US3196015A - Diffusion transfer process - Google Patents

Diffusion transfer process Download PDF

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US3196015A
US3196015A US170008A US17000862A US3196015A US 3196015 A US3196015 A US 3196015A US 170008 A US170008 A US 170008A US 17000862 A US17000862 A US 17000862A US 3196015 A US3196015 A US 3196015A
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image
emulsion
photosensitive
silver
silver halide
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William H Ryan
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Polaroid Corp
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Polaroid Corp
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Priority to US170008A priority patent/US3196015A/en
Priority to GB2892/63A priority patent/GB1023217A/en
Priority to FR923043A priority patent/FR1350957A/fr
Priority to DEJ23099A priority patent/DE1173338B/de
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
    • G03C8/06—Silver salt diffusion transfer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/142—Dye mordant

Definitions

  • This invent-ion relates to photography and, more particularly, to novel photosensitive photographic elements.
  • Another object of the present invention is to provide methods of fabricating same.
  • a further object of the present invention is to provide certain novel silver halide emulsions wherein photosensitive silver halide crystal-s are disposed in specified synthetic polymeric binder-s.
  • a still further object of the present invention is to provide specified photosensitive silver halide emulsions for employment in d'ifiusion transfer photographic processes.
  • the invention accordingly comprises the several steps and the relation and order of one or more of such steps with respect to each of the others, and the product possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • FIGURE 1 is a diagrammatic enlarged cross-sectional view illustrating the association of elements during one stage of the performance of a transfer process, for the production of silver prints, and showing, as one of the elements, embodiment of the novel photosensitive emulsions of the present invention, the thicknesses of the various materials being exaggerated;
  • FIG. 2 is a View similar to that of FIGURE 1 illustrating the association of elements during one stage of the performance of another diffusion-transfer process, for the production of silver prints, which illustrates another embodiment of novel photosensitive elements of the present invention
  • FIG. 3 is a diagrammatic enlarged cross-sectional view of one embodiment of the novel photosensitive element of the present invention, for use in obtaining additive multicolor images, comprising a support, an additive multicolor screen element, an embodiment of the present invention as the photosensitive emulsion, and an image-receiving stratum; and
  • FIG. 4 is a diagrammatic enlarged cross-sectional view of one embodiment of the novel photosensitive element of the present invention, for use in obtaining subtractive color images, comprising a photosensitive element which itself comprises a support, a layer containing color imageforming components and an embodiment of the present invention as the photosensitive emulsion; a rupturable container; and an image-receiving element.
  • the present invention comprehends improved photosensitive silver halide emulsions, comprising in whole or in part the specified synthetic binders detailed hereinafter, which find especially advantageous utilization in dilfusiont-ransfer processes.
  • an exposed photosensitive silver halide emulsion is developed and, substantially concurrently therewith, soluble imageforming components are obtained according to the pointto-point degree of exposure of the emulsion.
  • These soluble image-forming components are transferrd, in solution, from the emulsion to a suitable print-receiving layer to provide thereto the desired image formation.
  • the photosensitive silver halide emulsion is developed with a processing composition in a viscous condition which is spread between the photosensitive elements comprising 'the silver halide emulsion and an image-receiving element comprising a suitable silver precipitating layer.
  • the processing composition effects development of the latent image in the emulsion and, substantially contemporaneous therewith, form a soluble silver complex, for example, a thiosulfate or thiocyanate complex, with undeveloped silver halide.
  • a soluble silver complex for example, a thiosulfate or thiocyanate complex
  • This soluble silver complex is, at least in part, transported in the direction of the image-receiving element and the silver thereof is large precipitated in the silver precipitating layer of the element to form an image therein.
  • Additive color reproduction may be produced by exposing a photosensitive silver halide emulsion through an additive color screen having filter media or screen elements each of an individual additive color such as red or blue or green, and by viewing the reversed or positive silver image, formed by transfer to a transparent imagereceiving element, through the same or a similar screen which is suitably registered with the positive image carried by the image-receiving layer.
  • photosensitive silver halide emulsions comprising hydroxyethyl polyvinyl alcohol, as the colloid binder, are especially useful for diffusion transfer processes.
  • the novel photosensitive emulsions of the instant invention may be prepared by reacting a water-soluble silver salt, such as silver nitrate, with at least one water-soluble halide, such as potassium or sodium bromide, preferably together with potassium or sodium iodide, in an aqueous solution of a gelatin colloid peptizing agent.
  • a water-soluble silver salt such as silver nitrate
  • at least one water-soluble halide such as potassium or sodium bromide, preferably together with potassium or sodium iodide
  • the dispersion of silver halide thus formed contains Watersoluble salts, as a by product of the double decomposition reaction, in addition to an unreacted excess of either of the initial salts.
  • the gelatin dispersion has generally been set by means of chilling, the so-set dispersion noodled, and the noodles then washed with cold water.
  • Alternative procedures comprise coagulating the gelatin, separating the coagulum from the supernatant liquor, and washing the separated coagulum with water.
  • the coagulum or noodles which have been washed by either of the two general methods outlined above may be redissolved and used in forming silver halide-hydroxyethyl polyvinyl alcohol photographic emulsions by redispersing the silver halide-gelatin mixture in water and adding a solution of hydroxyethyl polyvinyl alcohol to the redispersed grains.
  • emulsions so prepared readily respond to the standard methods of chemical and optical sensitization. However, it should be noted that, where desired, sensitization may be carried out on the redispersed silver halide prior to the addition of the hydroxyethyl polyvinyl alcohol.
  • photosensitive silver halide crystals may be formed, for example, by vacuum deposition techniques, without the necessity of employing a dispersion medium during crystal formation, such as the previously described gelatin, and thereafter directly dispersed in the hydroxyethyl polyvinyl alcohol polymeric binder.
  • Silver halide crystals may also be directly deposited or formed on hydroxyethyl polyvinyl alcohol by vacuum deposition techniques.
  • the silver halide crystals may be formed on flake hydroxyethyl polyvinyl alcohol,
  • the silver halide crystals may be formed on the surface of a'continuous hydroxyethyl polyvinyl alcohol web which web, if desired, may be granulated and dissolved for subsequent coating or employed as formulated.
  • the photosensitive silver halide crystals may be formed directly in hydroxyethyl polyvinyl alcohol.
  • the silver halide crystals are formed by reacting a Water-soluble silver salt with at least one Water-soluble halide in an aqueous solution of hydroxyethyl polyvinyl alcohol.
  • the previously identified water-soluble by-products, formed during reaction may be removed by coagulating the silver halide hydroxyethyl polyvinyl alcohol dispersion by means of acetone, concentrated sodium sulfate solutions, or any of other known coagulating agents for hydrophilic synthetic hydroxyl polymers, and Washing the coagulated dispersion to eifect removal of the impurities.
  • the coagulate may then be redissolved by the addition of water or aqueous alcohol solutions, sensitized, the desired additives incorporated therein, and coated according to procedures known in the art.
  • the silver halide hydroxyethyl polyvinyl alcohol dispersion may also have the aforementioned water-soluble by-products removed by dialysis techniques or by contact of the dispersion with ion exchange resins and the like.
  • the light-sensitive material of a photographic emulsion is generally a compound of silver, for example, one or more of the silver halides, of which silver chloride, silver bromide and silver iodide are examples, it will be recognized that compounds of iron, chromium, and selected other metals, as well as certain organic compounds, for example, diazonium compounds, may be substituted for the aforementioned silver halide in the emulsions of the present invention.
  • a preferred silver halide emulsion comprises a silver iodobromide emulsion.
  • the resultant emulsion of the resent invention may be sensitized, the desired additives incorporated therein,
  • the emulsions of this invention may be coated onto various types of rigid or flexible supports, for example, glass, paper, metal, polymeric films of both the synthetic types and those derived from naturally occurring products, etc.
  • the specially suitable material includes paper; aluminums; polymethacryl-ic acid, methyl and ethyl esters; vinyl 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-propionate, or acetatebutyrate.
  • the preferred light-sensitive material of the instant photographic emulsions comprises a compound of silver, for example, one or more of the silver halides of which silver chloride, silver bromide and silver iodide are examples. It will be understood that silver halides of varying halide concentrations may be advantageously employed.
  • the emulsions of the present invention may be chemically sensitized by any of the accepted procedures.
  • the emulsions may be chemically sensitized with sulfur compounds such as sodium thiosulfate or thiourea; with reducing substances such as stannous chloride; with salts of noble metals such as gold, rhodium and platinum; with amines and polyamines; with quaternary ammonium compounds such as a-picolinium bromide, etc; and with polyethelene glycols and derivatives of same.
  • the emulsions may also be optically sensitized with cyanine and merocyanine dyes as described in US. Patent Nos. 1,846,301; 1,846,302; 1,942,854; 1,990,507; 2,112,- 2,165,338; 2,493,747; 2,493,748; 2,503,776; 2,519,- 001; 2,666,761; 2,734,900; 2,739,964; etc.
  • suitable anti-foggants may be included in the composition of the emulsion.
  • the hydroxyethyl polyvinyl alcohol which is employed as the vehicle in the herein described photographic emulsions may comprise either a high viscosity, medium viscosity or low viscosity type.
  • polyvinyl alcohol is obtained commerc1ally by hydrolyzing polyvinyl acetate whereby substantially all of the acetate groups are converted to hydroxyl groups, depending on the method of manufacture
  • the present invention includes the use of hydrolyzed polyvinyl acetates of which the major proportion of the resulting material is polyvinyl alcohol, most preferably those having a polyvinyl alcohol content of 75% or more.
  • the invention also includes within its scope the use of any of the far hydrolyzed polyvinyl acetates (and far propionates and far butyrates, etc.) as vehicles in the preparation of the instant photographic emulsions.
  • These polymers contain suflicient aliphatic hydroxyl groups or intralinear vinyl alcohol units to make them hydrophilic or soluble in cold and hot water.
  • One method of preparing the hydroxyethyl substituted polyvinyl alcohol polymers employed in the present invention is to react an aqueous solution of polyvinyl alcohol with liquid ethylene oxide at elevated temperatures in a pressure vehicle.
  • the liquid ethylene oxide preferably is in excess of that which is to participate in the reaction.
  • the reaction conditions may be vared within wide limits, preferaby the reaction temperature ranges from about 60 to 100 C., and the reaction duration ranges from about to 50 hours.
  • the number of hydroxyethyl substituents can be controlled by limiting the reaction temperature and varying the reaction duration.
  • the reaction itself may be catalyzed by a base, such as an alkali metal hydroxide or a tertiary amine.
  • a base such as an alkali metal hydroxide or a tertiary amine.
  • the polyvinyl alcohol may be contacted with the base.
  • the preferred hydroxyethyl polyvinyl alcohol polymers employed in the present invention contain from 17 to combined ethylene oxide by weight.
  • hydroxyethyl polyvinyl alcohol having more or less combined ethylene oxide by weight than the preferred range delineated may also be employed.
  • the combined ethylene oxide is within the range of about 25 to by weight
  • the polymer possesses rubber-like properties. Where the combined ethylene oxide is in excess of about 35% by weight, the polymer possesses gum properties. However, all are completely and readily soluble in water.
  • hydroxyethyl polyvinyl alcohol is employed throughout the instant specification to designate the reaction product of polyvinyl alcohol and ethylene oxide. It is generally believed that the reaction product comprises polyvinyl alcohols containing recurring groups represented by the general formula:
  • novel hydroxethyl polyvinyl alcohol of the instant invention will be illustrated in greater detail in conjunction with the following specific example which sets out a representative preparation of the novel emulsions, which, however, is not limited to the detailed description therein set forth and is intended to be illustrative only.
  • a phthalic anhydride derivative of gelatin was prepared by dissolving 100 grams of gelatin in 1100 cc. of water at a temperature of C. The pH of the resultant solution was adjusted, to within the range of 9.5 to 10.5, with aqueous 10% sodium hydroxide solution. 11 grams of phthalic anhydride, dissolved in 77 cc. of dry acetone, was then added gradually over a 30-minute period, during which addition the solution pH was maintained within the previously denoted range by the addition of aqueous 10% sodium hydroxide solution. The reaction was continued for 30 minutes, at a temperature of 40 C after which time the pH was lowered to within the range of 6 to 7, with an aqueous 10% sulfuric acid solution. The mixture was then chilled and set.
  • a silver halide gelatin derivative dispersion was prepared by formulating a solution comprising 226 grams of the last-prepared mixture, 161 grams of potassium bromide, 8 grams of potassium iodide, and 1250 cc. of distilled water. To this solution, maintained at a temperature of about C., was added a solution comprising 200 grams of silver nitrate dissolved in 1600 cc. of water.
  • the dispersion was cooled to approximately 10 C., with stirring, and then adjusted to a pH of about 3.0, with sulfuric acid.
  • the resultant precipitate was separated from the mother liquor and washed with chilled distilled water.
  • the emulsion contained 13.8 weight percent silver, 8.6 weight percent hydroxyethyl polyvinyl alcohol and 1.9 weight percent gelatin.
  • hydroxyethyl polyvinyl alcohol emulsions of the present invention possess unexpected advantages over those possessed by prior art emulsions containing conventional polyvinyl alcohol colloid binders. As an example of such advantages, in diffusion-transfer processes distinctly increased process speed has been achieved.
  • Emulsion A An emulsion, designated hereinafter as Emulsion A, was prepared in accordance with the previously detailed description.
  • Emulsion B A second emulsion, designated hereinafter as Emulsion B, was formulated as in accordance with the previously detailed procedure, except that the addition of sodium thiosulfate, a sensitizing agent, was deleted from the formulation.
  • Emulsion C A third emulsion, designated hereinafter as Emulsion C, was formulated in accordance with the previously described procedure with the exception that Elvanol 74-05 (trade name of E. I. du Pont de Nemours, Inc., Wilmington, Delaware, for polyvinyl alcohol) was substituted in the detailed formulation for the instant hydroxyethyl polyvinyl alcohol.
  • Each emulsion was coated on cellulose triacetate film base, dried and exposed in a sensitometer. Each photoexposed emulsion was then transfer processed by superposition of the exposed emulsion on a receiving sheet such as the commercial image-receiving sheet, a component of Polaroid Land Picture Roll Type 42 (Polaroid Corporation, Cambridge, Massachusetts), and distributing a transfer processing composition, by rupture of a frangible container holding same between the emulsion and the imagereceiving element and provided the results detailed hereinafter.
  • a receiving sheet such as the commercial image-receiving sheet, a component of Polaroid Land Picture Roll Type 42 (Polaroid Corporation, Cambridge, Massachusetts), and distributing a transfer processing composition, by rupture of a frangible container holding same between the emulsion and the imagereceiving element and provided the results detailed hereinafter.
  • the Diffusion Transfer Exposure Index is based on a curve relating original exposure of the emulsion to the It has been found experimentally that the Diffusion Transfer Exposure Index of a silver transfer process may be determined by plot-ting a characteristic curve of the reflection density of the positive as a function of the log exposure of the negative, determining the exposure in meter-candle seconds (m.c.s.) at the point on this curve corresponding to a density of 0.50, and dividing the constant, 4.0, by the exposure so determined.
  • the exposure index thus obtained indicates generally the correct exposure rating of a silver transfer process to which an exposure meter, calibrated to the ASA Exposure Index, must be set in order that it give correct exposure data for producting transfer prints of satisfactory high quality.
  • the aforementioned slope refers to the slope of the last-mentioned characteristic curve.
  • the exposure index of the hydroxyethyl polyvinyl alcohol emulsions of the instant invention, prepared in the same manner as conventional polyvinyl alcohol emulsions, is substantially greater, when processed in diffusion-transfer processes providing approximately equal maximum densities. While the reason for this increased exposure index is not definitely known, it may be possible that the matrix molecules may confer a sensitizing effect; however, it should also be noted that the hyd-roxyethyl polyvinyl alcohol emulsions possess a greater slope and a lower minimum density than that obtained when conventional polyvinyl alcohol emulsions are employed.
  • the diffusion transfer processes herein detailed require no long term physical stability of the emulsion layer. Inasmuch as development and transfer may be effected in less than a minute, preferably in a fraction of a second to seconds, it is possible for the emulsion layer itself to melt or dissolve completely in the processing fluid without any substantial detriment to the transfer image function. In fact, the ready solubility of the emulsion may actually assist materially in causing the transfer of image-forming components to take place in a shorter time interval than that obtainable when conventional materials are employed. In general, during transfer processing, any liquified emulsion is held in position between supporting layers, such that transfer formation is generally considered substantially completed prior to sufficient lateral diffusion to affect transfer image formation.
  • a preferred form of the processing agent comprises a Water solution of a developer, an alkali for imparting to the solution a sufficiently high alkalinity to permit the developer to carry out its developing function, a substance for forming :a soluble complex with silver halide, and a film-forming material.
  • the developer in the agent acts to develop any latent image in the emulsion and the silver halide solvent forms a soluble complex with the relatively unexposed silver halide during the development, which complex may be transported from the emulsion to another stratum of material of the lamination to form in said other stratum a positive image comprising silver.
  • the film-forming material which is preferably a high molecular weight polymer, imparts to the 0 composition a predetermined high viscosity and is of such character as to retain its viscosity-imparting and filmforming properties in an aqueous alkaline solution so that the processing agent, once its ingredients have been mixed and have attained an equilibrium, remains uniformly viscous for any given temperature for long periods of time.
  • the film-forming material in the foregoing alkaline composition is preferably one of the class of high molecular weight polymers which include in their chemical structure such groups as, for example, the ether, alkyl, hydroxyl, carboxyl and acetyl groups that are stable to alkalies and which contain none of the chemical groups, such as the ester and acid chloride groups, that are unstable to alkal'ies.
  • the polymers also contain groups such as the hydroxyl and/or carboxyl groups which tend to solubilize in aqueous alkaline solutions. Suitable examples of such polymers are the alkali-inert and watersoluble celluose derivatives such as sodium carboxymethyl cellulose and hydroxyethyl cellulose.
  • a high viscosity for the processing agent is very desirable since it makes possible the relatively uniform spreading of the composition and insuresa complete coverage of the desired area by said composition.
  • the film-forming material is preferably contained in the composition in suitable quantities to impart to the composition a vis cosity in excess of 1,000 centipoises at a temperature of approximately 24 C. and preferably of the order of 1,000 to 200,000 centipoises at said temperature.
  • developers useful in the foregoing composition alone or in mixture with one another are hydroquinone, monomethyl-p-aminophenol sulfate, p-aminophenol hydrochloride, p-hydroxyphenylaminoacetic acid, p-phenylenediamine, o-phenylenediamine, pyrocatechin (pyrocatechol, catechol), diaminophenol dihydrochloride, diaminophenol hydrochloride, pyrogallol, chlorohydroquinone, dichlorohydroquinone, tetrachlorohydroquinone, bromohydroquinone, toluhydroquinone, xylohydroquinone, o-aminophenol, Z-amino-S-diethylaminotoluene hydrochloride, p-tertiary butyl catec-hol, hydroquinone disulfonic acid (potassium salt), 2,5-ditertiary buty
  • Examples of materials which may be used in the composition for the purpose of forming a soluble silver complex with the undeveloped silver halide of the photosensitive layer are sodium thiosulfate, sodium thiocyanate, ammonium thiosulfate, ammonia and sodium cyanide. When a compound is toxic, such as sodium cyanide, precautions should be taken in the use thereof.
  • the composition may also contain sodium sulfite which acts in part as a preservative, and may also function as a silver halide solvent.
  • one embodiment of the novel photosensitive emulsion layers of the present invention in the performance of a transfer process for the production of positive silver prints comprises a spreader sheet 10, a layer of relatively viscous processing agent 11, a photosensitive emulsion layer 12 comprising the specified hydroxyethyl polyvinyl alcohol, an image-receiving layer 13 preferably containing silver precipitating nuclei, such as the silver precipitating nuclei, disclosed in the aforementioned US. Patent No. 2,698,237, and a suitable support layer 14.
  • Support layer 14 may comprise an opaque material where a reflection print is desired or may comprise a transparent material where a transparency is desired.
  • Liquid layer 11 may be obtained by spreading a photographic processing composition, for example, in a manner disclosed in US. Patent No. 2,698,244, issued December 28, 1954. As disclosed in the aforementioned US. patent, the liquid processing composition may be disposed in a rupturable container so positioned with regard to the appropriate surface of the photosensitive emulsion that, upon compression by spreader sheet 10, a substantially uniform layer 11 of processing composition is distributed over the surface of photosensitive emulsion 12,
  • the processing composition may be one of the film-forming processing compositions disclosed in US. Patent No. 2,543,181, issued February 27, 1951. It may comprise, for example, a developing agent such as hydroquinone, an alkali such as sodium hydroxide, a silver halide complexing agent such as sodium thiosulfate, and a high molecular weight film-forming thickening agent such as sodium carboxymethyl cellulose. All these materials are preferably in aqueous solution.
  • a developing agent such as hydroquinone
  • an alkali such as sodium hydroxide
  • a silver halide complexing agent such as sodium thiosulfate
  • a high molecular weight film-forming thickening agent such as sodium carboxymethyl cellulose. All these materials are preferably in aqueous solution.
  • the photographic agents are preferably contained in solution in the processing liquid prior to the spreadingthereof as layer 11, but they may be in part or in whole added to the processing composition as it is spread between spreader sheet 11 and photosensitive silver halide emulsion 12, said agents being so located on or adjacent to the surface of one or both of said layers as to be dissolved by or otherwise interacted with the liquid agent when the latter wets said surface.
  • photosensitive emulsion 12 is exposed to a predetermined subject matter to form therein a latent image of said subject matter.
  • a substantially uniform distribution of processing composition 11 is disposed on the external surface of said emulsion, for example, according to the previously described procedure.
  • Processing composition reagents permeate into the photosensitive emulsion, developing the latent image contained therein according to the pint-t0-point degree of exposure thereof.
  • an image-Wise distribution of soluble silver complex is formed from undeveloped silver halide within said emulsion. At least part of this silver complex, solubilized,
  • image-receiving stratum 13 is transferred, by imbibition, to image-receiving stratum 13.
  • the transferred silver complex is reacted to provide a positive, reversed image of the latent image.
  • dissociation: of this layer from the emulsion layer 12 may be effected.
  • the image-receiving layer 13 may be dissociated from emulsion layer 12 by stripping the emulsion from the surface thereof.
  • a conventional stripping layer may be provided to facilitate separation of emulsion layer 12 from image-receiving layer 13 subsequent to substantial transfer image formation.
  • the stripping layer may be coated on the surface of the image-receiving element and the photosensitive emulsion thereafter coated on the external surface of the stripping layer.
  • Suificient abrasion-resistant properties may be provided to imagereceiving element 13 such as to obviate any nemssity of subsequently over-coating to prevent subsequent laceration and resultant degradation of the transfer image.
  • spreading of the liquid processing composition on the external surface of the photosensitive emulsion is preferably effected by rupture of a suitably positioned frangible container and distribution of its processing composition content by means of a spreader sheet such as converted cellulose acetate; that is, a cellulose acetate sheet, the surface of which has been converted to cellulose.
  • a spreader sheet may be chosen which exhibits an adhesive capacity for the processing composition in excess of the adhesive capacity exhibited by the hydroxyethyl polyvinyl alcohol containing photosensitive emulsion.
  • a means is thus provided for effecting dissociation of the processing composition from contact with the photosensitive emulsion, preferably subsequent to image formation, dissociating the spreader sheet from proximate relationship to the external emulsion surface.
  • FIG. 2 A further embodiment of the present invention is illustrated in FIG. 2, which comprises a photosensitive hydroxyethyl polyvinyl alcohol emulsion 12, a layer of the previously-noted, relatively viscous, film-forming processing composition, and an image-receiving layer 15, preferably containing silver precipitating nuclei.
  • layer 11 of processing composition may be distributed in a substantially uniform manner, between photosensitive emulsion layer 12 and imagereceiving layer 15, for example, in accordance with the procedures disclosed in the aforementioned US. Patent No. 2,543,181.
  • one or more rupturable containers may be attached to either photosensitive emulsion layer 12 and/ or image-receiving layer 15 such that upon superposition of the respective layers 12 and 15 the container of containers are so positioned as to be capable, upon rupture, of releasing their contents in a substantially uniform layer between and in contact with the opposed surface of each of said layers.
  • Rupture of the container or containers and spreading of the contents thereof may be accomplished, for example, by compression between a pair of opposed, suitably gapped rollers.
  • the photosensitive emulsion 12 is exposed to a predetermined subject matter to form therein a latent image of said subject matter.
  • the exposed emulsion is superposed on image-receiving layer 1d and the photographic processing composition 11 spread between the opposed surfaces of photosensitive emulsion 12 and image-receiving layer 15.
  • Reagents permeate into the photosensitive emulsion 12, developing the latent image contained therein and forming a soluble silver complex of undeveloped silver halide.
  • Soluble silver complex is then transported from photosensitive emulsion layer 12, at least in part, by imbibition, to image-receiving stratum 15 and the silver of the complex there precipitated to provide the desired transfer image formation.
  • the lamination formed bythe spreading of processing composition in layer 11, between photosensitive emulsion 12 and image-receiving layerld, is kept intact for less than 90 seconds, preferably about 10 seconds or less, and at the termination of this time interval, image-receiving layer 15 is dissociated from emulsion 12, as for example, by stripping.
  • one embodiment of the present invention for use in additive multicolor diffusion transfer processes, is a composite film unit comprising a transparent support 16, an additive color screen element 17, an image-receiving layer 13 preferably containing silver precipitating nuclei, and a hydroxyethyl polyvinyl alcohol containing photosensitive emulsion 12.
  • a liquid processing composition is applied to photosensitive emulsion 12, as for example, according to the procedure previously described in explanation of FIG- URE 1.
  • the liquid processing composition permeates into photosensitive emulsion 12, developing the latent image contained therein, forming an image-wise distribution of soluble silver complex in undeveloped areas thereof, and transferring, at least part of said image-wise distribution, by imbibition, toward image-receiving layer 13, wherein the silver of said complex is precipitated to provide positive silver image formation.
  • Dissociation of emulsion layer 12 from image-receiving layer 13 may be accomplished, for example, according to the procedure previously described in explanation of FEGURE 1.
  • the viewing of the positive image takes place through a permanently registered color screen element, either that color screen element through which exposure was accomplished or a duplicate thereof.
  • exposure is accomplished through the stationary color screen element predisposed in the imagereceiving element, thus avoiding the problem incident upon attempts to register a mobile color screen element with the deposited silver image
  • the instant inventive concepts are equally applicable to the numerous additive multicolor diffusion transfer processes utilizing color screen elements in combination with silver transfer processes, such as, for example, the additive multicolor transfer processes disclosed in U.S. Patent No. 2,614,926, issued October 21, 1952.
  • U.S. Patent No. 2,707,150 discloses additive multicolor processes utilizing a color screen element in a photosensitive emulsion wherein, subsequent to the selective exposure of the photosensitive emulsion through said color screen and substantially simultaneous with the development of the latent image contained therein, the color screen element filter media, preferably soluble dyes, transfer, at least in part, by diffusion to an image-receiving element to provide thereto a substantially duplicate screen element of the original color screen element.
  • the color screen element filter media preferably soluble dyes
  • imageforming component is intended to signify the image-dye precursors utilized in the previously noted color coupling and dye developer diffusion transfer techniques, as well as the coupling dye techniques disclosed in U.S. Patent No. 2,774,668, issued December 18, 1956, and the copending U.S. application of Howard G. Rogers, Serial No. 613,691, filed October 3, 1956, to provide monochromatic and/ or multichromatic subtractive color image formation.
  • FIG. 4 of the accompanying drawing illustrates one method of processing a photosensitive element to obtain a subtractive color transfer image in accordance with this invention.
  • a photosensitive element 19 comprises a sup- .port 14, a layer 18 containing at least one color imageforming component, preferably at least one dye developer, and a photosensitive hydroxyethyl polyvinyl alcohol containing emulsion layer 12.
  • the photosensitive element is shown in a spread apart relationship (as, for example, during exposure) with an image-receiving layer 15 having mounted thereon a rupturable container 20 holding a processing composition.
  • imagereceiving element 15 After exposure, imagereceiving element 15 is brought into superposed relationship with the photosensitive element 19 and the rupturable container 20 is ruptured by application of suitable pressure, for example, by advancing between a pair of rollers (not shown), and a layer of the liquid processing composition permeates the photosensitive emulsion layer 12 and layer 18 containing image-forming components providing at least subtractive image color.
  • the image-forming components In exposed areas of the photosensitive element, the image-forming components, at least to some extent, exhibit decreased solubility in contradistinction to unexposed areas.
  • the image-forming components will transfer, at least in part, by diffusion, to superposed image-receiving element 15 to provide thereto a positive image in terms of said unexposed areas.
  • Image-receiving element 15 may then be separated from superposed relationship with the photosensitive element after at least a portion of the image-forming components have been transferred.
  • Multicolor images may be obtained using image-forming components and diffusion transfer processes by several techniques.
  • One such technique contemplates the use of a photosensitive stratum comprising at least two sets of selectively sensitized, minute, photosensitive elements arranged in the form of a photosensitive screen. Transfer processes of this type are disclosed in the aforementioned U.S. Patent No. 2,938,606.
  • each of the minute photosensitive elements I has associated therewith appropriate color image-forming components in or behind the photosensitive emulsion portion.
  • a suitable photosensitive screen prepared in accordance with the disclosure of the lastmentioned patent, comprises minute red-sensitive emulsion elements, minute green-sensitive emulsion elements and minute blue-sensitive emulsion elements arranged in a side-by-side relationship in a screen pattern and which have associated therewith, respectively, cyan color imageforming components.
  • Another process for obtaining multicolor transfer images utilizing image-forming components employs an integral multi-layer photosensitive element wherein at least two selectively sensitized photosensitive strata are superposed on a single support and are processed, simultaneously, and without separation, with a single, common image-receiving layer.
  • a suitable arrangement of this type comprises a support carrying a red-sensitive emulsion stratum, a green-sensitive emulsion stratum and a bluesensitive emulsion stratum, said emulsions having associated therewith, respectively, cyan image-forming components, magenta image-forming components and yellow image-forming components.
  • the color image-forming component may be disposed in the emulsion layer, for example, in the form of particles, or one or more may be employed, respectively, as a layer behind the appropriate photosensitive emulsion strata.
  • Each set of emulsions and associated color image-forming components may be separated from other sets by suitable interlayers, for example, by a layer or layers of gelatin or polyvinyl alcohol.
  • a further technique for obtaining multicolor image employs a plurality of photosensitive elements associated with appropriate numbers of image-receiving elements .and adapted to be treated with one or more liquid processing compositions, the appropriate color image-forming components being incorporated in the respective photosensitive elements.
  • Examples of film structures of this type are disclosed in aforementioned U.S. Patent No. 2,647,049.
  • a rupturable container such as container 20 in FIG.4, provides a convenient means for spreading a liquid processing composition between layers of a film unit whereby to permit the processing to be effected within a suitable camera apparatus
  • the processing of this invention may be otherwise effected.
  • a photosensitive element after exposure in a 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 image-receiving element for image formation in the manner heretofore described.
  • Details of such rupturable containers as are illustrated in FIG. 4 may be found in U.S. Patent No. 2,634,886, issued April 14, 1953.
  • theinventive concepts of the present invention may be employed in the spontaneous development transfer process disclosed and claimed in the copending U.S. application of Edwin H. Land, Serial No. 498,672, filed April 1, 1955.
  • a transfer processing composition is contacted with a photosensitive emulsion which is in superposed relationship to an image
  • photosensitive and other terms of similar import are herein employed in the generic sense to describe materials possessing physical and chemical properties which enable them to form usable images when photoexposed by radiation.
  • a diffusion transfer process which comprises the steps of developing an exposed photosensitive emulsion and forming thereby an image-wise distribution of imageforrning components in said photosensitive emulsion, as a function of the point-to-point degree of exposure thereof, and transferring, at least part of said image-wise distribution, by diffusion, to a contiguous image-receiving layer to provide thereto a visible transfer image
  • the improvement which comprises employing a hydroxyethyl polyvinyl alcohol silver halide photosensitive emulsion.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US170008A 1962-01-31 1962-01-31 Diffusion transfer process Expired - Lifetime US3196015A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE627760D BE627760A (de) 1962-01-31
US170008A US3196015A (en) 1962-01-31 1962-01-31 Diffusion transfer process
GB2892/63A GB1023217A (en) 1962-01-31 1963-01-23 Photographic products and processes
FR923043A FR1350957A (fr) 1962-01-31 1963-01-29 Produits et procédés photographiques
DEJ23099A DE1173338B (de) 1962-01-31 1963-01-31 Photographisches Silbersalzdiffusions-uebertragungsverfahren

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US3443941A (en) * 1967-07-24 1969-05-13 Polaroid Corp Dye transfer control by silver ions
US3590692A (en) * 1968-07-01 1971-07-06 Polaroid Corp Silver halide developing agents and photographic process
US3617272A (en) * 1969-02-06 1971-11-02 Eastman Kodak Co Multicolor dye developer systems
US3617277A (en) * 1969-02-06 1971-11-02 Eastman Kodak Co Dye developer diffusion transfer systems
US3620731A (en) * 1969-09-29 1971-11-16 Polaroid Corp Novel processes for forming two negative color transfer images
US3658524A (en) * 1969-09-29 1972-04-25 Polaroid Corp Photographic film unit comprising silver halide and a dyeable stratum contained on a common support and process employing same

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US2687478A (en) * 1949-09-29 1954-08-24 Polaroid Corp Radiation detection device
US3017270A (en) * 1958-03-31 1962-01-16 Eastman Kodak Co Photographic silver halide diffusion transfer process
US3043691A (en) * 1956-06-09 1962-07-10 Agfa Ag Process and material for the direct production of positives by the silver salt diffusion process
US3043698A (en) * 1960-08-18 1962-07-10 Du Pont Photographic gelatin-silver halide emulsions containing beta-hydroxyalkyl ethers of polyvinyl alcohol
US3061428A (en) * 1958-12-17 1962-10-30 Polaroid Corp Photographic products and processes using alkali permeable co-polymeric layers
US3077400A (en) * 1962-04-26 1963-02-12 Polaroid Corp Color diffusion transfer using gelatinsilver halide emulsions containing cellulose ethers
US3108001A (en) * 1959-08-17 1963-10-22 Polaroid Corp Novel photographic products, processes, and compositions

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Publication number Priority date Publication date Assignee Title
DE869008C (de) * 1950-01-13 1953-03-02 Bayer Ag Verfahren zur direkten Herstellung von Positiven

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2687478A (en) * 1949-09-29 1954-08-24 Polaroid Corp Radiation detection device
US3043691A (en) * 1956-06-09 1962-07-10 Agfa Ag Process and material for the direct production of positives by the silver salt diffusion process
US3017270A (en) * 1958-03-31 1962-01-16 Eastman Kodak Co Photographic silver halide diffusion transfer process
US3061428A (en) * 1958-12-17 1962-10-30 Polaroid Corp Photographic products and processes using alkali permeable co-polymeric layers
US3108001A (en) * 1959-08-17 1963-10-22 Polaroid Corp Novel photographic products, processes, and compositions
US3043698A (en) * 1960-08-18 1962-07-10 Du Pont Photographic gelatin-silver halide emulsions containing beta-hydroxyalkyl ethers of polyvinyl alcohol
US3077400A (en) * 1962-04-26 1963-02-12 Polaroid Corp Color diffusion transfer using gelatinsilver halide emulsions containing cellulose ethers

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3443941A (en) * 1967-07-24 1969-05-13 Polaroid Corp Dye transfer control by silver ions
US3590692A (en) * 1968-07-01 1971-07-06 Polaroid Corp Silver halide developing agents and photographic process
US3617272A (en) * 1969-02-06 1971-11-02 Eastman Kodak Co Multicolor dye developer systems
US3617277A (en) * 1969-02-06 1971-11-02 Eastman Kodak Co Dye developer diffusion transfer systems
US3620731A (en) * 1969-09-29 1971-11-16 Polaroid Corp Novel processes for forming two negative color transfer images
US3658524A (en) * 1969-09-29 1972-04-25 Polaroid Corp Photographic film unit comprising silver halide and a dyeable stratum contained on a common support and process employing same

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DE1173338B (de) 1964-07-02
GB1023217A (en) 1966-03-23

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