • ing agents will prevent or at least substantially reduce the stain observed in their absence. It will be recognized that a particular metal complexing agent may be more effective with a given metal ion than with another metal ion.
  • the pigment is titanium dioxide
  • reflection density curves ofa layer formed from an aqueous potassium hydroxide solution of the above optical filter agent containing a salicylic acid-like group, sodium carboxymethyl cellulose and titanium dioxide fol lowing neutralization with acetic acid to a pH of about 5 to 6 show a sizeable increase in blue absoprtion, i.e., the appearance of a yellow stain, after -l6 hours at 120F. Inclusion of the above-noted metal complexing agents gave substantial if not complete elimination of this yellow stain.
  • the added metal complexing agent may even be a member of a ternary complex of one metal with two different complexing groups.
  • Aluminum ions may be introduced by adding a soluble salt. of aluminum to the processing composition. If the pigment, e.g., titanium dioxide, includes an aluminum oxide, contact with a strongly'alkaline processing composition may dissolve sufficient aluminum ions for this purpose.
  • 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 imagematter contained in the above description shall be interpreted as illustrative and not in a limiting sense.
  • 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 containing a metal pigment between said imagereceiving 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 image-receiving layer may be viewed; means providing 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 halide solvent and a
  • a photographic product as defined in claim 1 wherein-said metal pigment is titanium dioxide.
  • 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 second silver halide complexing agent 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, and including a rupturable container releasably holding said processing composition, said rupturable container being so positioned as to distribute said processing composition between said predetermined layers, said processing composition being adapted to provide said permanent laminate following distribution and drying.
  • a photographic product comprising a first support; a redsensitive silver halide emulsion; a green sensitive 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 imagereceiving 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:
  • processing composition also being adapted to provide a permanent laminate including said developed silver halide emulsions and said imagereceiving layer; and means providing a light reflecting layer containing a metal pigment between said image-receiving layer and said silver halide emulsions effective to provide a white background for viewing said transfer image and for masking said developed silver halide emulsions;
  • said processing composition including a compound which will give a colored product with ions of said metal at an acidic pH and a metal complexing agent in a concentration effective to at least substantially prevent the formation of said colored product; said processing composition containing ions of a second metal which ions are effective to further reduce the formation of said colored product.
  • a photographic product as defined in claim 13 wherein said means for providing a light-reflecting layer comprises a preformed layer of a white pigment.
  • a photographic product as defined in claim 13 wherein said means for providing a light-reflecting layer comprises a titanium dioxide dispersed in said processing composition.
  • a photographic product as defined in claim 13 including means to reduce the pH of a layer of said pro cessing composition from a first pH to a second pH.
  • a photographic product as defined in claim 22 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 photographic product as defined in claim 13 wherein said metal complexing agent is N- (carboxymethyl)-N-2-hydroxyethyl-N,N"ethylene glycine.
  • said light-reflecting layer is provided by titanium dioxide present in the processing composition used to perform said process, and said processing composition further includes a compound containing a salicylic acid group, said N-(carboxymethyl)-N-2-hydroxyethyl-N,N- ethylene glycine being effective to provide a less colored metal complex with titanium ions than if said metal complex were formed with said salicylic acid group.
  • r-HaO 0H K -D)CHr-CHI L should be HO-CH -cH I N HO-CH cn N Q 0 v magenta: - ⁇ H2O Page 5 of 5 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,856,521 D t d December 24, 1974 I Ruth C. Bilofsky and Howard G. Rogers 7 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

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US00247022A 1972-04-24 1972-04-24 Diffusion transfer color film and process Expired - Lifetime US3856521A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US00247022A US3856521A (en) 1972-04-24 1972-04-24 Diffusion transfer color film and process
AU54449/73A AU464590B2 (en) 1972-04-24 1973-04-12 Diffusion transfer color film and process
GB1813873A GB1425835A (en) 1972-04-24 1973-04-16 Diffusion transfer colour film and process compositions for supplying magnesium to animals and a process fo
DE2319469A DE2319469C2 (de) 1972-04-24 1973-04-17 Photographisches Aufzeichnungsmaterial
FR7314294A FR2181915B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1972-04-24 1973-04-19
CA169,196A CA1012817A (en) 1972-04-24 1973-04-19 Diffusion transfer color film and process
JP7344985A JPS539738B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1972-04-24 1973-04-20
IT49645/73A IT980343B (it) 1972-04-24 1973-04-24 Procedimento per la formazione di immagini a colori mediante trasporto per diffusione e prodot to fotografico ottenuto
BE130335A BE798619A (fr) 1972-04-24 1973-04-24 Pellicule et procede perfectionnes utilises dans la photographie en couleurs par diffusion-transfert
NLAANVRAGE7305705,A NL179236C (nl) 1972-04-24 1973-04-24 Fotografisch produkt voor het vormen van een kleurdiffusieoverdrachtsbeeld in een permanent laminaat.

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Cited By (8)

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EP0009411A3 (en) * 1978-09-21 1980-07-09 Eastman Kodak Company Photographic recording material containing polymers which coordinate with metal ions, complexes produced thereby and novel polymers
EP0027461A4 (en) * 1979-04-24 1982-07-12 Polaroid Corp FILM FOR COLOR TRANSFER AND METHOD.
US4456674A (en) * 1982-11-01 1984-06-26 Polaroid Corporation Color transfer photographic processes and products
US4496651A (en) * 1983-07-25 1985-01-29 Polaroid Corporation Color transfer photographic processes and products
US4551411A (en) * 1984-12-28 1985-11-05 Eastman Kodak Company Sequestrants used in diffusion transfer elements with metallizable dyes
US4559291A (en) * 1984-12-28 1985-12-17 Eastman Kodak Company Ligands for metallizable dyes
US4649095A (en) * 1983-10-06 1987-03-10 Fuji Photo Film Co., Ltd. Color diffusion transfer photographic film unit containing aluminum compound
US6284426B1 (en) * 1993-02-09 2001-09-04 Agfa-Gevaert Process solution and method for making a lithographic aluminum offset plate by the silver salt diffusion transfer process

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FR2604900B1 (fr) * 1986-10-08 1989-01-13 Blomet Marie Claude Solution physiologique pour le lavage des parties du corps humain ayant ete mises en contact avec un acide fluorhydrique et concentre pour sa preparation
US5422233A (en) * 1994-05-17 1995-06-06 Polaroid Corporation Photographic processing compositions including hydrophobically modified thickening agent

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US3477849A (en) * 1964-03-23 1969-11-11 Eastman Kodak Co Multi-color dye developer systems
US3486901A (en) * 1966-10-21 1969-12-30 Eastman Kodak Co Direct-print silver halide emulsions containing a halogen acceptor and an amine compound as a stabilizer
US3647437A (en) * 1970-12-18 1972-03-07 Polaroid Corp Photographic products, processes and compositions
US3734727A (en) * 1971-10-28 1973-05-22 Polaroid Corp Photographic products and processes
US3785814A (en) * 1971-12-23 1974-01-15 Polaroid Corp Diffusion transfer color processes and products and compositions useful therein

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US3477849A (en) * 1964-03-23 1969-11-11 Eastman Kodak Co Multi-color dye developer systems
US3486901A (en) * 1966-10-21 1969-12-30 Eastman Kodak Co Direct-print silver halide emulsions containing a halogen acceptor and an amine compound as a stabilizer
US3647437A (en) * 1970-12-18 1972-03-07 Polaroid Corp Photographic products, processes and compositions
US3734727A (en) * 1971-10-28 1973-05-22 Polaroid Corp Photographic products and processes
US3785814A (en) * 1971-12-23 1974-01-15 Polaroid Corp Diffusion transfer color processes and products and compositions useful therein

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0009411A3 (en) * 1978-09-21 1980-07-09 Eastman Kodak Company Photographic recording material containing polymers which coordinate with metal ions, complexes produced thereby and novel polymers
EP0027461A4 (en) * 1979-04-24 1982-07-12 Polaroid Corp FILM FOR COLOR TRANSFER AND METHOD.
US4456674A (en) * 1982-11-01 1984-06-26 Polaroid Corporation Color transfer photographic processes and products
US4496651A (en) * 1983-07-25 1985-01-29 Polaroid Corporation Color transfer photographic processes and products
US4649095A (en) * 1983-10-06 1987-03-10 Fuji Photo Film Co., Ltd. Color diffusion transfer photographic film unit containing aluminum compound
US4551411A (en) * 1984-12-28 1985-11-05 Eastman Kodak Company Sequestrants used in diffusion transfer elements with metallizable dyes
US4559291A (en) * 1984-12-28 1985-12-17 Eastman Kodak Company Ligands for metallizable dyes
US6284426B1 (en) * 1993-02-09 2001-09-04 Agfa-Gevaert Process solution and method for making a lithographic aluminum offset plate by the silver salt diffusion transfer process

Also Published As

Publication number Publication date
FR2181915B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1982-06-04
CA1012817A (en) 1977-06-28
DE2319469A1 (de) 1973-11-15
NL179236C (nl) 1986-08-01
IT980343B (it) 1974-09-30
JPS539738B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1978-04-07
GB1425835A (en) 1976-02-18
JPS4948326A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1974-05-10
AU464590B2 (en) 1975-08-28
BE798619A (fr) 1973-10-24
NL7305705A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1973-10-26
AU5444973A (en) 1974-10-17
FR2181915A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1973-12-07
DE2319469C2 (de) 1987-02-05

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