US3647436A

US3647436A - Developers for diffusion transfer film units

Info

Publication number: US3647436A
Application number: US68478A
Authority: US
Inventors: Walter M Bush
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1970-08-31
Filing date: 1970-08-31
Publication date: 1972-03-07
Anticipated expiration: 1989-03-07
Also published as: CA943386A; NL7111992A; BR7105704D0; DE2143616A1; AU3285871A; BE771961A; FR2106181A5

Abstract

The use of 4-amino-3-alkoxy-N-ethyl-N- Beta -hydroxyethylaniline developing agents in a diffusion transfer film unit employing at least one nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible dye is more effective than analogous paraphenylenediamine color developing agents.

Description

United States Patent Bush us] 3,647,436 [451 Mar. 7, '1972 [54] DEVELOPERS FOR DIFFUSION TRANSFER FILM UNITS [72] Inventor: Walter M. Bush, Victor, NY.

[73] Assignee: Eastman Kodak Company, Rochester,

[22] Filed: Aug. 31, 1970 [21] Appl.No.: 68,478

[52] US. Cl. ..96/3, 96/29 D, 96/66 R,

96/76 C [51] Int. Cl. ..G03c 7/00, G03c 5/54, G03c 1/48 [58] Field of Search ..96/3, 29 D, 66 R, 76 C [56] References Cited UNITED STATES PATENTS 3,108,001 10/1963 Green ..96/29 D Primary Examiner-Norman G. Torchin Assistant Examiner-Alfonso T. Suro Pico Attorney-W. H. .l. Kline, J. R. Frederick and H. E. Cole [57] ABSTRACT The use of 22 Claims, No Drawings 1 DEVELOPERS FOR DIFFUSION TRANSFER FILM UNITS This invention relates to photography and more particularly to certain developers for color, diffusion transfer film units and methods of processing such film units.

In US. Pat. Nos. 3,227,550; 3,227,551; 3,227,552; and BritishPat. No. 904,364; page 19, there are described color, diffusion transfer systems employing nondiffusible couplers capable of reacting with oxidized color-developing agent to produce diffusible dyes.

It is an object of my invention to provide new p-phenylenediamine developing agents for use in the abovedescribed color, diffusion transfer systems which provide significantly better results than analogous p-phenylenediamine color-developing agents.

Another object of my invention is to provide a new p-phenylenediamine developing agent for use in the above-mentioned color, diffusion transfer systems wherein the dye image receiving layer is located in the photosensitive element itself or is provided on a separate support to be superposed on the photosensitive element after exposure thereof.

These and other objects are obtained by employing in the above-mentioned color, diffusion transfer systems a 4-amino- 3-alkoxy-N-ethyl-N-B-hydroxyethylaniline color-developing agent.

Accordingly, a photographic film unit of my invention which is adapted to 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 silver halide emulsion layer having associated therewith a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible dye;

b. a dye image-receiving layer; and

c. a rupturable container containing an alkaline processing composition and which is adapted to be positioned during processing of the 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 the film unit; the film unit containing a 4-aminO-B-alkOXy-N-ethyl-N-B- hydroxyethylaniline as the color-developing agent.

The 4-amino-3-alkoxy-N-ethyl-N-B-hydroxyethylaniline developing agents employed in my invention include those having the formula H562 CEHIOH wherein R is an alkyl group, preferably a lower alkyl group containing one-four carbon atoms. Especially preferred are the compounds wherein R is a methyl group. As will be shown in more detail hereinafter, these compounds are distinctly superior to closely analogous compounds in the present system.

In the photosensitive film units according to my invention, there is associated with each silver halide emulsion layer in the photosensitive element a dye image-forming coupler which is nondiffusing in photographic silver halide emulsions but which produces a diffusible dye on reaction with oxidized 4- amino-3-alkoxy-N-ethyl-N-B-hydroxyethylaniline developing agents in alkaline processing compositions. Such couplers include those having the formulas:

DYE-LINK--(COUPBALL),,

and

BALL-LINK-(COUP-SOL), wherein l. DYE is a preformed dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing radical;

2. LINK is a connecting radical such as an azo radical, a mercuri radical, an oxy radical, an alkylidene radical, a thio radical, a dithio radical or an azoxy radical;

3. COUP is a coupler radical such as a 5-pyrazolone coupler radical, a pyrazolotriazole coupler radical, a phenolic coupler radical or an open-chain ketomethylene coupler radical, COUP being substituted in the coupling position with LINK;

4. BALL is a photographically inert organic ballasting radical of such molecular size and configuration as to render such coupler nondiffusible during development in alkaline processing compositions;

5. SOL is a hydrogen atom or an acidic solubilizing group when the color-developing agent contains an acidic solubilizing group, and SOL is an acidic solubilizing group when the color-developing agent is free of an acidic solubilizing group; and

6. n is an integer of l to 2 when LINK is an alkylidene radical, and n is 1 when LINK is an azoradical, a mercuri radical, an oxyradical, a thioradical, a dithioradical or an azoxy radical.

The acidic solubilizing radicals attached to the difiusible dye-producing couplers described above can be solubilizing radicals which when attached to the coupler or developer moieties of the dyes, render the dyes diffusible in alkaline processing compositions. Typical of such radicals are carboxylic, sulfonic, ionizable sulfonamide, and hydroxy-substituted groups that lend to dyes negative charges.

The nature of the ballast groups in the difi'usible dyeproducing coupler compounds described above (BALL) is not critical as long as they confer nondifiusibility to the coupler compounds. Typical ballast groups include long-chain alkyl radicals linked directly or indirectly to the coupler molecules as well as aromatic radicals of the benzene and naphthalene series, etc., linked directly or indirectly to the coupler molecules by a splittable linkage, or by a removable or irremovable but otherwise nonfunctional linkage depending upon the nature of the coupler compound. Useful ballast groups have at least eight carbon atoms.

Typical dye radical substituents (DYE) include azo-, azomethine, indoaniline, indophenol, anthraquinone and related dye radicals well known in the art that exhibit selective absorption in the visible spectrum. The dye radicals contain acidic solubilizing moieties.

With regard to the above-described coupler radicals (COUP-), the coupling position is well known to those skilled in the photographic art. The 5-pyrazolone coupler radicals couple at the carbon atom in the 4-position, the phenolic coupler radical, including a-naphthols, couple at the carbon atom in the 4-position and the open-chain ketomethylene coupler radicals couple to the carbon atom forming the methylene moiety (eg.,

*denoting the coupling position). Pyrazolotriazole couplers and their coupling position are described, for example, in US. Pat. No. 3,061,432 and U.S. application Ser. No. 778,329 of Bailey et al., filed Nov. 22, 1968 and now abandoned.

Particularly good results are obtained when the cyanproducing coupler has the formula BALLOCYANCOUP, the magenta-producing coupler has the formula BALLN N-MAGCOUP and the yellow-producing coupler has the formula BALL-O-YELLCOUP wherein:

a. BALL is a photographically inert organic ballasting radical having at least eight carbon atoms and of such molecular size and configuration as to render the coupler nondiffusible during development in an alkaline processing composition;

b. CYANCOUP is a phenolic coupler radical substituted in the 2-position with a fully substituted amido group and attached to the --O moiety of the cyan-producing coupler in the coupling position;

c. MAGCOUP is a 5-pyrazolone coupler radical joined to the N N moiety of the magenta-producing coupler in the coupling position; and

d. YELLCOUP is an open-chain ketomethylene coupler radical attached to the O moiety of the yellow-producing coupler in the coupling position.

The term nondiffusing used herein as applied to the couplers, has the meaning commonly applied to the term in color photography and denotes materials which for all practical purposes do not migrate or wander through organic colloid layers, such as gelatin, comprising the sensitive elements of the invention when processed in alkaline processing compositions. The same meaning is to be attached to the term immobile."

The term diffusible as applied to the dyes formed from the nondiffusing" couplers in this invention has the converse meaning and denotes materials having the property of diffusing effectively through the colloid layers of the sensitive elements in the presence of the nondiffusing materials from which they are derived, when processed in alkaline processing compositions. Mobile has the same meaning.

When the couplers having the formula DYE-LlNK- (COUPBALL), as described above are reacted with oxidized color-developing agent, the connecting radical (LINK) is split and a diffusible preformed dye (DYE) is released which diffuses imagewise to a reception layer. An acidic solubilizing group on the preformed dye lends diffusibility to the dye molecule. Thecoupling portion of the coupler (COUP) couples with the color-developing agent oxidation product to form a dye that is nondiffusible because of the attached ballasting group (BALL) in a noncoupling position. In this type of coupler, the color of the diffusible dye is determined by the color of the preformed dye moiety (DYE), the color of the reaction product of color developer oxidation product and the coupler moiety (COUP) being unimportant to the color of the diffusible image.

When couplers having the formula BALL-LlNK (COUP-SOL), as described above are reacted with oxidized color-developing agent, the connecting radical (LINK) is split and a diffusible dye is formed with the color-developing agent oxidation product and the coupling portion (COUP) of the coupler which diffuses imagewise to a reception layer. Diffusibility is imparted to the dye by an acidic solubilizing group attached to a noncoupling position of the coupling portion (COUP) of the coupler or to the color-developing agent. The ballasting portion of the coupler;remains immobile. In' this type of coupler, the color of the diffusible dye is determined by the color of the reaction product of color developer oxidation product and the coupler moiety (COUP).

In a preferred embodiment of my invention, the photosensitive element contains at least one nondiffusible coupler which produces a diffusible dye image-providing material when employed in combination with physical development nuclei in a nuclei layer contiguous to each photosensitive silver halide emulsion layer. A film unit according to my invention contains a silver halide solvent, e.g., sodium thiosulfate, either in a rupturable container with the alkaline processing composition or in a layer of the photosensitive element and each photosensitive silver halide emulsion layer contains an immobilizing coupler, e.g., a coupler with a ballast group, which is capable of reacting with oxidized color-developing agent of the invention to form an immobile product. Each photosensitive silver halide emulsion layer and its contiguous nuclei layer are separated from the other silver halide emulsions and their contiguous nuclei layers in the film unit by means of an alkaline solution permeable barrier layer for retaining silver complexes. Other embodiments of my invention employ the photosensitive elements described in the above-mentioned U.S. Pat. Nos. 3,227,550; 3,227,551; and 3,227,552. These embodiments all employ the nondiffusible couplers described above which produce diffusible dyes on reaction with oxidized 4-amino-3-alkoxy-N-ethyl-N-B-hydroxyethylaniline developing agents.

In preforming a process of forming a transfer image according to the preferred embodiment of my invention, a photosensitive element of the invention is exposed imagewise and then treated with an alkaline processing composition in the presence of a 4-amino-3-methoxy-N-ethyl-N-B-hydroxyethylaniline color-developing agent and a silver halide solvent. The developing agent and solvent may be located in the alkaline processing composition or in the photosensitive element as a separate layer or layers. While the treatment step can be conveniently accomplished in a camera by positioning a rupturable container containing the alkaline processing composition between the photosensitive element and a superposed image-receiving element or process sheet and rupturing the container to discharge its contents between them, treatment can also be accomplished by merely inserting processing composition between the photosensitive element and imagereceiving element or process sheet by means of communicating members similar to hypodermic syringes which are attached either to a camera or camera cartridge.

After treating the exposed photosensitive element with alkaline processing composition, it permeates the various layers to initiate development of the latent image contained in each photosensitive silver halide emulsion layer. The developing agent which is present develops each of the exposed silver halide emulsion layers, thus causing the developing agent to become oxidized imagewise. The oxidized developing agent then reacts with the immobilizing coupler present in each said photosensitive silver halide emulsion layer to form an immobile product. The remaining silver halide in each silver halide emulsion layer corresponding to unexposed and thus undeveloped areas forms a soluble silver ion complex with the silver halide solvent present in or activated by the processing composition and migrates to each adjacent nuclei layer. The transferred silver complex is reduced or physically developed in the nuclei layer, thus causing developing agent which is present to become oxidized. The oxidized developing agent then reacts with the nondiffusible coupler present in each nuclei layer to form an imagewise distribution of diffusible dye. In three-color elements, imagewise distributions of diffusible cyan, magenta and yellow dye are formed as a function of the imagewise exposure of each said silver halide emulsion layer. The diffusible dye can be formed by the reaction of the oxidized developing agent with the nondiffusible coupler or a preformed dye can be released by the reaction of the oxidized developing agent with the nondiffusible coupler, as described above. At least a portion of each imagewise distribution of diffusible dye then diffuses to a dye image receiving layer to provide a positive dye image.

The dye image receiving layer in my film unit can be located on a separate support adapted to be superposed on the photosensitive element after exposure thereof. The general configuration of image-receiving elements is disclosed, for example, in U.S. Pat. No. 3,362,819. In such embodiment, the rupturable container is usually positioned during processing of the film unit so that a compressive force applied to the container by the pressure-applying members will effect a discharge of the containers contents between the imagereceiving element and the outermost layer of the photosensitive element. Reference is made to the above-mentioned British Pat. No. 904,364 for further details concerning the use of such a film unit in the conventional manner.

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 described in U.S. application Ser. No. 027,991 of Barr, Bush and Thomas filed Apr. 13, 1970. In such an embodiment the support for the photosensitive element is transparent and is coated with the image-receiving layer, a substantially opaque, light-reflective layer, e.g., TiO- and then the various layers forming the color-forming units. After exposure of the photosensitive element, a rupturable container containing an alkaline processing composition and an opaque process sheet are brought into superposed position. Pressure-applying members in a camera rupture the container and spread processing composition over the photosensitive element as the film unit is withdrawn from the camera. The processing composition develops the exposed silver halide emulsion layers and dye images are formed as a function of development which diffuse to the image-receiving layer to provide a positive, right-reading image which is viewed through the transparent support on the opaque reflecting layer background. For further details concerning this particular integral film unit, its preparation and use, reference is made to the above-mentioned Barr, Bush and Thomas, U.S. application Ser'. No. 027,991.

Another embodiment of integral receiver-negative photosensitive elements in which my invention can be employed is described in U.S. Ser. No. 027,990 of Cole, filed Apr. 13, 1970, wherein the support for the photosensitive element is transparent and is coated with the image-receiving layer, a substantially opaque, light-reflective layer, the various layers forming the color-forming units and a top transparent sheet. A rupturable container containing an alkaline processing composition and an opacifier is positioned adjacent to the top layer and sheet.

The film unit is placed in a camera, exposed through the top transparent sheet and then passed between a pair of pressureapplying members in the camera as it is being removed therefrom. The pressure-applying members rupture the container and spread processing composition and opacifier over the negative portion of the film unit to render it light insensitive. The processing composition develops the exposed silver halide layers and dye images are formed as a result of development which diffuse to the image-receiving layer to provide a positive, right-reading image which is viewed through the transparent support on the opaque reflecting layer background. For further details concerning this particular integral film unit, its preparation and use, reference is made to the above-mentioned Cole, U.S. application Ser. No. 027,990.

The physical development nuclei in the preferred embodiment of my invention can be any of those well known to those in the art, e.g., colloidal metals such as silver, palladium, gold, platinum, copper, etc., and colloidal metal sulfides such as silver sulfide, zinc sulfide, gold sulfide, cadmium sulfide, nickel sulfide, etc. The nuclei layer can also be split into two layers, one on each side of the photosensitive silver halide emulsion layer, if desired.

In the photosensitive elements of the preferred embodiment of my invention, spacer layers comprising gelatin are preferably employed between the nuclei layers and the photosensitive silver halide emulsion layers to prevent undesirable mixing of the two layers upon coating. The spacer layers may also contain nuclei and a nondiffusible coupler capable of reacting with oxidized color developing agent to form an immobile product in order to increase its efficiency. Other details concerning this system of photographic chemistry are found in the above-mentioned British Pat. No. 904,364, the Barr, Bush and Thomas application Ser. No. 027,991 and the Cole application Ser. No. 027,990.

In my invention, interlayers are generally employed between the various photosensitive color-forming units to scavenge oxidized developing agent and prevent it from forming an unwanted dye in another color-forming unit. Such interlayers would generally comprise a hydrophilic polymer such as gelatin and an immobilizing coupler, as described above, which is capable of reacting with oxidized colordeveloping agent to form an immobile product. Such interlayers may also scavenge other materials such as soluble silver ion complexes to prevent such materials from contaminating other color-forming units. A developer-scavenging interlayer may also be employed in the above-described integral receiver-negative embodiments adjacent to the light-reflective layer to prevent excess color-developing agent from staining the image-receiving layer. Such a layer may comprise, for example, a fogged silver halide emulsion, or a spontaneously developable silver halide emulsion, physical development nuclei, and a nondiffusible coupler capable of reacting with oxidized color-developing agent to form an immobile product. The developer scavenger interlayer may also contain carbon black, if desired. The developer scavenger interlayer may also be coated with a polymeric timing layer, e.g., gelatin, if desired, to allow for complete development before the developer scavenger interlayer becomes operative.

As previously mentioned, the novel developing agent employed in my invention is preferably present in the alkaline processing composition in the rupturable pod. The developing agent can also be incorporated into the photosensitive element as a separate layer, e.g., by employing a Schiff base derivative of the developing agent. Such incorporated developing agent will be activated by the alkaline processing composition. While the incorporated developing agent can be positioned in any layer of the photosensitive element from which it can be readily made available for development upon activation with alkaline processing composition, it is generally either incorporated in the light-sensitive silver halide emulsion layers or in layers contiguous thereto.

The rupturable container employed in various embodiments of my invention is well known to those skilled in the art and is illustrated, for example, in U.S. Pat. Nos. 2,543,18l; 2,643,886", 2,653,732; 2,723,051; 3,056,492; 3,056,491; 3,l52,5l5,etc. A

Typical cameras in which the film unit of my invention can be employed are illustrated in U.S. Pat. Nos. 3,079,849; 3,080,805; 3,161,118 and 3,l6l,l22 and described in the Cole application Ser. No. 027,990 mentioned above.

The film assembly of my invention can be used to produce positive images in single or multicolors. In a threecolor system, each silver halide emulsion layer of the film assembly will have associated therewith a dye image providing material possessing a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion, i.e., the blue-sensitive silver halide emulsion layer will have a yellow dye image providing material associated therewith, the green-sensitive silver halide emulsion layer will have a magenta dye image providing material associated therewith, and the red-sensitive silver halide emulsion layer will have a cyan dye image providing material associated therewith. The dye image providing material associated with each silver halide emulsion layer is preferably contained in a layer containing the physical development nuclei contiguous to the silver halide emulsion layer.

Spectral sensitizing dyes can be used conveniently 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 of 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 can 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. ll, 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 above cyanine classes can contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles. Such nuclei can contain alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine groups and can be fused to carbocyclic or heterocyclic ring systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano, or alkoxy groups. The dyes can be symmetrical or unsymmetrical and can contain alkyl, phenyl, enamine or heterocyclic substituents on the methine or polymethir'ie chain. The above merocyanine dyes can contain the basic nuclei mentioned above as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazol ineones, and malononitrile. These acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups, or heterocyclic nuclei. Combinations of these dyes can be used, if desired. In addition, supersensitizing addenda which do not absorb visible light can 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. 1

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

The silver halide emulsion used in this invention can comprise, for example, silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof. The emulsion can be coarse or fine grain and can be prepared by any of the well-known procedures, e.g., single-jet emulsion, double-jet emulsion, such as a Lippmann emulsion, an ammoniacal emulsion, a thiocyanate or thioether ripened emulsion such as those described in Nietz et al., U.S. Pat. No. 2,222,264; lllirlgsworth, U.S. Pat. No. 3,320,069; and McBride, U.S. Pat. No. 3,271,157. An emulsion that contains silver halide grains having substantial surface sensitivity canbe used, and an emulsion that contains silver halide grains having substantial sensitivity inside the grains 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 emulsion can be a regular-grain emulsion such as the type described in Klein and Moisar, J. Phat. Sci., Vol. 12, No. 5, Sept./Oct., 1964, pp. 242-251. A negative-type emulsion can be used .or a direct positive emulsion 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 used 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. 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.

The silver halide emulsions used in this invention may'contain speed-increasing compounds such as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper, U.S. Pat. No. 2,886,437; Dannet al., U.S. Pat. No. 3,046,134; Carroll et al., U.S. Pat. No. 2,944,900; and Goffe, U.S. Pat. No. 3,294,540.

The silver halide emulsions used in the practice of this invention 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 al., U.S. Pat. No. 2,694,716; the azaindenes described in Piper, U.S. Pat. No. 2,886,437 and l-leimbach 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; and 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.

If a transparent support is to be employed in my film unit, it can be any transparent material as long as it does not deleteriously effect the photographic properties of the film unit and is dimensionally stable. Typical actinic radiation transmissive fiexible sheet materials include cellulose nitrate film, cellulose acetate film, poly(vinylacetal) film, polystyrene film, poly(ethyleneterephthalate) film, polycarbonate film, poly-aolefins such as polyethylene and polypropylene film, and related films or resinous materials as well as glass. The transparent support is usually about 2 to 6 mils in thickness. If an opaque support is to be employed in my film unit, it can be any conventional support, such as those mentioned above for the transparent support, with an opacifying agent added during manufacture or otherwise coated thereon. A paper support is also quite useful.

Generally speaking, except where noted otherwise, the

silver halide emulsion layers in the invention comprise photosensitive silver halide dispersed in gelatin and are about 0.6 to 6 microns in thickness; the dye image providing materials 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 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. In addition to gelatin, other suitable hydrophilic materials include both naturally occurring substances such as proteins, cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as water-soluble polyvinyl compounds'like poly(vinylpyrrolidone). acrylamide polymers and the like.

The photographic emulsion layers and other layers of a photographic element employed in the practice of this invention can also contain alone or in combination with hydrophilic, water-permeable colloids, other synthetic polymeric compounds such as dispersed vinyl compounds such as in latex form and particularly those which increase the dimensional stability of the photographic materials. Suitable synthetic polymers include those described, for example, in Nottorf, U.S. Pat. No. 3,142,568, issued July 28, 1964; White, U.S. Pat. No. 3,193,386, issued July 6, 1965; l-louck et al. U.S. Pat. No. 3,062,674, issued Nov. 6, 1962; l-louck et al., U.S. Pat. No. 3,220,844, Issued Nov. 30, 1965; Ream et al., U.S. Pat. No. 3,287,289, issued Nov. 22, 1966; and Dykstra, U.S. Pat. No. 3,411,911, issued Nov. 19, 1968. Particularly effective are water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, those which have cross-linking sites which facilitate hardening or curing, and those having recurring sulfobetaine units as described in Dykstra, Canadian Pat. No. 774,054.

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 images will be obtained. The particular material chosen will, of course, depend upon the dye image to be mordanted. For mordanting acid dyes, the imagereceiving layer can contain basic mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone such as described in Minsk, U.S. Pat. No. 2,882,156, granted Apr. 14, 1959. Other mordants useful in our invention include the 2- vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in Sprague et al., U.S. Pat. No. 2,484,430 granted Oct. 1 1, 1949, and cetyl trimethylammoniurn bromide, etc. Effective mordanting compositions are also described in Whitmore, U.S. Pat. No. 3,271,148 and Bush, U.S. Pat. No. 3,271,147. The mordanting compositions described in the Whitmore patent comprise at least one hydrophilic organic colloid containing a finely divided, uniform dispersion of droplets or globules of a high-boiling, water-immiscible organic solvent in which is dissolved a high concentration of a cationic, nonpolymeric, organic dye-mordanting compound for acid dyes. The mordanting compositions described in the Bush patent comprise at least one hydrophilic organic colloid containing a finely divided, uniform dispersion of particles of a salt of an organic acidic composition containing free acid moieties and a cationic, nonpolymeric, organic dye-mordanting compound for acid dyes. Useful cationic or basic organic dye-mordanting compounds for dyes include quaternary ammonium and phosphonium, and ternary sulfonium compounds in which there is linked to the N, P or S onium atom at least one hydrophobic ballast group such as longchain alkyl or substituted alkyl groups. Furthermore, the image-receiving layer can be sufficient by itself to mordant the dye as in the case of use of an alkaline solution-permeable polymeric layer such as N-methoxymethyl polyhexylmethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plasticizers; cellulose acetate; gelatin; and other materials of a similar nature. Generally, good results are obtained when the image-receiving layer is about 0.25 to about 0.04 mil in thickness. This thickness, of course, can be modified depending upon the result desired. The image-receiving layer can also contain ultraviolet-absorbing materials to protect the mordanted dye images from fading due to ultraviolet light and/or brightening agents such as the stilbenes, coumarins, triazines, oxazoles, etc.

Use of a pH-lowering layer in the film unit of the invention may increase the stability of the transferred image. Generally, the pH-lowering 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. For example, polymeric acids as disclosed in U.S. Pat. No. 3,362,819 may be employed. 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. Examples of such polymeric acids include dibasic acid half-ester derivatives of cellulose which derivatives contain free carboxyl" groups, e.g., cellulose acetate hydrogen phthalate, cellulose acetate hydrogen glutarate, cellulose acetate hydrogen succinate, ethyl cellulose hydrogen succinate, ethyl cellulose acetate hydrogen succinate, cellulose acetate succinate hydrogen phthalate; ether and ester derivatives of cellulose modified with sulfoanhydrides, e.g., with orthosulfobenzoic anhydride; polystyrene sulfonic acid; carboxymethyl cellulose; polyvinyl hydrogen phthalate; polyvinyl acetate hydrogen phthalate; polyacrylic acid, acetals of polyvinyl alcohol with carboxy or sulfo substituted aldehydes, e.g., o-, mor p-benzaldehyde sulfonic acid or carboxylic acid; partial esters of ethylene/maleic anhydride copolymers; partial ester of methyl-vinyl ether/maleic anhydride copolymers, etc. In addition, solid monomeric acid materials could also be used such as palmitic acid, oxalic acid, sebacic acid, hydrocinnamic acid, metanilic acid,

paratoluenesulfonic acid and benzenedisulfonic acid. Other suitable materials are disclosed in U.S. Pat. Nos. 3,422,075 and 2,635,048.

If a pH-lowering layer is employed, it will usually be about 0.3 to about 1.5 mils in thickness and may be located in the receiver element or in the receiver portion of an integral negative-receiver film unit between the support and the imagereceiving layer or in a process sheet.

An inert timing or spacer layer coated over the pH-lowering 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 temperatures, e.g., premature pH reduction is prevented when imbibition is effected at temperatures above room temperature, for example, at 95 to 100 F. The timing layer is usually about 0.1 to about 0.7 mil in thickness. Especially good results are obtained when the timing layer comprises a hydrolyzable polymer or a mixture of such polymers which are slowly hydrolyzed by the processing composition. Examples of such hydrolyzable polymers include polyvinyl alcohol, polyvinyl acetate, polyamides, polyvinyl ethers, partial acetals of polyvinyl alcohol, etc.

The alkaline 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 excess of 12. The alkaline 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 sodium carboxymethyl cellulose. A concentration of viscosity-increasing compound of about 1 to about 5 percent by weight of the processing composition is preferred which will impart thereto a viscosity of about c.p.s. to about 200,000 c.p.s. When the novel developers of the invention are employed in the alkaline processing composition, they can be employed in any concentration useful for the intended purpose. Generally, good results are obtained when the developer is employed in a concentration ranging from about 2 to about 50 grams per liter of processing composition.

While the invention has been described with reference to layers of silver halide emulsions and dye image providing materials, dotwise coating, such as would be obtained using a gravure printing technique, could also be employed. In this technique, small dots of blue, green and red sensitive emulsions have associated therewith, respectively dots of yellow, magenta and cyan color-providing substances. After development, the transferred dyes would tend to fuse together into a continuous tone.

The photographic layers employed in the practice of this invention can 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. 3,133,8l6; and water-soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson, British Pat. No. 1,022,878.

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; Gaspar, 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.

The sensitizing dyes and other addenda used in the practice of this invention can be added from water solutions or suitable organic solvent solutions can 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. 3,342,605; Audran, U.S. Pat. No. 2,996,287 and Johnson et al., U.S. Pat. No. 3,425,835.

The photographic layers used in the practice of this invention can be coated by various coating procedures including 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.

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, sulfonated 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 following example further illustrates the invention:

EXAMPLE A A multilayer photosensitive element is prepared by coating the following layers in the order recited on a cellulose acetate film support:

l.-Red-sensitive gelatin-silver bromide emulsion (1 mg. gelatin/ft. and 60 mg. silver/ft?) and l-hydroxy-N-[a-(2,4-ditert-amylphenoxy)butyl]-2-naphthamide (87 mg./ft.

2. Barrier lnterlayer of l-hydroxy-N-[a-(2,4-di-tert amylphenoxy)butyll-Z-naphthamide (l mg./ft. and gelatin (50 mg./ft.

3. Nuclei layer of cyan image transfer coupler l-hydroxy-4-{ 4-[a-(3-pentadecylphenoxy)butyrarnido1-phenoxy} -N-ethyl- 3', 5'-dicarboxy-2-naphthanilide (107 mg./ft. colloidal palladium (0.48 mgJft?) and gelatin (100 mg./ft.

4. Overcoat layer of gelatin (50 mg./ft.

Samples of the above element are sensitometrically exposed to a graduated-density test object and processed at 70 F. with the following processing compositions:

Each processing composition also contains 5 grams of sodium thiosulfate, 0.8 grams of piperidinohexosereductone, 32 grams of hydroxyethyl cellulose and water to make 1 liter. The particular amounts chosen provide equimolar quantities of developer, hypo and free hydroxide.

The processing compositions are spread from a pod between the exposed surface of the elements and a superposed receiving sheet comprising an image-receiving layer of octadecyl-tri-n-butyl ammonium bromide (150 mg./ft. and gelatin (300 mgjft?) coated upon an opaque support by passing the transfer sandwich between a pair of juxtaposed pressure rollers. After 1% and 3 minutes the following D and D,,,,-,, values of the transferred dye images are obtained:

3.0 2.42 1.20 B 1.5 [.14 0.24 3.0 2.38 0.32 C l 5 [.18 0.18 3.0 2.18 0.20 D LS 1.92 0.18 3.0 2.68 0.24

It is seen that use of the developer according to my invention provides a significantly higher D,,,,, and lower D,,,,,, in comparison to closely related p-phenylenediamines.

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

lclaim:

1. In 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 nondiffusible coupler capable of reacting with oxidized aromatic primary amino colordeveloping agent to produce a difi'usible dye;

a dye image receiving layer; and c. a rupturable container containing an alkaline processing composition and 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 containers contents within said said film unit; said film unit containing an aromatic primary amino colordeveloping agent, the improvement comprising employing as said developing agent a 4-amino-3-alkoxy-N-ethyl-N-B- hydroxyethylaniline.

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.

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 1 wherein said developing agent is 4-amino-3-rnethoxyeN-ethyl-N-B-hydroxyethylaniline and is present in said rupturable container.

6. The film unit of claim 1 wherein said photosensitive element comprises a support having thereon a red-sensitive silver halide emulsion layerhaving associated therewith a cyan dye image providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible cyan dye, a green-sensitive silver halide emulsion layer having associated therewith a magenta dye image providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible' magenta dye, and a blue-sensitive silver halide emulsion layer having associated therewith a yellow dye image providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino colordeveloping agent to produce a diffusible yellow dye.

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

1. a photosensitive element comprising a support having thereon at least one color-forming unit comprising:

a. a nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible dye; and

b. a photosensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary amino color-developing agent to form an immobile product;

ll. a dye image receiving layer; and

III. a rupturable container containing an alkaline processing composition and 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 containers contents within said film unit;

said film unit containing a silver halide solvent and an aromatic primary amino color-developing agent; the improvement comprising employing as said developing agent a 4- amino-S-alkoxy-N-ethyl-N-B-hydroxyethylaniline.

8. The film unit of claim 7 wherein said dye image receiving layer is located in said photosensitive element between said support and the lowermost photosensitive silver halide emulsion layer.

9. The film unit of claim 7 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.

10. The film unit of claim 9 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.

11. The photographic film unit of claim 7 wherein said developing agent is 4-amino-3-methoxy-N-ethyl-N-B-hydroxyethylaniline and is present in said rupturable container.

12. The film unit of claim 7 wherein said photosensitive element comprises a support having thereon the following layers in sequence:

a. a nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible cyan dye;

b. a red-sensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary amino color-developing agent to form an immobile product;

. an alkaline solution-permeable barrier layer for retaining soluble silver ion complex;

a nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible magenta dye;

e. a green-sensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary amino colordeveloping agent to form an immobile product;

an alkaline solution-permeable barrier layer for retaining soluble silver ion complex;

g. a nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible yellow dye; and

h. a blue-sensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary amino color-developing agent to form an immobile product;

each said nondiffusible coupler having the formula:

DYELlNK-(COUPBALL),

BALL- LlNK(COUPSOL wherein:

. DYE is a preformed dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group;

2. LINK is a connecting radical selected selected from the group consisting of an azoradical, a mercuri radical, an oxyradical, an alkylidene radical, a thioradical, a dithioradical and an azoxy radical;

3. COUP is a coupler radical selected from the group consisting of a 5-pyrazolone coupler radical, a

pyrazolotriazole coupler radical, a phenolic coupler radical and an open-chain ketomethylene coupler radical, said COUP being substituted in the coupling position with said link;

4. BALL is a photographically inert organic ballasting radical of such molecular size and configuration as to render said coupler nondiffusible during development in said alkaline processing composition;

5. SOL is selected from the group consisting of a hydrogen atom and an acidic solubilizing group when said color developing agent contains an acidic solubilizing group, and SOL is an acidic solubilizing group when said colordeveloping agent is free of an acidic solubilizing group; and

6. n is an integer of l to 2 when said LlNK is an alkylidene radical, and n is 1 when said LINK is a radical selected from the group consisting of an azoradical, a mercuri radical, an oxyradical, a thioradical, a dithioradical and an azoxy radical.

13. The photographic film unit of claim 12 wherein said developing agent is 4-amino-3-methoxy-N-ethyl-N-B-hydroxyethylaniline and is present in said alkaline processing composition in said rupturable container and said silver halide solvent is also present in said rupturable container.

14. In 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 nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible dye;

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 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 diffusing to a dye image receiving layer; the improvement comprising employing as said developing agent a 4-amino-3-alkoxy-N-ethyl-N-B-hydroxyethylaniline.

15. The process of claim 14 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.

16: The process of claim 14 wherein said developing agent is 4-amino-3-methoxy-N-ethyl-N-fi-hydroxyethylaniline.

17. The process of claim 14 wherein said photosensitive element comprises a support having thereon a red-sensitive silver halide emulsion layer having associated therewith a cyan dye image providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible cyan dye, a green-sensitive silver halide emulsion layer having associated therewith a magenta dye image providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible magenta dye, and a blue-sensitive silver halide emulsion having associated therewith a yellow dye image providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible yellow dye.

18. In a process of forming a transfer image comprising:

I. imagewise a photosensitive element comprising a support having thereon at least one color-forming unit comprising:

II. treating said photosensitive element with an alkaline processing composition in the presence of an aromatic primary amino color-developing agent and a silver halide solvent;

III. thereby effecting development of each of said exposed silver halide emulsion layers, thus causing said aromatic primary amino color-developing agent to become oxidized imagewise;

IV. said oxidized developing agent reacting with said immobilizing coupler present in each said photosensitive silver halide emulsion layer to form an immobile product;

V. whereby remaining silver halide in each said silver halide emulsion layer corresponding to unexposed and thus undeveloped areas forms a soluble silver complex with said silver halide solvent and transfers to each said adjacent nuclei layer;

Vl, whereby said transferred silver complex is reduced in said nuclei layer, thus causing said developing agent to become oxidized;

VII. said oxidized developing agent reacting with said nondiffusible coupler present in each said nuclei layer to form an imagewise distribution of diffusible dye as a function of said imagewise exposure of each said. silver halide emulsion layer; and

VIII. whereby at least a portion of each said imagewise distribution of diffusible dye diffuses to a dye image-receiving layer to provide a positive dye image;

the improvement comprising employing as said developing agent a 4-amino-3-alkoxy-N-ethyI-N-B-hydroxyethylaniline.

19. The process of claim 18 wherein said treatment step (II) is effected by:

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

20. The process of claim 18 wherein said developing agent is 4-amino-3-methoxy-N-ethyl-N-B-hydroxyethylaniline.

21. The process of claim 18 wherein said photosensitive element comprises a support having thereon the following layers in sequence:

. a red-sensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary amino color-developing agent to form an immobile product;

c. an alkaline solution-permeable barrier layer for retaining soluble silver ion complex;

. a nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible magenta dye;

a blue-sensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary amino color-developing agent to form an immobile product;

each said nondiffusible coupler having the formula:

DY12--LINK-(COUI"--BALL),

BALLLINK(COUPSOL),,

wherein:

l. DYE is a preformed dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group;

2. LINK is a connecting radical selected from the group consisting of an azoradical, a mercuri radical, an oxyradical, an alkylidene radical, a thioradical, a dithioradical and an azoxy radical; I

3. COUP is a coupler radical selected from the group consisting of a S-pyrazolone coupler radical, a pyrazolotriazole coupler radical, a phenolic coupler radical and an open-chain ketomethylene coupler radical, said COUP being substituted in the coupling position with said LINK;

. BALL is a photographically inert organic ballasting radical of such molecular size and configuration as to render said coupler nondiffusible during development in said alkaline processing composition;

5. SOL is selected from the group consisting of a hydrogen atom and an acidic solubilizing group when said colordeveloping agent contains an acidic solubilizing group, and SOL is an acidic solubilizing group when said colordeveloping agent is free of an acidic solubilizing group; and

6. n is an integer of l to 2 when said LINK is an alkylidene radical, and n is 1 when said LINK is a radical selected from the group consisting of an azoradical, a mercuri radical, an oxyradical, a thioradical, a dithioradical and an azoxy radical.

22. The process of claim 21 wherein said developing agent is 4-amino-3-methoxy-N-ethyl-N-l3-hydroxyethylaniline.

Claims

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. LINK is a connecting radical selected selected from the group consisting of an azoradical, a mercuri radical, an oxyradical, an alkylidene radical, a thioradical, a dithioradical and an azoxy radical;
2. LINK is a connecting radical selected from the group consisting of an azoradical, a mercuri radical, an oxyradical, an alkylidene radical, a thioradical, a dithioradical and an azoxy radical;
3. COUP is a coupler radical selected from the group consisting of a 5-pyrazolone coupler radical, a pyrazolotriazole coupler radical, a phenolic coupler radical and an open-chain ketomethylene coupler radical, said COUP being substituted in the coupling position with said LINK;
3. COUP is a coupler radical selected from the group consisting of a 5-pyrazolone coupler radical, a pyrazolotriazole coupler radical, a phenolic coupler radical and an open-chain ketomethylene coupler radical, said COUP being substituted in the coupling position with said link;
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 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. BALL is a photographically inert organic ballasting radical of such molecular size and configuration as to render said coupler nondiffusible during development in said alkaline processing composition;
4. BALL is a photographically inert organic ballasting radical of such molecular size and configuration as to render said coupler nondiffusible during development in said alkaline processing composition;
5. SOL is selected from the group consisting of a hydrogen atom and an acidic solubilizing group when said color-developing agent contains an acidic solubilizing group, and SOL is an acidic solubilizing group when said color-developing agent is free of an acidic solubilizing group; and
5. SOL is selected from the group consisting of a hydrogen atom and an acidic solubilizing group when said color developing agent contains an acidic solubilizing group, and SOL is an acidic solubilizing group when said color-developing agent is free of an acidic solubilizing group; and
5. The film unit of claim 1 wherein said developing agent is 4-amino-3-methoxy-N-ethyl-N- Beta -hydroxyethylaniline and is present in said rupturable container.
6. n is an integer of 1 to 2 when said LINK is an alkylidene radical, and n is 1 when said LINK is a radical selected from the group consisting of an azoradical, a mercuri radical, an oxyradical, a thioradical, a dithioradical and an azoxy radical.
6. The film unit of claim 1 wherein said photosensitive element comprises a support having thereon a red-sensitive silver halide emulsion layer having associated therewith a cyan dye image providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible cyan dye, a green-sensitive silver halide emulsion layer having associated therewith a magenta dye image providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible magenta dye, and a blue-sensitive silver halide emulsion layer having associated therewith a yellow dye image providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible yellow dye.
6. n is an integer of 1 to 2 when said LINK is an alkylidene radical, and n is 1 when said LINK is a radical selected from the group consisting of an azoradical, a mercuri radical, an oxyradical, a thioradical, a dithioradical and an azoxy radical.
7. In a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising: I. a photosensitive element comprising a support having thereon at least one color-forming unit comprising: a. a nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible dye; and b. a photosensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary aminO color-developing agent to form an immobile product; II. a dye image receiving layer; and III. a rupturable container containing an alkaline processing composition and 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 within said film unit; said film unit containing a silver halide solvent and an aromatic primary amino color-developing agent; the improvement comprising employing as said developing agent a 4-amino-3-alkoxy-N-ethyl-N- Beta -hydroxyethylaniline.
8. The film unit of claim 7 wherein said dye image receiving layer is located in said photosensitive element between said support and the lowermost photosensitive silver halide emulsion layer.
9. The film unit of claim 7 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.
10. The film unit of claim 9 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.
11. The photographic film unit of claim 7 wherein said developing agent is 4-amino-3-methoxy-N-ethyl-N- Beta -hydroxyethylaniline and is present in said rupturable container.
12. The film unit of claim 7 wherein said photosensitive element comprises a support having thereon the following layers in sequence: a. a nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible cyan dye; b. a red-sensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary amino color-developing agent to form an immobile product; c. an alkaline solution-permeable barrier layer for retaining soluble silver ion complex; d. a nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible magenta dye; e. a green-sensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary amino color-developing agent to form an immobile product; f. an alkaline solution-permeable barrier layer for retaining soluble silver ion complex; g. a nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible yellow dye; and h. a blue-sensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary amino color-developing agent to form an immobile product; each said nondiffusible coupler having the formula: DYE-LINK-(COUP-BALL)n or BALL-LINK-(COUP-SOL)n wherein:
13. The photographic film unit of claim 12 wherein said developing agent is 4-amino-3-methoxy-N-ethyl-N- Beta -hydroxyethylaniline and is present in said alkaline processing composition in said rupturable container and said silver halide solvent is also present in said rupturable container.
14. In 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 nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible dye; 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 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 diffusing to a dye image receiving layer; the improvement comprising employing as said developing agent a 4-amino-3-alkoxy-N-ethyl-N- Beta -hydroxyethylaniline.
15. The process of claim 14 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.
16. The process of claim 14 wherein said developing agent is 4-amino-3-methoxy-N-ethyl-N- Beta -hydroxyethylaniline.
17. The process of claim 14 wherein said photosensitive element comprises a support having thereon a red-sensitive silver halide emulsion layer having associated therewith a cyan dye image providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible cyan dye, a green-sensitive silver halide emulsion layer having associated therewith a magenta dye image providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible magenta dye, and a blue-sensitive silver halide emulsion having associated therewith a yellow dye image providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible yellow dye.
18. In a process of forming a transfer image comprising: I. imagewise a photosensitive element comprising a support having thereon at least one color-forming unit comprising: a. a nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to producE a diffusible dye; and b. a photosensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary amino color-developing agent to form an immobile product; II. treating said photosensitive element with an alkaline processing composition in the presence of an aromatic primary amino color-developing agent and a silver halide solvent; III. thereby effecting development of each of said exposed silver halide emulsion layers, thus causing said aromatic primary amino color-developing agent to become oxidized imagewise; IV. said oxidized developing agent reacting with said immobilizing coupler present in each said photosensitive silver halide emulsion layer to form an immobile product; V. whereby remaining silver halide in each said silver halide emulsion layer corresponding to unexposed and thus undeveloped areas forms a soluble silver complex with said silver halide solvent and transfers to each said adjacent nuclei layer; VI. whereby said transferred silver complex is reduced in said nuclei layer, thus causing said developing agent to become oxidized; VII. said oxidized developing agent reacting with said nondiffusible coupler present in each said nuclei layer to form an imagewise distribution of diffusible dye as a function of said imagewise exposure of each said silver halide emulsion layer; and VIII. whereby at least a portion of each said imagewise distribution of diffusible dye diffuses to a dye image-receiving layer to provide a positive dye image; the improvement comprising employing as said developing agent a 4-amino-3-alkoxy-N-ethyl-N- Beta -hydroxyethylaniline.
19. The process of claim 18 wherein said treatment step (II) is effected by: a. superposing over the layer outermost from the support of said exposed 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.
20. The process of claim 18 wherein said developing agent is 4-amino-3-methoxy-N-ethyl-N- Beta -hydroxyethylaniline.
21. The process of claim 18 wherein said photosensitive element comprises a support having thereon the following layers in sequence: a. a nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible cyan dye; b. a red-sensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary amino color-developing agent to form an immobile product; c. an alkaline solution-permeable barrier layer for retaining soluble silver ion complex; d. a nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible magenta dye; e. a green-sensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary amino color-developing agent to form an immobile product; f. an alkaline solution-permeable barrier layer for retaining soluble silver ion complex; g. a nuclei layer containing physical development nuclei and a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color-developing agent to produce a diffusible yellow dye; and h. a blue-sensitive silver halide emulsion layer containing an immobilizing coupler which is capable of reacting with oxidized aromatic primary amino color-developing agent to form an immobile product; each said nondiffusible coupler having the formula: DYE-LINK-(COUP-BALL)n or BALL- LINK-(COUP-SOL)n wherein:
22. The process of claim 21 wherein said developing agent is 4-amino-3-methoxy-N-ethyl-N- Beta -hydroxyethylaniline.