US3567442A - Novel photographic products and processes - Google Patents

Novel photographic products and processes Download PDF

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Publication number
US3567442A
US3567442A US622133A US3567442DA US3567442A US 3567442 A US3567442 A US 3567442A US 622133 A US622133 A US 622133A US 3567442D A US3567442D A US 3567442DA US 3567442 A US3567442 A US 3567442A
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silver
print
layer
layers
image
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Edwin Land
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Polaroid Corp
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Polaroid Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/24—Photosensitive materials characterised by the image-receiving section
    • G03C8/26—Image-receiving layers
    • G03C8/28—Image-receiving layers containing development nuclei or compounds forming such nuclei

Definitions

  • the present invention is directed to a silver diffusion transfer photographic process print-receiving element which comprises a common support carrying on one surface a plurality of layers each of which comprises metallic sulfide, metallic selenide, colloidal metal, thiooxalate or thioacetamide silver precipitating agents disposed in a gelatin, deacetylated chitin or silica matrix wherein each such layer comprises a substantially constant concentration of silver precipitating agent per unit area, and a decreasing concentration, layer-wise, in the direction of the support; and to photographic silver diffusion transfer processes employing such print receiving element.
  • This invention relates to photographic products and processes for the fabrication and utilization of said products and more particularly to photographic products usefulin diffusion-transfer processes wherein a latent image contained in an exposed silver halide emulsion is developed therein and a soluble silver complex, obtained by reaction of the undeveloped silver halide of said emulsion with an appropriate silver halide solvent, is transferred from said emulsion to an image-receiving element to provide therein a reversed positive silver image of the latent image, and to processes for the fabrication of said products.
  • a principal object of the present invention is to provide transfer processes for the aforementioned type and products for utilization therein whereby positive prints are produced exhibiting enhanced quality and stability.
  • a further object of the present invention is to provide improved products particularly useful in the aforementioned diffusion-transfer processes as print-receiving elements, each of said products comprising a multilayer image-receiving stratum, wherein each layer of said stratum contains a progressively increasing concentration of silver precipitating nuclei in respect to the concentration of said nuclei contained in adjacent layers, positioned less distant from the surface of the print-receiving element in contact with a silver halide transferring medium, to thereby produce dense positive silver images of excellent pictorial quality and improved stability.
  • a still further object of the present invention is to provide transfer processes of the aforementioned type and products for utilization therein whereby silvering, due to surface precipitation of elemental silver on a print-receiving element, is avoided.
  • the invention accordingly comprises the several steps and 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 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.
  • FIG. 1 is a diagrammatic enlarged cross-sectional view illustrating the association of elements during one stage of the performance of a transfer process and showing as one of the elements an embodiment of the novel print-receiving elements of the present invention, the thickness of the various materials being exaggerated;
  • FIG. 2 is a diagrammatic enlarged cross-sectional view of one form of the novel print-receiving elements of the present invention.
  • FIG. 3 is a diagrammatic enlarged cross-sectional view illustrating the association of elements during one stage of the performance of another transfer process.
  • the present invention comprehends improved diffusiontransfer reversal processes and products of the type Whereby a positive print is obtained in a single step by suitably treating a silver halide emulsion containing a latent image with a processing liquid.
  • the processing liquid is in a viscous condition and is spread in a thin film between the photosensitive element comprising a silver halide emulsion and a multilayer image-receiving element containing varying concentrations of silver precipitants.
  • the processing composition develops the latent image in the emulsion and forms a soluble complex, for example, a thiosulfate or a thiocyanate compleX, with undeveloped silver halide.
  • This soluble silver complex is transferred, at least in part, by imbibition, to the print-receiving element and the silver component thereof is precipitated in the multilayer image-receiving stratum of the print-receiving element to provide a reversed, positive silver image of the latent image therein.
  • silver precipitating agents or nuclei of the preferred type are the so-called heavy metal sulfides of zinc, chromium, gallium, iron, cadmium, cobalt, nickel, lead, antimony, bismuth, silver, cerium, arsenic, copper and rhodium and the selenides of lead, zinc, antimony and nickel.
  • the silver precipitating agent is so dispersed as to effect a controlled precipitation of the soluble silver complex, the chosen matrix serving to receive and suitably aggregate the precipitated silver to produce therein positive images.
  • the silver precipitating agents are dispersed in a suitable matrix formed of particles, preferably colloidal in size, of a chemically inert, absorbent material.
  • colloidal silica such as silica aerogel, fullers earth, diatomaceous earth, kieselguhr, Wood flour, infusorial earth, bentonite, filter aids such as Celite and Super-Floss (trade names of Johns-Manville Sales Corp, New York, N.Y., for diatomaceous earth filtration aids), and finely powdered glass, talc, mica or zinc oxide.
  • filter aids such as Celite and Super-Floss (trade names of Johns-Manville Sales Corp, New York, N.Y., for diatomaceous earth filtration aids)
  • finely powdered glass talc, mica or zinc oxide.
  • the precipitation and aggregation of silver obtained by using silver precipitating agents is greatly improved and expedited by providing aboneceiving element having a plurality of layers containing a varying concentration of silver precipitating agents, especially wherein the concentration of silver precipitating nuclei progressively increases as the distance of the respective layers from the external surface of the imagereceiving stratum increases.
  • the novel print-receiving element is preferably fabricated by successively applying to a suitable support the respective silver precipitating nuclei-containing layers.
  • the respective layers are preferably dried prior to successive coating operations.
  • the support may be formed of a material such as, for example, paper, regenerated cellulose, polyvinyl alcohol, cellulose ethers such as methyl cellulose, ethyl cellulose, or their derivatives, and other natural and synthetic gums and resins which will form continuous films and which are relatively stable, mechani cally, in the presence of water and alkali.
  • the supporting sheets are preferably opaque when a reflection print is desired and transparent when a transparency is desired.
  • the respective layers be dried prior to successive coating operations.
  • the interface between contiguous layers may dissipate, particularly where a common matrix material is used for the several layers.
  • One method of preparing the respective silver precipitating agent-containing layers may comprise forming a dispersion of silver precipitating agents by vacuum depositing, as for example, by cathode sputtering, an appropriate silver precipitating agent on a suitable matrix and blending the resulting product in a coating solvent.
  • Processes of the aforementioned type are disclosed in the copending U.S. application of Edwin H. Land, ,Ser. No. 705,845, filed Dec. 30, 1957, abandoned and replaced by Ser. No. 249,922, filed Jan. 7, 1963, now U.S. Pat. No. 3,295,972, issued Jan. 3, 1967.
  • the coating compositions containing the desired concentration of silver precipitating agents are prepared by dilution of the aforementioned blended product.
  • the respective coating compositions comprising progressively decreasing concentrations of silver precipitating agents are successively coated on a suitable support. As previously mentioned, it is preferred that each successive layer be dried prior to succeeding coating operations.
  • a coating formulation is prepared by evaporating parts of silver onto 400 parts of twenty mesh carboxymethyl cellulose powder. 5 parts of the resultant product are dissolved in 100 parts of an aqueous gelatin composition containing 2% of gelatin and 2% deacetylated chitin.
  • image-receiving layers containing deacetylated chitin are disclosed and claimed in U.S. Pat. No. 3,087,815 issued Apr. 30, 1963 in the name of William H. Ryan and Elizabeth L. Yankowski.
  • a support comprising a polyvinyl butyral-coated baryta paper is coated with the aforementioned formulation. After the coating has dried, a second layer comprising the aforementioned formulation diluted in the ratio of 1 cc. to 9 cc. with the aforementioned gelatin-deacetylated chitin composition is coated on the exposed surface of the initial coating and dried.
  • the silver precipitating agents in the image-receiving layer are disposed in a matrix comprising a macroscopically continuous stratum comprising submacroscopic agglom crates of minute particles of a suitable water-insoluble, inorganic, preferably siliceous material, such, for example, as silica aerogel.
  • a suitable water-insoluble, inorganic, preferably siliceous material such, for example, as silica aerogel.
  • the silver-receptive stratum of the present invention is so constituted as to provide an unusually vigorous elemental silver precipitating environment which causes the elemental silver deposited therein, in comparison with the amount of silver developed in the silver halide photosensitive layer, to possess very high covering power, that is, opacity for given mass of reduced silver.
  • silver precipitating agents are the metallic sulfides and selenides, these terms being understood to include the selenosulfides, the polysulfides, and the polyselenides.
  • Preferred in this group are the socalled heavy metal sulfides previously noted.
  • sulfides whose solubility products in an aqueous medium at approximately 20 C. vary between 10- and 10 and especially the salts of zinc, cadmium and lead.
  • heavy metals such as silver, gold, platinum, palladium, and mercury, and in this category the noble metals are preferred and are preferably provided in the matrix as colloidal particles.
  • the salts of these heavy metals are also useful as silver precipitating agents.
  • the metals are introduced into the matrices as salts and then reduced in situ prior to the use of the reception material in the silver transfer process to give a layer whose silver precipitating agent is a colloidal metal.
  • this reduction may be accomplished simply by exposing the silver precipitating layer to diffused light or to heat.
  • silver precipitating agents are certain of the thio compounds, for example, dithiooxalate and its lead and zinc complexes, potassium dithiooxalate and the lead and nickel complexes thereof, and thioacetamide.
  • the silver precipitating agents as noted above are provided in highly dispersed condition, preferably as colloidal particles.
  • the silver precipitating agent is one or more of the heavy metal sulfides or selenides
  • This more soluble salt has, as its cation, a metal whose ion forms sulfides or selenides which are difficultly soluble in the processing agent and which give up their sulfide or selenide ions to silver by displacement.
  • the metal ions of the more soluble salts have the effect of immediately precipitating the sulfide or selenide ions from solution.
  • These more soluble or ion-capturing salts may be either soluble salts of any of the following metals: cadmium, cerium (ous), cobalt (ous), iron, lead, nickel, manganese, thorium, and tin.
  • Satisfactory soluble and stable salts of the above metals may be found, for example, among the following groups of salts: the acetates, the nitrates, the borates, the chlorides, the sulfates, the hydroxides, the formates, the citrates, and the dithionates.
  • the acetates and nitrates of zinc, cadmium, nickel, and lead are preferred.
  • the previously mentioned ion-capturing salts may also serve a function of improving the stability of the positive print provided they possess, in addition to the aforementioned characteristics, the requisites specified in US. Pat. No. 2,584,030 issued to Edwin H. Land.
  • the ion-capturing salt is a salt of a metal which slowly forms insoluble or slightly soluble metallic hydroxides with the hydroxyl ions in the alkaline processing liquid, it will suitably control the alkalinity of the print-receiving element to substantially, if not totally, prevent the formation of undesirable developer stains.
  • photosensitive element 12 comprises a support and a photosensitive silver halide emulsion layer 11; a layer 13 comprises a relatively vis cous processing composition; and print-receiving element 14 is one embodiment of the novel print-receiving elements of the present invention.
  • the print-receiving element 14 comprises a suitable support 16 and a multilayer image-receiving stratum with a varying concentration of silver precipitants.
  • Multilayer image-receiving stratum 15 is formed by successively coating a suitable support 16, for example of baryta paper, with a plurality of suspensions or sols containing progressively decreasing concentrations of silver precipitating nuclei in suitable matrices. Each successive layer is preferably permitted to dry preceding the coating of the succeeding layer.
  • Liquid layer 13 may be obtained by spreading the processing composition, for example, in a manner disclosed in US. Pat. No. 2,647,056, issued July 28, 1953 to Edwin H. Land.
  • a rupturable container may be positioned between the photosensitive element and the print-receiving element such that upon application of suitable pressure, for example by compression between a pair of opposed, suitably gapped rollers, said container fractures releasing a liquid processing composition in contact with the transfer surfaces of each of said elements.
  • the processing composition may be one of the film-forming processing compositions disclosed in said patent.
  • 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, for forming a soluble silver complex with unexposed and undeveloped silver halide, and a high. molecular weight, film-forming, thickening agent such as sodium carboxymethyl cellulose. All these materials are preferably in an aqueous solution.
  • the various photographic reagents are preferably contained in solution in the processing liquid prior to the spreading thereof as layer 13.
  • reagents may be in whole or in part added to the processing liquid as it is spread between elements 12 and 14, said reagents being so located on or adjacent to the surface of one or both of said elements as to be dissolved by or otherwise interacted with the liquid composition when the latter wets said elements.
  • a processing agent may be prepared which comprises:
  • the film-forming material in the processing agent which imparts the desired viscosity to the latter may be any of the high molecular weight polymers which are stable to alkali and which are soluble in aqueous akaline solutions.
  • such other plastics as hydroxyethyl cellulose, polyvinyl alcohol, and the sodium salts of polymethacrylic acid and polyacrylic acid may be used.
  • the plastic is preferably contained in the agent in suflicient quantity to impart to the composition a viscosity in excess of 1000 centipoises at a temperature of approximately 20 C.
  • the viscosity of the processing agent is of the order of 1000 to 200,000 centipoises.
  • developing agents may be used, for example, one of the following: p-aminophenol hydrochloride; bromohydroquinone; chlorohydroquinone; diaminophenol hydrochloride; diaminophenol dihydrochloride; toluhydroquinone; monomethyl-p-aminophenol sulfate; a mixture consisting by weight of /2 hydroquinone and /2 p-hydroxyphenylaminoacetic acid; and a mixture consisting by weight of A hydroquinone and p-hydroxyphenylaminoacetic acid.
  • Such other complex-forming substances as sodium thiocyanate, ammonium thiocyanate and ammonia may be employed.
  • another embodiment of the aforementioned difiusion-transfer processes comprises the relation of elements wherein spreader sheet 19 is associated with a rupturable container 20 holdmg at least a liquid photographic processing composition and a photosensitive silver halide emulsion layer 11 having in superposed relation thereto a novel print-receiving element 15 of the present invention on a support 16.
  • rupturable container 20 fractures, releasing its contents in a substantially uniform layer between spreader sheet 19 and a selectively exposed photosensitive silverhalide emulsion layer 11.
  • the processing composition permeates emulsion layer 11, developing the latent image contained therein.
  • Substantially simultaneously, undeveloped silver halide forms a soluble silver complex, by means of a silver halide solvent, as a function of the point-to-point degree of exposure of said photosensitive emulsion.
  • An imagewise distribution of soluble silver complex is formed in the unexposed areas of the photosensitive emulsion and transferred, at least in part, by imbibition, to print-receiving stratum 15, to form upon precipitation of elemental silver therein, a reversed positive silver image of the latent image.
  • photo- 7 sensitive emulsion 11 may be dissociated from print-receiving stratum 15, as by, for example, manual stripping.
  • the novel print-receiving elements of the present invention as illustrated in FIG. 2, it may be desirable to provide a coating on the silver precipitating layer 15 of a material, such as a plastic, more abrasionresistant than the matrix of the precipitating nuclei-con taim'ng layers in order to protect the external surface of the image-receiving stratum.
  • This overcoat of a plastic material may also serve as a layer which prevents adhesion of the film-forming processing composition 13 so that when element 17 is stripped from the photosensitive element 12, at the completion of processing, the filmforming processing composition layer 13 remains attached to photosensitive element 12.
  • layer 15 is a multilayer image-receiving stratum and there is applied over layer 15 a thin coating of an abrasion-resistant coating 18 which may be, for example, gum arabic, cellulose acetate hydrogen phthalate, polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, cellulose nitrate, sodium alginate, pectin, or poly-methacrylic acid.
  • Layer 18 preferably has a thickness of the order of 1 to 3 microns, although if it is relatively water permeable, its thickness may be appreciably greater. Layer 18 may also contain one or more neutralizing agents which tend to improve the stability of the finished print.
  • the protective coating 18 may further serve as a layer for minimizing the adhesion to the film-forming material of layer 13, particularly where said material is carboxymethyl cellulose.
  • the solid film obtained from the filmforming processing iluid 13 may be caused to adhere to the print-receiving element 14 to provide a protective coating thereon or caused to adhere to photosensitive emulsion layer 11 rather than the print-receiving element, as for example, according to the procedures disclosed in US. Pat. No. 2,647,056, issued July 28, 1953 to Edwin H. Land.
  • the positive print is subject to several sources of instability which stem, for example, from the oxidation of the developer in the highlights, the discoloration of some of the unexhausted chemical components in the positive print by exposure to visible and near visible radiation, the partial bleaching of the silver, and the interaction of the deposited silver with external sulfur and sulfides under conditions such that the structure of the precipitated silver is changed, usually to a yellow-to-brown form. This reduces the density and changes the tone of the positive transfer image.
  • Diffusion-transfer processes utilizing the single layer print-receiving structures of the prior art inherently result in the deposition of a substantial quantity of the elemental silver precipitate on or adjacent to an exposed surface of the print-receiving element with the resultant proclivity of a substantial proportion of the positive image to adverse externally caused deterioration.
  • the deposition of the elemental silver precipitate upon or in the surface area of the respective print-receiving elements provides an undesirable silvering effect.
  • the novel print-receiving structures of the present disclosure alleviate the aforementioned undesirable effects in that they provide a reception element wherein the tendency of the silver halide complex is to provide a precipitate of elemental silver removed from the surface of said element.
  • the novel print-receiving structures of the present disclosure provide image formation exhibiting decreased granularity and graininess.
  • the appearance of graininess in the transferred image is apparently not produced by the perception of individual submacroscopic grains of deposited elemental silver, but rather the optical impression of non-uniformity produced as a result of pattern effects which themselves appear to result from the irregular distribution of the elemental silver grains.
  • the optical effect is that of aggregation or clumping and, conversely, a deficiency in the concentration of deposited grains per unit area reflects incomplete image formation and definition.
  • the print-receiving structures of the present invention provide a vastly increased control of the elemental silver precipitation as well as the distribution of the precipitating sites in the image-receiving stratum, the aforementioned effects apparently due at least in part to random distribution of silver precipitate in prior art structures are avoided.
  • novel print-receiving structures disclosed herein provide increased resolving power, sharpness, density, contrast, covering power, and intensification resulting from an increased three-dimensional array of elemental silver precipitates per unit of viewed surface area.
  • novel print-receiving elements of this invention provide several other advantages. They are more stable during storage prior to use.
  • the images formed therein do not exhibit image rub-off, which may occur where the image silver is precipitated on or close to the surface of the print-receiving element.
  • the use of layers of varying concentrations of silver precipitants makes it possible to selectively encourage the characteristics of the toe or shoulder portions of the characteristic curve of the image. This, in turn, permits the formation of images with characteristic curves which are smooth, long, straight line curves, thereby facilitating true copying of the resulting silver transfer images, as well as of other images.
  • a process of forming a transfer image in silver which comprises the steps of developing an exposed silver halide emulsion with a processing composition comprising a silver halide developing agent and a silver halide solvent, forming an imagewise distribution of soluble silver complex in unexposed areas of said emulsion as a function of the point-to-point degree of exposure thereof, transferring from said emulsion, at least in part, by imbibition, said imagewise distribution of soluble silver complex to a documentcceiving element in superposed relationship with said emulsion so as to receive a depth-wise diffusion of said imagewise distribution and providing thereby a silver transfer image, and separating said print-receiving element from its superposed relationship with said emulsion subsequent to substantial transfer image formation
  • the im provement which comprises providing a visible silver transfer image of improved stability comprising image silver precipitated in each of at least two contiguous layers by transferring said imagewise distribution of said soluble silver complex to a preformed substantially photoinsensitive print-receiving element compris
  • a substantially photoinsensitive diffusion transfer print-receiving element which comprises a common support having on one surface a plurality of contiguous layers, each of said layers including, dispersed in the same matrix selected from the group consisting of gelatin, deacetylated chitin and a macroscopically continuous matrix comprising submacroscopic agglomerates of minute particles of Water-insoluble, chemically inert and absorbent silica matrices, a substantially constant concentration of the same silver precipitating agent selected from the group consisting of metallic sulfide, metallic selenide, colloidal metal, thiooxalate, and
  • thioacetamide silver precipitating agents per unit area, within said layer, and a decreasing concentration of said silver precipitating agent, layerwise, as the distance of the respective layer from the common support increases elfective to provide a visible silver transfer image comprising image silver precipitated in each of at least two said contiguous layers.
  • a substantially photoinsensitive diffusion transfer print-receiving element which comprises baryta paper carrying on one surface thereof, in order, first and second polymeric layers each comprising deacetylated chitin and gelatin and containing, as a silver precipitating agent, a substantially constant concentration of silver, said second polymeric layer containing said silver at a concentration per unit area of about oneninth of the concentration per unit area contained in said first polymeric layer next adjacent said surface of said baryta paper.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
US622133A 1959-12-09 1967-03-10 Novel photographic products and processes Expired - Lifetime US3567442A (en)

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US85845459A 1959-12-09 1959-12-09
US62213367A 1967-03-10 1967-03-10

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US (1) US3567442A (en:Method)
CH (1) CH417328A (en:Method)
DE (1) DE1113630B (en:Method)
GB (1) GB893652A (en:Method)
NL (2) NL258744A (en:Method)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3709687A (en) * 1970-04-06 1973-01-09 Polaroid Corp Diffusion transfer receiving element with varing concentration of precipitating nuclei
US3929481A (en) * 1972-02-25 1975-12-30 Fuji Photo Film Co Ltd Etch bleaching processes for making lithographic printing plates using silver halide and/or diffusion transfer layers and a hydrophilic layer
FR2461323A1 (fr) * 1979-07-06 1981-01-30 Drexler Tech Milieu reflechissant de memorisation de donnees, son procede de fabrication et bain de revelateur utilise dans ce procede
FR2480475A1 (fr) * 1980-04-14 1981-10-16 Drexler Tech Milieu reflechissant a large bande pour l'enregistrement par laser et la memorisation de donnees, comportant une sous-couche absorbante, et son procede de fabrication
FR2484119A1 (fr) * 1980-06-04 1981-12-11 Drexler Tech Procede de reproduction photographique d'informations de milieux optiques de memorisation de donnees, et milieu ainsi reproduit
US4379828A (en) * 1980-05-16 1983-04-12 Agfa-Gevaert Aktiengesellschaft Image receptor element for the dye diffusion transfer process
US5200296A (en) * 1987-05-14 1993-04-06 Mitsubishi Paper Mills Limited Image receiving material for silver complex diffusion transfer process

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3709687A (en) * 1970-04-06 1973-01-09 Polaroid Corp Diffusion transfer receiving element with varing concentration of precipitating nuclei
US3929481A (en) * 1972-02-25 1975-12-30 Fuji Photo Film Co Ltd Etch bleaching processes for making lithographic printing plates using silver halide and/or diffusion transfer layers and a hydrophilic layer
FR2461323A1 (fr) * 1979-07-06 1981-01-30 Drexler Tech Milieu reflechissant de memorisation de donnees, son procede de fabrication et bain de revelateur utilise dans ce procede
FR2480475A1 (fr) * 1980-04-14 1981-10-16 Drexler Tech Milieu reflechissant a large bande pour l'enregistrement par laser et la memorisation de donnees, comportant une sous-couche absorbante, et son procede de fabrication
US4379828A (en) * 1980-05-16 1983-04-12 Agfa-Gevaert Aktiengesellschaft Image receptor element for the dye diffusion transfer process
FR2484119A1 (fr) * 1980-06-04 1981-12-11 Drexler Tech Procede de reproduction photographique d'informations de milieux optiques de memorisation de donnees, et milieu ainsi reproduit
US5200296A (en) * 1987-05-14 1993-04-06 Mitsubishi Paper Mills Limited Image receiving material for silver complex diffusion transfer process

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NL122438C (en:Method)
CH417328A (fr) 1966-07-15
NL258744A (en:Method)
GB893652A (en) 1962-04-11
DE1113630B (de) 1961-09-07

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