US3295973A - Novel photographic products and processes - Google Patents

Novel photographic products and processes Download PDF

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US3295973A
US3295973A US506280A US50628065A US3295973A US 3295973 A US3295973 A US 3295973A US 506280 A US506280 A US 506280A US 50628065 A US50628065 A US 50628065A US 3295973 A US3295973 A US 3295973A
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Elkan R Blout
Saul G Cohen
Green Milton
Myron S Simon
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Polaroid Corp
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Polaroid Corp
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B43/00Preparation of azo dyes from other azo compounds
    • C09B43/18Preparation of azo dyes from other azo compounds by acylation of hydroxyl group or of mercapto group
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18One oxygen or sulfur atom
    • C07D231/20One oxygen atom attached in position 3 or 5
    • C07D231/22One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16Amino-anthraquinones
    • C09B1/20Preparation from starting materials already containing the anthracene nucleus
    • C09B1/26Dyes with amino groups substituted by hydrocarbon radicals
    • C09B1/28Dyes with amino groups substituted by hydrocarbon radicals substituted by alkyl, aralkyl or cyclo alkyl groups
    • C09B1/285Dyes with no other substituents than the amino groups
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02Photosensitive materials characterised by the image-forming section
    • G03C8/08Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G03C8/10Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
    • G03C8/12Photosensitive 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
    • G03C8/14Oxidation of the chromogenic substances
    • G03C8/16Oxidation of the chromogenic substances initially diffusible in alkaline environment
    • G03C8/18Dye developers

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 dye developer and wherein said hydrolyzable dye developer 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 dye developer is employed and said dye developer is of relatively low mobility until hydrolysis occurs.
  • 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 dye developers, which dye developers 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 dye developers, which dye developers 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 possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • the compounds employed in the present invention possess the properties of both a dye and a developing agent; thus they may be referred to as dye developers.
  • dye developers The nature of these dye developers 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 image-receiving element.
  • the photosensitive element contains a layer of hydrolyzab-le 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.
  • 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. 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 oxidized 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 image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, 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 tem- 3 perature or other conditions.
  • the desired positive image is revealed by stripping the image-receiving element from the photosensitive element at the end of the imbi bition period.
  • the compounds of the present invention may be utilized in the photosensitive element, for example in, on or behind the sliver 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 hydrolyzable dye 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 hydrolyzable dye developer 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 weigh-t, of the dye developer.
  • 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.
  • the liquid processing composition 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 dye developers of the present invention comprise dyes, preferably azo, anthraquinone, indophenol, indoaniline, and azomethine dyes, most preferably azo or anthraquinone dyes, characterized in that they contain not less than one and preferably not more than two groups selected from the group consisting of the alkoxalyl and aryloxalyl esters of aliphatic hydroxyl groups, said dyes being further characterized in that they contain not less than one and preferably not more than two groups selected from the group consisting of orthoand para-dihydroxyphenyl groups.
  • the preferred novel hydrolyzable dye developers of the present invention comprise azo, anthraquinone, indophenol, indoaniline, and azomethine dye developers characterized in that they contain not less than one and not more than two groups within the formula:
  • R is an alkylene group, preferably a lower alkyl-. ene group comprising from 1 to 5 carbon atoms, for example, ethylene, trimethylene, propylene 0H (-(EHOH2) etc.; R is an alkylene group comprising not less than two and not more than four carbon atoms, such as, for example, ethylene, trimethylene, propylene, etc.; n is 0 or an integer from 1 to 3, inclusive; and R is an alkyl or aryl group; said dye being further characterized in that it contains not less than one and not more than two groups selected from the group consisting of o-dihydroxyphenyl and p-dihydroxy-phenyl groups.
  • alkyl groups signified by the term R in Formula A, mention may be made of: ethyl, butyl, hexyl, lauryl, etc.
  • the alkyl group preferably contains from 1 to 12 carbon atoms where n is 0 and from 1 to 4 carbon atoms where n is a positive integer from 1 to 3, inclusive.
  • aryl groups contemplated by R mention may be made of phenyl and substituted phenyl groups, e.g., tolyl, etc.
  • divalent radicals suitable for use in the practice of the present invention, mention may be made of: divalent organic radicals such as alkylene radicals, preferably lower alkylene radicals such as ethylene, isopropylene, etc.; sulfonamido; sulfamyl; carboxamido; carbamyl; arylene radicals such as phenylene, etc.; aralkylene radicals such as phenethyl, etc.; acyl radicals such O -alkylene-i l etc.; and divalent radicals which contain more hetero and carbon atoms as constituent components, as for example
  • R is an ethylene group and the preferred dyes may be characterized in that they contain a single alkylene
  • 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 aliphatic hydroxyl groups with an alkyl and/or an aryl oXalyl halide such as an alkoxalyl or aryloxalyl bromide or chloride, preferably an alkoxalyl or aryloxalyl 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 aliphatic hydroxyl groups
  • an alkyl and/or an aryl oXalyl halide such as an alkoxalyl or aryloxalyl bromide or chloride, preferably an alkoxalyl or
  • the compounds of Formula A may be prepared by reacting a dye, preferably an azo, anthraquinone, indophenol, indoaniline, or azomethine dye, characterized in that it contains not less than one and preferably not more than two aliphatic hydroxyl groups and said dye is further characterized in that it contains not less than one and not more than two groups selected from the group consisting of o-dihydroxyphenyl and p-dihydroxyphenyl groups and halogen and alkyl derivatives thereof; with a compound selected from those represented by the formula:
  • R o(R -o)n iW wherein R R and n have the same significance as noted in Formula A and W is a halogen radical, preferably a chlorine radical; preferably in a reaction medium comprising a suitable anhydrous halogen acid acceptor, e.g., quinoline, pyridine, etc.
  • the reaction is preferably per formed on a steam bath, but it is within the scope of this invention also to employ temperatures that vary from below room temperature to above 100 C. The particular conditions employed will vary according to the oxalyl halide and the halogen acid acceptor employed. It will be understood that the aforementioned dye may contain additional unreacted hydroxyl groups as constituent components of an aromatic system.
  • 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, now abandoned, the subject matter of which has been in-v corporated in Serial No. 824,785 and Serial No. 824,- 786, both filed July 3, 1959, in turn now abandoned, the subject matter of which has been incorporated in, respectively, Serial No. 233,461, filed October 26, 1962 (now U.S. Patent No. 3,135,606, issued June 2, 1964) and Serial No. 318,827, filed October 25, 1963 (now U.S. Patent No. 3,209,016, issued September 28, 1965) Serial No. 485,342, filed January 31, 1955, in the name of Richard S. Corley (now U.S. 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. 678,439 filed August 15, 1957, in the name of Myron S. Simon, now abandoned, the subject matter of which has been incorporated in Serial No. 232,584, filed October 23, 1962 (now U.S. Patent No. 3,131,061, issued April 28, 1964), and Serial No. 232,585, filed October 23, 1962 (now U.S. Patent No. 3,255,206, issued June 7, 1966);
  • Example 1 To prep-are 4- [-p- (2,5'-dihydroxyphenethyl -phenylazo]-3-[N-(fl lauroxalyloxyethyl) carboxamido] 1- phenyl-S-pyrazolone, 20 g. of 3-carbethoxy-1-phenyl-5- pyrazolone are dissolved in 200 cc. of ethanolamine and the solution refluxed for 16 hours. The excess ethanolamine is then removed in vacuo, the residue dissolved in 100 cc. of ethanol and the resultant solution poured into a liter of dilute hydrochloric acid. The solid product, ,3-[N-(B-hydroxyethyl) carboxamido] 1-phenyl-5- pyrazolone, is filtered, crystallized from aqueous ethanol and exhibits a melting point at 160 C.
  • 2,5-bis-acetoxy-phenethyl-aniline prepared according to the procedure disclosed in the copendirug U.S. application of Milton Green and Helen P. Husek, Ser. No. 612,063, filed Sept. 25, 1956 (now abandoned and replaced by Ser. No. 805,673, filed April 1 3, 1959, now US. Patent No. 3,019,254, issued Jan. 30, 1962), is diazotized by adding (0.01 mol) thereof to 20 cc. of water, 1.6 cc. of concentrated hydrochloric acid, and treating at approximately 5 C. with 0.7 g. of sodium nitrite dissolved in 1 0 cc. of water.
  • the diazo product is added, dropwise with stirring, to a. solution of (0.01 mol) of 3-[N-(p-hydroxyethyl) Found 10 carbox-amido]-1-phenyl-5-pyrazolone in 50 cc. of water, 4.2 g. of sodium bicarbonate and 10 cc. of ethanol, the solution having previously been cooled to approximately 5 C.
  • the resulting yellow precipitate is filtered and then treated, under nitrogen, with 25 cc. of ethanol and 25 cc. of a 20% sodium hydroxide solution for five minutes at to C.
  • the resultant product is a solid, 4-[p-(2,5-dihydroxyphenethyl) phenylazo] 3 [N- (ela uroxalyloxyethyl)carboxamido] 1 phenyl-S-pyrazolone.
  • Example 3 To prepare 3 [N (butoxyethoxyethoxalyloxyethyl)- carboxamido] 4 [p-(2',5'-dihydroxyphenethyl)-phenylazo]-1-phenyl-5-pyrazolone, 2 g. (0.004 mol) of 4-[p- (2,5-dihydroxyphenethyl) phenylazo] 3 [N (fi-hydroxyethyD-carboxamido] 1 phenyl-S-pyrazolone, prepared according to the procedure disclosed in Example 1, are dissolved in 30 cc. of anhydrous pyridine. 2.1 g.
  • Example 4 jected to alkali hydrolysis.
  • 1.3 g. of the product 2-[p- (2,5 dihydroxyphenethyl) phenylazo] 4 hydroxyethoxy-l-naphthol are dissolved in 30 cc. of anhydrous pyridine and 2.3 g. (.009 mol) of but-oxyethoxyethoxalyl chloride are added to the solution.
  • the mixture is warmed in vacuo on a steam bath for 4 hours and let stand at room temperature for approximately 12 hours.
  • the solution is then mixed with a dilute hydrochloric acid solution and the resulting slurry filtered.
  • the filter cake exhibiting the consistency of a gum, is dried by repeated concentration from a benzene slurry under vacuum.
  • the resultant residual oil is washed by slurry with benzene and dissolved in 10 cc. of chloroform.
  • the chloroform solution is chilled to 40 C. and clarified with Celite.
  • the clarified solution is concentrated to dryness and the resultant gum redissolved in 5 cc. of chloroform.
  • the clarification procedure is repeated and the desired product obtained by evaporation of the chloroform solution to dryness.
  • Example 5 To prepare 4- [p-(2',5'-dihydroxyphenethyl)-phenylazo] 3 [N (/8 octaoxalyloxyethyl)-carboxamido]-1- phenyl-S-pyrazolone, 2 g. of 4-[p-(2',5'-dihydroxyphenethyl) phenylazo] 3- [N- (,B-hydroxyethyl) -carboxamido] l-phenyl-S-pyrazolone, prepared according to the procedure disclosed in Example 1, are dissolved in 50 cc. of anhydrous pyridine. 2.2 g. of octaoxalyl chloride are added to the solution.
  • the mixture is warmed in vacuo on a steam bath for 2 hours and let stand at room temperature for approximately 12 hours.
  • the solution is then mixed with a dilute hydrochloric acid solution and the resulting slurry filtered.
  • the filter cake is purified by extraction with an acetic-acid/ethyl-acetate mixture.
  • the extract is concentrated to dryness and washed several times with a benzene-hexane mixture.
  • a photosensitive element is prepared by coating a gelatin-coated film base with a solution containing 5% of 4- [p- 2',5 '-dihydroxyphenethyl) -phenylazo] -3- [N-( B- hexoxalyloxyethyl) carboxamido1-l-phenyl-5 -pyrazolone (Formula D as prepared in Example 2), 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 iodo-bromide 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 N-methoxymethyl polyhexamethylene adipamide in 80% aqueous ethanol. After an imbibition period of approximately 1 minute, the image-receiving element is separated and contains a yellow positive dye image of the photographed subject.
  • Example 7 A photosensitive element is prepared by coating a gelatin-coated film base with a solution containing 4% of 4- [p (2',5'-dihydroxyphenethyl) -phenylazo] -3- [N-(B-octaoxalyloxyethyl) carboxamido] 1-phenyl-5-pyrazolone (Formula I as prepared in Example 5), 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% N-methoxymethyl polyhexamethylene adipamide in aqueous ethanol. After an imbibition period of approximately 1 minute, the image-receiving element is separated and contains a yellow positive dye image of the photographed subject.
  • Example 8 A photosensitive element is prepared by coating a gelatin-coated film base with a solution containing 4% of 4- [p (2',5' dihydroxyphenethyl)-phenylazo]-3-[N-(filauroxalyloxyethyl) carboxamido] l-phenyl-S-pyrazolone (Formula F as prepared in Example 1), 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% N-imethoxymethyl polyhexamethylene adipamide in 80% aqueous ethanol. After an imbibition period of approximately 1 minute, the image-receiving element is separated and contains a yellow positive dye image of the photographed subject.
  • Example 9 A photosensitive element is prepared by coating a gelatin-coated film base with a solution containing 4% of 4- butoxyethoxyethoxalyloxyethoxy 2 [p-(2,5'-dihydroxyphenethyl) phenylazo] l-naphthol (Formula G as prepared in Example 4), in a 4% solution of cellulose acetate hydrogen phthalate in a 5 0:50 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 rate of hydrolysis preferably is less than the rate of development.
  • the rate of hydrolysis in the preferred embodiment, thus should exhibit a lag behind the rate of development.
  • the rate of hydrolysis, in unexposed areas of the photosensitive element will be high in comparison to the rate of hydrolysis in exposed areas due to the fact that hydrolyzable dye developer in the unexposed areas is in a reduced form and is thus substantially soluble and hydrolyzable.
  • the dye developer, oxidized as a result of development is during the process in a substantially insoluble form and thus a non-hydrolyzable state.
  • the failure of the hydrolyzable dye developer to hydrolyze in exposed areas serves to enhance the immobilization of oxidized dye developer in exposed areas of the photosensitive element.
  • the sensitivity of an associated silver halide emulsion may be affected by a reaction between the associated dye developer and a sensitlzer 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 employement of the hydrolyzable dye developers of the present invention as precursors to the ultimately desired dye developers ofiers a means of restricting the mobility 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 examples does, contain at least one auxiliary developer, such as p-methylaminophenol [Metol], 2,4-diaminophenol [Amidol], benzylaminophenol, or a 3-pyrazolidone, such as 1-phenyl-3-pyrazolidone [Phenidone].
  • the preferred auxiliary developer is 1- phenyl-3-pyrazolidone. This auxiliary developer serves to accelerate and possibly 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, such as tray or tank development of conventional photosensitive films, plates or papers containing said compounds to obtain black-and- 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-sufficient 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 image-receiving 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 photosensitized 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 containing a silver halide emulsion and a dye selected from the group consisting of monoazo dyes and anthraquinone dyes containing a single anthraquinonyl nucleus, said dyes possessing not less than one and not more than two groups within the formula:
  • R is an alkylene group comprising from 1 to 5 carbon atoms; R is an alkylene group consisting of not less than two and not more than four carbon atoms; n is selected from the group consisting of 0 and the integers from 1 to 3, inclusive; and R is selected from the group consisting of phenyl groups and alkyl groups, said alkyl groups comprising from 1 to 12 carbon atoms where n is 0, and from 1 to 4 carbon atoms where n is an integer from 1 to 3; said dye further possessing not less than one and not more than two groups selected from the group consisting of orthoand para-dihydroxyphenyl groups; effecting removal of the ester groups by hydrolysis subsequent to photoexposure, developing the latent image contained in the exposed silver halide emulsion, immobilizing the dye in exposed areas of the photosensitive element 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
  • hydrolyzable dye comprises 4- [p-(2',5 -dihydroxyphenethyl) -phenylazo] -3- [N- (B hexoxalyloxyethyl)-carboxamido]-1-phenyl-5-pyrazolone.
  • hydrolyzable dye comprises 4- [p- (2',5'-dihydroxyphenethyl) -phenylazo] -3- [N- (5 oetaoxalyloxyethyl)-carboxamido]-1-pheny1-5-pyrazclone.
  • hydrolyzable dye comprises 4- [p- (2,5 '-dihyd-roxyphenethyl) -phenylazo] -3 [N- (B lauroxalyloxyethyl)-carb0xamido]1-phenyl-5-pyrazolone.
  • hydrolyzable dye comprises 3-[N-(butoxyethoxyethoxalyloxyethyl)-carboxarniphenyl-S-pyrazolone.

Description

United States Patent Oilfice Patented Jan. 3, 1967 3,295,973 NOVEL PHOTOGRAPHIC PRODUCTS AND PROCESSES Elkan R. Blout, Belmont, Saul G. Cohen, Lexington, and
Milton Green and Myron S. Simon, Newton, Mass., assignors to Polaroid Corporation, Cambridge, Mass., a corporation of Delaware No Drawing. Continuation of application Ser. No. 813,702, May 18, 1959. This application Nov. 3, 1965, Ser. No. 506,280
6 Claims. (Cl. 96-29) This application is a continuation of our copending US. application, Serial No. 813,702, filed May 18, 1959 (now abandoned), which, in turn, is a continuation-inpart of our copending US. application, Serial No. 697,809, 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 diffusion-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 dye developer and wherein said hydrolyzable dye developer 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 dye developer is employed and said dye developer is of relatively low mobility until hydrolysis occurs.
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 dye developers, which dye developers 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 dye developers, which dye developers 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 possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
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 a developing agent; thus they may be referred to as dye developers. The nature of these dye developers 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 US. 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 image-receiving element. In a preferred embodiment, the photosensitive element contains a layer of hydrolyzab-le 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. 498,672, filed April 1, 1955 (now US. 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 oxidized 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 image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, 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 tem- 3 perature or other conditions. The desired positive image is revealed by stripping the image-receiving element from the photosensitive element at the end of the imbi bition period.
The compounds of the present invention may be utilized in the photosensitive element, for example in, on or behind the sliver 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 hydrolyzable dye developer 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 hydrolyzable dye developer 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 weigh-t, of the dye developer. 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, now abandoned, the subject matter of which has been incorporated in Serial No. 194,359, filed May 14, 1962 (now US. Patent No. 3,230,082, issued January 18, 1966), discloses diffusion-transfer processes of the previously disclosed type which employ hydrolyzable dye developers, These hydrolyzable dye developers are disclosed to be initially less mobile and thus prevent premature transfer of dye developers which might give rise to highlight stain and/or incomplete color separation. The present application is principally concerned with novel hydrolyzable dye developers particularly applicable for use in the processes therein disclosed.
The dye developers of the present invention comprise dyes, preferably azo, anthraquinone, indophenol, indoaniline, and azomethine dyes, most preferably azo or anthraquinone dyes, characterized in that they contain not less than one and preferably not more than two groups selected from the group consisting of the alkoxalyl and aryloxalyl esters of aliphatic hydroxyl groups, said dyes being further characterized in that they contain not less than one and preferably not more than two groups selected from the group consisting of orthoand para-dihydroxyphenyl groups.
The preferred novel hydrolyzable dye developers of the present invention comprise azo, anthraquinone, indophenol, indoaniline, and azomethine dye developers characterized in that they contain not less than one and not more than two groups within the formula:
wherein R is an alkylene group, preferably a lower alkyl-. ene group comprising from 1 to 5 carbon atoms, for example, ethylene, trimethylene, propylene 0H (-(EHOH2) etc.; R is an alkylene group comprising not less than two and not more than four carbon atoms, such as, for example, ethylene, trimethylene, propylene, etc.; n is 0 or an integer from 1 to 3, inclusive; and R is an alkyl or aryl group; said dye being further characterized in that it contains not less than one and not more than two groups selected from the group consisting of o-dihydroxyphenyl and p-dihydroxy-phenyl groups.
As illustrations of suitable alkyl groups signified by the term R in Formula A, mention may be made of: ethyl, butyl, hexyl, lauryl, etc. In general, the alkyl group preferably contains from 1 to 12 carbon atoms where n is 0 and from 1 to 4 carbon atoms where n is a positive integer from 1 to 3, inclusive.
As examples of suitable aryl groups contemplated by R mention may be made of phenyl and substituted phenyl groups, e.g., tolyl, etc.
The respective o-dihydroxyphenyl and p-dihydroxyphenyl group or groups may be linked to the chromopihore-containing component of the dye molecule by utilization of a divalent radical or a covalent bond. As examples of divalent radicals, suitable for use in the practice of the present invention, mention may be made of: divalent organic radicals such as alkylene radicals, preferably lower alkylene radicals such as ethylene, isopropylene, etc.; sulfonamido; sulfamyl; carboxamido; carbamyl; arylene radicals such as phenylene, etc.; aralkylene radicals such as phenethyl, etc.; acyl radicals such O -alkylene-i l etc.; and divalent radicals which contain more hetero and carbon atoms as constituent components, as for example In a preferred embodiment of Formula A, R is an ethylene group and the preferred dyes may be characterized in that they contain a single alkylene linked unsubstituted p-dihydroxyphenyl group. Such compounds may be represented by the formula:
While the preferred compounds of the present invention have been described above as containing a delimited number of recurring ether groups, that is 1 to 4 ether groups, it is to be understood that polyether groups of greater magnitude may be employed, where desired, in accordance with the requirements of the operator.
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 aliphatic hydroxyl groups with an alkyl and/or an aryl oXalyl halide such as an alkoxalyl or aryloxalyl bromide or chloride, preferably an alkoxalyl or aryloxalyl chloride. Where the dye developer has additional available reactive hydroxyl groups, reaction may occur at such additional groups.
The compounds of Formula A may be prepared by reacting a dye, preferably an azo, anthraquinone, indophenol, indoaniline, or azomethine dye, characterized in that it contains not less than one and preferably not more than two aliphatic hydroxyl groups and said dye is further characterized in that it contains not less than one and not more than two groups selected from the group consisting of o-dihydroxyphenyl and p-dihydroxyphenyl groups and halogen and alkyl derivatives thereof; with a compound selected from those represented by the formula:
R o(R -o)n iW wherein R R and n have the same significance as noted in Formula A and W is a halogen radical, preferably a chlorine radical; preferably in a reaction medium comprising a suitable anhydrous halogen acid acceptor, e.g., quinoline, pyridine, etc. The reaction is preferably per formed on a steam bath, but it is within the scope of this invention also to employ temperatures that vary from below room temperature to above 100 C. The particular conditions employed will vary according to the oxalyl halide and the halogen acid acceptor employed. It will be understood that the aforementioned dye may contain additional unreacted hydroxyl groups as constituent components of an aromatic system.
The praparations of numerous of the dye developers preferred for use in synthesizing the hydrolyzable dye developers of the present invention are set forth in the following copending U.S. applications:
Serial No. 445,171, filed July 22, 1954, in the name of Richard S. Corley, 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, now abandoned, the subject matter of which has been incorporated in Serial No. 1,442 and Serial No. 1,443, both filed January 11, 1960, the former in turn abandoned, the subject matter of which has been incorporated in 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 U.S. 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, now abandoned, the subject matter of which has been in-v corporated in Serial No. 824,785 and Serial No. 824,- 786, both filed July 3, 1959, in turn now abandoned, the subject matter of which has been incorporated in, respectively, Serial No. 233,461, filed October 26, 1962 (now U.S. Patent No. 3,135,606, issued June 2, 1964) and Serial No. 318,827, filed October 25, 1963 (now U.S. Patent No. 3,209,016, issued September 28, 1965) Serial No. 485,342, filed January 31, 1955, in the name of Richard S. Corley (now U.S. 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, now abandoned, the subject matter of which has been incorporated in Serial No. 799,427, filed March 16, 1959 (now U.S. 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, now abandoned, the subject matter of which has been incorporated in Serial No. 799,425, filed March 16, 1959, in turn abandoned, the subject matter of which has been incorporated in Serial No. 150,661, filed No- Member 7, 1961 (now U.S. 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. Rog ers, now abandoned, the subject matter of which has been incorporated in Serial No. 144,816, filed October 18, 1961 (now U.S. 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, now abandoned, the subject matter of which has been incorporated in Serial No. 165,930, filed January 12, 1962 (now U.S. Patent No. 3,135,604, issued June 2, 1964);
Serial No. 612,053, filed September 25, 1956, in the name of Myron S. Simon, now abandoned, the subject matter of which has been incorporated in Serial No. 196,523, filed May 21, 1962 (now U.S. Patent No. 3,183,089, issued May 11, 1965), and Serial No. 196,524, filed May 21, 1962 (now U.S. 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, now abandoned, the subject matter of which has been incorporated in Serial No. 197,259, filed May 24, 1962 (now U.S. Patent No. 3,134,763, issued May 26, 1964), and Serial No. 197,283, filed May 24, 1962 (now U.S. Patent No. 3,236,645, issued February 22, 1966);
Serial No. 612,055, filed September 25, 1956, in the name of Helen P. Husek, now abandoned, the subject matter of which has been incorporated in Serial No. 192,354, filed May 4, 1962 (now U.S. Patent No. 3,134,762, issued May 26, 1964), and Serial No. 192,355, filed May 4, 1962 (now U.S. Patent No. 3,236,643, issued February 22, 1966);
Serial No. 663,905, filed June 6, 1957, in the names 0 Milton Green and Howard G. Rogers, now abandoned, the subject matter of which has been incorporated in Serial No. 193,293, filed May 8, 1962 (now U.S. Patent No. 3,173,906, issued March 16, 1965 and Serial No. 193,326, filed May 8, 1962 (now U.S. Patent No.
- 3,222,169, issued December 7, 1965);
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, now abandoned, the subject matter of which has been incorporated in Serial No. 232,584, filed October 23, 1962 (now U.S. Patent No. 3,131,061, issued April 28, 1964), and Serial No. 232,585, filed October 23, 1962 (now U.S. Patent No. 3,255,206, issued June 7, 1966);
Serial No. 680,403, filed August 26, 1957, in the name of Milton Green, now abandoned, the subject matter of which has been incorporated in Serial No. 316,498, filed October 16, 1963 now abandoned;
Serial No. 680,434, filed August 26, 1957, in the name of Milton Green, now abandoned, the subject matter of which has been incorporated in Serial No. 230,287, filed October 12, 1962 (now U.S. Patent No. 3, 230,086,
7 issued January 18, 1966), and Serial No. 230,288, Serial No. 771,719, filed November 4, 1958, in the names filed October 12, 1962 (now US. Patent No. 3,218,312, of Elkan R. Blout and Richard S. Corley, now abanissued November 16, 1965); doned, the subject matter of which has been incorpo- Serial No. 680,437, filed August 26, 1957, in the names rated in Serial No. 193,320, filed May 8, 1962 (now of Elkan R. Blout and Myron S. Simon (now US. US. Patent No. 3,23 d ebruary 22, 1966); Patent No. 3,047,386, issued July 31, 1962); and Serial No. 680,619, filed August 27, 1957, in the name Serial No. 788,893, filed January 26, 1959, in the names of Elkan R. Blout and Myron S. Simon, now abandoned; of Milton Green and Myron S. Simon, now abandoned, Serial No. 685,081, filed September 20, 1957, in the names th u j t ma t r of Which has been incorporated in 1 of Elkan R. Blout, Milton Green, Howard G. Rogers, 10 Serial No. 359,998, filed April 15, 1964.
d Myron S Si b ndoned, the subject mat A preferred compound within the scope of this inventer of which has been incorporated in Serial No. 225,- tion comp 656, filed September 10, 1962 (now US. Patent No. (D) 3,142,565, issued July 28, 1964), and Serial No. 222,- O O OH 702, filed September 10, 1962 (now US. Patent No. I H 3,208,991, issued September 28, 1965); C2H4N=N -L J-NH-OaH4-0-c)- O-O H s rial NO. 703,515, fi1ed December 18, 1957, in the name LL of Milton Green, now abandoned; H0 Serial No. 707,109, filed January 6, 1958, in the names of Elkan R, Blout, Milton Green, Howard G. Rogers 0 0H and Robert B. Woodward, now abandoned; Serial No. 709,001, filed January 15, 1958, in the names of Milton Green, Helen P. Husek and Sydney Kasman, now abandoned, the subject matter of which has been 4- -(2',5-dihydroxyphenethyl)-phenylazo] 3 [N incorporated in Serial NO. 200,639, filed June 7, 1962 hexoxalyloxyethyl)-carboxamido] 1 phenyl-ipyrazo- (now US. Patent No. 3,214,469, issued November 26, 1 As examples of further compounds within the scope Serial No. 709,002, filed January 15, 1958, in the names f hi invention mention may b made of Milton Green and Helen P. Husek, now abandoned, (E the subject matter of which has been incorporated in 3 OH 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, now abandoned, the subject matter of which has been incorpo- 0 0 rated in Serial No. 75,127, filed December 12, 1960, H L & in turn abandoned, the subject matter of which has ih dr h been incorporated in Serial No. 339,615, filed January i gg g fl g li ggg i phenylazo] 4 ethox 23, 1964; 40 Serial N0. 711,811, filed January 29, 1958, in the name a) of Milton Green, now abandoned, the subject matter OH 0 0 0 of which has been incorporated in Serial No. 232,613, C2H4N=N -NH-CrHr-0-i J-( J-o-C H filed October 23, 1962 (now us. Patent NO. 3,246,985, 1 LL issued April 19, 1966); HO Serial No. 748,145, filed July 14, 1958, in the names of Milton Green and Howard G. Rogers, now abandoned, OR the subject matter of which has been incorporated in Serial No. 190,804, filed April 27, 1962 (now US. Patent No. 3,186,982, issued June 1, 1965); Serial NO. 755,804, August 18, in the names 4-[p-(z',s' dihydroxyphenethyl) phenylazo] 3 [N- of Elkan R. Blout, Saul G. Cohen, Milton Green and (fi-la-uroxalyloxyethyl) carboxamido] 1 pheny1-5 y- Serial No. 756,066, filed August 20, 8, in the name 4 butoxyethoxyethoxalyloxyethoxy 2 [p (2',5 dihyof Myron S. Simon, now abandoned; droxyphenethyl)-phenylazo] 1-naphthol 9 3-[N-butoxyethoxyethoxalyloxyethyl) carbox-amido1-4- [p-(2',5' dihydroxyphenethyl) phenylazo] 1 phenyl-5- pyrazolone OH x 4-[5-(2',5-dihydroxyphenyl) u-methyl ethylamino1-1- ethoxalyloxyethylamino-anthraquinone 4-[p-(2,5'-dihydroxyphenethyl) phenylazo] 3 [N- (fl-oct'aoxalyloxyethyl) carboxamido] l-phenyl 5- pyrazolone 4-( 8-ethoxalyloxyethoxy) -1-naphthol.
Example 1 To prep-are 4- [-p- (2,5'-dihydroxyphenethyl -phenylazo]-3-[N-(fl lauroxalyloxyethyl) carboxamido] 1- phenyl-S-pyrazolone, 20 g. of 3-carbethoxy-1-phenyl-5- pyrazolone are dissolved in 200 cc. of ethanolamine and the solution refluxed for 16 hours. The excess ethanolamine is then removed in vacuo, the residue dissolved in 100 cc. of ethanol and the resultant solution poured into a liter of dilute hydrochloric acid. The solid product, ,3-[N-(B-hydroxyethyl) carboxamido] 1-phenyl-5- pyrazolone, is filtered, crystallized from aqueous ethanol and exhibits a melting point at 160 C.
Analysis for nitr0gen.Calculated: 17.0%. 17.0%.
2,5-bis-acetoxy-phenethyl-aniline, prepared according to the procedure disclosed in the copendirug U.S. application of Milton Green and Helen P. Husek, Ser. No. 612,063, filed Sept. 25, 1956 (now abandoned and replaced by Ser. No. 805,673, filed April 1 3, 1959, now US. Patent No. 3,019,254, issued Jan. 30, 1962), is diazotized by adding (0.01 mol) thereof to 20 cc. of water, 1.6 cc. of concentrated hydrochloric acid, and treating at approximately 5 C. with 0.7 g. of sodium nitrite dissolved in 1 0 cc. of water.
The diazo product is added, dropwise with stirring, to a. solution of (0.01 mol) of 3-[N-(p-hydroxyethyl) Found 10 carbox-amido]-1-phenyl-5-pyrazolone in 50 cc. of water, 4.2 g. of sodium bicarbonate and 10 cc. of ethanol, the solution having previously been cooled to approximately 5 C. The resulting yellow precipitate is filtered and then treated, under nitrogen, with 25 cc. of ethanol and 25 cc. of a 20% sodium hydroxide solution for five minutes at to C. Acidification of the resulting solution with dilute hydrochloric acid and recrystallization from ethanol yields 4-[p-(2,5dihydroxyphenethyl) phenylazo]-S-[N-(B hydroxyethyl) carboxamido] 1- phenyl-S-pyrazolone melting at 246 to 248 C. The product is soluble in organic solvents such as acetone and ethanol, resulting in a yellow solution. The absorption spectrum of this compound in ethanol exhibits a kmax, at 450 my, e=26,300.
1.5 g. of the above yellow dye developer are dissolved in 100 cc. of dry pyridine and 2.5 g. of lauroxalyl chloride are added. The solution is warmed on a steam bath for two hours, taking care to exclude moisture, and then poured into a solution of ice and dilute hydrochloric acid. The solid residue which separated is warmed with 50 cc. of absolute ethanol, chilled approximately 12 hours and a small amount of the starting material which had precipitated is removed by filtration. The filtrate is evaporated to dryness, the residue triturated with benzene and then filtered. The resultant product is a solid, 4-[p-(2,5-dihydroxyphenethyl) phenylazo] 3 [N- (ela uroxalyloxyethyl)carboxamido] 1 phenyl-S-pyrazolone.
Analysis for 9.8%.
nitr0gen.Calculated: 9.8%. Found Example 2 To prepare 4- [p-(2,5'-dihydroxyphenethyl)-phenylazo] 3 [N (B hexoxalyloxyethyl) carboxamido]-1 phenyl-S-pyrazolone, 1.5 g. of 4-[p-(2,5-dihydr-oxyphenethyl)-phenylazo] 3 [N-(B-hydroxyethyl)-carbox amido]-l-phenyl-5-pyrazolone, prepared according to the procedure disclosed in Example 1, are dissolved in 100 cc. of anhydrous pyridine, 2.5 g. of hexoxalyl chloride are added to the solution and the esterification is conducted under conditions substantially similar to those disclosed in Example 1. The resultant product is a yellow solid, 4 [p (2,5'-dihydroxyphenethyl)-phenylazo]-3-[N-(fihexoxalyloxyethyl) -carboxamido] -1-phenyl-5pyrazolone.
Example 3 To prepare 3 [N (butoxyethoxyethoxalyloxyethyl)- carboxamido] 4 [p-(2',5'-dihydroxyphenethyl)-phenylazo]-1-phenyl-5-pyrazolone, 2 g. (0.004 mol) of 4-[p- (2,5-dihydroxyphenethyl) phenylazo] 3 [N (fi-hydroxyethyD-carboxamido] 1 phenyl-S-pyrazolone, prepared according to the procedure disclosed in Example 1, are dissolved in 30 cc. of anhydrous pyridine. 2.1 g. (.006 mol) of butoxyethoxyethoxalyl chloride are added to the solution, the mixture is warmed in vacuo on a steam bath for 3 hours and let stand at room temperature for approximately 12 hours. The solution is then mixed with a dilute hydrochloric acid solution and the resulting granular slurry filtered. The filter cake is washed with water and dried by concentrating several times, under vacuum, a benzene slurry of the filter cake. The resultant residual gum is washed several times by slurry with benzene and extracted with chloroform. The desired product is obtained by evaporation of the'chloroform solution to dryness.
Example 4 jected to alkali hydrolysis. 1.3 g. of the product 2-[p- (2,5 dihydroxyphenethyl) phenylazo] 4 hydroxyethoxy-l-naphthol are dissolved in 30 cc. of anhydrous pyridine and 2.3 g. (.009 mol) of but-oxyethoxyethoxalyl chloride are added to the solution. The mixture is warmed in vacuo on a steam bath for 4 hours and let stand at room temperature for approximately 12 hours. The solution is then mixed with a dilute hydrochloric acid solution and the resulting slurry filtered. The filter cake, exhibiting the consistency of a gum, is dried by repeated concentration from a benzene slurry under vacuum. The resultant residual oil is washed by slurry with benzene and dissolved in 10 cc. of chloroform. The chloroform solution is chilled to 40 C. and clarified with Celite. The clarified solution is concentrated to dryness and the resultant gum redissolved in 5 cc. of chloroform. The clarification procedure is repeated and the desired product obtained by evaporation of the chloroform solution to dryness.
Example 5 To prepare 4- [p-(2',5'-dihydroxyphenethyl)-phenylazo] 3 [N (/8 octaoxalyloxyethyl)-carboxamido]-1- phenyl-S-pyrazolone, 2 g. of 4-[p-(2',5'-dihydroxyphenethyl) phenylazo] 3- [N- (,B-hydroxyethyl) -carboxamido] l-phenyl-S-pyrazolone, prepared according to the procedure disclosed in Example 1, are dissolved in 50 cc. of anhydrous pyridine. 2.2 g. of octaoxalyl chloride are added to the solution. The mixture is warmed in vacuo on a steam bath for 2 hours and let stand at room temperature for approximately 12 hours. The solution is then mixed with a dilute hydrochloric acid solution and the resulting slurry filtered. The filter cake is purified by extraction with an acetic-acid/ethyl-acetate mixture. The extract is concentrated to dryness and washed several times with a benzene-hexane mixture.
Example 6 A photosensitive element is prepared by coating a gelatin-coated film base with a solution containing 5% of 4- [p- 2',5 '-dihydroxyphenethyl) -phenylazo] -3- [N-( B- hexoxalyloxyethyl) carboxamido1-l-phenyl-5 -pyrazolone (Formula D as prepared in Example 2), 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 iodo-bromide emulsion is applied. This photosensitive element is exposed and processed by spreading an aqueous liquid processing composition comprising:
Percent Sodium carboxymethyl cellulose 4.5 1-phenyl-3-pyrazolidone 0.2 Sodium hydroxide 2.5 Potassium bromide 0.2
between said photosensitive element and an imagereceiving 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 N-methoxymethyl polyhexamethylene adipamide in 80% aqueous ethanol. After an imbibition period of approximately 1 minute, the image-receiving element is separated and contains a yellow positive dye image of the photographed subject.
Example 7 A photosensitive element is prepared by coating a gelatin-coated film base with a solution containing 4% of 4- [p (2',5'-dihydroxyphenethyl) -phenylazo] -3- [N-(B-octaoxalyloxyethyl) carboxamido] 1-phenyl-5-pyrazolone (Formula I as prepared in Example 5), 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:
Percent Sodium carboxymethyl cellulose 4.5 1-phenyl-3-pyrazolidone 0.2 Sodium hydroxide 1.5 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 yellow positive dye image of the photographed subject.
Example 8 A photosensitive element is prepared by coating a gelatin-coated film base with a solution containing 4% of 4- [p (2',5' dihydroxyphenethyl)-phenylazo]-3-[N-(filauroxalyloxyethyl) carboxamido] l-phenyl-S-pyrazolone (Formula F as prepared in Example 1), 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:
Percent Sodium carboxymethyl cellulose 5.0 lphenyl-3-pyrazolidone 0.6 Sodium hydroxide 3.0 6-nitrobenzimidazole 0.009
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-imethoxymethyl polyhexamethylene adipamide in 80% aqueous ethanol. After an imbibition period of approximately 1 minute, the image-receiving element is separated and contains a yellow positive dye image of the photographed subject.
Example 9 A photosensitive element is prepared by coating a gelatin-coated film base with a solution containing 4% of 4- butoxyethoxyethoxalyloxyethoxy 2 [p-(2,5'-dihydroxyphenethyl) phenylazo] l-naphthol (Formula G as prepared in Example 4), in a 4% solution of cellulose acetate hydrogen phthalate in a 5 0:50 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:
Percent Sodium carboxymethyl cellulose 5.0 1-phenyl-3-pyrazolidone 0.8 Sodium hydroxide 3.0 6-nit-robenzimidazole 0.12 2,5-bis-ethyleneiminohydroquinone 0.6
1 3 tion of dye developers Whose rate of diffusion might be too rapid to permit effective control if utilized initially in the free or hydrolyzed state.
Although hydrolysis may initiate immediately, the rate of hydrolysis preferably is less than the rate of development. The rate of hydrolysis, in the preferred embodiment, thus should exhibit a lag behind the rate of development.
In all embodiments of the present invention where the developing function is available for reaction prior to hydrolysis, the rate of hydrolysis, in unexposed areas of the photosensitive element, will be high in comparison to the rate of hydrolysis in exposed areas due to the fact that hydrolyzable dye developer in the unexposed areas is in a reduced form and is thus substantially soluble and hydrolyzable. In exposed areas of the photosensitive element the dye developer, oxidized as a result of development, is during the process in a substantially insoluble form and thus a non-hydrolyzable state. The failure of the hydrolyzable dye developer to hydrolyze in exposed areas serves to enhance the immobilization of oxidized dye developer in exposed areas of the photosensitive element.
In certain instances, the sensitivity of an associated silver halide emulsion may be affected by a reaction between the associated dye developer and a sensitlzer 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 employement of the hydrolyzable dye developers of the present invention as precursors to the ultimately desired dye developers ofiers a means of restricting the mobility 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 examples does, contain at least one auxiliary developer, such as p-methylaminophenol [Metol], 2,4-diaminophenol [Amidol], benzylaminophenol, or a 3-pyrazolidone, such as 1-phenyl-3-pyrazolidone [Phenidone]. The preferred auxiliary developer is 1- phenyl-3-pyrazolidone. This auxiliary developer serves to accelerate and possibly 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, such as tray or tank development of conventional photosensitive films, plates or papers containing said compounds to obtain black-and- White, monochromatic or toned prints or negatives. By the 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-sufficient 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 image-receiving 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 photosensitized 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 containing a silver halide emulsion and a dye selected from the group consisting of monoazo dyes and anthraquinone dyes containing a single anthraquinonyl nucleus, said dyes possessing not less than one and not more than two groups within the formula:
wherein R is an alkylene group comprising from 1 to 5 carbon atoms; R is an alkylene group consisting of not less than two and not more than four carbon atoms; n is selected from the group consisting of 0 and the integers from 1 to 3, inclusive; and R is selected from the group consisting of phenyl groups and alkyl groups, said alkyl groups comprising from 1 to 12 carbon atoms where n is 0, and from 1 to 4 carbon atoms where n is an integer from 1 to 3; said dye further possessing not less than one and not more than two groups selected from the group consisting of orthoand para-dihydroxyphenyl groups; effecting removal of the ester groups by hydrolysis subsequent to photoexposure, developing the latent image contained in the exposed silver halide emulsion, immobilizing the dye in exposed areas of the photosensitive element 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 imagewise distribution to a superposed irnage-receiving layer to impart thereto a positive dye image.
2. The process of forming transfer images in color as defined in claim 1, wherein said hydrolyzable dye comprises 4- [p-(2',5 -dihydroxyphenethyl) -phenylazo] -3- [N- (B hexoxalyloxyethyl)-carboxamido]-1-phenyl-5-pyrazolone.
3. The process of forming transfer images in color as defined in claim 1, wherein said hydrolyzable dye comprises 4- [p- (2',5'-dihydroxyphenethyl) -phenylazo] -3- [N- (5 oetaoxalyloxyethyl)-carboxamido]-1-pheny1-5-pyrazclone.
4. The process of forming transfer images in color as defined in claim 1, wheren said hydrolyzable dye comprises 4- [p- (2,5 '-dihyd-roxyphenethyl) -phenylazo] -3 [N- (B lauroxalyloxyethyl)-carb0xamido]1-phenyl-5-pyrazolone.
5. The process of forming transfer images in color as defined in claim 1, wheren said hydrolyzable dye comprises 3-[N-(butoxyethoxyethoxalyloxyethyl)-carboxarniphenyl-S-pyrazolone.
6. The process of forming transfer images in color as defined in claim 1, wheren said hydrolyzable dye cornl 6 prises 4 (butoxyethoxyethoxalyloxyethoxy) -2- [p- (2',5 dihydroxyphenethyl) -phenylazo] -1-naphthol.
References Cited by the Examiner UNITED STATES PATENTS 2,751,295 6/1956 Salminen 96-100 2,756,142 7/1956 Yutzy 96-3 2,983,606 5/1961 Rogers 9629 3,134,672 5/1964 Blout et a1. 96-29 FOREIGN PATENTS 554,935 8/1957 Belgium. 569,080 1/ 1959 Belgium.
NORMAN G. TORCHIN, Primary Examiner.
J. TRAVIS BROWN, Examiner.

Claims (1)

1. A PROCESS OF FORMING TRANSFER IMAGES IN COLOR WHICH COMPRISES THE STEPS OF EXPOSING A PHOTOSENSITIVE ELEMENT CONTAINING A SILVER HALIDE EMULSION AND A DYE SELECTED FROM THE GROUP CONSISTING OF MONOAZO DYES AND ANTHRAQUINONE DYES CONTAINING A SINGLE ANTHRAQUINONYL NUCLEUS, SAID DYES POSSESSING NOT LESS THAN ONE AND NOT MORE THAN TWO GROUPS WITHIN THE FORMULA:
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