US2789054A - Print-receiving elements for diffusion transfer reversal processes and film assemblies embodying said elements - Google Patents

Print-receiving elements for diffusion transfer reversal processes and film assemblies embodying said elements Download PDF

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Publication number
US2789054A
US2789054A US401022A US40102253A US2789054A US 2789054 A US2789054 A US 2789054A US 401022 A US401022 A US 401022A US 40102253 A US40102253 A US 40102253A US 2789054 A US2789054 A US 2789054A
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United States
Prior art keywords
print
stratum
elements
receiving
silver
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Expired - Lifetime
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US401022A
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English (en)
Inventor
Edwin H Land
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Polaroid Corp
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Polaroid Corp
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Publication date
Priority to BE534464D priority Critical patent/BE534464A/xx
Application filed by Polaroid Corp filed Critical Polaroid Corp
Priority to US401022A priority patent/US2789054A/en
Priority to GB36564/54A priority patent/GB755412A/en
Priority to FR1117780D priority patent/FR1117780A/fr
Priority to DEI9579A priority patent/DE960607C/de
Application granted granted Critical
Publication of US2789054A publication Critical patent/US2789054A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42—Structural details
    • G03C8/52—Bases or auxiliary layers; Substances therefor

Definitions

  • This invention relates to photographic products and more particularly to print-receiving elements useful in silver diffusion transfer reversal processes and to film structures embodying such elements.
  • Transfer processes involving the development of a latent image in a silver halide emulsion and the transfer ofcomponents from said emulsion to another layer to effect the formation of a print of said latent image in saidother layer,- are now well known.
  • a species of this type of processing involves the transfer by diffusion of silver from the silver halide emulsion in the form of a soluble silver complex and the reduction of the silver of the complex in or on a suitable print-receiving element. Certain of these processes have been disclosed in my Patent No. 2,543,l8l,issued February 27, 1951 for Photographic Product Comprising a Rupturable Container Carrying a Photographic Processing Liquid, and my Patent No. 2,647,056, issued July 28, 1953 for One Step Photographic Transfer Process.
  • Prints of superior pictorial quality have been obtained by using aistiving element equipped with a print-receiving stratum which is relatively thin and which comprises an inert matrix, preferably of colloidal particles of a siliceous material, and a silver precipitating agent distributed throughout said matrix.
  • Such print-receiving elements preferably comprise a relatively water-impervious subcoat for the silver precipitating stratum and examples of this type 'of reception material have been described in my copending application Serial No. 234,622, filed June 30, 1951 for Photographic Silver Halide Transfer Process and the Print-Receiving Products Useful in Connection Therewith.
  • the invention accordingly comprises the product possessing the features, properties and the relation of components which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • Figure l is a diagrammatic, enlarged, sectional View illustrating one type of print-receiving element embodying the present invention, the thicknesses of some of the layers of the print-receiving element being exaggerated and not necessarily in correct relative proportion, and
  • Fig. 2 is a similar view of a composite film unit or assembly embodying a print-receiving element of the foregoing type.
  • the print-receiving elements of the present invention are particularly useful in processes of the type wherein a positive print is obtained in a single step by suitably treating a silver halide emulsion containing a latent image with a uniformly applied layer of processing liquid.
  • the processing liquid is preferably in a viscous condition and is spread in a relatively thin layer between the photo-sensitive element comprising the silver halide emulsion and the print-receiving element.
  • the latter preferably comprises a support and a print-receiving stratum and said stratum, as noted above, includes a suitable silver precipitating layer which may constitute all or just a part of said stratum.
  • the said stratum is separated from the support of the print-receiving element by a subcoat that is water impervious and which possesses other novel properties to be more fully described hereinafter.
  • the Water impermeability of the subcoat is sufficient to prevent any substantial penetration of the liquid processing agent beyond the print-receiving stratum during the performance of the transfer process.
  • the process for forming the positive print takes less than five minutes for completion, and more usually only about 1 minute.
  • water mpermeable pertains to an impermeability to water of :his order and that said subcoat is not necessarily impervious to water vapor.
  • the print-receiving stratum of the print-receiving element is permeated to any appreciable extent by the ionic reagents contained in the liquid processing composition.
  • the outer surface of the print-receiving stratum which contacts the layer of processing composition is preferably so constituted as to have a lesser adhesion for the solid residue of the liquid processing composition than does the photosensitive element.
  • the entire print-receiving stratum may be essentially formed of a material having this desired stripping property.
  • a thin film of a suitable stripping composition may constitute the outer surface portion of the print-receiving stratum while the remainder of said print-receiving stratum is formed of another material more suitable for carrying the silver precipitating agents which are dispersed throughout a part at least of the thickness of said stratum.
  • These agents function to improve the amount and character of silver precipitated during image formation.
  • agents such materials as, for example, the metallic sulfides and selenides, the thiooxalates, the thioacetamides, and certain colloidal metals such as colloidal silver, gold, and mercury have been proposed.
  • the precipitation and aggregation of silver obtained by using the silver precipitating agents including the above-mentioned materials are very greatly improved by providing in the print-receiving stratum as a vehicle for said agents a macroscopically continuous matrix consisting essentially of submacroscopic agglomerates of particles of a water-insoluble, inorganic, chemically inert, adsorbent substance.
  • the term subrnacroscopic is herein intended to include, Within its scope, sizes generally known as submicroscopic.
  • This matrix material preferably has a low coefficient of absorption for light as compared to silver, and the matrix formed therefrom is essentially free of protective colloid action for silver.
  • a layer of silica such as is formed by drying a liquid dispersion of silica aerogel available under the trade name Santocel C.
  • the subcoat for this print-receiving stratum which includes the silver precipitating layer is preferably formed of a plurality of mate- K rials which together impart to said subcoat not only said desired water impermeability but also perform the novel function of excluding from the print-receiving stratum any oils, plasticizers, or other liquids which may originate on the underside of the print-receiving element.
  • the presence of plasticizers in a position to reach the print-receiving stratum is not in itself necessarily detrimental, provided the plasticizer is incapable of penetrating entirely through the underside of the silver precipitating layer.
  • This condition is achieved in one form of the present invention by providing as the subcoat a pair of layers of plastic, one of which is so constituted as to be incompatible and impermeable to many of the plasticizers, which can penetrate the other plastic.
  • the latter plastic is so constituted as to be substantially impenetrable to many of the plasticizers which might permeate the first plastic.
  • a novel print-receiving element 19 comprehended by the present invention.
  • said element comprises a support 12,.a novel subcoat 14 and a print-receiving stratum 16.
  • Support 12 may be formed with any suitable sheet material satisfactory for serving as a base for a photographic print. It may be, for example, an uncoated or coated paper or a film of plastic such as a 4 cellulosic ester.
  • baryta pape which comprises a relatively inert and pure alpha paper having coated on the surface thereof a thin film comprising a mixture of gelatin and barium sulfate.
  • Print-receiving stratum 16 preferably comprises a silver precipitating layer having the preferred structure noted above, namely, a matrix or vehicle comprising particles of a Water-insoluble, inorganic, chemically inert, adsorbent substance such as silica, said matrix having dispersed therethrough a silver precipitating agent such as a metallic sulfide, a metallic selenide, a thiooxalate, a thioacetarnide, colloidal silver, colloidal gold, colloidal mercury or mixtures thereof.
  • a silver precipitating layer having the preferred structure noted above, namely, a matrix or vehicle comprising particles of a Water-insoluble, inorganic, chemically inert, adsorbent substance such as silica, said matrix having dispersed therethrough a silver precipitating agent such as a metallic sulfide, a metallic selenide, a thiooxalate, a thioacetarnide, colloidal silver, colloidal gold, colloidal mercury or
  • This silver precipitating layer is preferably coated directly on subcoat 14 and may have one or more over-coats applied thereto. As disclosed in the aforesaid copending application Serial No. 234,622, there may be' applied to the silver precipitating layer an abrasion-resistant coating and, on top of this, a stripping layer.
  • novel subcoat 14 preferably comprises two superposed films 14a and 141; formed of dif ferent high molecular weight polymers, i. e., plastics.
  • layer 14a nearest the support has a thickness of the order of .0004 inch and is formed of a cellulosic ester, such as cellulose acetate, which is free of plasticizer.
  • Film 14b is preferably a polyvinyl acetal such as polyvinyl butyral or an acrylic resin such as Acryloid and in a preferred form has a thickness of the order .00015 inch.
  • the plastic of film 14b may contain a plasticizer such as dioctyl phthalate, the methyl ester of resin sold as Abalyn, the hydrogenated rosin sold as Abytal, or the hydrogenated methyl ester of rosin sold as Hercolyn, the latter being types of plasticizers which are incompatible with cellulose acetate and therefore not capable of permeating through film 14a.
  • a suitable solvent for cellulose acetate such as a mixture of ethyl acetate and ethanol in an approximate ratio of 8 parts to 2 parts by weight, may be used.
  • a suitable solvent for the plastic a material in which the plastic of layer 14a is insoluble.
  • layer 14a is cellulose acetate, a mixture of isopropyl acetate and methanol in the approximate ratio of 3 parts to 1 part by weight satisfies these requirements for polyvinyl butyral.
  • the novel print-receiving element may comprise a part of a composite film unit.
  • a simplified and somewhat diagrammatic illustration of such film unit is shown in Fig. 2 as comprising a photosensitive element 18 which includes a fihn support or base layer 22 carrying on one surface thereof a silver halide photosensitive emulsion 20.
  • Print-receiving element 10 is superposed on said photosensitive emulsion and there is positioned between said photosensitive layer and said print-receiving element a container 24 which carries a liquid processing composition and is capable of discharging its liquid content in a thin uniform layer between said print-receiving element and said photosensitive emulsion.
  • container 24 Preferably, there is included in container 24 a viscous, aqueous, alkaline solution of a silver halide developer and a silver halide solvent.
  • the support 22 for the photosensitive emulsion 20 may be transparent so that the exposure can take place through said support, in which case the photosensitive layer and the print-receiving element may be intheir superposed relation during this exposure.
  • Support 22 may also be opaque, in which case the photosensitive element is hingedly or otherwise secured to thetreuceiving element so that it may be separated from the latterto permit exposure from the photosensitive layer side of the element.
  • Element 18 is thereafter super" posed on the print-receiving element as shown in Fig. 2 to efiect the processing.
  • Other film assemblies of which the novel print-receiving element may constitute a part are shown and described in my aforementioned Patent No. 2,543,181 and my Patent No. 2,579,587, issued on December 25, 1951 for Photographic Product Containing a Rupturable Container.
  • a photographic film assembly capable of performing a ditfusion transfer reversal process and comprising a photosensitive element including a silver halide layer, a print-receiving element and a container carrying a processing liquid, said elements and said container being operatively secured together so that said container is capable of releasing its liquid content to permeate superposed portions of said elements, said print-receiving element comprising a support and a permeable35ceiving stratum, the combination with said support and said stratum of a subcoat located therebetween, said subcoat comprising two superposed films of plastic, one of said films being from the class consisting of the polyvinyl acetals and the polyacrylics, and the other of said films being a cellulosic ester.
  • a photographic print-receiving element for having positive prints formed thereon by means of silver transfer from a photosensitive silver halide emulsion, said print-receiving element being essentially nonphotosensitive and comprising a support, a subcoat and a thin print-receiving stratum, said print-receiving stratum comprising a silver precipitating layer coated directly on said subcoat, said silver precipitating layer being a macroscopically continuous film and consisting essentially of submacroscopic agglomerates of inert particles of a water-insoluble, inorganic substance among which a colloidal silver precipitating agent is dispersed, said particles being particles of silica, said subcoat being between said print-receiving stratum and said support and comprising two superposed films of plastic, one of said films being from the class consisting of the polyvinyl acetals and the polyacrylics, and the other of said films being a cellulosic ester.
  • a photographic print-receiving element for having positive prints formed thereon by means of silver transfer from a photosensitive silver halide emulsion, said print-receiving element being essentially nonphotosensitive and comprising a support, a subcoat and a thin print-receiving stratum, said print-receiving stratum comprising a silver precipitating layer coated directly on said subcoat, said silver precipitating layer being a macroscopically continuous film and consisting essentially of submacroscopic agglomerates of inert particles of a water-insoluble, inorganic substance among which a colloidal silver precipitating agent is dispersed, said subcoat being between said print-receiving stratum and said support and comprising two superposed films of plastic, one of said films being from the class consisting of the polyvinyl acetals and the polyacrylics, and the other of said films being a cellulosic ester.

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US401022A 1953-12-29 1953-12-29 Print-receiving elements for diffusion transfer reversal processes and film assemblies embodying said elements Expired - Lifetime US2789054A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE534464D BE534464A (fr) 1953-12-29
US401022A US2789054A (en) 1953-12-29 1953-12-29 Print-receiving elements for diffusion transfer reversal processes and film assemblies embodying said elements
GB36564/54A GB755412A (en) 1953-12-29 1954-12-17 Improvements in or relating to transfer reversal photography
FR1117780D FR1117780A (fr) 1953-12-29 1954-12-27 Perfectionnements relatifs à la photographie
DEI9579A DE960607C (de) 1953-12-29 1954-12-28 Bildaufnahmematerial fuer Silbersalz-Diffusionsverfahren

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US401022A US2789054A (en) 1953-12-29 1953-12-29 Print-receiving elements for diffusion transfer reversal processes and film assemblies embodying said elements

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BE (1) BE534464A (fr)
DE (1) DE960607C (fr)
FR (1) FR1117780A (fr)
GB (1) GB755412A (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2966103A (en) * 1958-10-21 1960-12-27 Polaroid Corp Photographic apparatus for treating photosensitive material
US2973262A (en) * 1956-06-22 1961-02-28 Gevaert Photo Prod Nv Light-sensitive photographic paper
US3234022A (en) * 1960-08-08 1966-02-08 Polaroid Corp Diffusion-transfer reversal processes and elements useful in such processes
US3326712A (en) * 1964-01-20 1967-06-20 Mead Corp Transfer print receiving paper and method of producing same
US3547641A (en) * 1966-06-20 1970-12-15 Du Pont Planographic offset printing masters
US3753764A (en) * 1970-11-19 1973-08-21 Eastman Kodak Co Photographic diffusion transfer product and process

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL59365C (fr) * 1939-11-02
US2216736A (en) * 1938-09-27 1940-10-08 Du Pont Photographic film
GB546559A (en) * 1941-01-13 1942-07-20 Eastman Kodak Co Improvements in photographic materials
US2360216A (en) * 1943-06-08 1944-10-10 Eastman Kodak Co Subbing photographic paper supports
US2366723A (en) * 1941-02-13 1945-01-09 Eastman Kodak Co Baryta coating of melt-coated paper
GB568782A (en) * 1943-10-15 1945-04-19 Ronald James Cox Improvements in or relating to photographic materials
US2415631A (en) * 1945-03-30 1947-02-11 Eastman Kodak Co Photographic paper
US2433515A (en) * 1945-04-18 1947-12-30 H P Andrews Paper Company Method of making photographic paper
US2462151A (en) * 1946-09-23 1949-02-22 Du Pont Photographic elements having hydrophilic polyvinyl acetal colloid sublayers
US2513189A (en) * 1947-01-18 1950-06-27 Du Pont Preparation of polyvinyl acetals
US2543181A (en) * 1947-01-15 1951-02-27 Polaroid Corp Photographic product comprising a rupturable container carrying a photographic processing liquid
US2606832A (en) * 1946-11-27 1952-08-12 Du Pont Photographic elements having an anchoring substratum composed of a water-insoluble vinylpyridine polymer
GB687751A (en) * 1950-01-13 1953-02-18 Bayer Ag Process and material for the direct production of positive photographic images

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2216736A (en) * 1938-09-27 1940-10-08 Du Pont Photographic film
NL59365C (fr) * 1939-11-02
GB546559A (en) * 1941-01-13 1942-07-20 Eastman Kodak Co Improvements in photographic materials
US2366723A (en) * 1941-02-13 1945-01-09 Eastman Kodak Co Baryta coating of melt-coated paper
US2360216A (en) * 1943-06-08 1944-10-10 Eastman Kodak Co Subbing photographic paper supports
GB568782A (en) * 1943-10-15 1945-04-19 Ronald James Cox Improvements in or relating to photographic materials
US2415631A (en) * 1945-03-30 1947-02-11 Eastman Kodak Co Photographic paper
US2433515A (en) * 1945-04-18 1947-12-30 H P Andrews Paper Company Method of making photographic paper
US2462151A (en) * 1946-09-23 1949-02-22 Du Pont Photographic elements having hydrophilic polyvinyl acetal colloid sublayers
US2606832A (en) * 1946-11-27 1952-08-12 Du Pont Photographic elements having an anchoring substratum composed of a water-insoluble vinylpyridine polymer
US2543181A (en) * 1947-01-15 1951-02-27 Polaroid Corp Photographic product comprising a rupturable container carrying a photographic processing liquid
US2513189A (en) * 1947-01-18 1950-06-27 Du Pont Preparation of polyvinyl acetals
GB687751A (en) * 1950-01-13 1953-02-18 Bayer Ag Process and material for the direct production of positive photographic images

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2973262A (en) * 1956-06-22 1961-02-28 Gevaert Photo Prod Nv Light-sensitive photographic paper
US2966103A (en) * 1958-10-21 1960-12-27 Polaroid Corp Photographic apparatus for treating photosensitive material
US3234022A (en) * 1960-08-08 1966-02-08 Polaroid Corp Diffusion-transfer reversal processes and elements useful in such processes
US3326712A (en) * 1964-01-20 1967-06-20 Mead Corp Transfer print receiving paper and method of producing same
US3547641A (en) * 1966-06-20 1970-12-15 Du Pont Planographic offset printing masters
US3753764A (en) * 1970-11-19 1973-08-21 Eastman Kodak Co Photographic diffusion transfer product and process

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FR1117780A (fr) 1956-05-28
DE960607C (de) 1957-03-21
GB755412A (en) 1956-08-22
BE534464A (fr)

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