US3630730A - Diffusion transfer processes and elements comprising dye developers and bis-sulfonyl alkane speed-increasing agents - Google Patents

Abstract

Increased print speeds are provided in color diffusion transfer systems by processing in the presence of 1,1 bis-sulfonyl alkane speed increasing agents.

Description

United States Patent 1, Paul H. Stewart; Donald W. I-leseltine, both of Rochester, N.Y. 42,608 June 1, 1970 Dec. 28, 1971 Eastman Kodak Company Rochester, N.Y.

Inventors App]. No.

Patented Assignee DIFFUSION TRANSFER PROCESSES AND ELEMENTS COMPRISING DYE DEVELOPERS AND BIS-SULFONYL ALKANE SPEED- INCREASING AGENTS 33 Claims, No Drawings us. Cl

[51] Int. Cl G03c 7/00, G03c 5/54, G030 1/48 [50] Field of Search 96/663, 107, 3, 56.6

[56] References Cited UNITED STATES PATENTS 3,287,133 11/1966 Williams,Jr 96/77 Primary ExaminerNorman G. Torchin Assistant Examiner-Alfonso T. Suro Pico Attorneys-W. H. J. Kline, J. R. Frederick and H. E. Cole ABSTRACT: Increased print speeds are provided in color diffusion transfer systems by processing in the presence of 1,1 bis-sulfonyl alkane speed increasing agents.

DIFFUSION TRANSFER PROCESSES AND ELEMENTS COMPRISING DYE DEVELOPERS AND BIS-SULFONYL ALKANE SPEED-INCREASING AGENTS This invention relates to the art of photography and to a multicolor diffusion transfer system. More particularly, this in vention relates to dye developer transfer systems having increased speed.

A diffusion transfer color process has been described wherein photographic elements containing silver halide emulsion layers and layers containing diffusible dye developers (dyes having a silver halide developing function) are exposed to record the latent image in the silver halide and then treated with an alkaline processing composition which permeates the emulsion layers and layers containing the dye developers which then develop the latent images to silver images. At the same time, oxidation products of the dye developers are formed in situ with the silver images and which are relatively nondiffusing in the colloid vehicle of the layers.

The nondiffusing character of the oxidized dye developers is apparently due, at least in part, to a decrease in solubility in the alkaline processing liquid, and may also be due to a hardening efi'ect of the oxidized developer upon the colloid vehicles of the layers which retards the diffusion of the oxidized dye developers. The residual unoxidized dye developers remaining in the layers in imagewise distribution aretransferred by diffusion to a superposed reception element substantially to the exclusion of the silver image and oxidized dye developer to provide a positive dye image.

When an element containing differentially sensitized silver halide emulsion layers is used and substractively colored dye developers are present in or are contiguous to the respective emulsion layers, the dye developers are oxidized and rendered nondiffusing in the developed regions of the layers upon treatment with the processing liquid. The residual dye developer images in the positive regions are transferred by diffusion and in register to the reception element to provide a multicolor reproduction.

Various addenda have been suggested as development modifiers for diffusion transfer systems. For example, it has been suggested to add polyalkylene glycols, cationic surface active agents and thioethers, or combinations of these, to silver halide emulsions as speed-increasing compounds. Such speed-increasing compounds are described in Piper U.S. Pat. No. 2,886,437; Dann et al. U.S. Pat. No. 3,046,134; Carroll et al. U.S. Pat. No. 2,944,900; and Goffe U.S. Pat. No. 3,294,450. It would be highly desirable to provide a novel class of speed-increasing addenda for dye developer diffusion transfer systems.

lt is therefore an object of this invention to provide novel color diffusion transfer materials capable of providing increased speeds.

A further object of this invention is to provide a novel process for the production of a multicolor diffusion transfer image employing novel film units having increased speed.

These and other objects are achieved in accordance with the present invention whereby color diffusion transfer processes are conducted in the presence of a l,l bis-sulfonyl alkane (or fi-disulfone) speed-increasing agent. lt has been found that the B-disulfones used in the present invention substantially increase the speed of dye developer-silver halide coatings that are processed with an alkaline activator.

The B-disulfones and their chemical reactions have been described in the literature. For example, the preparation of these compounds and reactions in which they are involved is described in Suter, Organic Chemistry of Sulfur, on pages 735 and 739. However, it has now been discovered that particular B-disulfones, namely, l,l bis-sulfonyl alkanes provide increased film speeds in color diffusion transfer systems.

Suitable l,l bis-sulfonyl alkanes used in the present invention can be represented by the general formula.

wherein R, and R each represent a lower alkyl group and R represents H or a lower alkyl group. The term "lower alkyl as employed herein is preferably an alkyl group containing from about one to four carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl and the like. The tenn "alkyl" as employed herein also includes substituted alkyl groups, and is preferably a substituted lower alkyl group containing from one to four carbon atoms. Thus, substituted lower alkyl groups such as a hydroxyalkyl group, e.g., B-hydroxyethyl, w-hydroxybutyl, etc.; an alkoxy-alkyl group, e.g., B-methoxyethyl, w-butoxybutyl, etc.; a carboxyalkyl group, e.g., B-carboxyethyl, m-carboxybutyl, etc.; a sulfoalkyl group, e.g., B-sulfoethyl, w-sulfobutyl, etc.; a sulfatoalkyl group, e.g.; B-sulfatoethyl, m-sulfatobutyl, etc.; an acryloxyalkyl group, e.g., B-acetoxyethyl, w-butyryloxybutyl, etc.; an alkoxycarbonylalkyl group, e.g., B- methoxycarbonylethyl, w-ethoxycarbonylbutyl, etc., are preferred.

l,l Bis-sulfonyl alkanes within the above formula include l,l bis-(methylsulfonyl)ethane; l,l bis-(ethylsulfonyl)- ethane; l,l bis-(methylsulfonyl)propane; l,l bis-(ethylsulfonyl)-propane; l-ethylsulfonyl-l-methylsulfonyl methane; lethylsulfonyl-l-methylsulfonyl ethane; etc. Especially preferred l,l bis-sulfonyl alkanes are bis(methylsulfonyl)rnethane, bis(ethyl-sulfonyl)methane, bis(B-hydroxyethylsulfonyl)methane, bis( carboxymethylsulfonyl )methane, and bis(B-carboxyethylsulfonyl )methane.

A photographic film unit of our invention which is adapted to be processed by passing the unit between a pair of juxtaposed pressure-applying members, such as would be found in a camera designed for in-camera processing, comprises:

a. a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, each said silver halide emulsion layer having associated therewith a dye developer, i.e., a compound which contains in the same molecule both the chromophoric system of a dye and also silver halide developing function;

b. a dye image-receiving layer; and

c. a rupturable container containing an alkaline processing composition;

the film unit containing as a speed-increasing agent, a 1,1 bissulfonyl alkane; the rupturable container being adapted to be positioned during processing of said film unit so that a compressive force applied to the container by the pressure-applying members will effect a discharge of the containers contents within said film unit.

The dye image-receiving layer of the film unit can be located on a separate support adapted to be superposed on the photosensitive element after exposure thereof. Such imagereceiving elements are disclosed, for example, in U.S. Pat. No. 3,362,819. The rupturable container is usually positioned during processing of said film unit so that a compressive force applied to the container by pressure-applying members in a camera will effect a discharge of the containers contents between the image-receiving element and the outermost layer of the photosensitive element.

The dye image-receiving layer can also be located integral with the photosensitive element between the support and the lowermost photosensitive silver halide emulsion layer. Such integral receiver-negative photosensitive elements are disclosed, for example, in U.S. Pat. No. 3,415,644, and are useful in camera apparatus of the type disclosed in Belgian Pat. Nos. 7 l 8,553 and 718,554.

As previously indicated, the process of the invention is carried out in the presence of particular B-disulfones. These compounds may be utilized in the alkaline processing composition or in one or more layers of the photosensitive element, e.g., as an emulsion addendum or a layer contiguous thereto, or in the reception element.

The B-disulfone compounds of the invention can be used in a wide range of concentrations in a photographic film unit, with optimum amounts varied with the particular B-disulfone compound employed. For example, typical useful amounts of the disulfone compound in the alkaline processing composition ranges from between about 0.1 and about 1.0 percent by weight, and preferably between about 0.2 and about 0.5 percent of the activator composition. 1f the disulfone compound is to be employed in the photosensitive element or reception element, good results are obtained when between about 0.1 and about 1.0 mole of the disulfone is employed per mole of silver halide with processing generally taking place at a pH above about 9.5.

The film assembly of the present invention may be used to produce positive images in single or multicolors. In a threecolor system, each silver halide emulsion layer of a film assembly of the present invention will have associated therewith a dye developer possessing a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion. Thus, the blue-sensitive silver halide emulsion will have a yellow dye developer associated therewith, the green-sensitive silver halide emulsion layer will have a magenta dye developer associated therewith, and the red-sensitive silver halide emulsion layer will have a cyan dye developer associated therewith. The dye developer associated with each silver halide emulsion layer may be contained either in the silver halide emulsion layer itself or in a layer contiguous to the silver halide emulsion layer, typically under the silver halide layer with respect to the exposure direction.

Good results are obtained when dye developers are employed in separate layers contiguous to each silver halide emulsion layer. Such layers may be applied by using a coating solution containing between about 0.5 and about 8 percent, by weight, of the dye developer distributed in a hydrophilic filmforming natural material or synthetic polymer such as gelatin, polyvinyl alcohol, etc., which is adapted to the permeated by aqueous alkaline processing composition.

The various silver halide emulsion layers of a color film assembly of the present invention may be disposed in the usual order, i.e., the blue-sensitive silver halide emulsion layer first with respect to the exposure side, followed by the green-sensitive and red-sensitive silver halide emulsion layers. 1f desired, a yellow dye layer or a Carey Lea silver layer may be present between the blue-sensitive and green-sensitive silver halide emulsion layers for absorbing or filtering blue radiation that may be transmitted through the blue-sensitive layer. if desired, the selectively sensitized silver halide emulsion layers may be disposed in a different order. For example, the red-sensitive layer may be placed first with respect to the exposure side, followed by the green-sensitive and blue-sensitive layers.

As previously mentioned, dye developers are compounds which contain both the chromophoric system of a dye and a silver halide developing function in the same molecule. A preferred silver halide developing moiety in such dye developers is a hydroquinonyl group. Dye developers and their functioning in color diffusion transfer systems are well known in the art as shown, for example, by U.S. Pat. Nos. 2,983,606; 2,992,106; 3,047,386; 3,076,808; 3,076,820; 3,077,402; 3,126,280; 3,131,061; 3,134,762; 3,134,765; 3,135,604; 3,135,605; 3,135,606; 3,135,734; 3,141,772; and 3,142,565.

The liquid processing composition employed in this invention is the conventional aqueous solution of an alkaline material, e.g., sodium hydroxide, sodium carbonate or an amine such as diethylamine, preferably possessing a pH in ex cess of 12. The processing composition also preferably contains a viscosity-increasing compound such as a high molecular weight polymer e.g., a water-soluble ether inert to alkaline solutions such as hydroxyethyl cellulose or alkali metal salts of carboxymethyl cellulose such as sodium carboxymethyl cellulose. A concentration of viscosity-increasing compound of about 1 to percent by weight of the processing composition is preferred which will impart thereto a viscosity of about 100 to about 200,000 c.p.s.

The processing composition can also contain sodium thiosulfate, for example, in an amount of about 1 percent by weight of the activator composition. The presence of hypo in the activator in an amount of, e.g., 1 mole per mole of disulfone is a preferred aspect of the present invention. The hypo coacts with the disulfone to produce prints with increased speed.

The silver halide emulsions employed in the film unit of the invention can comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof. The emulsions can be coarse or fine grain and can be prepared by any of the well-known procedures, e.g., single jet emulsions, double jet emulsions, such as Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions such as those described in Nietz et al. U.S. Pat. No. 2,222,264; lllingsworth U.S. Pat. No. 3,320,069; and McBride U.S. Pat. No. 3,271,157. Surface image emulsions can be used or internal image emulsions can be used such as those described in Davey et al. U.S. Pat. No. 2,592,250; Porter et al. U.S. Pat. No. 3,206,313; and Bacon et al. U.S. Pat. No. 3,447,927. The emulsions may be regular grain emulsions such as the type described in Klein and Moisar, J. PhOI. Sci., Vol. 12, No. 5, Sept/Oct, 1964, pp. 242-251. If desired, mixtures of surface and internal image emulsions can be used as described in Luckey U.S. Pat. No. 2,996,382. Negative-type emulsions can be used or direct positive emulsions can be used such as those described in Leermakers U.S. Pat. No. 2,184,013; Kendall et al. U.S. Pat. No. 2,541,472; Berriman U.S. Pat. No. 3,367,778; Schouwenaars British Pat. No. 723,019; lllingsworth et al. French Pat. No. 1,520,821; lves U.S. Pat. No. 2,563,785; Knott et al. U.S. Pat. No. 2,456,953 and Land U.S. Pat. No. 2,861,885.

The emulsions in this invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur; selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these. Suitable procedures are described in Sheppard et al. U.S. Pat. No. 1,623,499; Waller et al. U.S. Pat. No. 2,399,083; McVeigh U.S. Pat. No. 3,297,447; and Dunn U.S. Pat. No. 3,297,446.

Likewise, the silver halide emulsions can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping. Suitable antifoggants and stabilizers each used alone or in combination include thiazolium salts described in Brooker et al. U.S. Pat. No. 2,131,038 and Allen et a1. U.S. Pat. No. 2,694,716; the azaindenes described in Piper U.S. Pat. No. 2,886,437 and Heimbach et al. U.S. Pat. No. 2,444,605; the mercury salts as described in Allen et al. U.S. Pat. No. 2,728,663; the urazoles described in Anderson et al. U.S. Pat. No. 3,287,135; the sulfocatechols described in Kennard et al. U.S. Pat. No, 3,236,652; the oximes described in Carroll et al. British Pat. No. 623,448; nitron; nitroindazoles; the mercaptotetrazoles described in Kendall et al. U.S. Pat. No. 2,403,927; Kennard et al. U.S. Pat. No. 3,266,897 and Luckey et al. U.S. Pat. No. 3,397,987; the polyvalent metal salts described in Jones U.S. Pat. No. 2,839,405; the thiuronium salts described in Herz et al. U.S. Pat. No. 3,220,839; the palladium, platinum and gold salts described in Trivelli et al. U.S. Pat. No. 2,566,263 and Yutzy et al. U.S. Pat. No. 2,597,915.

The photographic elements of the present invention can contain incorporated auxiliary developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and phenylenediamines. Combinations of developing agents can be employed in the practice of the invention. The developing agents can be in a silver halide emulsion and/or in another suitable location in the photographic element. Especially useful auxiliary developing agents are colorless hydroquinone derivatives such as those listed in column 6 of U.S. Pat. No. 3,253,915 of Weyerts et al. issued May 31, 1966.

Spectral sensitizing dyes can be used to confer additional sensitivity to the light-sensitive silver halide emulsion of the multilayer photographic elements of the invention. For instance, additional spectral sensitization can be obtained by treating the emulsion with a solution of a sensitizing dye in an organic solvent or the dye may be added in the form of a dispersion as described in Owens et al. British Pat. No.

1,154,781. For optimum results, the dye may either be added to the emulsion as a final step or at some earlier stage.

Sensitizing dyes useful in sensitizing such emulsions are described, for example, in Brooker et al. U.S. Pat. No. 2,526,632, issued Oct. 24, 1950; Sprague U.S. Pat. No. 2,503,776, issued Apr. 11, 1950; Brooker et al. U.S. Pat. No. 2,493,748; and Taber et al. U.S. Pat. No. 3,384,486. Spectral sensitizers which can be used include the cyanines, merocyanines, complex (tri or tetranuclear) merocyanines, complex (tri or tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines ('e.g., enamine hemicyanines), oxonols and hemioxonols. Dyes of the cyanine classes may contain such basic nuclei as the thiaaolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles. Such nuclei may contain alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine groups and may be fused to carbocyclic or heterocyclic ring systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano, or alkoxy groups. The dyes may be symmetrical or unsymmetrical and may contain alkyl, phenyl, enamine or heterocyclic substituents on the methine or polymethine chain. The merocyanine dyes may contain the basic nuclei mentioned above as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones, and malononitrile. These acid nuclei may be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups, or heterocyclic nuclei. Combinations of these dyes may be used, if desired. in addition, supersensitizing addenda which do not absorb visible light may be included, for instance, ascorbic acid derivatives, azaindenes, cadmium salts, and organic sulfonic acids as described in McFall et al. U.S. Pat. No. 2,933,390 and Jones et al. U.S. Pat. No. 2,937,089.

The various layers, including the photographic layers, employed in the practice of this invention can contain light absorbing materials and filter dyes such as those described in Sawdey U.S. Pat. No. 3,253,921; Gasper U.S. Pat. No. 2,274,782; Silberstein et al. U.S. Pat. No. 2,527,583 and Van- Campen U.S. Pat. No. 2,956,879. If desired, the dyes can be mordanted, for example, as described in Jones et al. U.S. Pat. No. 3,282,699.

The sensitizing dyes and other addenda used in the practice of this invention may be added from water solutions or suitable organic solvent solutions may be used. The compounds can be added using various procedures including those described in Collins et al. U.S. Pat. No. 2,912,343; McCrossen et al. U.S. Pat. No. 3,342,604; Audran U.S. Pat. No. 2,996,287 and Johnson et al. U.S. Pat. No. 3,425,835.

In a color film unit according to the present invention, each silver halide emulsion layer containing a dye developer or having the dye developer present in a contiguous layer may be separated from the other silver halide emulsion layers in the film unit by materials including gelatin, calcium alginate, or any of those disclosed in U.S. Pat. No. 3,384,483, polymeric materials such as polyvinylamides as disclosed in U.S. Pat. No. 3,421,892, or any of those disclosed in U.S. Pat. Nos. 2,992,104; 3,043,692; 3,044,873; 3,061,428; 3,069,263; 3,069,264; 3,121,01 1;and 3,427,158.

Generally speaking, except where noted otherwise, the silver halide emulsion layers of the invention comprise photosensitive silver halide dispersed in gelatin and are about 0.6 to 6 microns in thickness; the dye developers are dispersed in an aqueous alkaline solution-permeable polymeric binder, such as gelatin, as a separate layer about 1 to 7 microns in thickness; and the alkaline solution-permeable polymeric interlayers, e.g., gelatin, are about 1 to 5 microns in thickness. Of course, these thicknesses are approximate only and can be modified according to the product desired.

The layers of the photographic element employed and described herein can be coated on a wide variety of supports. Typical supports include cellulose nitrate film, cellulose ester film, poly(vinyl acetal)film, polystyrene film, po1y(ethylene terephthalate) film, polycarbonate film and related films or resinous materials, as well as glass, paper, metal and the like. Typically, a flexible support is employed, especially a paper support, which can be partially acetylated or coated with baryta and/or an alpha-olefin polymer, particularly a polymer of an alpha-olefin containing two to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.

Any material can be employed as the image-receiving layer in this invention as long as the desired function of mordanting or otherwise fixing the dye developer images will be obtained. Suitable image-receiving materials include Nmethoxymethyl polyhexylmethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plasticizers; cellulose acetate; gelatin; and other materials of a similar nature. Polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine as disclosed in U.S. Pat. No. 3,148,061 can also be employed in the invention with good results. Generally the image-receiving layer is from about 0.25 to about 0.04 mil in thickness. This thickness, of course, may be modified depending upon the result desired. The imagereceiving layer may also contain ultraviolet absorbing materials to protect the mordanted dye images from fading due to ultraviolet light.

ln addition to conventional techniques for the direct dispersion of a particulate solid material in a polymeric or colloidal matrix such as ball-milling and the like techniques, the preparation of a dye developer dispersion can also be obtained by dissolving the dye developer in an appropriate solvent or mixture of solvents, dispersing the resultant solution in the polymeric binder, with optional subsequent removal of the solvent or solvents employed. Further details concerning these dispersing techniques and the solvents employed are found, for example, in U.S. Pat. Nos. 2,269,158; 2,322,027; 2,304,939; 2,304,940; 2,801 ,17 1, etc.

The following examples will serve to further illustrate the present invention.

EXAMPLES l-3 A photosensitive element is prepared by coating a subbed film support comprising cellulose acetate with suitable hardened gelatin layers successively as follows:

1. Cyan Dye Developer Layer The cyan dye developer 5,8-dihydroxy-1,4-bis[(B- hydroquinonyl-a-methyl)ethylamino] anthraquinone is dissolved in a mixture of N-n-butylacetanilide and 4-methylcyclohexanone and dispersed in an aqueous gelatin solution with a sodium alkylnaphthalene sulfonate dispersing agent. The mixture is passed through a colloid mill several times, coated on the subbed support and dried so as to volatilize the 4-methylcyclohexanone.

2. Red-Sensitive Emulsion Layer A gelatino silver bromoiodide emulsion layer, which is sensitized to the red region of the spectrum is coated upon the cyan dye developer layer.

3. lnterlayer A gelatin interlayer is then coated on the red-sensitive emulsion layer.

4. Magenta Dye Developer Layer The magenta dye developer 2-[p-(2",5"-dihydroxyphenethyl)phenylazo1-4-n-propoxy-1-napthol is dissolved in a mixture of cyclohexanone and N-n-butylacetanilide and dispersed in an aqueous gelatin solution with a sodium alkylnaphthalene sulfonate dispersing agent. The mixture is passed through a colloid mill several times, coated on the interlayer dried to volatilize the cyclohexanone.

5. Green-Sensitive Emulsion Layer A green-sensitive silver bromoiodide emulsion is coated on the magenta dye developer layer. 6. lnterlayer A gelatin interlayer is coated onto the green-sensitive emulsion layer.

7. Yellow Dye Developer Layer The yellow dye deve1opET-phenyl-3-N-n-hexyl-carbamyl- 4-[p-(2",5"-dihydroxyphenethyl)-phenylazo]-5-pyrazolone is dissolved in a mixture of ditetrahydrofurfuryl adipate and ethylene glycol monobenzyl and dispersed in an aqueous gelatin solution with a sodium alkylnaphthalene sulfonate dispersing agent. The mixture is passed through a colloid mill several times. The resulting dispersion is chilled to set it, washed to remove ethylene glycol monobenzyl ether followed by coating upon the second interlayer and drying. 8. Blue-Sensitive Emulsion Layer A blue-sensitive silver bromoiodide emulsion is coated onto the yellow dye developer layer. 9. Overcoat Layer A final gelatin overcoat layer is provided on the foregoing layers having dispersed therein an auxiliary developing agent 4-methylphenylhydroquinone. A sample of the freshly coated film is air dried exposed imagewise on an Eastman 18 Sensitometer 1/50 inch a 500-watt positive lamp a 4.08 Corning filter and processed with a processing composition disposed in a processing pod and having the composition set forth in table 1 below:

The exposed film is processed at a gap of 0.004 inch (corresponding to the thickness of the activator layer) for a period of 60 seconds at 20 C. while in contact with a color receiving sheet. The receiving sheet is a paper support coated with barium sulfate and subbed with cellulose acetate having in the following order:

1. a polymeric acid layer of acrylic acid-butyl acrylate for pH control,

2. a polyvinyl alcohol spacer layer,

3. a mordant layer comprising poly-4-vinyl pyridine and polyvinyl alcohol, and

4. a polyvinyl alcohol protective layer. The receiver is separated from the negative and contains a positive trichrome image of the test object. The foregoing procedure is repeated with additional negatives. However, the B-disulfones of the present invention are added to the activator composition in order to illustrate the speed increases obtained by the use of the compounds of the present invention. The following results are obtained:

Upon viewing the results listed in table 11, it is readily apparent that increased speed is obtained by the use of the present disulfoncs in the activator employed for the processing of dye developer negatives.

EXAMPLES 4-8 A photosensitive element is prepared by coating a subbed film support comprising cellulose acetate with suitable hardened gelatin layers as follows: 1. Magenta Dye Developer Layer The magenta dye developer, 2-[p-(2",5-dihydroxyphenethyl)phenylazo1-4-n-propoxyl-naphthol, is dissolved in a mixture of cyclohexanone and N-n-butylacetanilide and dispersed in an aqueous gelatin solution with a sodium alkylnaphthalene sulfonate dispersing agent. The mixture is passed through a colloid mill several times, coated on the support and dried to volatilize the cyclohexanone. 2. Emulsion Layer A silver bromoiodide emulsion is coated on the magenta dye developer layer. 3. Overcoat Layer A final gelatin overcoat layer is provided on the foregoing layers having dispersed therein an auxiliary developing agent 4'-methylphenylhydroquinone. Four additional magenta dye developer negatives are prepared in the manner described with the exception that increasing amounts of the speed-increasing compound, bis(methylsulfonyl)-methane, are added to the silver bromoiodide emulsion layer in the concentrations shown in table [11, below. Negatives are exposed in an imagewise manner and are processed in the manner described in examples l-3. The results are set forth below:

TABLE 111 Example Bis(rnethylsulfonyl)methune Relative No. Concentration (mg/sq. FL) Speed 1 dissolved in the "makeup" gelatin used for the emulsion coating preparation.

2. taken at a density of0.8.

3. equivalent to 34.4 g. (0.3 mole) cpd. per silver mole.

The results indicate that increased speed is obtained by employing the compounds taught by the present invention as an emulsion addendum.

EXAMPLES 9-14 TABLE IV.CONCENTRATION OF BISUHETHYLSULFO- NYL)-METHANE (MGJSQUARE FI.)

Emulsion Relative speed 2 Example Red- Green- Blue- No. sensitive sensitive sensitive Red Green Blue Dissolved in the make-up" gelntin used for the emulsion contlng preparation.

7 Neutral senle. tnken til it rienslty 0l0.8. J q vnlent to 20 grunts (012111010) cpd. net sliver mole.

As seen from the foregoing results in table IV, the addition of the speed increasing agents of the present invention greatly increases the speed of the trichrome negatives containing the disulfone in the respective emulsion layers.

The photographic and other hardenable layers used in the practice of this invention can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides, and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguargum and the like.

The photographic emulsions and elements described in the practice of this invention may contain various colloids alone or in combination as vehicles, binding agents and various layers. Suitable hydrophilic materials include both naturally occurring substances, such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, gurn arabic and the like; and synthetic polymeric substances such as water-soluble polyvinyl compounds like poly(vinylpyrrolidone), acrylamide polymers and the like.

The photographic elements used with this invention may contain antistatic or conducting layers, such layers may comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk U.S. Pat. No. 2,861,056 and Sterman et al. U.S. Pat. No. 3,206,312 or insoluble inorganic salts such as those described in Trevoy U.S. Pat. No. 3,428,451.

The various photographic layers may contain plasticizers and lubricants such as polyalcohols, e.g., gylcerin and diols of the type described in Milton et al. U.S. Pat. No. 2,960,404; fatty acids or esters such as those described in Robijns U.S. Pat. No. 2,588,765 and Duane U.S. Pat. No. 3,121,060; and silicone resins such as those described in DuPont British Pat. No. 955,061.

The photographic layers employed in the practice of this invention may contain surfactants such as saponin; anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen U.S. Pat. No. 2,600,831; amphoteric compounds such as those described in Ben-Ezra U.S. Pat. No. 3,133,816; and water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson British Pat. No. 1,022,878. Also, the photographic elements may contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in .lelley et al. U.S. Pat. No. 2,992,101 and Lynn U.S. Pat. No. 2,701,245.

The photosensitive elements of the invention can contain brightening agents including stilbenes, triazines, oxazoles and coumarin brightening agents. Water soluble brightening agents may be used such as those described in Albers et al. German Pat. No. 972,067 and McFall et al. U.S. Pat. No. 2,933,390 or dispersions of brighteners may be used such as those described in Jansen German Pat. No. 1,150,274, Oetiker et al. U.S. Pat. No. 3,406,070 and Heidke French Pat. No. 1,530,244.

The photographic layers used in the practice of this invention can be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in Beguin U.S. Pat. No. 2,681,294. If desired, two or more layers may be coated simultaneously by the procedures described in Russell U.S. Pat. No. 2,761,791 and Wynn British Pat. No. 837,095. This invention also can be used for silver halide layers coated by vacuum evaporation as described in British Pat. No. 968,453 and Lu Valle et al. U.S. Pat. No. 3,219,451.

Use of a polymeric acid layer, as disclosed in U.S. Pat. No. 3,362,819, in the film unit of the present invention will enhance the results obtained. Generally, the polymeric acid layer will effect a reduction in the pH of the image layer from about 13 or 14 to at least 1 l and preferably -8 within a short time after imbibition. Such polymeric acids reduce the pH of the film unit after development to terminate further dye transfer and thus stabilize the dye image. Such polymeric acids comprise polymers containing acid groups, such as carboxylic acid and sulfonic acid groups, which are capable of forming salts with alkali metals, such as sodium or potassium, or with organic bases particularly quaternary ammonium bases, such as tetramethyl ammonium hydroxide. The polymers can also contain potentially acid-yielding groups such as anhydrides or lactones or other groups which are capable of reacting with bases to capture and retain them. Generally the most useful polymeric acids contain free carboxyl groups, being insoluble in water in the free acid form and which form water-soluble sodium and/or potassium salts.

The polymeric acid layer is usually about 0.3 to about 1.5 mils in thickness. Although the polymeric acid layer is usually located in the receiver portion of the film unit between the support and the image-receiving layer, it can also be located in the negative portion of the film unit, as disclosed in U.S. Pat. No. 3,362,821.

An inert timing or spacer layer coated over the polymeric acid layer may also be used to time" or control the pH reduction of the film unit as a function of the rate at which the alkali diffuses through the inert spacer layer. Examples of such timing layers include gelatin, polyvinyl alcohol or any of those disclosed in U.S. Pat. No. 3,455,686. The timing layer is also effective in evening out the various reaction rates over a wide range of temperature, e.g., premature pH reduction is prevented when imbibition is effected at temperatures above room temperature, for example, at to F. The timing layer is usually about 0.1 to about 0.7 mil in thickness.

The invention has been described with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications may be effected within the spirit and scope of the invention.

What is claimed is:

1. A photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:

a. A photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, each said silver halide emulsion layer having associated therewith a dye developer;

b. a dye image-receiving layer; and

c. a rupturable container containing an alkaline processing composition; said film unit containing a 1,1 bis-sulfonyl alkane speed increasing agent; said rupturable container being adapted to be positioned during processing of said film unit so that a compressive force applied to said container by said pressure-applying members will effect a discharge of the containers contents within said film unit.

2. The film unit of claim 1 wherein said dye image-a'eceiving layer is located in said photosensitive element between said support and the lowermost photosensitive silver halide emulsion layer.

3. The film unit of claim 1 wherein said dye image-receiving layer is coated on a separate support and is adapted to be superposed on said photosensitive element after exposure thereof.

4. The film unit of claim 3 wherein said rupturable container is so positioned during processing of said film unit that a compressive force applied to said container by said pressureapplying members will effect a discharge of the containers contents between said dye image-receiving layer and the outermost layer of said photosensitive element.

5. The film unit of claim 4 wherein said photosensitive element comprises a support having thereon the following layers in sequence: (a) a cyan dye developer layer, (b) a red-sensitive silver halide emulsion layer, (c) a magenta dye developer layer, (d) a green-sensitive silver halide emulsion layer, (e) a yellow dye developer layer, and (f) a blue-sensitive silver halide emulsion layer.

6. The film unit of claim 5 wherein said 1,1 bis-sulfonyl alkane is provided in said rupturable container.

Ell

7. The film unit of claim wherein said 1,1 bis-sulfonyl alkane is provided in a layer of said photosensitive element.

8, The film unit of claim 5 wherein said speed increasing agent has the formula wherein R, and R each represent an alkyl group containing one to four carbon atoms and R represents H or an alkyl group containing one to four carbon atoms.

9. The film unit of claim 8 wherein R, and R 2 each represent methyl, ethyl, hydroxyethyl, carboxymethyl or carboxyethyl groups and R represent H.

10. The film unit of claim 8 wherein R, and R each represent a methyl group.

11. The film unit of claim 5 wherein the photosensitive element contains an auxiliary developing agent.

12. A photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:

A. a photosensitive element comprising a support having thereon the following layers in sequence: (a) a cyan dye developer layer, (b) a red-sensitive silver halide emulsion layer, (0) a magenta dye developer layer, (d) a green-sensitive silver halide emulsion layer, (e) a yellow dye developer layer, and (f) a blue-sensitive silver halide emulsion layer;

B. a dye image-receiving layer coated on a support and adapted to be superposed over said blue-sensitive silver halide emulsion layer after exposure of said photosensitive element; and

C. a rupturable container containing an alkaline processing composition which is adapted to be positioned during processing of said film unit so that a compressive force applied to said container by said pressure-applying members will effect a discharge of the container's contents between said dye image-receiving layer and said blue-sensitive silver halide emulsion layer of said photosensitive element, said rupturable container additionally containing a 1,1 bis-sulfonyl alkane in an amount of between about 0.1 and about 10 percent by weight of said processing composition.

13. A process for producing a photographic transfer image in color comprising:

a. imagewise exposing a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, each said silver halide emulsion layer having associated therewith a dye developer,

b. treating said photosensitive element with an alkaline processing composition to effect development of each of said exposed silver halide emulsion layers;

c. forming an imagewise distribution of diffusible dye developer as a function of said imagewise exposure of each of said silver halide emulsion layers; and

d, at least a portion of each of said imagewise distributions of diffusible dye developer diffusing to a dye imagereceiving layer; said development being effected in the presence of a 1,1 bis-sulfonyl alkane speed increasing agent. 14. The process of claim 13 wherein said treatment step (b) is effected by:

a. superposing over the layer outermost from the support of said photosensitive element said dye image-receiving layer coated on a support;

b. positioning a rupturable container containing said alkaline processing composition between said exposed photosensitive element and said dye image-receiving layer; and

c. applying a compressive force to said container to effect a discharge of the containers contents between said outermost layer of said exposed photosensitive element and said dye image-receiving layer.

15. The process of claim 14 wherein said photosensitive element comprises a support having thereon the following layers in sequence:

a. a cyan developer layer,

b. a red-sensitive silver halide emulsion layer,

c. a magenta dye developer layer,

d. a green-sensitive silver halide emulsion layer,

e. a yellow dye developer layer and f. a blue-sensitive silver halide emulsion layer.

16. The process of claim 15 wherein said 1,1 bis-sulfonyl a1- kane is provided in said rupturable container.

17. The process of claim 15 wherein said 1,1 bis-sulfonyl alkane is provided in a layer of said photosensitive element.

18. The process of claim 15 wherein said speed increasing agent has the formula wherein R, and R each represent an alkyl group containing one to four carbon atoms and R represents H or an alkyl group containing one to four carbon atoms.

19. The process of claim 18 wherein R, and R each represents methyl, ethyl, hydroxyethyl, carboxymethyl or carboxyethyl groups and R represents H.

20. The process of claim 10 wherein R, and R each represent a methyl group.

21. The process of claim 15 wherein said alkaline processing composition contains sodium thiosulfate.

22. A process for producing a photographic transfer image in color comprising:

a. imagewise exposing a photosensitive element comprising a support having thereon the following layers in sequence:

a. a cyan dye developer layer,

b. a red-sensitive silver halide emulsion layer,

0. a magenta dye developer layer,

d. a green-sensitive silver halide emulsion layer,

e. a yellow dye developer layer, and

f. a blue-sensitive silver halide emulsion layer;

b. superposing over the layer outermost from the support of said photosensitive element a dye image-receiving layer coated on a support;

c. positioning a rupturable container containing an alkaline processing composition between said exposed photosensitive element and said dye image-receiving layer;

d. applying a compressive force to said container to effect a discharge of the containers contents between said outermost layer of said exposed photosensitive element and said dye image-receiving layer;

e. thereby effecting development of each of said exposed silver halide emulsion layers;

. forming an imagewise distribution of diffusible dye developer as a function of said imagewise exposure of each of said silver halide emulsion layers; and

g. at least a portion of each of said imagewise distributions of diffusible dye developer diffusing to said dye imagereceiving layer; said rupturable container additionally containing a 1,1 bis-sulfonyl alkane in an amount of between about 0.1 and about 1.0 percent by weight of said processing composition.

23. A photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, each said silver halide emulsion having associated therewith a dye developer, said photosensitive element containing a 1,1 bis-sulfonyl alkane speed-increasing agent.

24. A photosensitive element comprising a support having thereon the following layers in sequence:

a. a cyan dye developer layer,

b. a red-sensitive silver halide emulsion layer,

c. a magenta dye developer layer,

d. a green-sensitive silver halide emulsion layer,

e. a yellow dye developer layer, and

l3 f. a blue-sensitive silver halide emulsion layer; said photosensitive element containing a 1,1 bis-sulfonyl alkane speed-increasing agent. 25. The photosensitive element of claim 24 wherein said speed-increasing agent has the formula:

wherein R and R each represent an alkyl group containing one to four carbon atoms and R represents H or an alkyl group containing one to four carbon atoms.

26. The photosensitive element of claim 25 wherein R and R each represent methyl, ethyl, hydroxyethyl, carboxymethyl or carboxyethyl groups and R represents H.

27. The photosensitive element of claim 25 wherein R, and R each represent a methyl group.

28. The photosensitive element of claim 24 wherein said 1,] bis-sulfonyl alkane speed-increasing agent is present in an amount of from about 0.1 to about 1.0 moles per mole of silver halide in the photosensitive element.

29. The photosensitive element of claim 24 which also contains an auxiliary developing agent.

30. A reception element comprising a support having thereon a dye image-receiving layer, said element containing a 1,1 bis-sulfonyl alkane.

31. The reception element of claim 30 wherein said 1,] bissulfonyl alkane has the formula

Claims (32)

1. 2. The film unit of claim 1 wherein said dye image-receiving layer is located in said photosensitive element between said support and the lowermost photosensitive silver halide emulsion layer.
2. 3. The film unit of claim 1 whereIn said dye image-receiving layer is coated on a separate support and is adapted to be superposed on said photosensitive element after exposure thereof.
3. 4. The film unit of claim 3 wherein said rupturable container is so positioned during processing of said film unit that a compressive force applied to said container by said pressure-applying members will effect a discharge of the container''s contents between said dye image-receiving layer and the outermost layer of said photosensitive element.
4. 5. The film unit of claim 4 wherein said photosensitive element comprises a support having thereon the following layers in sequence: (a) a cyan dye developer layer, (b) a red-sensitive silver halide emulsion layer, (c) a magenta dye developer layer, (d) a green-sensitive silver halide emulsion layer, (e) a yellow dye developer layer, and (f) a blue-sensitive silver halide emulsion layer.
5. 6. The film unit of claim 5 wherein said 1,1 bis-sulfonyl alkane is provided in said rupturable container.
6. 7. The film unit of claim 5 wherein said 1,1 bis-sulfonyl alkane is provided in a layer of said photosensitive element.
7. 8. The film unit of claim 5 wherein said speed increasing agent has the formula wherein R1 and R2 each represent an alkyl group containing one to four carbon atoms and R3 represents H or an alkyl group containing one to four carbon atoms.
8. 9. The film unit of claim 8 wherein R1 and R2 each represent methyl, ethyl, hydroxyethyl, carboxymethyl or carboxyethyl groups and R3 represents H.
9. 10. The film unit of claim 8 wherein R1 and R2 each represent a methyl group.
10. 11. The film unit of claim 5 wherein the photosensitive element contains an auxiliary developing agent.
11. 12. A photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising: A. a photosensitive element comprising a support having thereon the following layers in sequence: (a) a cyan dye developer layer, (b) a red-sensitive silver halide emulsion layer, (c) a magenta dye developer layer, (d) a green-sensitive silver halide emulsion layer, (e) a yellow dye developer layer, and (f) a blue-sensitive silver halide emulsion layer; B. a dye image-receiving layer coated on a support and adapted to be superposed over said blue-sensitive silver halide emulsion layer after exposure of said photosensitive element; and C. a rupturable container containing an alkaline processing composition which is adapted to be positioned during processing of said film unit so that a compressive force applied to said container by said pressure-applying members will effect a discharge of the container''s contents between said dye image-receiving layer and said blue-sensitive silver halide emulsion layer of said photosensitive element, said rupturable container additionally containing a 1,1 bis-sulfonyl alkane in an amount of between about 0.1 and about 1.0 percent by weight of said processing composition.
12. 13. A process for producing a photographic transfer image in color comprising: a. imagewise exposing a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, each said silver halide emulsion layer having associated therewith a dye developer, b. treating said photosensitive element with an alkaline processing composition to effect development of each of said exposed silver halide emulsion layers; c. forming an imagewise distribution of diffusible dye developer as a function of said imagewise exposure of each of said silver halide emulsion layers; and d. at least a portion of each of said imagewise distributions of diffusible dye developer diffusing to a dye image-receiving layer; said development being effected in the presence of a 1,1 bis-sulfonyl alkane speed increasing agent.
13. 14. The process of claim 13 wherein said treatment step (b) is effected by: a. superposing over the layer outermost from the support of said photosensitive element said dye image-receiving layer coated on a support; b. positioning a rupturable container containing said alkaline processing composition between said exposed photosensitive element and said dye image-receiving layer; and c. applying a compressive force to said container to effect a discharge of the container''s contents between said outermost layer of said exposed photosensitive element and said dye image-receiving layer.
14. 15. The process of claim 14 wherein said photosensitive element comprises a support having thereon the following layers in sequence: a. a cyan developer layer, b. a red-sensitive silver halide emulsion layer, c. a magenta dye developer layer, d. a green-sensitive silver halide emulsion layer, e. a yellow dye developer layer and f. a blue-sensitive silver halide emulsion layer.
15. 16. The process of claim 15 wherein said 1,1 bis-sulfonyl alkane is provided in said rupturable container.
16. 17. The process of claim 15 wherein said 1,1 bis-sulfonyl alkane is provided in a layer of said photosensitive element.
17. 18. The process of claim 15 wherein said speed increasing agent has the formula wherein R1 and R2 each represent an alkyl group containing one to four carbon atoms and R3 represents H or an alkyl group containing one to four carbon atoms.
18. 19. The process of claim 18 wherein R1 and R2 each represents methyl, ethyl, hydroxyethyl, carboxymethyl or carboxyethyl groups and R3 represents H.
19. 20. The process of claim 10 wherein R1 and R2 each represent a methyl group.
20. 21. The process of claim 15 wherein said alkaline processing composition contains sodium thiosulfate.
21. 22. A process for producing a photographic transfer image in color comprising: a. imagewise exposing a photosensitive element comprising a support having thereon the following layers in sequence: a. a cyan dye developer layer, b. a red-sensitive silver halide emulsion layer, c. a magenta dye developer layer, d. a green-sensitive silver halide emulsion layer, e. a yellow dye developer layer, and f. a blue-sensitive silver halide emulsion layer; b. superposing over the layer outermost from the support of said photosensitive element a dye image-receiving layer coated on a support; c. positioning a rupturable container containing an alkaline processing composition between said exposed photosensitive element and said dye image-receiving layer; d. applying a compressive force to said container to effect a discharge of the container''s contents between said outermost layer of said exposed photosensitive element and said dye image-receiving layer; e. thereby effecting development of each of said exposed silver halide emulsion layers; f. forming an imagewise distribution of diffusible dye developer as a function of said imagewise exposure of each of said silver halide emulsion layers; and g. at least a portion of each of said imagewise distributions of diffusible dye developer diffusing to said dye image-receiving layer; said rupturable container additionally containing a 1,1 bis-sulfonyl alkane in an amount of between about 0.1 and about 1.0 percent by weight of said processing composition.
22. 23. A photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, each said silver halide emulsion having associated therewith a dye developer, said photosensitive element containing a 1,1 bis-sulfonyl alkane speed-increasing agent.
23. 24. A photosensitive element comprising a support having thereon the following layers in sequence: a. a cyan dye developer layer, b. a red-sensitive silver halide emulsion layer, c. a magenta dye developer layer, D. a green-sensitive silver halide emulsion layer, e. a yellow dye developer layer, and f. a blue-sensitive silver halide emulsion layer; said photosensitive element containing a 1,1 bis-sulfonyl alkane speed-increasing agent.
24. 25. The photosensitive element of claim 24 wherein said speed-increasing agent has the formula: wherein R1 and R2 each represent an alkyl group containing one to four carbon atoms and R3 represents H or an alkyl group containing one to four carbon atoms.
25. 26. The photosensitive element of claim 25 wherein R1 and R2 each represent methyl, ethyl, hydroxyethyl, carboxymethyl or carboxyethyl groups and R3 represents H.
26. 27. The photosensitive element of claim 25 wherein R1 and R2 each represent a methyl group.
27. 28. The photosensitive element of claim 24 wherein said 1,1 bis-sulfonyl alkane speed-increasing agent is present in an amount of from about 0.1 to about 1.0 moles per mole of silver halide in the photosensitive element.
28. 29. The photosensitive element of claim 24 which also contains an auxiliary developing agent.
29. 30. A reception element comprising a support having thereon a dye image-receiving layer, said element containing a 1,1 bis-sulfonyl alkane.
30. 31. The reception element of claim 30 wherein said 1,1 bis-sulfonyl alkane has the formula wherein R1 and R2 each represent an alkyl group containing one to four carbon atoms and R3 represents H or an alkyl group containing one to four carbon atoms.
31. 32. The reception element of claim 31 wherein R1 and R2 each represent methyl, ethyl, hydroxyethyl, carboxymethyl or carboxyethyl groups and R3 represents H.
32. 33. The reception element of claim 32 wherein R1 and R2 each represent a methyl group.