US3230084A - Novel photographic products and processes - Google Patents

Novel photographic products and processes Download PDF

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US3230084A
US3230084A US813701A US81370159A US3230084A US 3230084 A US3230084 A US 3230084A US 813701 A US813701 A US 813701A US 81370159 A US81370159 A US 81370159A US 3230084 A US3230084 A US 3230084A
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dye
serial
filed
image
photosensitive element
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Myron S Simon
Stanley H Mervis
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Polaroid Corp
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Polaroid Corp
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    • 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
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/18—Preparation of azo dyes from other azo compounds by acylation of hydroxyl group or of mercapto group
    • 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
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
    • C09B1/28—Dyes with amino groups substituted by hydrocarbon radicals substituted by alkyl, aralkyl or cyclo alkyl groups
    • C09B1/285—Dyes with no other substituents than the amino groups
    • 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
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
    • C09B1/51—N-substituted amino-hydroxy anthraquinone
    • C09B1/515—N-alkyl, N-aralkyl or N-cycloalkyl derivatives
    • C09B1/5155—N-alkyl, N-aralkyl or N-cycloalkyl derivatives only amino and hydroxy groups
    • 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
    • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
    • C09B33/02—Disazo dyes
    • C09B33/06—Disazo dyes in which the coupling component is a diamine or polyamine
    • 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
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/24—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position
    • C09B5/2409—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position not provided for in one of the sub groups C09B5/26 - C09B5/62
    • C09B5/2436—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position not provided for in one of the sub groups C09B5/26 - C09B5/62 only nitrogen-containing hetero rings
    • C09B5/2445—Phtaloyl isoindoles
    • C09B5/2454—5,6 phtaloyl dihydro isoindoles
    • C09B5/2463—1,3 oxo or imino derivatives
    • C09B5/2472—1,3 dioxo derivatives
    • 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
    • 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
    • Y10S430/156—Precursor compound

Definitions

  • This invention relates to photography and more particularly to products and processes for the development of photosensitive silver halide elements.
  • a further object of the present invention is to provide novel photographic processes and products for obtaining color images by a diffusion-transfer process wherein a dye developer is initially present in the form of a hydrolyzable derivative of said dye developer and wherein said hydrolyzable derivative is subjected to hydrolysis during processing.
  • a still further object of the present invention is to provide novel photographic processes and products wherein a hydrolyzable derivative of a dye developer is employed and said derivative is of relatively low mobility until hydrolysis occurs.
  • a still further object of the present invention is to provide photographic processes and products wherein hydrolyzable derivatives of dye developers are employed, said derivatives being initially nonreactive with an associated photosensitive silver halide emulsion and rendered reactive by hydrolysis occurring during processing.
  • a still further object of the present invention is to provide photographic processes and products for use in monochromatic and multicolor diffusion-transfer processes utilizing hydrolyzable derivatives of dye developers, which derivatives contain groups removable during photographic processing, to provide thereby improved color rendition.
  • a still further object of the present invention is to provide novel processes for the development of silver halide emulsions, in which the novel developing agent is capable of developing a latent image and imparting a positive colored image of said latent image to a superposed imagereceiving layer.
  • a still further object of the present invention is to provide novel photographic processes and products for obtaining color images by diffusion-transfer processes which employ hydrolyzable derivatives of dye developers, which derivatives comprise the hydrolyzable alkoxalyl and aryloxalyl esters of specified dye developers.
  • 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 processing 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.
  • the compounds employed in the present invention possess the properties of both a dye and, during the photographic processes herein disclosed, a developing agent;
  • dye developer precursors thus they may be referred to as dye developer precursors.
  • the nature of these dye developer precursors will be described hereinafter.
  • photographic processes and compositions disclosed herein are particularly useful in the treatment of a latent image present in a photosensitive element, such as an exposed silver halide emulsion, whereby a positive dye image thereof may be imparted to another element, herein referred to as an image-carrying or image-receiving element.
  • a photosensitive element such as an exposed silver halide emulsion
  • a positive dye image thereof may be imparted to another element, herein referred to as an image-carrying or image-receiving element.
  • 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 imagereceiving element.
  • the photo sensitive element contains a layer of dye developer precursor, 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 dis closure in the copending application of Edwin H.
  • the liquid processing composition permeates the emulsion to provide a solution of dye developer substantially uniformly distributed therein.
  • 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.
  • the layer of the liquid processing composition may be utilized as the image-receiving layer.
  • the latter element receives a depthwise diffusion, from the emulsion, of unoxidized dye developer Without appreciably disturbing the imagewise distribution thereof to provide a reversed or positive, colored image of the developed image.
  • the imagereceiving element may contain agents adapted to mordant or otherwise fix the diiiused, unoxidized dye developer. If the color of the diffused dye developer is affected by changes in the pH of the image-receiving element, 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 photosensitive element at the end of the imbibition period.
  • the compounds of the present invention may be utilized in the photosensitive element, for example in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element.
  • a coating or layer of the compound is placed behind the silver halide emulsion, i.e., on the side of the emulsion adapted to be located most distant from the photographed subject when the emulsion is exposed and preferably also adapted to be most distant from the image-receiving element when in superposed relationship therewith.
  • Placing the dye developer hydrolyzable derivative 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 hydrolyzable derivative may be applied by using a coating solution so selected as not to induce hydrolysis during preparation of the negative and containing about 0.5 to 8%, by Weight, of the derivative.
  • 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. In some instances, it may contain an auxiliary or accelerating 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 comprising a film-forming material of the type which, when said composition is spread and dried, will form a relatively firm and relatively stable film.
  • 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.
  • 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 used.
  • the dye developer precursors of the present invention comprise dyes, preferably azo, anthraquinone, indophenol, indoaniline, and azomethine dyes, characterized in that they contain not less than one and not more than two groups selected from the group consisting of the alkoxalyl aryloxalyl monoand diesters of orthoand para-dihydroxyphenyl groups.
  • novel hydrolyzable dye developer derivatives also may be represented by the formula:
  • -D represents a dye system, that is, an auxochromophoric system, preferably an azo, anthraquinone, indophenol, indoaniline or azomethine dye system
  • Y is a covalent bond or a divalent radical
  • a is l or 2
  • Z is a group selected from the group consisting of the alkoxalyl and aryloxalyl monoand diesters of orthoand paradihydroxyphenyl groups.
  • a preferred group of compounds of the present invention comprise the hydrolyzable dye developer derivatives of the formula:
  • each R is an alkyl or aryl group; a has the same significance as previously set forth; Y is an alkylene group, preferably a lower alkylene group comprising from 1 to 5 carbon atoms, for example, methylene, ethylene, propylene, trimethylene, etc.; and D represents an azo or anthraquinone auxochromophoric system.
  • dihydroxyphenyl as used herein is intended to include the nuclear substituted derivatives thereof, especially the nuclear substituted alkyl and halogen derivatives thereof.
  • the phenyl nucleus may be sub stituted by additional substituents, that is, radicals so situated as not to impair the respective silver halide developing function of the phenyl group when said group is subjected to hydrolysis by the photographic processing composition.
  • novel dyes of the present invention may be prepared by reacting a dye developer, preferably an azo, anthraquinone, indophenol, indoaniline, or azomethine dye developer, having not less than one and preferably not more than two ortho-dihydroxyphenyl or para-dihydroxyphenyl groups or nuclear substituted derivatives thereof with an alkyl and/or an aryl oxalyl halide such as an oxalyl bromide or chloride, preferably an oxalyl chloride.
  • a dye developer preferably an azo, anthraquinone, indophenol, indoaniline, or azomethine dye developer, having not less than one and preferably not more than two ortho-dihydroxyphenyl or para-dihydroxyphenyl groups or nuclear substituted derivatives thereof
  • an alkyl and/or an aryl oxalyl halide such as an oxalyl bromide or chloride,
  • the variance of the mole ratios of reactants that is, the mole ratios of the respective haloformate to dye developer molecule provides either the desired monoor bis-esters of the dihydroxybenzene nuclei or mixtures thereof.
  • a decrease in the mole ratio of the respective oxalyl halide to dye developer molecule effects an increased formulation of the mono-ester.
  • the dye molecule is devoid of aliphatic alcohol groups, which, if present during the synthesis of the novel compounds of this invention, would preferentially esterify and thus subordinate the esterification of the dihydroxy groups of the benzene nucleus.
  • the synthesis preferably is effected in a reaction medium comprising a suitable anhydrous halogen acid acceptor, e.g., pyridine, quinoline, etc.
  • a suitable anhydrous halogen acid acceptor e.g., pyridine, quinoline, etc.
  • the particular conditions, i.e., temperature, etc. will vary according to the oxalyl halide and the halogen acid acceptor utilized, e.g., the reaction is preferably performed on a steam bath, but it is within the scope of this invention to employ a temperature ranging from a lower temperature such as room temperature to the highest temperature at which the substituted oxalyl halide and dye molecule are stable.
  • Serial No. 478,922 filed December 30, 1954, in the names of Elkan R. Blout, Marilyn R. Cohler, Milton Green, Myron S. Simon and Robert B. Woodward, abandoned and replaced by Serial No. 824,785 and Serial No. 824,- 786, both filed July 3, 1959, in turn abandoned and replaced, respectively, by Serial No. 233,461, filed October 26, 1962, now US. Patent No. 3,135,606, issued June 2, 1964, and Serial No. 318,827, filed October 25, 1963;
  • Example 1 2 [p (2,5-dihydroxyphenethyl)-phenylazo]-4-methoxy-l-naphthol (1 mol), disclosed in the aforementioned copendingUS. application Serial No. 144,816, (new U.S. Patent No. 3,134,672, issued May 26, 1964), is dissolved in dioxane by refluxing in a nitrogen atmosphere. Pyridine (2 mols) is added to the resultant solution. Eth xalyl chloride (2 mols) is then added and the resultant mixture refluxed for 1 to 3 hours. The solvent is removed in vacuo, the residue washed with ice water and dried ether in a vacuum oven at 60 C.
  • Example 2 A photosensitive element is prepared by coating a gelatin-coated film base with a solution containing 4% of 2 [p (2',5 bis-ethoxalyloxyphenethyl)-phenylazo]-4- methoxy-l-naphthol, (Formula I as prepared in Example 1), in a 4% solution of cellulose acetate hydrogen phth-alate 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 equeous liquid processing composition comprising:
  • the image-receiving element comprises a cellulose acetate-coated baryta paper which has been coated with a solution comprising 10% N-methoxymethyl polyhexamethylene adipamide in aqueous ethanol. After an imbibition period of approximately 1 minute, the image-receiving element is separated and contains a magenta positive dye image of the photographed subject.
  • the sensitivity of an associated silver halide emulsion may be affected by a reaction between the associated dye developer and a sensitizer employed in said silver halide emulsion, or by means of a displacement of sensitizing dye absorbed on the silver halide, resulting in decreased sensitivity. It has been found that the employment of the hyd'rolyzable derivatives of the present invention as precursors to the ultimately desired dye developers offers a means of restricting themobility of the respective dye developers and of thus avoiding or reducing such desensitizing side reactions as might otherwise occur during storage of the photosensitive product.
  • the liquid processing composition may, and in the above example does, contain at least one auxiliary developer, such as p methylaminophenol [Metol], 2,4 diaminophenol [Amidol], benzyl'aminophenol, or a 3-pyrazolidone, such as 1-phenyl-3-pyrazolidone [Phenidone].
  • the preferred auxiliary developer is l-phenyl-3-pyrazolidone. This auxiliary developer serves to accelerate and possibily initiate the action of the dye developer. A portion of the dye developer may be oxidized by an energy transfer reaction with oxidized auxiliary developer.
  • the compounds of this invention may be used also in conventional photographic processes, suchas tray or tank development of conventional photosensitive films, plates or papers containing said compounds to obtain blackand-white, monochromatic or toned prints or negatives.
  • a processing composition suitable for such use may comprise an aqueous solution of approximately 1% sodium hydroxide, 2% sodium sulfite and 0.05% potassium bromide.
  • any unreacted dye developer is washed out of the photosensitive element, preferably with an alkaline washing medium or other medium in which the unreacted dye developer is soluble.
  • the expression toned is used to designate photographic images wherein the silver is retained with the precipitated dye, whereas monochromatic is intended to designate dye images free of silver.
  • the compounds of this invention are self-suiiicient to provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photographic color processes in which the color is produced by a coupling reaction involving the oxidized developing agent.
  • the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of imagereceiving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developer hydrolyzable derivatives suitable to impart the desired subtractive colors being incorporated in the photo sensitized elements. Examples of such photographic materials are disclosed in US. Patent No. 2,647,049 to Edwin H. Land.
  • inventive concepts herein set forth are also adaptable for the formation of colored images in accordance with the photographic products and processes described and claimed in the copending application of Edwin H. Land, Serial No. 448,441, filed August 9, 1954 (now US. Patent No. 2,968,554, issued January 17, 1961), and also the copending application of Edwin H. Land and Howard G. Rogers, Serial No. 565,135, filed February 13, 1956.
  • a process of forming transfer images in color which comprises the steps of exposing a photosensitive element comprising a plurality of layers including a layer containing a silver halide emulsion, at least one of said layers containing a dye selected from the group consisting of azo and anthraquinone dyes which possess not less than one and not more than two groups selected from the group consisting of the alkoxalyl and aryloxalyl monoand diesters of orthoand para-dihydroxyphenyl groups; contacting the exposed photosensitive element with an aqueous alkaline solution; thereby providing hydrolysis of said ester groups, subsequent to photoexposure, and development of the exposed silver halide emulsion; immobilizing said dye in developed areas of said photosensitive element, as a function of the point-to-point degree of exposure of emulsion; thereby providing an imagewise distribution of mobile dye, in undeveloped areas of said photosensitive element; and transferring, by imbibition, at least a portion of said irnagewise distribution
  • a process of forming transfer images in color which comprises the steps of exposing a photosensitive element comprising a plurality of layers including a layer containing a silver halide emulsion, at least one of said layers containing a dye of the formula:
  • R0-oo wherein Y is a lower alkylene group; each R is an alkyl group; and D is a monoazo auxochromophoric system; effecting removal of the 0 0 at am ester groups by hydrolysis, developing the latent image contained in the exposed silver halide emulsion, immobilizing the dye in exposed areas of the photosensitive ele ment as a function of the point-to-point degree of exposure of said emulsion, thereby providing an imagewise distribution of dye in unexposed areas of said photosensitive element, and transferring a portion of said image wise distribution to a superposed image-receiving layer to impart thereto a positive monoazo dye image.

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Description

United States Patent 3,230,084 NOVEL PHOTOGRAPHEC PRODUCTS AND PROCESSES Mlyron S. Simon, Newton Center, and Stanley H. Mervis,
Newton Highlands, Mass, assignors to Polaroid Corporation, Cambridge, Mass a corporation of Delaware N0 Drawing. Filed May 18, 1959, Ser. No. 813,701 7 Claims. ((12. 96-29) The present application is a continuation-in-part of our copending U.S. application Serial No. 697,808, filed November 21, 1957, now abandoned.
This invention relates to photography and more particularly to products and processes for the development of photosensitive silver halide elements.
It is a primary object of the present invention to provide novel difiusion-transfer photographic processes and products whereby improved control of the transfer of mobile dye developer to an image-receiving layer may be obtained.
A further object of the present invention is to provide novel photographic processes and products for obtaining color images by a diffusion-transfer process wherein a dye developer is initially present in the form of a hydrolyzable derivative of said dye developer and wherein said hydrolyzable derivative is subjected to hydrolysis during processing.
A still further object of the present invention is to provide novel photographic processes and products wherein a hydrolyzable derivative of a dye developer is employed and said derivative is of relatively low mobility until hydrolysis occurs.
A still further object of the present invention is to provide photographic processes and products wherein hydrolyzable derivatives of dye developers are employed, said derivatives being initially nonreactive with an associated photosensitive silver halide emulsion and rendered reactive by hydrolysis occurring during processing.
A still further object of the present invention is to provide photographic processes and products for use in monochromatic and multicolor diffusion-transfer processes utilizing hydrolyzable derivatives of dye developers, which derivatives contain groups removable during photographic processing, to provide thereby improved color rendition.
A still further object of the present invention is to provide novel processes for the development of silver halide emulsions, in which the novel developing agent is capable of developing a latent image and imparting a positive colored image of said latent image to a superposed imagereceiving layer.
A still further object of the present invention is to provide novel photographic processes and products for obtaining color images by diffusion-transfer processes Which employ hydrolyzable derivatives of dye developers, which derivatives comprise the hydrolyzable alkoxalyl and aryloxalyl esters of specified dye developers.
Other objects of the invention will in part be obvious and will in part appear hereinafter.
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 processing 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.
For a fuller understanding of the nature and objects of the invention, reference should be had to the following detailed description.
The compounds employed in the present invention possess the properties of both a dye and, during the photographic processes herein disclosed, a developing agent;
ice
thus they may be referred to as dye developer precursors. The nature of these dye developer precursors will be described hereinafter.
The photographic processes and compositions disclosed herein are particularly useful in the treatment of a latent image present in a photosensitive element, such as an exposed silver halide emulsion, whereby a positive dye image thereof may be imparted to another element, herein referred to as an image-carrying or image-receiving element.
The copending application of Howard G. Rogers, Serial No. 748,421, filed July 14, 1958 (now U.S. Patent No. 2,983,606, issued May 9, 1961), a continuation-in-part of Serial No. 415,073, filed March 9, 1954 (now abandoned), discloses diffusion-transfer reversal processes wherein a photographic negative material such as a photographic element comprising an exposed silver halide emulsion layer containing a latent image, is processed to impart to an image-receiving element a reversed or positive dye image of said latent image by permeating into said emulsion layer a suitable liquid processing composition and bringing said emulsion layer into superposed relationship with an appropriate image-receiving layer. It is an object of this invention to provide additional compounds suitable for use in such processes.
In carrying out the process of this invention, 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 imagereceiving element. In a preferred embodiment, the photo sensitive element contains a layer of dye developer precursor, 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 dis closure in the copending application of Edwin H. Land, Serial No. 498,672, filed April 1, 1955 (now U.S. Patent No. 3,087,816, issued April 30, 1963). The liquid processing composition permeates the emulsion to provide a solution of dye developer substantially uniformly distributed therein. As the latent image is developed, 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 and to localized exhaustion of alkali due to development. 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 oxi dized dye developer. Under certain circumstances, the layer of the liquid processing composition may be utilized as the image-receiving layer. The latter element receives a depthwise diffusion, from the emulsion, of unoxidized dye developer Without appreciably disturbing the imagewise distribution thereof to provide a reversed or positive, colored image of the developed image. The imagereceiving element may contain agents adapted to mordant or otherwise fix the diiiused, unoxidized dye developer. If the color of the diffused dye developer is affected by changes in the pH of the image-receiving element, 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 photosensitive element at the end of the imbibition period.
The compounds of the present invention may be utilized in the photosensitive element, for example in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element. In a preferred embodiment, a coating or layer of the compound is placed behind the silver halide emulsion, i.e., on the side of the emulsion adapted to be located most distant from the photographed subject when the emulsion is exposed and preferably also adapted to be most distant from the image-receiving element when in superposed relationship therewith. Placing the dye developer hydrolyzable derivative behind the emulsion layer, as in the preferred embodiment, has the advantage of providing increased contrast in the positive image, and also minimizes any light-filtering action by the colored dye developer. In this preferred embodiment, the layer of dye developer hydrolyzable derivative may be applied by using a coating solution so selected as not to induce hydrolysis during preparation of the negative and containing about 0.5 to 8%, by Weight, of the derivative.
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. In some instances, it may contain an auxiliary or accelerating 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 comprising a film-forming material of the type which, when said composition is spread and dried, will form a relatively firm and relatively stable film. 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 used.
The copending application of Edwin H. Land and Howard G. Rogers, Serial No. 669,542, filed July 2, 1957, abandoned and replaced by Serial No. 194,359, filed May 14, 1962, discloses diffusion-transfer processes of the previously disclosed type which employ dye developers in the form of hydrolyzable derivatives thereof. These hydrolyzable derivatives are disclosed to be initially less mobile and thus prevent premature transfer of dye developer which might give rise to highlight stain and/ or incomplete color separation. The present application is principally concerned with novel dye developer hydrolyzable derivatives particularly applicable for use in the processes therein disclosed.
The dye developer precursors of the present invention comprise dyes, preferably azo, anthraquinone, indophenol, indoaniline, and azomethine dyes, characterized in that they contain not less than one and not more than two groups selected from the group consisting of the alkoxalyl aryloxalyl monoand diesters of orthoand para-dihydroxyphenyl groups.
The last-mentioned novel hydrolyzable dye developer derivatives also may be represented by the formula:
wherein -D represents a dye system, that is, an auxochromophoric system, preferably an azo, anthraquinone, indophenol, indoaniline or azomethine dye system; Y is a covalent bond or a divalent radical; a is l or 2; and Z is a group selected from the group consisting of the alkoxalyl and aryloxalyl monoand diesters of orthoand paradihydroxyphenyl groups.
etc.; and divalent radicals which contain both hetero and carbon atoms as constituent components, as for example,
etc.
A preferred group of compounds of the present invention comprise the hydrolyzable dye developer derivatives of the formula:
O Du. 1
a a pa e.-.
wherein each R is an alkyl or aryl group; a has the same significance as previously set forth; Y is an alkylene group, preferably a lower alkylene group comprising from 1 to 5 carbon atoms, for example, methylene, ethylene, propylene, trimethylene, etc.; and D represents an azo or anthraquinone auxochromophoric system.
The term dihydroxyphenyl as used herein is intended to include the nuclear substituted derivatives thereof, especially the nuclear substituted alkyl and halogen derivatives thereof. Where desired, the phenyl nucleus may be sub stituted by additional substituents, that is, radicals so situated as not to impair the respective silver halide developing function of the phenyl group when said group is subjected to hydrolysis by the photographic processing composition.
The novel dyes of the present invention may be prepared by reacting a dye developer, preferably an azo, anthraquinone, indophenol, indoaniline, or azomethine dye developer, having not less than one and preferably not more than two ortho-dihydroxyphenyl or para-dihydroxyphenyl groups or nuclear substituted derivatives thereof with an alkyl and/or an aryl oxalyl halide such as an oxalyl bromide or chloride, preferably an oxalyl chloride. Where the dye developer has additional available reactive hydroxyl groups, reaction may occur at such additional groups.
The variance of the mole ratios of reactants, that is, the mole ratios of the respective haloformate to dye developer molecule provides either the desired monoor bis-esters of the dihydroxybenzene nuclei or mixtures thereof. A decrease in the mole ratio of the respective oxalyl halide to dye developer molecule effects an increased formulation of the mono-ester.
In the preferred embodiment, the dye molecule is devoid of aliphatic alcohol groups, which, if present during the synthesis of the novel compounds of this invention, would preferentially esterify and thus subordinate the esterification of the dihydroxy groups of the benzene nucleus.
The synthesis preferably is effected in a reaction medium comprising a suitable anhydrous halogen acid acceptor, e.g., pyridine, quinoline, etc. The particular conditions, i.e., temperature, etc., will vary according to the oxalyl halide and the halogen acid acceptor utilized, e.g., the reaction is preferably performed on a steam bath, but it is within the scope of this invention to employ a temperature ranging from a lower temperature such as room temperature to the highest temperature at which the substituted oxalyl halide and dye molecule are stable.
The preparations of numerous of the dye developers preferred for use in synthesizing dye developer precursors of the present invention are set forth in the following copending US. applications:
Serial No. 445,171, filed July 22, 1954, in the name of Richard S. Corle, now abandoned;
Serial No. 449,514, filed August 12, 1954, in the names of Elkan R. Blout and Myron S. Simon, now abandoned;
Serial No. 471,542, filed November 26, 1954, in the names of Elkan R. Blout, Saul G. Cohen, Milton Green, Howard G. Rogers, Myron S. Simon, and Robert B. Woodward, abandoned and replaced by Serial No. 1,442 and Serial No. 1,443, both filed January 11, 1960, the former in turn abandoned and replaced by Serial No. 401,714, filed October 5, 1964;
Serial No. 473,458, filed December 6, 1954 in the names of Elkan R. Blout, Saul G. Cohen, Milton Green and Myron S. Simon (now US. Patent No. 3,077,402, issued February 12, 1963);
Serial No. 478,922, filed December 30, 1954, in the names of Elkan R. Blout, Marilyn R. Cohler, Milton Green, Myron S. Simon and Robert B. Woodward, abandoned and replaced by Serial No. 824,785 and Serial No. 824,- 786, both filed July 3, 1959, in turn abandoned and replaced, respectively, by Serial No. 233,461, filed October 26, 1962, now US. Patent No. 3,135,606, issued June 2, 1964, and Serial No. 318,827, filed October 25, 1963;
Serial No. 485,342, filed January 31, 1955, in the name of Richard S. Corley (now US. Patent No. 2,983,605, issued May 9, 1961);
Serial No. 485,840, filed February 3, 1955, in the names of Elkan R. Blout and Howard G. Rogers;
Serial No. 521,874, filed July 13, 1955, in the names of Elkan R. Blout, Milton Green, Myron S. Simon, and Howard G. Rogers (abandoned and replaced by Serial No. 799,427, filed March 16, 1959, now US. Patent No. 3,076,820, issued February 5, 1963);
Serial No. 522,848, filed July 18, 1955, in the names of Elkan R. Blout, Sydney Kasman and Myron S. Simon (abandoned and replaced by Serial No. 799,425, filed March 16, 1959, in turn abandoned and replaced by Serial No. 150,661, filed November 7, 1961, now US. Patent No. 3,076,808, issued February 5, 1963);
Serial No. 612,045, filed September 25, 1956, in the names of Elkan R. Blout, Milton Green and Howard G. Rogers, abandoned and replaced by Serial No. 144,816, filed October 18, 1961, now US. Patent No. 3,134,672, issued May 26, 1964;
Serial No. 612,052, filed September 25, 1956, in the names of Milton Green and Howard G. Rogers, abandoned and replaced Serial No. 165,930, filed January 12, 1962, now US. Patent No. 3,135,604, issued June 2, 1964;
Serial No. 612,053, filed September 25, 1956, in the name of Myron 5. Simon, abandoned and replaced by Serial No. 196,523 and Serial No. 196,524, both filed May 21, 1962, the latter now US. Patent No. 3,134,765, issued May 26, 1964;
Serial No. 612,054, filed September 25, 1956, in the names of Helen P. Husek and Myron S. Simon, abandoned and replaced by Serial No. 197,259 and Serial No. 197,283, both filed May 24, 1962, the former now US. Patent No. 3,134,763, issued May 26, 1964;
Serial No. 612,055, filed September 25, 1956, in the name of Helen P. Husek, abandoned and replaced by Serial No. 192,354 and Serial No. 192,355, both filed May 4, 1962, the former now US. Patent No. 3,134,762, issued May 26, 1964;
Serial No. 663,905, filed June 6, 1957, in the names of Milton Green and Howard G. Rogers, abandoned and replaced by Serial No. 193,293 and Serial No. 193,326, both filed May 8, 1962;
Serial No. 669,969, filed July 5, 1957, in the name of Milton Green, now abandoned;
Serial No. 678,439, filed August 15, 1957, in the name of Myron S. Simon, abandoned and replaced by Serial No. 232,584 and Serial No. 232,585, both filed October 23, 1962, the former now US. Patent No. 3,131,061, issued April 28, 1964;
Serial No. 680,403, filed August 26, 1957, in the name of Milton Green, abandoned and replaced by Serial No. 316,498, filed October 16, 1963;
Serial No. 680,434, filed August 26, 1957, in the name of Milton Green, abandoned and replaced by Serial No. 230,287 and Serial No. 230,288, both filed October 12, 1962;
Serial No. 680,437, filed August 26, 1957, in the names of Elkan R. Blout and Myron S, Simon (now US. Patent No. 3,047,386, issued July 31, 1962);
Serial No. 680,619, filed August 27, 1957, in the names of Elkan R. Blout and Myron S. Simon, now abandoned;
Serial No. 685,081, filed September 20, 1957, in the names of Elkan R. Blout, Milton Green, Howard G. Rogers, and Myron S. Simon, abandoned and replaced by Serial No, 225,656 and Serial No. 222,702, both filed September 10, 1962, the former now US. Patent No. 3,142,565, issued July 28, 1964;
Serial No. 703,515, filed December 18, 1957, in the name of Milton Green, now abandoned;
Serial No. 707,109, filed January 6, 1958, in the names of Elkan R. Blout, Milton Green, Howard G. Rogers and Robert B. Woodward;
Serial No. 709,001, filed January 15, 1958, in the names of Milton Green, Helen P. Husek and Sydney Kasman, abandoned and replaced by Serial No. 200,639, filed June 7, 1962;
Serial No. 709,002, filed January 15, 1958, in the names of Milton Green and Helen P. Husek, abandoned and replaced by Serial No. 75,128, filed December 12, 1960, now US. Patent No, 3,158,595, issued November 24, 1964;
Serial No. 709,005, filed January 15, 1958, in the names of Sydney Kasman and Helen P. Husek, abandoned and replaced by Serial No. 75,127, filed December 12, 1960, in turn abandoned and replaced by Serial No. 339,615, filed January 23, 1964;
Serial No. 711,811, filed January 29, 1958, in the name of Milton Green, abandoned and replaced by Serial No. 232,613, filed October 23, 1962;
Serial No. 748,145, filed July 14, 1958, in the names of Milton Green and Howard G. Rogers, abandoned and replaced by Serial No. 190,804, filed April 27, 1962;
Serial No. 755,804, filed August 18, 1958, in the names of Elkan R. Blout, Saul G. Cohen, Milton Green and Myron S. Simon, now abandoned;
Serial No. 756,066, filed August 20, 1958, in the name of Myron S. Simon;
Serial No. 771,719, filed November 4, 1958, in the names of Elkan R. Blout and Richard S. Corley, abandoned and replaced by Serial No. 193,320, filed May 8, 1962; and
Serial No. 788,893, filed January 2-6, 1959, in the names of Milton Green and Myron S. Simon, abandoned and replaced by Serial No. 359.998, filed April 15, 1964.
As examples of compounds contemplated within the scope of the present invention, mention may be made of the following:
(11 0 ll ll 1-phenyl-3-methyl-4-[p- 2 ,5'-bis-ethoxalyloxyphenethyl) phenylazo1-5-pyrazolone 2- [p- 3,4'-bis-ethoxa1yloxyphenethyl) pheny1azo] -4- methoxy-l-naphthol (III) 0 0 1-phenyl-3-methyl-4- [p- (2 ,5-bis-ethoxalyloxyphenyl-thioethyl) -pl1eny1azo] -5-pyrazolone 1-phenyl-3-methyl-4- [p- 2' ,5 -bis-n-hexoxalyloxyphenethyl phenylazo1-5-pyrazolone The invention will be illustrated in greater detail in conjunction with the following specific examples which set out a representative preparation and photographic utilization of the novel compounds of this invention, which, however, are not limited to the details therein set forth and are intended to be illustrative only.
Example 1 2 [p (2,5-dihydroxyphenethyl)-phenylazo]-4-methoxy-l-naphthol (1 mol), disclosed in the aforementioned copendingUS. application Serial No. 144,816, (new U.S. Patent No. 3,134,672, issued May 26, 1964), is dissolved in dioxane by refluxing in a nitrogen atmosphere. Pyridine (2 mols) is added to the resultant solution. Eth xalyl chloride (2 mols) is then added and the resultant mixture refluxed for 1 to 3 hours. The solvent is removed in vacuo, the residue washed with ice water and dried ether in a vacuum oven at 60 C. or in a vacuum dessicator containing a dehydrating agent such as potassium hydroxide. The infrared absorption curve of the resultant product, 2-[p (2',5-bis-ethoxalyloxyphenethyl) phenylazo]-4-methoxy-l-naphthol [Formula I], in chloroform, exhibits ester bands at 1751 and 1772 cm.- An infrared spectrum of the bis-ethoxalyl ester of hydroquinone exhibits ester bands at 1750 and 1775 cm.- thus confirming the presence of the ethoxalyl ester groups in the above product.
Example 2 A photosensitive element is prepared by coating a gelatin-coated film base with a solution containing 4% of 2 [p (2',5 bis-ethoxalyloxyphenethyl)-phenylazo]-4- methoxy-l-naphthol, (Formula I as prepared in Example 1), in a 4% solution of cellulose acetate hydrogen phth-alate 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 equeous liquid processing composition comprising:
Percent Sodium carboxymethyl cellulose 5.0 1-phenyl-3-pyrazolidone 0.2 Sodium hydroxide 3.0 Potassium bromide 0.2
between said photosensitive element and an image-receiving element as said elements are brought into superposed relationship. The image-receiving element comprises a cellulose acetate-coated baryta paper which has been coated with a solution comprising 10% N-methoxymethyl polyhexamethylene adipamide in aqueous ethanol. After an imbibition period of approximately 1 minute, the image-receiving element is separated and contains a magenta positive dye image of the photographed subject.
In certain instances, the sensitivity of an associated silver halide emulsion may be affected by a reaction between the associated dye developer and a sensitizer employed in said silver halide emulsion, or by means of a displacement of sensitizing dye absorbed on the silver halide, resulting in decreased sensitivity. It has been found that the employment of the hyd'rolyzable derivatives of the present invention as precursors to the ultimately desired dye developers offers a means of restricting themobility of the respective dye developers and of thus avoiding or reducing such desensitizing side reactions as might otherwise occur during storage of the photosensitive product.
It will be noted that the liquid processing composition may, and in the above example does, contain at least one auxiliary developer, such as p methylaminophenol [Metol], 2,4 diaminophenol [Amidol], benzyl'aminophenol, or a 3-pyrazolidone, such as 1-phenyl-3-pyrazolidone [Phenidone]. The preferred auxiliary developer is l-phenyl-3-pyrazolidone. This auxiliary developer serves to accelerate and possibily initiate the action of the dye developer. A portion of the dye developer may be oxidized by an energy transfer reaction with oxidized auxiliary developer.
The compounds of this invention may be used also in conventional photographic processes, suchas tray or tank development of conventional photosensitive films, plates or papers containing said compounds to obtain blackand-white, monochromatic or toned prints or negatives. By way of example, a processing composition suitable for such use may comprise an aqueous solution of approximately 1% sodium hydroxide, 2% sodium sulfite and 0.05% potassium bromide. After development is completed, any unreacted dye developer is washed out of the photosensitive element, preferably with an alkaline washing medium or other medium in which the unreacted dye developer is soluble. The expression toned is used to designate photographic images wherein the silver is retained with the precipitated dye, whereas monochromatic is intended to designate dye images free of silver.
It should be noted that the compounds of this invention are self-suiiicient to provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photographic color processes in which the color is produced by a coupling reaction involving the oxidized developing agent.
It should be noted that it is within the scope of this invention to use mixtures of the compounds to obtain a desired color.
It will be apparent that, by appropriate selection of the image-receiving element from among suitable known opaque and transparent materials, it is possible to obtain either a colored positive reflection print or a colored positive transparency. Likewise, the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of imagereceiving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developer hydrolyzable derivatives suitable to impart the desired subtractive colors being incorporated in the photo sensitized elements. Examples of such photographic materials are disclosed in US. Patent No. 2,647,049 to Edwin H. Land.
The inventive concepts herein set forth are also adaptable for the formation of colored images in accordance with the photographic products and processes described and claimed in the copending application of Edwin H. Land, Serial No. 448,441, filed August 9, 1954 (now US. Patent No. 2,968,554, issued January 17, 1961), and also the copending application of Edwin H. Land and Howard G. Rogers, Serial No. 565,135, filed February 13, 1956.
In the preceding portions of the specification the expression color has been frequently used. This expression is intended to include the use of a plurality of colors to obtain black, as well as the use of a single black dye developer precursor.
Since certain changes may be made in the above products and processes without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.
What is claimed is:
1. A process of forming transfer images in color which comprises the steps of exposing a photosensitive element comprising a plurality of layers including a layer containing a silver halide emulsion, at least one of said layers containing a dye selected from the group consisting of azo and anthraquinone dyes which possess not less than one and not more than two groups selected from the group consisting of the alkoxalyl and aryloxalyl monoand diesters of orthoand para-dihydroxyphenyl groups; contacting the exposed photosensitive element with an aqueous alkaline solution; thereby providing hydrolysis of said ester groups, subsequent to photoexposure, and development of the exposed silver halide emulsion; immobilizing said dye in developed areas of said photosensitive element, as a function of the point-to-point degree of exposure of emulsion; thereby providing an imagewise distribution of mobile dye, in undeveloped areas of said photosensitive element; and transferring, by imbibition, at least a portion of said irnagewise distribution of mobile dye to a superposed image receiving element to impart thereto a dye image.
2. The process of forming transfer images in color as defined in claim 1, wherein said silver halide development is efiected in the presence of at least one auxiliary developing agent.
3. The process of forming transfer images in color as defined in claim 1, wherein said dye is disposed in a separate liquid-permeable layer superposed on said silver halide emulsion and a photographic processing composition containing said dye in hydrolyzed form is formed by permeating said photosensitive element with an aqueous alkaline liquid capable of hydrolyzing and solubilizing said dye.
4. The process of forming transfer images in color as defined in claim 1, wherein said dye is dispersed in said silver halide emulsion and a photographic processing composition containing said dye in hydrolyzed form is formed by permeating said photosensitive element with an aqueous alkaline liquid capable of hydrolyzing and solubilizing said dye.
5. The process of forming transfer images in color as defined in claim 1, wherein said dihydroxyphenyl groups comprise lower alkyl nuclear substituted derivatives thereof.
6. A process of forming transfer images in color which comprises the steps of exposing a photosensitive element comprising a plurality of layers including a layer containing a silver halide emulsion, at least one of said layers containing a dye of the formula:
0 0 II II R0-oo wherein Y is a lower alkylene group; each R is an alkyl group; and D is a monoazo auxochromophoric system; effecting removal of the 0 0 at am ester groups by hydrolysis, developing the latent image contained in the exposed silver halide emulsion, immobilizing the dye in exposed areas of the photosensitive ele ment as a function of the point-to-point degree of exposure of said emulsion, thereby providing an imagewise distribution of dye in unexposed areas of said photosensitive element, and transferring a portion of said image wise distribution to a superposed image-receiving layer to impart thereto a positive monoazo dye image.
7. A process of forming transfer images in color as define-l in claim 6, wherein said hydrolyzable dye cornprises 2-[p (2',5-bis-ethoxalyloxyphenethyl)-phenylazo]- 4-methoxy-1-naphthol.
References Cited by the Examiner UNITED STATES PATENTS 2,225,443 12/ 1940 Fleischhauer et al. 260-162 2,518,078 8/1950 Schmid et al 260162 2,751,295 6/1956 Salrninen et al 9666 X 2,756,142 7/1956 Yutzy 96-22 X 2,774,668 12/1956 Rogers 96-29 2,860,974 11/1958 Williams 96-9 2,892,710 6/1959 COhler et al 9629 2,983,605 5/1961 Corley 9629 2,983,606 5/1961 Rogers 96-29 3,047,386 7/1962 Blout et al 9629 2,134,672 5/1964 Blout et al.
FOREIGN PATENTS 554,212 7/ 1957 Belgium.
554,935 10/1957 Belgium.
569,080 1/1959 Belgium.
NORMAN G. TORCHIN, Primary Examiner.
MILTON STERMAN, PHILIP E. MANGAN,
Examiners.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,230,084 January 18, 1966 Myron S. Simon et a1.
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 1, lines 62 and 63, for "processing" read possessing column 3, line 64, before "aryloxalyl" insert and column 4, line 6, for "fanyl" read famyl line 62, for "formulation" read formation column 5, line 8, for "Corle" read Corley line 54, after "replaced" insert by column 6, line 23, for "225,656" read 222,656 lines 66 to 75, after the formula insert 2-[p-(2,5-bisethoxalyloxyphenethyl)-phenylaz0]4- methoxy-l-naphthol column 10, line 65, for "2,134,672" read 3,134,672
Signed and sealed this 29th day of October 1968.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents

Claims (1)

1. A PROCESS OF FORMING TRANSFER IMAGES IN COLOR WHICH COMPRISES THE STEPS OF EXPOSING A PHOTOSENSITIVE ELEMENT COMPRISING A PLURALITY OF LAYERS INCLUDING A LAYER CONTAINING A SILVER HALIDE EMULSION, AT LEAST ONE OF SAID LAYERS CONTANINING A DYE SELECTED FROM THE GROUP CONSISTING OF AZO AND ANTHRAQUINONE DYES WHICH POSSESS NOT LESS THAN ONE AND NOT MORE THAN TWO GROUPS SELECTED FROM THE GROUP CONSISTING OF THE ALKOXALYL AND ARYLOXALYL MONOAND DIESTERS OF ORTHO- AND PARA-DIHYDROXYPHENYL GROUPS; CONTACTING THE EXPOSED PHOTOSENSITIVE ELEMENT WITH AN AQUEOUS ALKALINE SOLUTION; THEREBY PROVIDING HYDROLYSIS OF SAID ESTER GROUPS, SUBSEQUENT TO PHOTOEXPOSURE, AND DEVELOPMENT OF THE EXPOSED SILVER HALIDE EMULSION; IMMOBILIZING SAID DYE IN DEVELOPED AREAS OF SAID PHOTOSENSITIVE ELEMENT, AS A FUNCTION OF THE POINT-TO-POINT DEGREE OF EXPOSURE OF EMULSION; THEREBY PROVIDING AN IMAGEWISE DISTRIBUTION OF MOBILE DYE, IN UNDEVELOPED AREAS OF SAID PHOTOSENSITIVE ELEMENT; AND TRANSFERRING, BY IMBIBITION, AT LEAST A PORTION OF SAID IMAGEWISE DISTRIBUTION OF MOBILE DYE TO A SUPERPOSED IMAGE-RECEIVING ELEMENT TO IMPART THERETO A DYE IMAGE.
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