Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
  • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
  • G03C8/12—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors characterised by the releasing mechanism
  • G03C8/14—Oxidation of the chromogenic substances
  • G03C8/16—Oxidation of the chromogenic substances initially diffusible in alkaline environment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
  • C09B31/02—Disazo dyes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
  • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
  • G03C8/12—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors characterised by the releasing mechanism
  • G03C8/14—Oxidation of the chromogenic substances
  • G03C8/16—Oxidation of the chromogenic substances initially diffusible in alkaline environment
  • G03C8/18—Dye developers

Definitions

• This invention relates to photography and, more particular y, to improvements in photographic diffusiontransfer reversal processes for obtaining color images.
• a principal object of the present invention is to provide novel processes wherein developing agents capable of developing a latent image and imparting a reversed or positive colored image of said latent image to a superposed image-receiving material are stabilized subsequent to formation of said positive colored image.
• Another object is to provide novel processes suitable for use in preparing stabilized monochromatic and multichromatic photographic images.
• a still further object is to increase the stability of positive diffusion-transfer colored images against the deleterious effects of humidity and/ or temperature variations.
• a still further object is to stabilize transferred d e in a diffusion-transfer image-receiving element by complexing said dye with an appropriate metal.
• the invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each of the others, and the products possessing the features, properties and the re ation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
• the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, thereby providing an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition.
• This immobilization is apparently, at least in part, due to a change in the solubility characteristics of the dye developer upon oxidation, and especially as regards its solubility in alkaline solutions. It may also be due, in part, to a tanning effect on the emulsion by the oxidized developing agent.
• At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer or element, said transfer substantially excluding silver or oxidized dye developer.
• the latter element receives a depthwise diffusion, from the emulsion, of unoxidized mobile dye developer Without appreciably disturbing the imagewise distribution thereof to provide a reversed or positive, colored image of the developed image.
• this pH may be adjusted in accordance with well-known techniques to provide a pH affording the desired color. Imbibition periods of approximately one minute have been found to give good results, but this contact period may be adjusted where necessary to compensate for variations in temperature or other conditions.
• the desired, positive image is revealed by stripping the image-receiving element from the photo-- sensitive element at the end of the imbibition period.
• the aforementioned dye developers may be utilized in the photosensitive e ement, for example in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element or in the liquid processing composition.
• a coating or layer of the dye developer is placed behind the silver halide emulsion, i.e.,'on the side of the emulsion adaptedto be located most distant from the photographedsubject when th emulsion is exposed and preferably also adapted to be most distant from the image-receiving elementwhen in superposed relationship therewith. Placing the dye liquid processing composition and bringing said emulsion layer into superposed relationship image-receiving layer.
• a photosensitive element containing a silver halide emulsion is exposed and wetted with a liquid processing composition, for example, by immersing, coating, spraying, flowing, etc., in the dark, and the photosensitive element superposed, prior to, during or after wetting, on a sheetlike support element, which may be utilized as an image-receiving element.
• sensitive element contains a layer of dye developer, and the liquid processing composition is applied to the photosensitive element in a uniform layer as the photosensitive element is brought into superposed position with an image-receiving element. It is also within the scope of this invention to apply the liquid processing composition prior to exposure, in accordance with the disclosure in the copending application of Edwin H. Land, Serial No.
• the liquid processing comwith an appropriate developer behind the emulsion layer has the advantage of providing increased contrast in the positive image, and also minimizes any" light-filtering action by the colored dye developer.
• the layer of dye developer may be applied by using a coating solution containing about 0.5 to 8%, by weight, of the dye developer. Simi-' lar concentrations may be used if the dye developer is utilized as a component of the liquid processing corn position, concentrations as low as 0.2% in the liquid processing composition being suitable in certain instances.
• the liquid processing composition above referred to comprises at least an aqueous solution of an alkaline compound, for example, diethylamine, sodium hydroxide or sodium carbonate, and may contain the dye developer. In some instances, it may contain a minor amount of'a conventional developing agent. If the liquid processing composition is to be applied to the emulsion by being spread thereon, preferably in a relatively thin, uniform layer, it may also include a viscosity-increasing compound constituting the film-forming material of the type which, when said composition is spread and dried, will form a relatively firm and relatively stable film.
• an alkaline compound for example, diethylamine, sodium hydroxide or sodium carbonate
• a preferred film-forming material is a high molecular weight polymer such as a polymeric, water-soluble ether inert to an alkali solution, as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.
• Other film-forming materials or thickening agents whose ability to increase viscosity is substantially unaffected when left in solution for a long period of time may also be usedf
• certain dyes i.e., monoand disazo dyes which contain hydroxyl or carboxyl radicals, substituted on aryl nuclei in positions ortho and ortho' to at least one azo group, preferably those azo dyes which comprise dye developers, i.e., dyes which possess a silver halide developing function, have unique properties in that said dyes may be stabilized against the color degradation effects or" actinic radiation, humidity and/or temperature variations by appropriate metallization, i.e., metal complexing said dyes with a copper, nickel or cobalt ion, subsequent to transfer of mobile
• the aforementioned complexing may be accomplished as a result of contacting the appropriate dye with a nickel, copper or cobalt salt and/or an appropriate nickel or copper chelate, for example, a nitrate, suliiate, oxalate, etc., salt and/or a chelate of the formula:
• enolizable B-diketone such as acetylacetone
• an enolizable S-keto ester such as ethyl acetoacetate
• the metallic salt and/or chelate may be dis- .persed within and/or disposed in a separate layer superposed on the respective image-receiving elements such that transferred dye contacts said metallic salt and/or chelate on and/or Within said receiving layer to form the desired complex thereon and/ or therein.
• the metallic salt and/or chelate may also be disposed in an appropriate processing solution, for example where desirable, the image-receiving element may be contacted with a solution of the metallic salt and/or chelate subsequent to formation of the desired image as well as subsequent to displacement of the image-receiving element from its superposed relation to a photosensitive negative element.
• process utilized may comprise in whole or in part one or more of the previously enumerated procedures to suit the requirements of the operator.
• a preferred procedure has been determined to be that of dispersing an appropriate metal chelate within the image-receiving element.
• the concepts herein disclosed are applicable to diffusion-transfer processes wherein the formation of an imagewise distribution of dye components is controlled by the concentration of alkali present, as for example, the alkali exhaustion transfer processes disclosed in the copending US. application of Edwin H. Land, Serial No. 640,821, filed February 18, 1957.
• the aforementioned concepts are also applicable to processes wherein the transfer of the dye is controlled by a physically and/or chemically induced matrix obstruction as, for example, by differential tanning or hardening of a dye carrier and/or light-sensitive stratum, such as employed in im-' bibition dyeing processes.
• Example 1 Monochrome photographic prints may be prepared according to the following procedure.
• a photosensitive element is prepared by coating 2. gelatin-coated film base with a solution containing 4% of 2-hydroxynaphthalenazo-hydroquinone, which is disclosed in the copending US. application of Elkan R. Blout, Saul G. Cohen, Milton Green, and Myron S. Simon, Serial No. 755,804, filed August 18, 1958, a continuationin-part of application Serial No. 450,208, filed August 16, 1954 (now abandoned), in a 4% solution of cellulose acetate hydrogen phthalate in a 50:50 mixture, by volume, of acetone and tetrahydrofuran. After this coating has dried, a silver iodobromide emulsion is applied. This photosensitive element is exposed and processed by spreading an aqueous liquid processing composition comprising:
• the image-receiving element comprises a cellulose acetate-coated baryta paper which has been coated with a solution comprising 10% Nylon Type F8 (trade name of E. I. du Pont de Nemours & Co., Wilmington, Delaware, for N-methoxymethyl polyhexamethylene adipamide) in aqueous isopropanol. After an imbibition period of approximately one minute, the image-receiving element is separated and contains a magenta dye image of the photographed subject.
• Nylon Type F8 trade name of E. I. du Pont de Nemours & Co.
• Example 2 A monochrome print prepared according to the procedure stated in Example 1 is exposed to a 275 watt sunlamp at a distance of ca. 20 inches for 72 hours.
• Densimetric measurement of the accelerating fading test on the dye image showed a loss of density, e.g., from a density of 2.30 to a density of 1.05.
• Example 3 A monochrome print is prepared according to the procedure stated in Example 1.
• the resultant print containing a magenta dye image of the photographed subject, is swabbed with an approximately 0.5% solution of bis-(acetylacetono) copper (II) in a 50:50 solution, by volume, of water and methanol and exposed to heat and actinic radiation according to the procedure disclosed in Example 2.
• the copper-complexed dye image exhibits substantially no degradation due to the heat and actinic radiation of the aforementioned procedure.
• the resultant print containing the complexed dye image of the photographed subject, exhibits an initial density substantially equivalent to the noncomplexed dye images of Example 1 and is exposed to heat and actinic radiation according to the procedure disclosed in Example 2.
• the copper-complexed dye image exhibits substantially no degradation due to the heat and actinic radiation of the aforementioned procedure.
• a photosensitive element is prepared according to the procedure stated in Example 1. This photosensitive element is exposed and processed by spreading the liquid processing composition of Example 1 between said photosensitive element and an image-receiving element as said elements are brought into superposed relationship.
• the image-receiving element comprises a cellulose acetatecoated baryta paper which has been coated with a solution comprising approximately 0.5% of bis-(ethylacetoacetato) copper (II) and 4% Nylon Type F8 in 80% aqueous isopropanol. After an imbibition period of approximately one minute, the image-receiving element is separated and contains a copper-complexed reversed positive dye image of the photographed subject.
• a photosensitive element is prepared by coating a gelatin-coated film base with a solution containing 4% of l- (4' [,8-(hydroquinonyl)-ethyl]-2'-hydroxy-phenylazo)-2- naphthol, which is disclosed in the copending US. application of Milton Green and Myron S. Simon, Serial No. 788,893, filed concurrently herewith, in a 4% solution of cellulose acetate hydrogen phthalate in a 50:50 mixture, by volume, of acetone and tetrahydrofuran. After this coating has dried, a silver iodobromide emulsion is applied. This photosenstive emulsion is exposed and processed according to the procedure of Example 1. After an imbibition period of approximately one minute, the image-receiving element is separated and contains an orange-red dye image of the photographed subject.
• the copper-complexed dye image exhibits substantially no degradation due to the heat and actinic radiation of the aforementioned procedure.
• the resultant print containing a magenta dye image of the photographed subject, is swabbed with an approximately 0.5 solution of bis-(trifluoroacetylacetono) copper (II) in a 50:50 solution, by volume, of water and methanol and exposed to heat and act nic radiation according to the procedure disclosed in Example 2.
• Example 11 A monochrome print is prepared according to the following procedure. 7
• a photosensitive element is prepared according to the procedure stated in Example 1. This photosensitive element is exposed and processed by spreading the liquid processing composition of Example 1 between said photo sensitive element and an image-receiving element as said elements are brought into superposed relationship.
• the image-receiving element comprises a cellulose acetatecoated baryta paper which has been coated with a solution comprising approximately 0.5% of bis-(trifiuoroacetyl acetono) copper (II) and 4% Nylon Type F8 in 80% aqueous isopropanol. After an imbibition period of approximately one minute, the image-receiving element is separated and contains a copper-complexed reversed positive purple dye image of the photographed subject.
• the resultant print containing the complexed dye image of the photographed subject, exhibits an initial density substantially equivalent to the noncomplexed dye images of Example 1 and is exposed to heat and actinic radiation according to the procedure disclosed in Example 2.
• the copper-complexed dye image exhibits substantially no degradation due to the heat and actinic radiation of the aforementioned procedure.
• Example 12 A monochrome print is prepared according to the procedure stated in Example 1.
• the resultant print containing a magenta dye image of the photographed subject, is swabbed with an approximately 0.5% solution of bis-(salicylaldoximo) copper (II) in a water-methanol solvent and exposed to heat and actinic radiation according to the procedure disclosed in Example 2.
• the copper-complexed dye image exhibits increased stability against the degradation eifects of exposure to the heat and actinic radiation of the aforementioned procedure.
• Example 13 A monochrome print is prepared according to the following procedure.
• a photosensitive element is prepared according to the procedure stated in Example 1. This photosensitive element is exposed and processed by spreading the liquid processing composition of Example 1 between said photosensitive element and an image-receiving element as said elements are brought into superposed relationship.
• the image-receiving element comprises a cellulose acetatecoated baryta paper which has been coated with a solution comprising approximately 0.5% of bis-(salicylaldoximo) copper (II) and 4% Nylon Type F8 in 80% aqueous isopropanol. After an imbibition period of approximately one minute, the image-receiving element is separated and contains a copper-complexed reversed positive dye image of the photographed subject.
• the resultant print containing the complexed dye image of the photographed subject, exhibits increased stability against the degradation effects of exposure to the heat and actinic radiation of the accelerated aging test procedure disclosed in Example 2.
• Example 14 A monochrome print is prepared according to the procedure stated in Example 1.
• the resultant print containing a magenta dye image of the photographed subject, is swabbed with an approximately 0.5% solution of bis-(ethylacetoacetato) nickel (II) in a water-methanol solvent and exposed to heat and actinic radiation according to the procedure disclosed in Example 2.
• the nickel-complexed dye image exhibits increased stability against the degradation effects of exposure to the heat and actinic radiation of the aforementioned procedure.
• Example 15 A monochrome print is prepared according to the following procedure.
• a photosensitive element is prepared according to the procedure stated in Example 1. This photosensitive element is exposed and processed by spreading the liquid processing composition of Example 1 between said photosensitive element and an image-receiving element as said elements are brought into superposed relationship.
• image-receiving element comprises a cellulose acetatecoated baryta paper which has been coated with a solution comprising approximately 0.5% of bis(ethylacetoacetato) nickel (II) and 4% Nylon Type F8 in aqueous isopropanol. After an imbibition period of approximately one minute, the image-receiving element is separated and contains a copper-complexed reversed positive dye image of the photographed subject.
• Example 16 A monochrome print is prepared according to the procedure stated in Example 1.
• Example 17 A monochrome print is prepared according to the following procedure.
• a photosensitive element is prepared according to the procedure stated in Example 1. This photosensitive element is exposed and processed by spreading the liquid processing composition of Example 1 between said photosensitive element and an image-receiving element as said elements are brought into superposed relationship.
• the image-receiving element comprises a cellulose acetatecoated baryta paper which has been coated with a solution comprising approximately 0.5 of bis-(acetylacetono) nickel (II) and 4% Nylon Type F8 in 80% aqueous isopropanol. After an imbibition period of approximately one minute, the image-receiving element is separated and contains a copper-complexed reversed positive dye image of the photographed subject.
• the resultant print containing the complexed dye image of the photographed subject, exhibits increased stability against the degradation effects of exposure to the heat and actinic radiation of the accelerated aging test procedure disclosed in Example 2.
• Example 18 Monochrome photographic prints may be prepared according to the following procedure.
• the image-receiving element is separated and contains an orange-red dye image of the photographed subject.
• a photosensitive element is prepared according to the procedure stated in Example 18. This photosensitive element is exposed and pnocessed by spreading the liquid processing composition of Example 18 between said photosensitive element and an image-receiving element as said elements are brought into superposed relationship.
• the image-receiving element comprises a cellulose acetatecoated baryta paper which has been coated with a solution comprising approximately 0.5% bis-(acetylaceton-o) copper (II) and 4% Nylon Type F8 in 80% aqueous isopropanol. After an imbibition period of approximately one minute, the image-receiving element is separated and contains a copper-complexed magenta dye image of the photographed subject.
• the resultant print containing the complexed dye image, exhibits increased stability against the degradation eifects of exposure to ithe heat and actinic radiation of the accelerated aging test procedure disclosed in Example 2.
• metalcomplexed dye image comprises a nickel-complexed 2- hydroxynaphthaleneazohydroquinone image.
• a photographic product for receiving a color image which comprises an image-receiving element comprising a support, a dye-receiving layer on said support, and at least one chelate in a layer on the same side of said support as said dye-receiving layer, said chelate being of the formula:
• a photographic product as defined in claim 14 wherein said chelate comprises an enolizable /3-diketone copper chelate.
• a photographic product as defined in claim 14 wherein said chelate comprises bis-(acetylacetono) copper (II).
• a photographic product as defined in claim 14 wherein said chelate comprises bis-(ethylacetoacetato) copper (II).
• a photographic product as defined in claim 14 wherein said chelate comprises bis-(trifiuoroacetylacetone) copper (II).
• a photographic product as defined in claim 14 wherein said chelate comprises bis- (salicylaldoximo) copper (II).
• a photographic product as defined in claim 14 wherein said chelate comprises bis-(ethylacetoacetato) nickel (II).
• a photographic product as defined in claim 14 wherein said chelate comprises bis-(acetylacetono) nickel (II).
• said dye comprises a dye developer, said dye developer being a compound which is both a dye and a silver halide developing agent, said dye developer further being selected from the group consisting of monoand disazo dye dcvelopers substituted at positions ortho and ortho to an azo linkage with a group selected from the group consisting of hydroxyl and carboxyl groups.
• the step which comprises contacting, subsequent to transfer image formation, an image dye possessing at least one metallizable group, with a chelate exhibiting less intermolecular bonding stability than the metal image dye complex ultimately formed, complexing thereby at least part of said image dye to impart to an image-receiving element a dye image, at least in part metal-complexed, of the photographed subject.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Color Printing (AREA)

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• 0
  • NL NL247649D patent/NL247649A/xx unknown
  • NL NL247650D patent/NL247650A/xx unknown
• 1959
  • 1959-01-26 US US788743A patent/US3081167A/en not_active Expired - Lifetime
  • 1959-01-26 US US788742A patent/US3196014A/en not_active Expired - Lifetime
• 1960
  • 1960-01-06 GB GB532/60A patent/GB905701A/en not_active Expired
  • 1960-01-22 DE DEJ17574A patent/DE1111938B/de active Pending
  • 1960-01-22 DE DEJ17575A patent/DE1116532B/de active Pending
  • 1960-01-25 FR FR816593A patent/FR1248727A/fr not_active Expired
  • 1960-01-25 FR FR816592A patent/FR1248726A/fr not_active Expired
  • 1960-01-26 CH CH72860A patent/CH429443A/fr unknown

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