US3748129A - Dye image providing materials within diffusion transfer barrier layers - Google Patents

Dye image providing materials within diffusion transfer barrier layers Download PDF

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US3748129A
US3748129A US00205053A US3748129DA US3748129A US 3748129 A US3748129 A US 3748129A US 00205053 A US00205053 A US 00205053A US 3748129D A US3748129D A US 3748129DA US 3748129 A US3748129 A US 3748129A
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layer
dye
silver halide
image
halide emulsion
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J Avtges
L Taylor
J Reid
H Schlein
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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

Definitions

  • the present invention relates to photography and, more particularly, to photographic products particularly adapted for employment in photographic diffusion transfer color processes.
  • a photosensitive element containing a dye developer that is, a dye which is a silver halide developing agent, and a silver halide emulsion
  • a photosensitive element containing a dye developer may be exposed to actinic radiation and Wetted by a liquid processing composition, for example, by immersion, coating, spraying, flowing, etc., in the dark, and the exposed photosensitive element is superposed prior to, during or after wetting, on a sheetlike support element which may be utilized as an imagereceiving element.
  • the liquid processing composition is applied to the photosensitive element in a substantially uniform layer as the photosensitive element is brought into superposed relationship with the image-receiving layer.
  • the liquid processing composition positioned intermediate the photosensitive element and the image-receiving layer, permeates the emulsion to initiate developement of the latent image contained therein.
  • the dye developer is immobilized or precipitated in exposed areas as a consequence of the development of the latent image. This immobilization is apparently, at least in part, due to a change in the solubility characteristics of the dye developer upon oxidation and especially as regards its solubility in alkaline solutions.
  • the dye developer is unreacted and dilfusible and thus provides an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition, as a function of the point-to-point degree of exposure of the silver halide emulsion.
  • At least part 3,748,129 Patented July 24, 1973 of this imagewise distribution of unoxidized dye developer is transferred, by diffusion, to a superposed image-receiving layer or element, said transfer substantially excluding oxidized dye developer.
  • the image-receiving element receives a depth-wise diffusion, from the developed emulsion, of unoxidized dye developer without appreciably disturbing the imagewise distribution thereof to provide the reversed or positive color image of the developed image.
  • the image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer.
  • the desired positive image is revealed by stripping the image-receiving layer from the photosensitive element at the end of a suitable imbibition period.
  • the dye developers are compounds which contain, in the same molecule, both the chromophoric system of a dye and also a silver halide developing function.
  • a silver halide developing function is meant a grouping adapted to develop exposed silver halide.
  • a prefered silver halide development function is a hydroquinonyl group.
  • Other suitable developing functions include ortho-dihydroxyphenyl and orthoand paraamino 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.
  • Multicolor images may be obtained using color imageforming components such as, for example, the previously mentioned dye developers, in diffusion transfer processes by several techniques.
  • One such technique contemplates obtaining multicolor transfer images utilizing dye developers by employment of an integral multilayer photosensitive element, such as is disclosed in the aforementioned U.S. Pat. No. 2,983,606, and particularly with reference to FIG. 9 of the patents drawing, wherein at least two selectively sensitized photosensitive strata, superposed on a single support, are processed simultaneously and without separation, with a single, common imagereceiving layer.
  • a suitable arrangement of this type comprises a support carrying a red-sensitive silver halide stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, for example, a cyan dye developer, a magenta dye developer and a yellow dye developer.
  • the dye developer may be utilized in the silver halide emulsion layer, for example, in the form of particles, or it may be employed as a layer behind the appropriate silver halide emulsion stratum.
  • Each set of silver halide emulsion and associated dye developer strata are disclosed to be optionally separated from.
  • interlayers for example, by a layer of gelatin or polyvinyl alcohol.
  • a yellow dye developer of the appropriate spectral characteristics and present in a state capable of functioning as a yellow filter may be employed. In such instances, a separate yellow filter may be omitted.
  • the dye developers are dye image-forming materials which are preferably selected for their ability to provide colors that are useful in carrying out substractive color photography, that is, the previously mentioned cyan, magenta and yellow. In many processes they may be incorporated in the respective silver halide emulsion while, in the present invention, at least one such dye developer must be dispersed in a separate layer behind the respective associated silver halide emulsion.
  • Solid dispersions of dye developers adapted for utilization in a diffusion transfer system are disclosed and claimed in U.S. Pat. No. 3,438,775.
  • the particulate dye developer is dispersed in an alkali permeable matrix polymer in a ratio of between about 0.1 to 25 mgs. of dye per mg. of polymer, with preferably 75 percent of the dye particles being less than about 1 micron in diameter.
  • the preparation of the dye developer dispersion may also be obtained by dissolving the dye in an appropriate solvent, or mixture or solvents, and the resultant solution distributed in the polymeric binder, with optional subsequent removal of the solvent, or solvents, employed, as, for example, by vaporization where the selected solvent, or solvents, possesses a sufficiently low boiling point or washing where the selected solvent, or solvents, possesses a sufficiently high diiferential solubility in the wash medium, for example, water, when measured against the solubility of the remaining composition components, and/or obtained by dissolving both the polymeric binder and dye in a common solvent.
  • US. Pat. No. 3,362,819 discloses image-receiving elements, particularly adapted for employment in the preceding diffusion transfer processes, which comprise a support layer possessing on one surface thereof, in se quence, a polymeric acid layer, preferably an inert timing or spacer layer, and an image-receiving layer adapted to provide a visible image upon transfer to said layer of diffusible dye image-forming substance.
  • the polymeric acid layer comprises polymers which contain acid groups, such as carboxylic acid and sulfonic acid groups, which are capable of forming salts with alkali metals, such as sodium, potassium, etc., or with organic bases, particularly quaternary ammonium bases, such as tetramethyl ammonium hydroxide, or potentially acid-yielding groups, such as anhydrides or lactones, or other groups which are capable of reacting with bases to capture and retain them.
  • the acid-reacting group is, of course, nondilfusible from the acid polymer layer.
  • the acid polymer contains free carboxyl groups and the transfer processing composition employed contains a large concentration of sodium and/ or potassium ions.
  • the acid polymers stated to be most useful are characterized by containing free carboxyl groups, being insoluble in water in the free acid form, and by forming water-soluble sodium and/or potassium salts.
  • dibasic acid half-ester derivatives of cellulose modified with sulfoanhydrides e.g., with ortho-sulfobenzoic anhydride
  • polystyrene sulfonic acid carboxymethyl cellulose
  • polyvinyl hydrogen phthalate polyvinyl acetate hydrogen phthalate
  • polyacrylic acid acetals of polyvinyl alcohol with carboxy or sulfo-substituted aldehydes, e.g., 0-, m, or p-benzaldehyde sulfonic acid or carboxylic acid
  • partial esters of ethylene/maleic anhydride copolymers partial esters of methyl-vinyl ether/maleic anhydride copolymers
  • the acid polymer layer is disclosed to contain at least sufficient acid groups to effect a reduction in the pH of the image layer from a pH of about 13 to 14 to a pH of at least 11 or lower at the end of the imbibition period, and preferably to a pH of about 5 to 8 within a short time after imbibition.
  • the pH of the processing composition preferably is of the order of at least 13 to 14.
  • the action of the polymeric acid be so controlled as not to interfere with either development of the negative or image transfer of unoxidized dye developers.
  • the pH of the image layer is kept at a level of pH 12 to 14 until the positive dye image has been formed, after which the pH is reduced very rapidly to at least about pH 11, and preferably about pH 9 to 10, which renders unoxidized dye developer substantially non-diifusible.
  • Unoxidized dye developers containing hydroquinonyl developing radicals diffuse from the negative to the positive as the sodium or other alkali salt.
  • the diifusion rate of such dye image-forming components thus is at least partly a function of the alkali concentration, and it is necessary that the pH of the image layer remain on the order of 12 to 14 until transfer of the necessary quantity of dye has been accomplished.
  • the subsequent pH reduction in addition to its desirable effect upon image light stability, serves a highly valuable photographic function by substantially terminating further dye transfer. This processing technique thus effectively minimizes changes in color balance which might result from a longer than necessary imbibition time for multicolor transfer processes using multilayer negatives.
  • the acid groups are disclosed to be so distributed in the acid polymer layer that the rate of their availability to the alkali is controllable, e.g., as a function of the rate of swelling of the polymer layer which rate in turn has a direct relationship to the diffusion rate of the alkali ions.
  • the desired distribution of the acid groups in the acid polymer layer may be effected by mixing the acid polymer with a polymer free of acid groups, or lower in concentration of acid groups and compatible therewith, or by using only the acid polymer but selecting one having a relatively lower proportion of acid groups.
  • the layer containing the polymeric acid may contain a water insoluble polymer, preferably a cellulose ester, which acts to control or modulate the rate at which the alkali salt of the polymer acid is formed.
  • a water insoluble polymer preferably a cellulose ester
  • cellulose esters contemplated for use mention is made of cellulose acetate, cellulose acetate butyrate, etc.
  • the particular polymers and combinations of polymers employed in any given embodiment are, of course, selected so as to have adequate wet and dry strength and when necessary or desirable, suitable subcoats may be employed to help the various polymeric layers adhere to each other during storage and use.
  • the inert spacer layer of the aforementioned patent acts to time control the pH reduction by the polymeric acid layer. This timing is disclosed to be a function of the rate at which the alkali diffuses through the inert spacer layer. It was stated to have been found that the pH does not drop until the alkali has passed through the spacer layer, i.e., the pH is not reduced to any significant extent by the mere diffusion into the interlayer, but the pH drops quite rapidly once the alkali diffuses through the spacer layer.
  • Other such spacer layers which are suitable for use in the image-receiving element are disclosed and claimed in U.S. Patent No. 3,421,893.
  • solution dyeable polymers such as nylons as, for example, N-methoxymethyl polyhexamethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plasticizers; cellulose acetate with fillers as, for example, one-half cellulose acetate and one-half oleic acid; gelatin; and other materials of a similar nature.
  • Preferred materials comprise polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine, as disclosed in U.S. Patent No. 3,148,061.
  • the liquid processing composition referred to for effecting multicolor diffusion transfer processes comprises at least an aqueous solution of an alkaline material, for example, diethylamine, sodium hydroxide or sodium carbonate and the like, and preferably possessing a pH in excess of 12, and most preferably, 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 also disclosed to be capable of utilization.
  • the filmforming 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.
  • the silver halide crystals may be prepared by reacting a. water-soluble silver salt, such as silver nitrate, with at least one water-soluble halide, such as ammonium, potassum or sodium bromide, preferably together with a corresponding iodide, in an aqueous solution of a peptizing agent such as a colloidal gelatin solution; digesting the dispersion at an elevated temperature, to provide increased crystal growth; washing the resultant dispersion to remove undesirable reaction products and residual water-soluble salts by chilling the dispersion, noodling the set dispersion, and washing the noodles with cold water, or, alternatively, employing any of the various floc systems, or procedures, adapted to effect removal of undesired components, for example, the procedures described in U.S.
  • Optical sensitization of the emulsions silver halide crystals may be accomplished by contact of the emulsion composition with an effective concentration of the selected optical sensitizing dyes dissolved in an appropriate dispersing solvent such as methanol, ethanol, acetone, water, and the like; all according to the traditional procedures of the art, as described in Hammer, F. M., The Cyanine Dyes and Related Compounds.
  • an appropriate dispersing solvent such as methanol, ethanol, acetone, water, and the like
  • Additional optional additives such as coating aids, hardeners, viscosity-increasing agents, stabilizers, preservatives, and the like, for example, those set forth hereinafter, also may be incorporated in the emulsion formulation, according to the conventional procedures known in the photographic emulsion manufacturing art.
  • the photoresponsive material of the photographic emulsion will, as previously described, preferably comprise a crystal of silver, for example, one or more of the silver halides such as silver chloride, silver iodide, silver bromide, or mixed silver halides such as silver chlorobromide or silver iodobromide, of varying halide ratios and varying silver concentrations.
  • the silver halides such as silver chloride, silver iodide, silver bromide, or mixed silver halides such as silver chlorobromide or silver iodobromide, of varying halide ratios and varying silver concentrations.
  • the emulsions may include the various adjuncts, or addenda, according to the techniques disclosed in the art.
  • the aforementioned gelatin may be, in whole or in part, replaced with some other colloidal material such as albumin; casein; or zein; or resins such as a cellulose derivative, as described in U.S. Pats. No. 2,322,085 and 2,327,808; polyacrylamides, as described in U.S. Pat. No. 2,541,474; vinyl polymers such as described in a'multiplicity of readily available US. patents.
  • an image-receiving element need not be separated from superposed contact with a photosensitive element comprising a silver halide emulsion subsequent to substantial transfer image formation if the image-receiving element is transparent and a processing composition containing a substance rendering the processing composition layer opaque is spread between the image-receiving layer and the photosensitive element.
  • a processing composition containing a substance rendering the processing composition layer opaque is spread between the image-receiving layer and the photosensitive element.
  • an integral diffusion transfer photographic film unit particularly adapted for the production of a dye transfer image of improved stability will be constructed, for example, in accordance with aforementioned U.S. Pat. No. 3,415,644 to include a photosensitive element comprising a laminate having in sequence as essential layers, a dimensionally stable opaque support layer, a photosensitive silver halide emulsion layer having associated therewith dye image-providing material which is soluble and diffusible in alkali at a first pH, an alkaline solution permeable polymeric layer dyeable by the dye image-providing material, a polymeric acid layer containing sufificient acidifying material to effect reduction subsequent to substantial transfer dye image formation of a processing solution having the first pH to a second pH at which said dye image-providing material is insoluble and nondiffusible, and a dimensionally stable transparent support layer, said dimensionally stable support layers comprising extremities of the described photographic film unit composite structure.
  • a rupturable container retaining an aqueous alkaline processing composition having the first pH and containing an opacifying agent in a quantity sufficient to mask the dye image-providing material is fixedly positioned and extends transverse the leading edge of the laminate whereby to effect unidirectional discharge of the containers contents between the alkaline solution permeable and dyeable polymeric layer and the photosensitive silver halide emulsion layer next adjacent thereto upon application of compressive force to the container.
  • the primary objects of the present invention are to provide photographic products, particularly adapted for employment in diffusion transfer photographic color processes; to provide photographic products which include a photosensitive element which comprises a plurality of essential layers including, superposed on a common support, at least two selectively sensitized photosensitive strata each having associated therewith, as color transfer image-forming components, a dye of predetermined color, which is preferably a silver halide developing agent, at least one of said dyes comprising a dispersion in a layer immediately adjacent its associated silver halide emulsion layer, the dispersion matrix comprising a polymer which is peremable to processing composition and solubilized dye developer at a rate which insures substantial development of each dye associated silver halide emulsion layer prior to contact of such layer with substantial amounts of solubilized unassociated dye developer; to provide photographic diffusion transfer products comprising a photosensitive element, of the last identified type, in combination with a photographic diffusion transfer image-receiving element comprising a plurality of
  • the invention accordingly comprises the product possessing the features, properties and the 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 cross-sectional view illustrating the association of elements during one stage of the performance of a diffusion transfer process, for the production of a multicolor positive transfer print, the thickness of the various materials being exaggerated;
  • FIGS. 2 and 3 illustrate the migration of processing composition and solubilized dye image-forming material in the environment of the present invention.
  • the multilayer exposed photosensitive element 25 is in processing relationship with an image-receiving element 26 which, as aforenoted, may be permanently integral therewith, and a layer of processing composition distributed intermediate elements 25 and 26.
  • Image-receiving element 26 comprises: a support 24 which may comprise a transparent material; an acid reacting neutralizing layer 23; a spacer layer 22; and an image-receiving layer 21.
  • liquid processing composition 20 is effective to initiate development of latent images in the denoted silver halide emulsion strata and solubilize the dye developers associated with such strata to ultimately cause the respective dyes associated with the denoted silver halide emulsions to migrate from areas where the dye associated silver halide emulsion has not been subjected to exposure, in the direction of the image-receiving element 26 to thereby proprovide a dye image thereto substantially in relation to the point-to-point degree of actinic radiation stimulus incident on each respective dye associated silver halide emulsion.
  • the image-receptive element may be separated from the photosensitive element or, in certain embodiments, may be permanently integral therewith.
  • FIG. 2 of 'the drawings a microscopic slice of thickness through either layers 13 or 15 of element 25 shown in FIG. 1 (from layer interface to interface) is depicted with dye material dispersed in a synthetic polymer matrix which is permeable to hydroxyl ion and solubilized dye developer at a rate which insures substantial development of an associated silver halide emulsion layer prior to contact of such layer with substantial amounts of solubilized unassociated dye developer.
  • hydroxyl ion proceeds from the aqueous alkaline processing composition denoted as in FIG. 1 through photosensitive element it meets a substantial impediment when it reaches layer 15.
  • a booster developer such as methyl phenyl hydroquinone, contained in overcoat layer 17, is carried by the processing composition to initiate development of latent images in blue-sensitive emulsion layer 16. Since the hydroxyl ion is only slowly permeable through the matrix material in which dye developer is dispersed, it provides a substantial release of dye developer from layer 15 to cause development of silver halide emulsion layer 16 before it proceeds downstream. As processing composition permeates the matrix material, for example, of layer 15, it reaches areas of dye developer which it quickly dissolves, as will be discussed further hereinbelow. The dye developer then migrates toward the image-receiving layer denoted in FIG. 1 as 21.
  • a booster developer such as methyl phenyl hydroquinone
  • Processing composition proceeds quickly through the area previously occupied by the dye developer until it reaches additional matrix material at which time it is again slowed.
  • dye developer As dye developer is solubilized and migrates from its matrix material, it provides an area with substantially no impediment to diffusion of processing composition. Accordingly, channeling through the matrix material favoring areas in which dye material has occupied will, in a predetermined time lag, cause processing composition to completely penetrate the layer comprising dispersed dye material as it proceeds downstream through the photosensitive element.
  • the double cross-hatching generally depicts processing composition penetration through the system wherein it is generally impeded from moving toward the support layer 10, except in areas in the dye dispersion layer wherein channels through areas containing dispersed dye material are formed.
  • a positive image is generally formed within about sixty seconds, that is, it takes approximately sixty seconds for sufficient image-forming dye material to be fixed in the image-receiving layer, or image-receiving element, to provide a finished multicolor photograph.
  • permeability of a polymeric material to a given liquid material will be a function of the thickness of the polymer utilized, it may be seen that in certain thicknesses polymeric layers will be impermeable to given liquid materials in a predetermined time while thicknesses of a smaller magnitude may be permeated by such liquid material within such given time.
  • Interimage problems in a diffusion transfer color system comprising a multilayer photosensitive negative such as that depicted in the drawing may result from, among other things, the combination of a given silver halideassociated dye with a silver halide emulsion layer other than the silver halide emulsion layer by which its diffusion is intended to be controlled.
  • the combination of a dye with an exposed silver halide emulsion other than its intended controlling silver halide emulsion reduces the number of dye associative sites available in such emulsion to its associated dye material with a concomitant undercontrol of such dye material. It will be accordingly appreciated that color purity is severely effected due to an overcontrol of the migration of certain dye systems and an undercontrol of others.
  • red-sensitive emulsion For example, assume an element such as that depicted in the drawing is exposed to electromagnetic radiation actinic only to the red-sensitive emulsion. In the ideal situation, upon imbibition of processing composition and development of the red-sensitive silver halide emulsion, all of the cyan dye present behind the redsensitive emulsion should be controlled to the extent that it is prevented from migrating toward the image-receiving element to thereby provide a red image in said element by the total migration of the magenta and yellow dyes.
  • the resultant image will be desaturated by a lack of magenta, which is tied up with the red-sensitive emulsion, and contaminated by the presence of a small amount of cyan dye which has been allowed to migrate since the magenta dye developer has been combined with areas of the cyan dye-associated silver halide emulsion.
  • interimage effects due to back migration are substantially obviated by the interlayers of the present invention with the concomitant increase in ultimate color purity in the transferred image.
  • the primary advantage provided thereby over other systems is that substantial reductions in interimage effects are achieved with concomitant improvements in color isolation and purity.
  • a diffusion transfer photosensitive element by dispersing such dye image-forming material in a layer adjacent its associated silver halide emulsion in a matrix of a thickness which, by itself, would be impermeable to processing composition during the period generally required to complete development and diffusion procedures, such layer may be permeated through areas containing dye image-forming material within such period due to the fact that dye image-forming material is dissolved therefrom by processing composition and is caused to migrate from the matrix material toward the image-receiving element thereby selectively providing processing composition migratory paths through the matrix.
  • aqueous alkaline processing composition difiuses from position 20 toward support 10, it first passes through layer 17 into blue-sensitive emulsion layer 16 where, for example, latent image development may be initiated by a booster developer. As the aqueous alkaline processing composition wavefront progresses through the photosensitive element, it next confronts layer 15 which comprises a polymeric material of a thickness which would be impermeable to the aqueous alkaline processing composition during the time normally employed to complete the diffusion transfer image formation in the image-receiving layer.
  • solubilized dye image-forming material begins migrating, for example, from layer 13 toward image-receiving layer 21, emulsion layer 16 will have been developed to a substantial degree by contact with solubilized yellow dye developer. Accordingly, with regard, for example, to solubilized dye image-forming material diffusing from layer 15 toward image-receiving layer 21, layer 16, the blue-sensitive silver halide emulsion layer, will be developed as a function of its point-to-point degree of exposure by solubilized yellow dye developer which will only be permitted to pass therethrough in unexposed areas. All exposed areas of emulsion layer 16 will be tied up with yellow dye developer and will not be available to control cyan or magenta.
  • aqueous alkaline processing composition to solubilize yellow dye developer, for example, from layer 15, in order to provide sufficient channels, as depicted, for example, in FIG. 3, to continue its progress through the photosensitive element.
  • the yellow dye image-forming material will migrate, for reasons which will be discussed hereinbelow, toward the image-receiving layer 21 and will not back diffuse into the green-sensitive silver halide emulsion layer, which obviates the possibility of its combining therewith to provide undercontrol of magenta dye imageforming material with concomitant overcontrol of yellow dye image-forming material.
  • the instant invention provides a degree of color purity not before achieved in the diffusion transfer photographic art, while concomitantly reducing the complexity of the system used to provide such purity.
  • the particular dye image-forming material dispersion utilized in the context of the present invention is preferably a solid dispersion, that is, a dispersion as hereinbefore described comprising solid particles of dye imageforming material dispersed in a matrix which provides the permeability parametric considerations defined hereinabove.
  • a solid dis persion of dye image-forming material may be used as, for example, a dispersion comprising microdroplets, that is, microscopic droplets of a solution of dye image-forming material, which droplets are immiscible with the trix.
  • a solid or liquid dye dispersion it should be employed for optimum results at a volume of approximately thirty to forty percent of the volume of the matrix material employed.
  • the thirty to forty percent volume is based upon the fact that if the matrix comprised hardpacked spheres as, for example, a latex before coalescence, the spheres would fill about sixty-seven percent of the volume, theoretically. Accordingly, it will be appreciated that the ideal theoretical volume for the dye image-forming material dispersed in the matrix will be about onethird, or about thirty-three percent, of the volume of the matrix.
  • the dispersion should comprise perhaps slightly more than one third of the volume of the matrix for optimum effects. As will be appreciated, too much dye loading in the matrix will cause processing composition to permeate the layer too quickly while too little dye in the matrix will deleteriously impede the transfer of processing composition through the system.
  • the dye image-forming material dispersion utilized in the present invention is not a solid dispersion, which is the preferred embodiment, then, as hereinbefore noted, the liquid microdroplets of dissolved dye image-forming material should comprise approximately one-third the volume of the matrix.
  • Specific compositions which are recomended for dissolving dye imageforming material for ultimate dispersion into the matrix are recited in the US. patents listed hereinabove and are well known in the art.
  • the matrix materials into which the dye image-forming materials of the present invention are dispersed comprise coalesced lattices.
  • the matrix will be a continuous phase containing a dye material as a discontinuous phase.
  • lattices of: polyvinylidene chloride; lightly carboxylated styrene-butadiene copolymers; polyvinyl chloride; vinylchloride-vinylacetate copolymers; acrylic copolymers and copolymers as, for example, a terpolymer of butylacrylate, methylmethacrylate and small amounts of acrylic or methacrylic acid; and enumerable other lattices which will readily come to mind of one of ordinary skill in polymer chemistry.
  • Preferred latex materials for utilization in the present invention comprise a 60-38-2 copolymer of methylmethacrylate, butyl acrylate and acrylic acid; a 60-30-4-6 copolymer of butyl acrylate, diacetone ,acrylamide, styrene and methacrylic acid; a 60-30-443- 1.5-0.5 copolymer of butyl acrylate, diacetone acrylamide, styrene, methacrylic acid, 2-sulfoethylmethacrylate, and divinylbenzene; and a 99-1 copolymer of ethyl acrylate and methacrylic acid which contains 1.5 parts of 2-sulfoethylmethacrylate; all proportion designations being on a weight basis unless otherwise denoted.
  • the thickness of the dye dispersion-comprising layers will be on the order of about one and one-half to five microns.
  • the dye imageforming material component particles or microdroplets should be on the order of between about 0.3 to 1.6 microns, and preferably on the order of about 0.5 micron, while the latex material should comprise particles from about 0.1 to about 1.0 microns.
  • the present invention produces a diffusion transfer photographic system in which various photosensitive emulsions associated with given dye imageforming material components are developed in relatively insulated steps, that is, the blue-sensitive silver halide emulsion would see the processing composition wavefront, and be substantially fully developed by its associated dye image-forming material, amounts of which diffuse toward the image-receiving element before the next exposed photosensitive emulsion sees the processing composition wavefront.
  • the paramount consideration is balancing the processing composition and solubilized dye image-forming material permeation characteristics of the various dye dispersion matrices to the dynamics desired of the entire system; that is, providing permeability characteristics which will satisfy performance considerations in a predetermined time span.
  • Absolute numbers may only be used to describe one given system. Broadly speaking, one of ordinary skill in the art possessing the present invention would be able to determine the specific parameters in terms of layer thicknesses, particle sizes and volumemetric ratios in order to provide appropriate development and diffusion rates to facilitate formation of a finished multicolor photographic image in a predetermined time span.
  • gelatino silver halide emulsion layers will be about 0.6 to 6 microns thick and the dye dispersion layers will be from about 1.5 to microns thick.
  • the image-receiving layer will be about 0.25 to 0.4 mil. thick
  • the polymeric acid layer will be about 0.3 to 1.5 mils. thick
  • the spacer layer will be about 0.1 to 0.7 mil. thick. It will be specifically recognized that the relative dimensions recited may be appropriately modified in accordance with the desires of the operator with respect to the specific product to be ultimately prepared.
  • the positioning of the respective silver halide emulsion/dye developer units of the configuration detailed in FIG. 1 may be varied. However, it is generally preferred to constitute the configuration of the photosensitive units of the present invention according to that depicted herein, that is, the cyan dye image-forming material/red-sensitive emulsion unit next contiguous the support surface and the yellow dye image-forming material/blue-sensitive emulsion unit most distal from the support surface.
  • a photosensitive element (hereinafter Control) may be prepared by coating in succession, on a polyethylene terephthalate base, the following layers:
  • the first series of test negatives was fabricated according to the formula denoted above with the following changes.
  • the gelatin denoted in layer 1 was moved into layer 2 providing thereby about 140 mgs. of silver and 241 mgs. of gelatin/fe 50 mgs./ft. of a composition comprising parts of a 99/1 copolymer of ethylacrylate/methacrylic acid, 1.5 parts 2-sulfothylmethacry1ate and 0.2 parts of a surfactant (Dowfax ZAL) were utilized as a matrix for the dye material in layer 1 to provide a suitable binder therefor.
  • Layer 3 was eliminated and layer 4 comprised 65 mgs./ft. of the denoted dye to 65 mgs./ ft.
  • ethylacrylate/methacrylic acid composition denoted with reference to layer 1 in lieu of the gelatin.
  • the gelatin was removed from layer 4 and was incorporated in layer 5 to provide a coverage of 80 mgs./ft. silver and 101 mgs./ft. gelatin.
  • Layer 6 was eliminated and layer 7 had the gelatin removed and incorporated in layer 8 with varying ratios of latex material substituted for the gelatin in layer 7, as well be discussed hereinbelow.
  • Layer 8 then comprised 65 mgs. of silver/ft. and 75 mgs. of gelatin/ftP.
  • Layer 9 was unchanged.
  • Three test negatives formulated as disclosed immediately above were prepared with layer 7 comprising, respectively, 35, 70, and 140 mgs./ft. of the latex material described with respect to layer 1 along with the recited 70 mgs./ft. of yellow dye developer.
  • a multiplicity of diffusion transfer image-receiving elements may be prepared by coating a cellulose nitrate subcoated baryta paper with the partial butyl ester of polyethylene/maleic anhydride copolymer prepared by refluxing for 14 hours 300 grams of high viscosity poly- (ethylene/maleic anhydride), 140 grams of n-butyl alcohol and 1 cc. of 85% phosphoric acid to provide a polymeric acid layer approximately 0.75 mil. thick.
  • the external surface of the acid layer may be coated with a 4% solution of polyvinyl alcohol in water to provide a polymeric spacer layer approximately 0.3 mil. thick.
  • the external surface of the spacer layer may then be coated by a 2:1 mixture by weight of polyvinyl alcohol and poly-4-vinyl pyridine at a coverage of approximately 600 mgs./ft. to provide a polymeric image-receiving layer approximately 0.40 mil. thick.
  • the thus-prepared imagereceiving elements may then be baked at 180 F. for 30 minutes and then allowed to cool.
  • the three test negatives having the varying ratios of yellow dye developer to polymer were exposed through a sensitometer to light in columns of blue, red and green ranges of the visible spectrum, by interposing between the negatives and a xenon light source appropriate Wratten Filters, all such exposures being made through a step wedge (Eastman Kodak standard colloidal carbon in glass wedge with a slope of 1.18 density units per inch with a cutoff at 340 nms.) and adjusted to provide an exposure in the maximum exposure area of two meter candle seconds; the minimum exposure area, of course, representing zero exposure. Reflection readings of integral densities were then taken on a MacBeth densitometer, Model RD400, using Wratten Filters Nos. 72B, 93 and 94, respectively, each of which was used in conjunction with a Wratten Filter No. 301.
  • the exposed photosensitive elements may then -be processed by spreading an aqueous liquid processing composition comprising:
  • the image-receiving element may be separated from the remainder of the film assembly.
  • Table 1 below lists various resultant photographic properties attributed to the photosensitive elements of the present invention compared to the control described here- 1 6 inabove. All experiments and measurements were carried out at room temperature, i.e., 75 F.
  • the following table contains similar experimental data as read from the magenta column in a test negative where the ratio of magenta dye developer to matrix material is varied as compared to the control.
  • negatives like that denoted as Neg. 1 in Table 1, wherein the layer containing the magenta dye developer (layer '4) comprised, respectively, in Neg. 4, '65 mgs./ft. magenta dye developer and 65 mgs./ft. polymeric material as denoted with respect to Neg. 1, layer 4; in Neg. 5, 65 mgs./ft. of magenta dye developer and 97.5 mgs./ ft. of polymer composition as denoted above; and in Neg. 6, 65 mgs./ft. of magenta dye developer and 130 mgs./ft. of polymer as denoted above; were used.
  • the yellow dye developer (layer 7) was coated at 70 mgs./ft. in a polymer matrix as described above at mgs/ftfi.
  • blue density does not change appreciably while the green density is significantly elevated.
  • much of the blue and red contamination denoted is reflected by blue and red tails of the magenta dye image-forming material which, when considered, enhances the experimental data.
  • liquid processing composition employed may contain an auxiliary or accelerating developing agent, such as p-methylaminophenol, 2,4- diaminophenol, p-benzylaminophenol, hydroquinone, toluhydroquinone, phenylhydroquinone, 4-methylpyenylhydroquinone, etc. It is also contemplated to employ a plurality of auxiliary or accelerating developing agents, such as a 3-pyrazolidone developing agent and a benzenoid developing agent, as disclosed in U.S. Pat. No. 3,039,869, issued June 19, 1962.
  • auxiliary developing agents examples include l-phenyl-S-pyrazolidone in combination with pbenzylaminophenol and 1 phenyl 3 pyrazolidone in combination with 2,5-bis-ethyleneimino hydroquinone.
  • auxiliary developing agents may be employed in the liquid processing composition or they may be initially incorporated, at least in part, in any one or more of the silver halide emulsion strata, the strata containing the dye developers, the interlayers, the overcoat layer, the image-receiving layer, or in any other auxiliary layer, or layers, of the film unit. It may be noted that at least a portion of the dye developer oxidized during development may be oxidized and immobilized as a result of a reaction, e.g., an energy-transfer reaction, with the oxidation product of an oxidized auxiliary developing agent, the latter developing agent being oxidized by the development of exposed silver halide. Such a reaction of oxidized developing agent with unoxidized dye developer would regenerate the auxiliary developing agent for further reaction with the exposed silver halide.
  • a reaction e.g., an energy-transfer reaction
  • development may be effected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed in U.S. Pat. No. 3,173,786.
  • dye image-forming materials such as those disclosed in U.S. Pats. Nos. 2,647,049, 2,661,293, 2,698,244, 2,698,798, and 2,802,735, wherein color diffusion transfer processes are described which employ color coupling techniques comprising, at least in part, reacting one or more color developing agents and one or more color formers or couplers to provide a dye transfer image to a superposed image-receiving layer, and those disclosed in U.S. Pat. No. 2,774,668, wherein color diffusion transfer processes are described which employ the imagewise differential transfer of complete dyes by the mechanisms therein described to provide a transfer dye image to a contiguous image-receiving layer.
  • a camera apparatus suitable for processing film of the type just mentioned is provided by the Polaroid Land Camera, sold by Polaroid Corporation, Cambridge Mass., USA, or similar camera structure such, for example, as the roll film type camera forming the subject matter of U.S. Pat. No. 2,435,717 or the film pack type camera forming the subject matter of U.S. Pat. No. 2,991,702.
  • Camera apparatus of this type permits successive exposure of individual frames of the photosensitive element from the emulsion side thereof as well as individual processing of an exposed frame by bringing said exposed frame into superposed relation with a predetermined portion of the image-receiving element while drawing these portions of the film assembly between a pair of pressure members which rupture a container associated therewith and effect the spreading of the processing liquid released by rupture of said container, between and in contact with the exposed photosensitive frame and the predetermined, registered area of the imagereceiving element.
  • the relative proportions of the agents of the diffusion transfer processing composition may be altered to suit the requirements of the operator.
  • modify the herein described developing compositions by the substitution of preservatives, alkalies, silver halide solvents, etc., other than those specifically mentioned, provided that the pH of the composition is preferably in excess of at least 10 initially.
  • components such as restrainers, accelerators, etc.
  • concentration of various components may be varied over a wide range and when desirable adaptable components may be disposed in the photosensitive element, prior to exposure, in a separate permeable layer of the photosensitive element and/or in the photosensitive emulsion.
  • the support layers referred to may comprise any of the various types of conventional rigid or flexible supports, for example, glass, paper, metal, and polymeric films of both synthetic types and those derived from naturally occurring products.
  • Suitable materials include paper; aluminum; polymethacrylic acid methyl and ethyl esters; vi nyl chloride polymers; polyvinyl acetal; polyamides such as nylon; polyesters such as polymeric films derived from ethylene glycol terephthalic acid; and cellulose derivatives such as cellulose acetate, triacetate, nitrate, propionate, butyrate, acetate-propion'ate, or acetate-butyrate.
  • a rupturable container provides a convenient means for spreading a liquid processing composition between layers of a film unit whereby to permit the processing to be carried out within a camera apparatus
  • the practices of this invention may be otherwise effected.
  • a photosensitive element after exposure in suitable apparatus and while preventing further exposure thereafter to actinic light, may be removed from such apparatus and permeated with the liquid processing composition, as by coating the composition on said photosensitive element or otherwise wetting said element with the composition, following which the permeated, exposed photosensitive element, still, without additional exposure to actinic light, is brought into contact with the imagereceiving element for image formation in the manner heretofore described.
  • the film unit structure may also comprise an integral positive/ negative construction carried on a single support.
  • the film unit may also contain one or more subcoats or layers, which, in turn, may contain one or more additives such as plasticizers, intermediate essential layers for the purpose, for example, of improving adhesion, etc.
  • a photosensitive element which comprises a support layer carrying, in order, from the support layer, at least first and second selectively sensitized silver halide emulsion layers, each emulsion layer having associated therewith a processing composition soluble dye imageforming material, at least the dye image-forming material associated with said second silver halide emulsion layer being dispersed in a matrix layer comprising a coalesced latex intermediate said second silver halide emulsion layer and said first silver halide emulsion layer, said matrix layer being permeable to processing composition applied to the surface of its associated silver halide emulsion layer on the side opposed to said support layer at a rate which insures substantial development of said second silver halide emulsion layer prior to contact of said second silver halide emulsion layer with substantial amounts of processing composition solubilized dye imageforming material initially associated with said first silver halide emulsion layer.
  • said dye imageforming materials are silver halide developing agents and said processing composition comprises an aqueous alkaline composition.
  • said latex comprises about a 99-1 copolymer of ethylacrylate and methacrylic acid, respectively, and additionally contains about 1.5 parts Z-sulfoethylmethacrylate per 100 parts of copolymer.
  • a photographic diffusion transfer unit which comprises, in combination, a photosensitive element having a dilfusion transfer image-receiving element affixed to at least one edge thereof, such photosensitive element comprising, as essential layers, a support layer carrying, in order, from the support layer, at least first and second selectively sensitized silver halide emulsion layers, each emulsion layer having associated therewith a processing composition soluble dye image-forming material, at least the dye image-forming material associated with said second silver halide emulsion layer being dispersed in a matrix layer comprising a coalesced latex intermediate said second silver halide emulsion layer and said first silver halide emulsion layer, said matrix layer being permeable to processing composition applied to the surface of its associated silver halide emulsion layer on the side opposed to said support layer at a rate which insures substantial development of said second silver halide emulsion layer prior to contact of said second silver halide emulsion layer with substantial amounts of processing composition solubil
  • said dye imageforming materials are silver halide developing agents and said processing composition comprises an aqueous alkaline composition.
  • latex comprises about a 991 copolymer of ethylacrylate and methacrylic acid, respectively, and additionally contains about 1.5 parts 2-sulfoethylmethacrylate per parts of copolymer.
  • the invention of claim 8 including a rupturable container retaining said aqueous alkaline processing composition afiixed one edge of said photosensitive and said image-receiving element and adapted upon rupture to distribute its contents intermediate said superposed photosensitive and image-receiving elements.
  • said imagereceiving element includes a polymeric acid layer adapted to reduce the alkalinity of said aqueous alkaline processing composition upon contact therewith positioned intermediate said dyeable polymeric layer and said support layer adjacent thereto.
  • aqueous alkaline processing composition possesses a pH of not less than about 12.
  • said diffusion transfer unit comprises a composite structure including said photosensitive element and said image-receiving element permanently affixed each to the other in superposed relationship, the support layers of each of said elements comprising the extremities of said composite structure.
  • said photosensitive element contains a plurality of essential layers including, in sequence:
  • a magenta dye image-forming material which is a silver halide developing agent dispersed in a matrix layer comprising a coalesced latex, said layer being permeable to processing composition applied to the surface of its associated silver halide emulsion layer at a rate which insures substantial development of its associated silver halide emulsion layer prior to contact of such layer with substantial amounts of solubilized unassociated dye image-forming material;
  • a yellow dye image-forming material which is a silver halide developing agent dispersed in a matrix layer comprising a coalesced latex, said layer being permeable to processing composition applied to the surface of its associated silver halide emulsion layer at a rate which insures substantial development of its associated silver halide emulsion layer prior to contact of such layer with substantial amounts of solubilized unassociated dye image-forming material;
  • At least one of said matrix materials comprises a coalesced latex comprising about a 99-1 copolymer of ethylacrylate and methacrylic acid, respectively, and additionally contains about 1.5 parts 2-sulfoethylmethacrylate per 100 parts of copolymer.
  • a process for forming diffusion transfer photographic images in color which comprises the steps of:
  • a photosensitive element comprising a support layer carrying, in order, from the support layer, at least first and second selectively sensitized silver halide emulsion layers, each emulsion layer having associated therewith a processing composition soluble dye image-forming material, at least the dye imageforming material associated with said second silver halide emulsion layer being dispersed in a matrix layer comprising a coalesced latex intermediate said second silver halide emulsion layer and said first silver halide emulsion layer, said matrix layer being permeable to processing composition applied to the surface of its associated silver halide emulsion layer on the side opposed to said support layer at a rate 21 which insures substantial development of said second silver halide emulsion layer prior to contact of said second silver halide emulsion layer with substantial amounts of processing composition solubilized dye image-forming material initially associated with said first silver halide emulsion layer; contacting the surface of said exposed photosensitive element opposed to its support layer With processing composition effecting thereby sequential development
  • said latex comprises about a 99-l copolymer of ethylacrylate and methacrylic acid, respectively, and additionally contains about 1.5 parts 2-sulfoethylmethacrylate per 100 parts copolymer.
  • a process for forming diffusion transfer photographic images in color which comprises the steps of:
  • exposing a photosensitive element which comprises, in
  • a magenta dye image-forming material which is a silver halide developing agent dispersed in a matrix layer comprising a coalesced latex, said layer being permeable to processing composition applied to the surface of its associated silver halide emulison layer at a rate which insures sub- 3,421,892 1/1969 Taylor 9629 D 3,477,849 11/1969 Becker 9629 D 3,687,660 8/1972 Gondolfe et al. 9629 D NORMAN G. TORCHIN, Primary Examiner R. L. SCHILLIN'G, Assistant Examiner U.S. c1. x1e 40 9629, 77

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856522A (en) * 1972-12-26 1974-12-24 Polaroid Corp Spacer layer for dye diffusion transfer film
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
US4203716A (en) * 1976-11-24 1980-05-20 Eastman Kodak Company Photographic elements having hydrophilic colloid layers containing hydrophobic addenda uniformly loaded in latex polymer particles
US4214047A (en) * 1979-05-04 1980-07-22 Eastman Kodak Company Photographic elements having hydrophilic colloid layers containing hydrophobic addenda uniformly loaded in latex polymer particles
US4247627A (en) * 1979-10-10 1981-01-27 Eastman Kodak Company Photographic elements having hydrophilic colloid layers containing hydrophobic ultraviolet absorbers uniformly loaded in latex polymer particles
US4304769A (en) * 1974-09-17 1981-12-08 Eastman Kodak Company Process for achieving uniform, efficient distribution of hydrophobic materials through hydrophilic colloid layers and loaded latex compositions
US4512969A (en) * 1974-09-17 1985-04-23 Eastman Kodak Company Compositions containing hydrophobic addenda uniformly loaded in latex polymer particles
US5006450A (en) * 1989-11-15 1991-04-09 Eastman Kodak Company Mordant polymer photographic element containing
US5077187A (en) * 1989-11-15 1991-12-31 Eastman Kodak Company Photographic elements silver halide containing a specific polymer and water soluble dye layer

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3477849A (en) * 1964-03-23 1969-11-11 Eastman Kodak Co Multi-color dye developer systems
US3384483A (en) * 1964-03-23 1968-05-21 Eastmean Kodak Company Multicolor dye developer image transfer systems

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856522A (en) * 1972-12-26 1974-12-24 Polaroid Corp Spacer layer for dye diffusion transfer film
US4304769A (en) * 1974-09-17 1981-12-08 Eastman Kodak Company Process for achieving uniform, efficient distribution of hydrophobic materials through hydrophilic colloid layers and loaded latex compositions
US4512969A (en) * 1974-09-17 1985-04-23 Eastman Kodak Company Compositions containing hydrophobic addenda uniformly loaded in latex polymer particles
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
US4203716A (en) * 1976-11-24 1980-05-20 Eastman Kodak Company Photographic elements having hydrophilic colloid layers containing hydrophobic addenda uniformly loaded in latex polymer particles
US4214047A (en) * 1979-05-04 1980-07-22 Eastman Kodak Company Photographic elements having hydrophilic colloid layers containing hydrophobic addenda uniformly loaded in latex polymer particles
US4247627A (en) * 1979-10-10 1981-01-27 Eastman Kodak Company Photographic elements having hydrophilic colloid layers containing hydrophobic ultraviolet absorbers uniformly loaded in latex polymer particles
US5006450A (en) * 1989-11-15 1991-04-09 Eastman Kodak Company Mordant polymer photographic element containing
US5077187A (en) * 1989-11-15 1991-12-31 Eastman Kodak Company Photographic elements silver halide containing a specific polymer and water soluble dye layer

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DE2259797C2 (de) 1982-10-07
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AU4972272A (en) 1974-06-06
NL171747B (nl) 1982-12-01
GB1414160A (en) 1975-11-19
JPS4865926A (en:Method) 1973-09-10
DE2259797A1 (de) 1973-06-07
NL171747C (nl) 1983-05-02
FR2162467B1 (en:Method) 1977-01-14
AU465470B2 (en) 1975-09-25
CA982864A (en) 1976-02-03
JPS5852213B2 (ja) 1983-11-21
FR2162467A1 (en:Method) 1973-07-20

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