US3243294A

US3243294A - Photographic direct-positive color process

Info

Publication number: US3243294A
Application number: US321925A
Authority: US
Inventors: Charles R Barr
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1963-11-06
Filing date: 1963-11-06
Publication date: 1966-03-29
Anticipated expiration: 1983-03-29
Also published as: GB1086208A; DE1246406B; BE655249A

Description

March 29, 1966 c. R. BARR 3,243,294

PHOTOGRAPHIC DIREc-r-PosITIvE COLOR PROCESS Filed Nov. 6, 1963 ll NUCLEATED SILVER HA LIDE EMULSION LAYER CONTAINING wLOR COUPLER AND BLACK 'AND' WHITE DEVELOPER 7 suPPORT Fig.1.

23 /COLOR DEVELOPER LAYER 91 NUCLEATED s/LVER l-MUDEEMULSIONZAYER OOIvTA/Iv/NO OOLOR OOOPLER AND eLAcK-A/vD- 4 WHITE DEVELOPER uPP RT F1 2 3 0 SUPPORT 4O MORDANT LAYER 38 P 00 CONTAINING PROCESSING MATERIAL PROTECTIVE LA YER BLUE SENS! TI VE NUCLEA TED SILVER HALI DE EMULSION LAYER CONTAIN/N6 YELLOW FORMING COUPLER AND BLA CKAND WHITE DE VE LOPE R INTERLA YER GREEN'SENSITIVE NUCLEATED SILVER HALIDE EMULSION LAYER CONTAINING MAGENTA FORMING COUPLER AND BLA CK AND'WHI TE DEVELOPER INTERLAYER RED SENSITIVE N U C LEATED SILVER HAUDE EMULSION LAYER CONTAINING CWlN'FORM/NG COUPLER AND BLA CK AND WHITE DEVELOPER 5 UPPOR 7 GharlesR.Barr F 3 INVEN OR BY PPM/ QL Rf 2;

.A'I'IONEYS United States Patent 3,243,294 PHOTOGRAPHIC DIRECT-POSITIVE COLOR PRQCESS Charles R. Barr, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed Nov. 6, 1963, Ser. No. 321,925 23 Claims. (Cl. 96-3) This invention relates to color photography, and more particularly, to photographic direct-positive color processes and photographic elements suitable for use in such processes.

Direct-positive photographic color processes are known in the art, and generally comprise a number of steps. A typical color process comprises such steps as a black-and- White development to form a negative image, a reversal exposure, development with an aromatic primary amino color developing agent to form dye images in areas of development and bleach and fix steps to remove developed silver. Color processes are also known whereby positive color images are transferred to receiving elements by diffusion of the color images. However, processes of the latter type commonly involve several steps, several processing baths with large volumes of processing solutions, the diffusion of silver halide, special emulsions such as direct-positive emulsions, the use of special color compounds having developing properties and/or a plurality of emulsion layers for each color produced by the photographic element.

It is an object of the present invention to provide a new direct-positive color process in the photographic art.

It is another object of the invention to provide a new photographic process for preparing direct-positive color images without the use of direct-positive silver halide emulsions.

It is another object of this invention to provide a new photographic process for preparing direct-positive color images without the use of a separate reversal exposure step.

It is still another object of this invention to provide a novel photographic diffusion transfer process for preparing direct-positive color images.

It is another object of this invention to provide a novel color diffusion transfer process that can be efiected in one wet processing step.

It is also an object of this invention to provide novel photographic elements for producing direct-positive color images wherein the color-forming unit for forming each color image consists of a single silver halide emulsion layer.

These and other objects of the invention are attained by means described hereinafter with respect to preferred embodiments thereof.

The present invention concerns photographic elements comprising a support having coated thereon at least one light-sensitive silver halide emulsion layer containing physical development nuclei, at least one diffusible blackand-white developer, and at least one nondiffusible color coupler. Such a photographic element can be color processed to a direct-positive color image by developing in an aqueous alkaline composition in the presence of an aromatic primary amino color developing agent and a silver halide solvent. In the process of the invention, the black-and-white developer in the silver halide emulsion in the presence of the color developing agent and aqueous alkaline material initially develops the latent image to form a negative metallic silver image by chemical development without the formation of a color image. Thereafter, unexposed and undeveloped silver halide corresponding to the positive image area is physically de- 3,243,294 Patented Mar. 29, 1966 veloped by the color developing agent to form a positive color image. If the color coupler in the photo-graphic element produces a dilfusible dye image, such a dye image can be allowed to diffuse to a reception element which could be either an integral layer on the photographic element or a separate receiving sheet. If the color coupler forms a nondiffusible dye image, the photographic element can thereafter be treated with a bleach and fixed to remove metallic silver from the photographic element to leave a positive dye image thereon.

The silver halide emulsions of the present photographic elements are conventional developing-out, negative-type photographic silver halide emulsions including silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, and silver chlorobromoiodide emulsions. There can be employed as the dispersing agent or substrate for the silver halide in its preparation, gelatin or some other commonly employed photographic hydrophilic colloidal material such as co-lloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound, although gelatin is preferred. Such hydrophilic colloidal materials can also be used in non-light-sensitive layers in the subject elements in accordance with the usual practice. Such hydrophilic colloids are well known in the art. The subject photographic emulsions can contain the addenda generally utilized in such products including optical sensitizers, speed-increasing materials, antifoggants, coating aids, gelatin hardeners, plasticizers, ultraviolet absorbers and the like.

The silver halide emulsions of the present photographic elements contain physical development nuclei ad denda. Typical physical development nuclei include col loidal noble metals such as silver and gold; colloidal metal sulfides, selenides and tellurides such as lead sulfide, nickel sulfide, cadmium sulfide, silver sulfide, silver selenide, silver telluride, copper sulfide, zinc sulfide and mercury sulfide; metal proteinates such as silver proteinates; sodium sulfide; colloidal sulfur; and such organic sulfur compounds as thiourea, and xanthates.

A substantially colorless photographic black-and-white silver halide developing agent is incorporated in the silver halide emulsions of the photographic elements of the invention. The black-and-white developing agent serves to chemically develop the latent image in the regions of exposure '(negative image regions) before the color developing agent physically develops the unexposed silver halide in the unexposed regions (positive image regions). As used herein, the term black-and-white developing agent refers to a developing agent that chemically develops to metallic silver exposed silver halide, and which developing agent does not produce development oxidation product that will react with color couplers to form dyes. Illustrative suitable black-and-white silver halide developing agents include:

(1) Ditfusible hydroquinones having at least one aminosubstituted lower alkyl group, and including hydroquinones having aqueous alkali-hydrolyzable carbonyl groups masking the hydroxyl groups,

(2) Dilfusible catechols having at least one amino-substituted lower alkyl group, and including catechols having aqueous alkali hydrolyzable sulfonyl or carbonyl groups masking the hydroxyl groups,

(3) Combinations of (a) Dilfusible 3-pyrazolidones, .and (b) Nonodiifusible hydroquinones containing a photographically inert ballasting group; or

(4) Mixtures of more than one of the above three classes of black-and-white silver halide developing agents.

Typical suitable diffusible hydroquinone black-andwhite silver halide developing agents having at least one amino-substituted lower alkyl radical can be represented by the following formula wherein: R is an amino-substituted lower alkyl radical,

the alkyl moiety preferably being methyl, the amino moiety being suitably substituted with such substituents as lower alkyl radicals, substituted lower alkyl radicals such as lower alkanol and halo lower akyl, cyclic radicals such as the necessary carbon, hydrogen and oxygen atoms to form a morpholino group with the nitrogen atom, as well as quaternary salts of such amino moieties; R is an amino-substituted lower alkyl radical as described for R,

and the like. Such hydroquinones and precursors include:

2,5 -bis [N,N-bis S-hydroxyethyl) aminornethyl] hydroquinone 2,5-bis (N,N-dimethylarninomethyl)hydroquinone 2- (N,N-dimethylaminomethyl -5-methylhydroquinone 2- [N,N-bis fi-hydroxyethyl) aminornethyl] -5-methylhydroquinone 2- [N,N-bis B-hydroxyethyl) aminornethyl] -5-methylhydroquinone metho-methanesulfonate 2,5 -bis (N-morpholinomethyl) hydroquinone bis achloroacetate) 2-{' [bis ,B-hydroxyethyl) amino] propyl} -5-methylhydroquinone 2,5-bis (N,N-dimethylaminomethyl) hydroquinone bis (metho-p-toluenesulfonate) 2,5 -bis (N-morpholinomethyl hydroquinone bis(metl1o-ptoluenesulfonate) 2- [N,N-bis(fl-hydroxyethyl) aminornethyl] -5-methylhydroquinone etho-ethanesulfonate 5 -methyl-2- (N-rnorpholinornethyl etho-ethanesulfonate 2,5 -bis (N-morpholinomethyl) hydroquinone bis (ethoethane'sulfonate) r 2- [N,'N-bis p-hydroxyethyl) an1inomethyl]-5-( l-phenyl- S-tetrazolylthio)hydroquinone dipropionate 2- [N,N-bis ,B-hydroxyethyl) aminornethyl]-5-(1-phenyl- S-tetrazolythio hydroquinone etho-ethansulfonate .-2-hydroquinolyl-triphenylphosplioniurn chloride X,Y-bis (N,N-di-methylaminomethyl) -2-methylhydroquinone X,Y-bis (N,N-di-methylarninomethyl -2-t-butylhydroquinone S-methyl-Z- (N-morpholinomethyl) hydroquinone 2,5 -bis [N,N-bis ,B-hydroxypropyl) aminomethyl1hydrohydroquinone 4 2,5 -bis [N,N-bis B-hydroxyethyl) aminornethyl] hydroquinone bis (methomethanesulfonate) 2,5-poly [4,4'-piperazinomethylhydroquinone metho-ptoluenesulfonate] Typical suitable diffusible catechol black-and-white silver halide developing agents having at least one aminosubstituted lower alkyl radical can be represented by the following formula wherein R and R can be the same substituents as described above for R and R respectively, and R and R can be hydrogen atoms, or separately or together, the necessary atoms that form sulfonyl or carbonyl ma'ksing radicals that hydrolyze or split in the presence of aqueous alkaline processing material, typical masking radicals including ll II II 8:0, 0:0, -CO-l0wer alkyl, -CCO-lower alkyl ll H II OO-(halo lower alkyl) such as CC F -OC HzCl and the like. Such catechols and precursors include:

4- [N,N-bis ,B-hydroxyethyl) aminomethyl1-5-methylcatechol 4- [N,N-bis ,B-hydroxyethyl) aminornethyl] -5-methylcatechol carbonic ester 4- [N,N-bis (fl-hydroxyethyl) aminomethyl1-5-methylcatechol sulfurous ester 4- [N,N-bis (fi-hydroxyethyl) amin0methyl1-5-methylcathechol sulfurous ester ethoethane sulfonate 4- [N,N-bis fi-hydroxyethyl) aminornethyl] -5-methylcatechol carbonic ester ethoethane sulfonate 4- [N,N-bis ,B-hydroxyethyl) aminomethyl1-5-methylcatechol bis a-chloroacetate) A wide variety of diffusible 3-pyrazolidone black-and- White developing agents can be used in the silver halide emulsions of the invention. Typical suitable 3-pyrazolidone black-and-white silver halide developing agents, including the corresponding enolic form, are disclosed in U.S. Patent 2,289,367; U.S. Patent 2,685,516; U.S. Patent 2,751,297; U.S. Patent 2,772,282; and the Journal of Organic Chemistry, 26, 2803 (1961). Typical of such developing agents can be represented by the following formulas wherein R R R R and R can be lower alkyl radicals and including substituted lower radicals such as chloro-substituted lower alkyl radicals, hydrogen atoms and aryl radicals and including substituted aryl radicals such as phenyl, chlorophenyl, p-tolyl and fl-hydroxyethylphenyl, and the like; R can be a hydrogen atom or a carbonyl masking radical that hydrolyzes or splits in the presence of aqueous alkaline processing material, typical masking radicals are the radicals described above for R and R and R 'can be a masking radical as described .above for R and R Such 3-pyrazolidones include: l-phenyl-3-pyrazolidone 1-phenyl-4-methyl-3-pyrazolidone l-phenyl-4,4-dirnethyl-3-pyrazolidone ,l-(4-aminophenyl)-3rirninopyrazolidone 1-phenyl-2-acetyl-3 pyrazolidone l-phenyl-2-acetyl-4-methyl-3-pyrazolidone l-phenyl-2-acetyl-4,4-dimetl1yl-3-pyrazolidone 1-phenyl-3-acetoxy-4-methyl-pyrazoline 1-phenyl-3-acetoxypyrazoline 1-phenyl-2-chloroacetyl-3-pyrazolidone l phenyl-2-chloroacetyl-4-methyl-3-pyrazolidone 1-phenyl-2-chloroacetyl-4,4-dimethyl-3-pyrazolidone lphenyl-2-dichloroacetyl-3-pyrazolidone l-phenyl-Z-(pyridinium acetyl)-3-pyrazolidone chloride I-phenyLZ-( yridinium acetyl)-4-methyl-3-pyrazolidone chloride 1-phenyl-2-(pyridinium acetyl)-4,4-dimethyl-3-pyrazolidone chloride l-p-tolyl-3-pyrazolidone 1- o-chlorophenyl) -4-methy1-4-ethyl-3-pyrazolidone 1- [p- (p-hydroxyethyl phenyl] -4,4-dimethyl-3-pyrazolidone 1-phenyl-3-acetoxy-2-pyrazoline 1-phenyl-3-acetoxy-4-methyl-Z-pyrazoline Typical suitable nondifiusible ballasted hydroquinones that are utilized as auxiliary black-and-white developers in combination with the above-described 3-pyrazolidones can be represented by the following formula:

wherein R is a photographically inert organic ballasting group of such molecular size and configuration as to render the hydroquinone nondiffusing and typically includes long chain or higher alkyl radicals having 8 to 22 carbon atoms; R can also be a ballasting group as described for R or a solubilizing group such as a sulfo group and alkali metal salts thereof, such solubilizing group facilitating the addition of the hydroquinone into the silver halide emulsion in an aqueous medium but not rendering the hydroquinone diifusible. Such ballasted hydroquinones include: 2-n-octadecyl-S-sulfo-hydroquinone, 2-n-octyl-S-sulphohydroquinone, 2-n-pentadecyl-5- sulfohydroquinone, 2,5-di-isooctylhydroquinone and the like.

As used herein the term lower alkyl refers to alkyl radicals having 1 to 6 carbon atoms.

The amounts of black-and-white silver halide developing agent utilized in the present photographic elements can be Widely varied in accordance with usual practice, sufficient amounts being used to assure substantially complete chemical development of the negative latent images in the respective emulsions. The diffusible hydroquinones and catechols are used at concentrations of at least /2 mole for each mole of silver halide in the respective emulsions. At least one mole of the diffusible 3-pyrazolidones for each mole of silver halide in the respective emulsions is utilized. At least about mole of the nondiffusi'ble ballasted hydroquinones is used with each mole of the diifusible 3-pyrazolidones.

The incorporated black-and-white developing agents are at least as strong silver halide reducing agents as the color developing agents, and generally stronger. The presence of the color developing agent appears to facilitate the black-and-white development without the formation of dye in negative image areas.

The photographic silver halide emulsions of the photographic elements of the invention contain at least one nondiffusible photographic color coupler that reacts with oxidized aromatic primary amino color developing agent to form a dye. Such couplers are well known in the art and are generally S-pyrazolone, phenolic or openchain ketomethylene compounds. Particularly useful couplers are nondiffusible couplers that form diffusible 6 dyes on color development, such being referred to herein as DDR or diffusible dye-releasing couplers. DDR couplers are useful in direct-positive color diffusion transfer processes of the invention. Nondiifusible coupler-s that form nonditfusible dyes on color development can also be utilized.

The DDR couplers used in preparing photographic elements of the invention having utility in diffusion transfer processes include those having the formulas DYE--LINK COUP-BALL) n and BALL-LINK(COUP--SOL n wherein:

(l) DYE is a dye radical containing an acidic solubilizing radical; (2) LINK is a connecting or linkage radical such as R alkylidene (includes both 1- and =C- wherein R is a hydrogen atom or an alkyl radical generally having 1 to 4 carbon atoms), monothio (--S), or dithio (SS-);

(3) COUP is a photographic color coupler radical such as a 5apyrazolone coupler radical, a phenolic coupler radical or an open-chain ketomethylene coupler radical, the coupler radical being substituted in the coupling position with the connecting or linkage radical;

(4) BALL is a photographically inert organic radical of such molecular size and configuration as to render the coupler nondifr'using in the element in the alkaline processing solution;

(5) SOL is either a hydrogen atom or an acidic solubilizing group when the color developing agent contains an acidic solubilizing radical, SOL always being an acidic solubilizing radical when the color developing agent is free of an acidic solubilizing group; and

(6) n is an integer of 1 or 2 when LINK is an alkylidene radical, and n is always 1 when LINK is one of the other aforementioned connecting radicals, namely, azo, azoxy, mercury, oxy, monothio, or dithio.

The acidic solubilizing radicals attached to the diffusi-ble dye-releasing (DDR) couplers described above can be solubilizing radicals which when attached to the coupler or developer moieties of the dyes, render the dyes diffusible in the element in alkaline processing solutions. Typical of such radicals are carboxylic, sulfonic, ionizable 'sulfonamido, and hydroxy-substituted groups that lend to dyes negative charges.

Typical dye radical substituents (DYE) of the DDR couplers 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.

When DDR couplers having the formula DYE- LINK-(COUP---BALL) as described above are reacted with oxidized color developing agent, the connecting radical (LINK) is split and a diffusible preformed acid dye (DYE) is released which diffuses imagewise to a reception layer. An acidic solubilizing group on the preformed dye lends diffusibility and mordantability to the dye molecule. The coupling portion of the DDR coupler (COUP) couples with color developing agent oxidation product to form a dye that is nondiffusible in the element because of the attached ballasting group (BALL) in a noncoupling position. In this type of DDR coupler, the color of the diifusib-le dye is deter mined by the color of the preformed dye moiety (DYE), the color of the reaction product of color developer oxidation product and the coupler moiety 7 (COUP) being unimportant to the color of the diffusible image.

When DDR couplers having the formula BALL-LINK(COUP-SOL) n as described above are reacted with oxidized color developing agent, the connecting radical (LINK) is split and a difl usilble dye is formed with the color developing agent oxidation product and the coupling portion (COUP) of the DDR coupler which diffuses i-nragewise to a reception layer. rDitf usibility is imparted to the dye by an acidic solubilizing group attached to a noncoupling position of the coupling portion (COUP) of the DDR coupler or to the color developing agent. The ballast portion of the DDR coupler remains immobile. In this type of DDR coupler, the color of the difiusible dye is determined by the color of the reaction product of color developer oxidation product and the coupler moiety (COUP).

When the coupler radical (COUP) in the DDR couplers is a -pyrazolone radical, I prefer to have substituted in the 3-position of the pyrazolone moiety an anilino group or an alkoxy group. When the coupler radical (COUP) in the DDR couplers is a cyan-forming phenolic coupler radical, I prefer to have substituted in the ortho or 2-position or the phenolic moiety a fully substituted amido group (e.g.,

R C Ol IR wherein R is an alkyl group or a phenyl group). Also, when the connecting radical (LINK) in the DDR couplers having the formula,

BALLLINK(COUPSOL) n is an azo radical, I prefer that the ballasting radical (BALL) be a phenyl radical containing either a hydroxy group or an amino group (NH substituted in the ortho or 2-position of the phenyl moiety.

The nature of the ballast groups (BALL) in the DDR coupler compounds described above is not critical as long as they confer nondiifusibility to the coupler compounds. Typical ballast groups exemplified hereinafter in the speciric couplers disclosed include long chain alkyl radicals or several short chain alkyl radicals having e.g., 8 to 22 carbon atoms, 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 generally have at least 8 carbon atoms.

The fiollowing are representative DDR couplers used in the present invention, to wit, nondiffusible coupler compounds that release or form ditfusi-ble acid dyes on coupling with the oxidation products of color developing agents.

Couplers I to X below are substituted in the coupling position with preformed yellow dyes that are split from the Ib=allasted couplers and become ditfusi ble when said couplers react with oxidized color developers.

(I) 1-hydroxy-4-{ 3 [4- (N-ethyl-N-B-sulfoethylamino) Z-methylphenylazo]phenylazo}-N- 6- (2,4-di-tertamylphenoxy)-butyl] -2-naphtharmide sodium salt.

(11) 1 hydroxy-4-{4- 1- (4-sulfophenyl) -3 -methyl-4- pyrazol-S-onylazo] -3-sulfophenylazo}-N- 5- (2,4-ditert-amylphenoxy) butyl] -2-naphthamide disodium salt.

(III) 1-hydroxy-4-[3-{4- [N-ethyl-N- (fi-carboxyethyl) amino] -2 methylphen-ylazo}phenylaz0]-N- [6- (2,4- di-tert-amylphenoxy) butyl] -2-naphthamide sodium salt.

(IV) 1-hydroxy-4- (2,4-dinitrophenylthio) -N- [6- (2,4-ditertamylphenoxy) butyl] -2-naphth amide.

(V) lhydroxy-4-{4- 1- 4-sulfophenyl) -3-qnethy1- 4-pyrazol-5-onylazo] -3-sulfophenylazo}-N-{4- [oc- 8 (2,4-di-tert-amylphenoxy) butyramido] phenethyl} -2- naphthamide dipotassiurn salt.

(VI) 1-hydroxy-4-{4- 3-methy1-4-( 1,5 -disulfo-3- naphthylazo) -1-pyraz0l-5-onyl]phenylazo}-N-{4- [w (2,4 di-tert-amylphenoxy) butyramido]phenethyI}-2- naphthamide dipotassium salt.

(VII) 1-hydroxy-4 {4- 3-methyl-4-( 1,5 -disulfo-3- naphthylazo) -1-pyrazol-5-onyl] phenylazo}-N- 5- 3- pentadecylphenoxy) butyl] -2-naphthamide disodium salt.

(VIII) 1- (p-t-butylphenoxyphenyl) -3 -[0L-(4-ll-b11tYlr phenoxy) propionamido] -4- 2-bromo-4-rnethylamino-5- sulfo-1-anthra-9,10-quinonylazo) -5-pyrazolone.

(IX) oc-{3-[oc-(2,4-dl-i61't-21111Ylpl'18nOXY) acetamidoJ- benzoyl}-a-{3- [4- (N-ethyl-N-p-sutfoethylamino -2- methylphenylazo]phenylazo}-2-methoxyacetanilide sodium salt.

(X) 1-hydroxy-4- {4- 1- (4-sulfophenyl) -3-canboxy-4- pyrazol-5 -ony lazo] -3-sul fophenylazo}-N- {4- oc- (2,4-di-tert-amylphenoxy butyramido]phenethyl}-2- naphtha'mide.

Each of the couplers XI to XLVI below contain an acid solubilizing group in a noncoupling position and on coupling with oxidized color developer forms a diifusible dye by the elimination of a ballasting group from the coupling position as a direct result of said coupling reaction.

Couplers XI to XXIX below form diffusible cyan dyes.

(XI) 1-hydroxy4-stearoyloxymercury-2-naphthoic acid.

(XII) 1-hydroxy-4-dodecyloxy-Z-naphthoic acid.

(XIII) l-hydroxy-4-(4-o'ctadecyloxyphenylazo)-2- naphthoic acid.

(XIV) l-hydroxy-4- (4-octadecyloxyphenylazo) -N- 18- 3 ,5 -disulfobenzamido) ethyl] -2-naphthamide dipotassium salt.

(XV) l-hydroxy-N- (,B-sul=foethyl) -4-(4-octadecyloxyphenylazo)-2-naphthamide potassium salt.

(XVI) 1-hydroxy-4- 4-octadecyloxyphenylazo) -3 car-boxy-4'-hydroxy-2-naphthanilide.

(XVII) 1-hydroxy-3',5-dicarboXy-4-dodecyloxy-2- naphthanilide.

(XVIII) 1hydroXy-4(2-hydroxy-4-pentadecylphenylazo -N-ethyl-3 ,5 '-di1ca-rboxy-2-n aphthanilide.

(XlX) 1-hydroxy-4-octad-ecyloxy-N-ethyl-3,5-

dicarboxy-Z-naphthanilide.

(XX) 1qhydroxy-4- 3-octadecylcarb amylphenylthio N-ethyl-3,5'-dicarboxy-Z-naphthanilide.

(XXI) 4,4-p-octadecyloxybenzylidenebis l-hydroxy- N-ethyl-S ,5 '-dicarboxy-Z-naphthanilide) (XXII) 1-hydroxy-S-acetamido-4-octadecyloxy-8- phenylazo-Z-naphthoic acid.

(XXIII) 2-( 3,5 -disulfobenzamido -5-1methyl-4- 4- octadecyloxyphenylazo)phenol dipotassium salt.

(XXIV) 2- (3 ,5 -disulfo benzarnido) -4- (4-hydr0xy-2- pelntadecylphenylazo)-5-methylphenol dipotassium -sa t.

(XXV) 2-( 3 ,5 -disulfobenzamido -5 -methyl-4- (4- nitrophenylthio) phenol.

(XXVI) l hydroxy-4-(3-octadecylcarbamylphenylthio)- N-methyl-N- (,B-canboxyet-hyl) -2-naphthamide.

(XXVZI-I) 1-hydroXy-4-( 3-octade cylcarbamy-lphenylthio N-isopropyl-3',5-dicarbQXy-Z-naphthanilide.

(XXVIII) 5 (3,5 disulfobenzamid o)-4-(4-octadecyloxyphenyl azo -2-heptafiuorobutyramidophenol dipotassium salt.

(XXIX) 2,5 -bis 3 ,5 -disulfobenzamido -4- 4-octadecyloxyphenylazo)phenol tetra potassium salt.

d Couplers XXX to XLI below form diifusible magenta yes.

(XXX) 1-phenyl-3-( 3-sulfobenzamido) -4-(4-octadecy-loxyphenylazo)-5-pyrazolone sodium salt. (XXXI) l-phenyl-3-(3,5-disul-fobenzamido) -4- (4- 9 octadecyloxyphenylazo)-5-pyrazolone disodium salt. (XXXII) l [4 (4-t-butylphenoxy)phenyl]-3-(3,5-di

sulfobenzamido)-4-(4-octadecyloxyphenylazo) 5 pyrazolone dipotassium sa-lt.

(XXXIII) l phenyl 3 (3,5-disulfobenzamido)4-(4- hydroxy 2 pentadecylphenylazo)-5-pyrazolone dipotassium salt. I

(XXXIV) 1 (p sulfophenyl) 3 car-boxymethyl-4-(4- hydroxy-Z-pentadecylphenylazo) 5-pyrazolone sodium salt.

(XXXV) l (4 sulfophenyl) 3-carboxy-4-(4-hydroxy- Z-pentaclecylphenylazo)-5-pyrazolone sodium salt.

(XHVI) 1 phenyl 3 (3,5-disulfobenzamido)-4-4[4- (3 methyl 5 pentadecyl)pyrazolylazo]-5-pyrazolone dipotassium salt.

(XXXVII) l (4 sulfophenyl) 3 (4-sulfoanilino)-4- (2 hydroxy-4-pentadecylphenylazo)-5-pyrazolone dipotassium salt.

(XXXVIII) 1 (4 sulfophenyl) 3 (4-sulfoanilino)-4- (2 amino 4 pentadecylphenylazo)-5-pyrazolone dipotassiurn salt.

(XXXIX) 1 [4 (3,5 dicarboxybenzamido)phenyl1- 3 ethoxy 4 (3-octadeeylcarbamylphenylthio)-5-pyrazolone.

(XL) 1 (4 sulfophenyl) 3 (4 sulfoanilino)-4-(3- octadecylcarbamylphenylthio) S-pyrazolone disodium salt.

(XLI) 4,4 (4-octadecyloxybenzylidene)bis[1-phenyl-3- (3,5 disulfobenzamido) 5 pyrazolone1tetra potassium salt.

Couplers XLII to XLVI below form diffusible yellow dyes.

(XLII) u Benzoyl a (4-hydroXy-2-pentadecylphenylazo) 4 (S-sulfobenzamido)acetanilide sodium salt. (XLIII) u Benzoyl oz (4-hydroxy-2-pentadecylphenylazo) 4 (3,5-disulfobenzamido)acetanilide dipotassium salt.

(XLIV) a Benzoyl :1 [4-(3-methyl-5-pentadecyl)pyrazolylazo] 4 (3,5-disulfobenzamido)acetanilide dipotassium salt.

(XLV) a Benzoyl c (3 octadecylcarbamylphenylthio) 3,5 dicarboxyacetanilide.

(XLVI) a Pivalyl a (3 octadecylcarbamylphenylthio) 4 sulfoacetanilide potassium salt.

Diffusible dyes are formed when the above listed (i.e., I to XLVI) nondiflusing couplers are employed in the process of the invention with well-known p-phenylenediamine developing agents, e.g., N,N-diethyl-p-phenylenediamine, 2 amino diethylamino toluene, Nethyl-B-methanesulfonamido-ethyl 3 methyl-4-aminoaniline, and other N,N dialkyl p phenylenediamine developing agents described by Bent et al., J.A.C.S. 73, 3l003l25 (1951).

Couplers XLVII to LV are nondiffusible couplers which can also be used in our invention when the color developing agent is supplied with the alkali solubilizing function.

Couplers XLVII to L be ow form difiusible cyan dyes.

(XLVII) l hydroxy 4 (4-octadecyloxyphenylazo)-N- methyl-Z-naphthanilide.

(XLVIII) 1 hydroxy 4 dodecyloXy-2-naphthanilide.

(XLIX) l hydroxy 4 (2-amino-4-octadecylphenylazoXy)-2-naphthamide.

(L) 1 hydroxy 2,5 dibutoxy-4-[4-(sulfomethyl)- phenylazo] -2-naphthanilide.

Couplers L1 to LIII below form difiusible magenta dyes.

(LI) 1 phenyl-3-rnethyl-4-(4-octadecyloxybenzylidene)- 5-pyrazolone.

(LII) 4,4 thiobis(l phenyl-3-methyl-5-pyrazol0ne).

(LIII) 4,4 bithiobis(l phenyl-3-methyl-5-pyrazolone).

Couplers LIV and LV below form diffusible yellow dyes.

10 (LIV) oz,ot' (4 octadecyloxybenzylidene) bis[a benzoylacetanilide]. (LV) oc,a' Dithiobisbenzoylacetanilide.

Representative color developing agents possessing the solubilizing functions useful with the nondiffusing couplers above are as follows:

4-amino-N-ethyl-3-methyl-N- (B-sulfoethyl) aniline 4-amino*N-ethy1-3-methoxy-N- (,B-sulfoethyl) aniline 4-amino-N-ethyl-N-(fi-hydroxyethyl) aniline 4-amino-N,N-diethyl-3-hydroxymethyl aniline 4-amino-N-methyl-N(,B-carboxyethyl) aniline 4-amino-N,N-bis [3-hydroxyethyl) aniline 4-amino-N,N-bis (fl-hydroXyethyl)-3 -methyl aniline 3-acetamido-4-amino-N,N-bis (fi-hydroxyethyl) aniline 4 amino N ethyl-N- (2,3-dihydroxypropyl -3-methyl aniline sulfate salt 4-amino-N,N-diethyl-3- 3-hydroxyprop0xy) aniline When the DDR or diffusible dye-releasing couplers given above were incorporated into exposed silver halide emulsions that were developed in contact with a mor danted reception layer using an alkaline color developing composition containing the aromatic primary amino color developing agent, 4 amino-N-ethyl-N-(B-hydroxyethyl)- aniline, the following colors of dye images were obtained on the reception layer from the respective couplers.

Coupler:

I Yellow.

II Do.

III Do. IV Orange-yellow. V Yellow. VI Do. VII Do. VIII Do. IX Do.

X Do. XI Cyan. XII Do. XIII Do. XIV Do. XV Do. XVI Do. XVII D-o. XVIII Do. XIX Do.

XX Do. XXI Do.

XXII Do. I XXIII Do. XXIV Do. XV Do. XXVI Do. XXVII Do. XXVIII Do. XXIX Cyan. XXX Magenta. XXXI Do.

XXXII Do.

XXXIII Do.

XXXIV Do. XXXV Do.

XXXVI Do. XXXVII Do. XXXVIII Do.

XXXIX Do.

XL Do. XLI Do. XLII Yellow.

XLIII Do. XLIV Do. XLV Do. XLVI Do.

XLVII Cyan.

XLVIII Cyan. XLIX Do. L DO. LI Magenta. LII Do. LIII Do. LIV Yellow. LV Do.

The above-identified couplers have been described in the patent literature. Typical methods for preparing such couplers and related suitable couplers are described in the following patents:

Canada, 602,606, granted August 2, 1960 Canada, 602,607, granted August 2, 1960 Great Britain, 840,731, published July 7, 1960 Great Britain, 904,364, published August 29, 1962. France, 1,224,012, dlivr June 19, 1961 France, 1,291,110, dlivr March 12, 1962 France, 1,293,709, dlivr April 9, 1962 Belgium, 578,470, granted November 6, 1959 Belgium, 591,444, granted June 30, 1960 Belgium, 603,213, granted May 15, 1961 Belgium, 603,747, granted May 31, 1961 Belgium, 625,137, granted December 14, 1962.

The following are representative couplers used in the invention to form nondiffusible dyes on coupling with oxidation products of color developing agents:

COUPLERS PRODUCING NONDIFFUSIBLE CYAN DYES -(p-amylphenoxybenzenesulfonamino -1-naphthol 5- (N-benzyl-N-naphthalenesulfonamino -1-naphtho1 5-(n-benzyl-N-n-valerylamino -1-naphthol 5-caproylaminol-naphthol 2-chloro-5- (N-n-valeryl-N-p-isopropylbenzy1amino) *1- naphthol 2,4-dichloro-5- (p-nitrobenzoyl-B-o-hydroxyethylamino) l-naphthol 2,4-dichloro-5-palmitylaminol-naphthol 2,2'-dihyd roXy-5 ,5 '-dibromostilbene 5-diphenylethersulfonamido-l-naphthol 1-hydroXy-2- (N-isoamyl-N-phenyl naphthamide 1-hydroXy-2- (N-p-sec. amylphenyl naphthamide S-hydroxy-l a-naphthoy1-1,2, 3 ,4-tetrahydroquino1ine 2-lauryl-4 -chlorophenol 1-naphtho1-2-carboXylic-ot-naphthalide 1-naphtho1-S-sulfo-cyclohexylamide 5 -phenoxyacetaminol-naphthol 5-,8-pheny1propiony1amino-l-naphthol v Mono chlor-S- (N-y-phenylpropyl-N-p-sec.-amy1benzoylamino 1 -naphtho1 2-acetylamino-5-methy1phenol 2-benzoylan1ino-3 ,5 -dimethylphenol 2-u (p-tert amylphenoxy n-butyrylamino-S-methyl- 1 phenol 1 6- {'y-{4- ['y- 2,4-di-tert.amylphenoxy butyramido] phenoxy}acetamido}-2,4-dichloro-S-methylphenol 1-hydroxy-2- [5 (2,4-di-tert. amylphenoxy -n-butyl] naphthamide i 2-u (p-tert. amylphenoxy -n-butyrylamino-4-chloro-5- methylphenol 2- (p-tert. amylphenoxy-p-benzoyl) amino-4-chloro-5- methylphenol 2- (4"-tert. arny1-3'-phenoxybenzoylamino) -3,5-dimethyll-phenol 2-phenylacetylamino-4-chloro-S-methylphenol 2-benzoylamino-4-chl0ro-5 -methy1phenol Z-anilinoacetylamino-4-chloro-5-methylphenol 2-{4'- OL- (4"-tert. amylphenoxy -n-butyrylamino] benzoyl amino} -4-chloro-5 -methylphenol 2- [4,3 (4"-tert. amylphenoxy benzoylamino] benzoylamin0-4-chloro-imethylphenol 2-p-nitrobenzoyl amino-4-chloro-5-methylphenol 2-m-aminobenzoy1-4-chloro-S-methylphenol 2-acetarnino-4-chloro-5-rnethylphenol 2(4'-sec. amylbenzamino)-4-chloro-5-methylphenol 2 (4-n-amy1oxybenzamino) -4-chloro-5-1nethylphenol 2 (4'-phenoxybenzoylamino phenol 2 (4-tert. amy1-3-phenoxybenzoylamino phenol 2- ot- (4-tert. butylphenoxy) propionylamino] phenol 2- a- 44tert. lamyl phenoxypropionylamino] phenol 2- [N-methyl-N- (4-tert. amyl-3 '-phenoxybenzoylarnino) phenol 2- (4-tert. amyl-3-phenoxybenzoylamino) -3-methyll-phenol 2- (4"-tert. amyl-3'-phenoxybenzoylamino -6-methyll phenol 2- (4"-tert. amy1-3'-phenoxybenzoylamino -3,6-dirnethylphenol 2,6-di (4"-tert. amyl-3-phenoxybenzoylamino) -1-phenol 2- 06- (4'-tert.amyl) phenoxypropionylamino phenol 2- (4"-tert. :amyl-3 -phenoxybenzoylamino) -3,5-:dimethyll-phenol 2- [u- (4'-tert. amylphenoxy -n-butyrylamino] -5-methyl-1 phenol 2 (4"-tert. amyl-3 -phenoxybenzoylamino -4-chloro-1- phenol 3- a- (4'-tert. amylphenoxy) -n-butyrylamino] -6-chlorophenol 3- (4-tert. arny1-3 '-phenoxybenzoy1amino phenol 2- [a- (4'-tert. amylphenoxy) -n-butyrylamino] -6- chloro phenol 3- Ot- (4-tert. amylphenoxy -n-butyry1amino] -4- chlorophenol 3- a- (4-tert. amylphenoxy) -n-butyrylamino] -5- chlorophenol 3- oc- (4'-tert. amylphenoxy -n-butyrylamino] -2- chlorophenol Z-oc- (4'-tert. amylphenoxybutyrylamino -5-chlorophenoi 2- (4-tert, amyl-3 -phenoxybenzoylamino -3- chlorophenol S-benzene sulfonamino-l-naphthol 2,4-dichloro-S-benzenesulfonamino-1-naphtho1 2,4-dichloro-5- (p-toluenesulfonamino -1-naphthol 5-( 1,2,3 ,4-tetrahydronaphthalene-6-sulfarnino) '1- naphthol 2,4-dichloro-5-(4'-bromodipheny1-4-su1fonamino)-1- naphthol 5 (quinoline-S -su1famino) -1-naphthol Any of the acylaminophenol couplers disclosed in Salminen and Weissberger US. Patent 2,423,730, dated July 8, 1947, can be used as couplers for the cyan image,

COUPLERS PRODUCING NONDIFFUSIBLE MAGENTA DYES l-p-sec. amylphenyl-3-n-amyl-5-pyrazolone 2-cyanoacetyl-5- (p-sec. amylbenzoylamino) coumarone 2-cyanoacetylcoumarone-S- (n-amyl-p-sec.

amylsulfanilide) 2-cyanoacetylcoumarone-5- (N-n-amyl-p-tert.

amylsulfanilide) 2-cyanoacetylcoumarone-S-sulfon-N-n-butylanilide 2-cyanoacetyl-5-benzoylamino-coumarone Z-cyanoac'etylcoumarone-5-sulfondimethylamide Z-cyanoacetylcoumarone-5-sulfon-N-rnethylanilide 2-cyanoacetylnaphthalene-sulfon-N-methylanilide Z-cyanoacetylcoumarone-S- (N-v-phenylpropyl) -p-tert.

amylsulfonanilide 1-p-laurylphenyl-3 -methyl-S-pyrazlone 1-B-naphthyl-3-amyl-5-pyrazolone l-p-nitrophenyl-3-n-amyl-5-pyrazolone 1-p-phenoXyphenyl-3 -n-amyl--pyrazolone l-phenyl-3-n-amyl-5-pyrazolone 1,4-phenylene bis-3-( l-phenyl-S-pyrazolone) 1-phenyl-3-acetylamino-S-pyrazolone 1-phenyl-3-propionylamino-S-pyrazolone 1-phenyl-3-n-valerylaminO-S-pyrazolone l-phenyl-3 -chloroacetylarnino-5-pyrazolone 1-phenyl-3-dichloroacetylamino-S-pyrazolone l-phenyl-3 -benzoylamino-5-pyrazolone l-phenyl-3- (rn-aminobenzoyl) amino-S-pyrazolone l-phenyl-3- (p-sec. amylbenzoylamino -5-pyrazolone 1-phenyl-3 -diarnylbenzoylamino-S-pyrazolone 1-phenyl-3-fl-naphthoyla-mino-5-pyrazolone l-phenyl-3 -phenylcarbarnylamino-S-pyrazolone l-phenyl-3-palmitylamino-S-pyrazolone l-phenyl-3-benzenesulfonylamino-5-pyrazolone 1- (p-phenoxyphenyl -3 (p-tert. amyloxybenzoyl) amino- S-pyrazolone 1- 2,4',6'-tribromophenyl -3-benzamido-5-pyrazolone 1- (2',4',6-trichlorophenyl -3'benzamido-5-pyrazolone l- 2,4',6'-trichlorophenyl) -3-phenylacetamido-5- pyrazolone 1- 2,4',6'-tribromophenyl -3-phenylacetamido-5- pyrazolone 1- (2,4'-dichlorophenyl -3- [3- (2', 4'-di-tert.amylphenoxyacetamido) benzamido] -5-pyrazolone 1- (2',4',6-trichlorophenyl) -3- [3 2"',4"'-di-tert.amylphenoxyacetarnido) benzamido] -5-pyrazol0ne 1- 2,4,6'-tribromophenyl -3- [3- (2",4"'-di-tert.amylphenoxyacetamido)benzamido1-5-pyrazolone 1- 2,4,6'-trichlorophenyl -3- [B- 2,4"'-di-tert.amylphenoxy -propionarnido 1 -5-pyrazolone 1- 2,4,6'-tribromoph'enyl -3- ,8- (2"',4"-di-tert.amylphenoxy) -propionamido -5-pyrazo1one 1- 2,5-dichloro -3- 3 (4'-tert.amylphenoxy benzamido1-5-pyrazolone l- (2,4,6-tribrornophenyl) -3- [3 "-4"'-tert.amylphenoxy -benzarnido] -5-pyrazolone 1- (2',5'-dichlorophenyl) -3- 3"- (2",4"-di-tert.amylphenoxyacetamido benzamido] -5-pyrazolone COUPLERS PRODUCING NONDIFFUSIBLE YELLOW DYES N-amyl-p-benzoylacetaminobenzenesulfonate N-(4-anisoylacetaminobenzenesulfonyl)-N benzyl n1- toluidine N-(4-benzoylacetaminobenzenesulfonyl) -N-'benzyl-mtoluidine N- (4-benzoylacetaminobenzenesulfonyl) -N-n-amyl-ptoluidine N- (4-benzoylacetaminobenzenesulfonyl -N-benzylaniline w-(p-Benzoyl'benzoyl)acetanilide w-Benzoylacet-2,5dichloroanilide w-BBIIZOYl-P-SGC. amylacetanilide N,N-di w-benzoylacetyl) -p-phenylenediarnine N,N-diaceto acetamino diphenyl tat-{3-[u-(2,4-di-tert.-amylphenoxy)butyramido]benzoyl}- Z-methoxyacetanilide a- 3 a- 2,4-di-te rt.-amylphenoxy) acetamido] benzoyl}- Z-methoxyacetanilide 4,4-di-(acetoacetamino) -3,3-dimethyldiphenyl p, p-di-(acetoacetamino)diphenylmethane Ethyl-p-benzoylacetaminobenzenesulfonate Nonyl-p-benzoylacetaminoyenzenesulfonate N-phenyl-N-(p-acetoacetaminophenyl)urea n-Propyl-p-benzoylacetaminobenzenesulfonate acetoacetpiperidine w-Benzoylacetpiperidide N(w-benzoylacetyl)-1,2,3,4-tetrahydroquinoline N(w-benzoylacetyl)morpholine The coupling position of the above-described couplers is well-known to those skilled in the art, this being the position on the coupler molecule that reacts or couples with oxidized color developing agent. Phenolic couplers, including a-naphthols, couple at the 4-position, openchain ketomethylene couplers couple at the carbon atom forming the methylene moiety (e.g.,

O CI-I2 denoting the coupling position), and S-pyrazolone couplers couple at the carbon atom in the 4-position,

The terms nondiffusing and nondifi'usible used herein as applied to the developing agents, couplers and coupler reaction products, have the meaning commonly applied to the term in color photography and denote materials which for all practical purposes do not migrate or wander through organic colloid layer, such as gelatin, comprising the sensitive elements of the invention in the presence of aqueous alkaline processing compositions. The terms dilfusible and diffusing as applied to the dyes released from the DDR couplers in the present processes and the developing agents have the converse meaning and denote materials having the property of diffusing effectively through the colloid layers of the sensitive elements in the presence of aqueous alkaline processing compositions.

The photographic elements of the invention are processed with aqueous alkaline compositions in the presence of an aromatic primary amino color developing agent, pphenylenediamine developing agents being particularly useful. The color developing agent can be either incorporated in an alkaline photographic developing solution that is applied to the present photographic elements on processing, or the color developing agent can be incorporated in the element.

When the color developing agent is used in the present photographic elements, it is advantageous to use forms that have substantial stability in emulsions such as Schiff base derivatives of primary amino developing agents. Such Schift" bases are prepared by reacting primary amino developing agents with sulfonated, hydroxylated or carboxylated aromatic aldehydes of the benzene or naphthalene series. Such Schifl" bases typically have the formula R -N=CHR wherein R is an aryl radical such as a phenyl radical substituted in the ortho or para position with a hydroxyl group or an amino group (e.g., OH, -NH NHR or -N(R wherein R is a lower alkyl radical having 1 to 6 carbon atoms); and R is an aryl radical such as phenyl or naphthyl substituted with an acidic group such as carboxyl, sulfo, and hydroXy lower alkyl groups. A typical Schiff base color developing agent can be prepared by reacting Z-amino-S- diethylaminotoluene and o-sulfobenzaldehyde. Other Schitf base developers that are useful as such, as salts or as sulfur dioxide complexes include:

(1) N-ethyl-N-(fl-hydroxyethyl) 4 (o sulfobenzylideneamino)aniline sodium salt,

(2) N,N-diethyl 4 (2,4 dihydroxybenzylideneamino)- 3-methylaniline,

(3) N-ethyl-3-methyl-N (p3 methylsulfonamidoethyl)- 4-(2-sulfobenzylideneamino)aniline sodium salt, and the like.

Such incorporated developing agents can be activated by immersing the photographic element in an aqueous alkaline solution or by spreading an aqueous alkaline solution on the surface of the element. Such incorporated developing agents can be positioned in any layer of the present photographic elements from which the developing agents can be readily made available for de velopment on activation with aqueous alkaline solutions. Generally, such incorporated color developing agents are incorporated .in layers contiguous to the light-sensitive silver halide emulsion layers, although the color developing agent can be utilized in the silver halide emulsion layers.

The aqueous alkaline processing or activating compositions used in processing the present photographic elements contain silver halide solvents. Typical silver halide solvents include ammonium and alkali metal thiosulfates, thiocyanates, sulfites and the like, as Well as N,N-diethyl1,3-propanediamine, triethanol amine, ammonium hydroxide, ammonium sulfate, ammonium nitrate, ammonium chloride, aminoethanol, and the like.

The reception layer used to receive the diffused dye images on color development when DDR couplers are used in the photoelements of the invention can be either a separate receiving sheet pressed in contact with the photoelement or a layer integral with the photoelement.

When the reception layer is a separate reception sheet, the development and transfer operations can be eflected by bathing either or both the exposed photographic element and the mordanted reception sheet in the developing solution before rolling into contact with each other. Alternatively, a viscous developing composition can be placed between the elements for spreading in a predetermined amount across and in contact with the exposed surface of the sensitive element so as to provide all of the solution required for the picture area. The viscous developing composition is desirably utilized in one or more pods integral with the photographic element or the reception sheet that can be readily ruptured when development is desired, suitable viscous developer utilization techniques being disclosed in U.S. Patents 2,543,181, 2,559-

643, 2,647,049; 2,647,056; 2,661,293, 2,698,244; 2,698- 798; and 2,774,668.

When the reception layer for receiving the diifusible dye is an integral part of the photosensitive assembly, it is also useful. A typical element of this type can comprise a support, a mordanted colloid layer thereon and the various emulsion layers described above coated thereover. When easily dissolved emulsions are used such as those containing polyvinyl alcohol or an alkali-soluble cellulose ether phthalate vehicles, or a wet or dry stripping layer containing such vehicles is provided between the emulsions and reception layer, the developed emul- -s1on layers can then be readily separated from the reception layer leaving the dye image thereon. Similarly, the reception layer can be initially bonded to the outer emuls1on surface. In this case, it is preferred to expose through the support of the sensitive element unless the reception layer itself is transparent. Such photoelenients can be processed in the same manner as those not containing integral reception layers.

The dye reception layers used in the invention can contain any of the conventional mordant materials for dyes. The reception layer can contain mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone described in U.S. Patent 2,882,156. Other mordants include the 2-vinyl pyridine polymer metho-ptoluene sulfonate and similar compounds described in U.S. Patent 2,484,430 and cetyl trimethyl-ammonium bromide, etc. Particularly effective mordanting compositions are described in copending applications of Knechel et al.,

U.S. Serial No. 211,095 filed July 19, 1962, and Bush, U.S. Serial No. 211,094 filed July 19, 1962. The mordanting compositions described in the Knechel et al. application 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, nonpolyrneric, organic dye-mordanting compound for acid dyes. The mordanting compositions described in the Bush application 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 com;- pound for acid dyes. Useful cationic or basic organic dye-mordanting compounds for acid 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 long-chain alkyl or substituted alkyl groups. Furthermore, the reception layer or sheet can be sufficient by itself to mordant the dye as in the case of the use of a sheet or layer of a polyarnide or related polymeric material. Receiving sheets that release acidic material at a controlled rate such as are described in U.S. Patent 2,584,030 are useful.

Typical supports comprising the photographic elements of the invention, or those used in receiving sheets for dyes transferred in accordance with the invention, include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polyethylene film, polypropylene film, poylethylene-coated paper, paper, glass, and others.

FIGS. 1, 2 and 3 of the drawings illustrate typical light-sensitive elements or color films of the invention. FIG. 3 also illustrates a typical receiving sheet for receiving dye images from the light-sensitive element and a pod containing processing material positioned between the light-sensitive element and'the receiving sheet.

In the light-sensitive element of FIG. '1 of the drawings, on support 10 is coated nucleated silver halide emulsion layer 11 containing a nondiifusible color coupler and a black-and-white developer. The light-sensitive element of FIG. 1 can be processed to a positive color image by immersing in an aqueous alkaline processing composition containing an aromatic primary amino color developing agent and a silver halide solvent. If a DDR or diffusible dye-releasing coupler is utilized in layer 11, the resulting positive color image can be transferred to a juxtaposed receiving sheetto form a positive color print. If the coupler utilized in layer 11 is a coupler that forms a nondifiusible dye on color development, the photographic element can thereafter be further processed by bleaching in a bath containing a metallic silver oxidizing agent, such as an alkali metal ferricyanide, permanganate, dichromate, or the like, to convert the developed silver in the negative and positive image areas to silver halide, and thereafter fixing the resulting element with a bath containing a'silver halide solvent such as alkali metal thiosulfate, thiocyanates, and the like to remove resulting silver halide.

FIG. 2 of the drawings illustrates a light-sensitive element of the invention that contains an incorporated color developing agent. In the light-sensitive element of FIG. 2 of the drawings on support 20 is coated nucleated silver halide emulsion layer 21 containing a color coupler and a black-and-white developer. On layer 21 is coated color developer layer 23 comprising a primary amino aromatic color developing agent in a hydrophilic substrate. The light-sensitive element of FIG. 2 of the drawings can be processed as described above for the light-sensitive element of FIG. 1 except that a color developing agent need not be added to the aqueous alkaline processing composition.

FIG. 3 of the drawings illustrates a typical photographic element of the invention containing a plurality of silver halide emulsion layers that can be utilized to prepare a three-color direct-positive image. The silver halide emulsion layers of such multilayer light-sensitive elements typically contain color couplers that form dyes that are substantially complementary in color to the spectral sensitivity of the silver halide emulsion in which they are positioned. In the light-sensitive element of FIG. 3 of the drawings, on support 30 is coated red-sensitive nucleated silver halide emulsion layer 31 containing a cyan-forming coupler and a black-and-white developer. Over layer 31 is coated interlayer 32 which can contain various addenda such as ballasted reducing agents to consume and prevent the wandering of oxidized color developing agent and filter dyes such as a magenta filter dye for example to compensate for any green sensitivity of the red sensitizing dye in layer 31. Over layer 32 is coated green-sensitive nucleated silver halide emulsion layer 33 containing a magenta-forming coupler and a black-and-white developer. Over layer 33 is coated interlayer 34 which like interlayer 32 can contain a ball-asted reducing material to consume and prevent the wandering of oxidized color developing agent and a yellow filter material such as a yellow dye or yellow Carey Lea silver. Over layer 34 is coated blue-sensitive nucleted silver halide emulsion layer 35 containing a yellowforming coupler and a black-and-white developer. Over layer 35 is coated protective layer 36 which can contain the color developing agent, an ultraviolet absorber or the like. The color couplers in

layers

31, 33 and 35 can be any of the nondiffusible color couplers described above including couplers that form nondilfusible dyes when reacted With oxidized color developing agent as Well as those that form diifusible dyes when reacted with oxidized color developing agents. When color couplers that form diffusible dyes are utilized in a photographic element of the type illustrated by layers 30 to 36 of FIG. 3, a receiving sheet of the type illustrated by

layers

39 and 40 of FIG. 3 is typically utilized in conjunction therewith to form a direct-positive color print. As illustrated in FIG. 3 of the drawings, a receiving sheet comprising support 40 having coated thereon mordant layer 39 can be used to receive dye images from the light-sensitive element during processing when superposed thereon. Positioned between the light-sensitive element and the receiving sheet is rupturable pod 38 containing processing material 37 such as a viscous composition. As noted above, the processing material contains a color developing agent if the color developing agent is not integral with the light-sensitive element and a silver halide solvent. After exposure of the light-sensitive element illustrated by FIG. 3 of the drawings in a camera to an image, rupturable pod 38 can be ruptured by positioning the assembly illustrated by FIG. 3 of the drawings between rollers in the camera or remote from the camera and the processing composition in the pod uniformly distributed across a predetermined area of the light-sensitive element. The processing composition penetrates through layers 31 to 36, latent images develop to silver images without color development in light-

sensitive layers

31, 33 and 35 by chemical development, color physical development thereafter taking place in the resulting unexposed and undeveloped areas which correspond to positive image areas in light-

sensitive layers

31, 33 and 35 to form diffusible dyes on reaction of the color couplers positioned in the light-sensitive layers and resulting oxidized color developing agent, and thereafter the :dyes produced in the respective positive image areas diifuse imagewise in register to mordant layer 39 of the receiving sheet to form a full-color positive transfer print.

, The invention is further illustrated by the following examples of preferred embodiments thereof.

Example 1 A color film having the structure substantially as shown in FIG. 3 of the drawings (layers 30 to 36) was prepared by coating on a subbed cellulose acetate film support successively the following layers:

(1) Red-sensitive layer (e.g., layer No. 31, FIG. 3).

A coating of a developing-out, negative gelatino-silver bromoiodide (98% bromide, 2% iodide) emulsion sensitized to red light, containing 0.15 mg. per square foot of colloidal silver, 250 mg. per square foot of gelatin, mg. per square foot of 1-hydroxy-4-(3-n-octadecylcarbamylphenylthio) N ethyl 3',5' dicarboxy 2- naphthanilide, 63 mg. per square foot of 2-[N,N-bis(,B- hydroxyethyl)aminomethyl] 5 methylhydroquinone metho-methanesulfonate and the silver halide at a coverage of 45 mg. per square foot of silver.

(2) Interlayer (e.g., layer No. 32, FIG. 3).-A gelatin coating containing 100 mg. per square foot of gelatin, 3 mg. per square foot of 2-n-ostadecyl-S-sulfohydroquinone sodium salt, and 22 mg. per square foot of l-hydroxy-4-(4-tert-butylphenoxy)-4-phenylazo 2 na-phthanilide.

(3) Green-sensitive layer (e.g., layer N0. 33, FIG. 3).A coating of a developing-out negative gelatinosilver bromoiodide (98% bromide, 2% iodide) emulsion sensitized to green light containing 400 mg. per square foot of gelatin, 90 mg. per square foot of 1-phenyl-3- (3,5 disulfobenzamido) 4 (2 hydroxy 4 pentadecylphenylazo)-5-pyrazolone, 0.24 mg. per square foot of colloidal silver, 126 mg. per square foot of 2-[N,N bis(fl hydroxyethyl)aminomethyl] 5 methylhydroquinone metho-methanesulfonate, and silver halide at a coverage of 45 mg. per square foot of silver.

(4) lnterlayer (e.g., layer N0. 34, FIG. 3).A gelatin layer containing 100 mg. per square foot of gelatin, 30 mg. per square foot of 2-n-octadecyl-5-sulfohydroquinone sodium salt, and 60 mg. per square foot of yellow Carey Lea silver.

(5) Blue-sensitive layer (e.g., layer N0. 35, FIG 3).- A coating of a developing-out, negative gelatino-silver bromoiodide (98% bromide, 2% iodide) emulsion that was inherently sensitive to blue light and containing 250 mg. per square foot of gelatin, mg. per square foot of oz benzoyl a (3 n octadecylcarbamylphenylthio) 3,5 dicarboxyacetanilide (disodium salt), 0.15 mg. per square foot of colloidal silver, 31.5 mg. per square foot of 2-[N,N-bis(,B-hydroxyethyl)aminomethyIJ-S-methylhydroquinone metho methanesulfonate and the silver halide at a coverage of 45 mg. per square foot of silver.

(6) Protective layer (e.g., layer No. 36, FIG. 3).A gelatin coating at a coverage of 75 mg. per square foot.

The film prepared as described above was then exposed through a multicolor transparency in an Eastman Ib sensitometer. The resulting exposed color film was processed by immersing in an aqueous color developer for one minute at 75 F. and thereafter squeegeed together with a mordanted receiving sheet for four minutes at 75 F. The receiving sheet was then stripped away from the film. The receiving sheet comprised a cellulose acetate support containing a white pigment having coated thereon a mordanted reception layer composed of a gelatin substrate containing the mordant N,N-dimethyl-N-( 8 hydroxyethyD-N-(y stearamidopropyl)ammonium dihydrogen phosphate. The color developer utilized had the following composition:

4-amino-N-ethyl-N-(B-hydroXyethyl)an1l1ne g 7.5 Sodium metaborate octahydrate g 10.0 Sodium sulfite (anhydrous) g 1.0 Ascorbic acid g 0.1 Potassium bromide g 4.0 Potassium iodide g 0.04 Amino ethanol ml 5.0 N,N-diethyl-1,3-propanediamine ml 5.0 Benzyl alcohol ml 5.0 Sodium hydroxide g 2.75

Water to make one liter.

A positive full-color image having good color separation was transferred to the receiving sheet, the transferred cyan image having a D of .2 and a D of 1.2, the trans- 1) 2,5-bis(N,N-dimethylaminomethyl)hydroquinone 'bis(metlroap-toluenesulfonate),

(2) 2,5-bis(N-morpholinomethyl)hydroquinone *bis(methoap-to luenesulfonate),

(3 4- [N,N-bis B-hydroxyethyl) aminomethyl] -5- methylcatechol sulfurous ester, and

(4) 4- [N,N-bis (B-hydroxyethyl) aminomethyl] -5- methylcatechol carbonic ester ethoethane sulfonate.

Likewise, similar results were obtained when, in lieu of 2- [N,N-bis B hydroxyethyl aminomethyl] -5-methylhydroquinone metho-methanesulfonate, a combination of l-phenyl-3-pyrazolidone plus 2-n-octadecyl-S-sulfohydroquinone sodium salt in each of the light-sensitive silver halide emulsion layers at coverages of 80 and 18 mg. per square foot respectively was utilized as the incorporated black-and-white developer.

Example 2 A series of single-layer color films having the structure substantially as shown in FIG. 1 of the drawings were prepared by coating on subbed cellulose acetate film supports various developing-out, negative gelatino-silver halide emulsions containing .15 mg. per square foot of colloidal silver physical development nuclei, 300 mg. per square foot of gelatin and the silver halide at a coverage of 45 mg. per square foot of silver. The emulsion was unsensitized but inherently sensitive to blue light. Various black-and-white developers and including ballasted auxiliary black-and-white developers were incorporated in the various coatings. The coatings prepared are summarized in the table below.

TABLE Black-and- Auxiliary Coupler, White De- Black-and- Coatiug No. mgJitJ. veloper, White De- Emulsion Type rug/it. veloper, nag/ft.

1,90 0 .AgClBr (2/98). I, 90 0 a, 18 .AgClBr (2/98). I, 90 A, 100 a, 18 AgClB! (2/98) I, 90 11,100 0 AgClBr (2/98). I, 90 B, 88 0 AgClBr (2/98). I, 90 C, 65 0 AgClBr (2/98). I, 90 D, 100 0 AgBrI (98/2). I, 90 D, 100 a, 18 .AgBrI (98/2). I, 90 D, 200 0 AgBrI (98/2). I, 90 E, 80 a, 18 .AgClBr (2/98). I, 90 F, 80 a, 18 AgOlBr (2/98). I, 90 G, 80 41,18 AgOlBr (2/98). 1,90 H, 80 a, 18 .AgOlBr (2/98). I, 90 I, 80 a, 18 AgGlBr (2/98). 1,90 J, 80 a, 18 AgClBr (2/98).

11, 90 A, 150 a, 24 AgClBr (2/98) II, 90 A, 150 a, 30 AgClBr (2/98).

II, 90 A, 200 a, 18 .AgClBr (2/98). I, 90 A, 100 0 AgClBr (2/98). I, 90 D, 100 0 AgClBr (2/98).

*.36 microgram of zincsulfide per square foot were utilized as the physical development nuclei in lieu of the colloidal silver used in the other coatings.

In the above table, the color couplers designated as I and II were as follows:

(I) 1-hydroxy-4-(3-n-octadecylcarbamylphenylthio)- N-ethyl-3',5-dicarboxy-2-naphthanilide, and

(II) 1-phenyl-3-(3,5-disulfobenzamido)-4-(Z-hydroxy- 4-pentadecylphenylazo -pyrazolone.

In the above table, the black-and-white developers designated as A to I were:

(A) 2,5 -bis [N,N-bis (,B-hydroxyethyl) aminomethyl] hydroquinone,

(B 2- (N,N-dimethylaminomethyl) -5-methylhydrcquinone,

(C) 2- [N,N-bis (B-hydroxyethyl) aminomethyl] -5- methylhydroquinone,

(D) 2,5-bis(N,N-dimethylaminomethyl)hydroquinone bis(rnetlro p-toluenesulfonate),

(E) 1-phenyl-3-pyrazolidone,

(F) l-phenyl-4-methyl-3-pyrazolidone,

(G) 1-phenyl-4,4-dimethyl-3-pyrazolidone,

(H) 1-phenyl-2-acetyl-3-pyrazolidone,

(I) 1-phenyl-3-acetoxy-4-methyl-pyrazolidone, and

(J) 1-phenyl-2-chloroacetyl-3-pyrazolidone.

In the above table, the auxiliary black-and-white developer designated as a was 2-n-octadecyl-5-sulfohydroquinone sodium salt. The above-described films or coatings were then exposed through a neutral density step tablet in an Eastman Ib sensitometer. The resulting exposed films were then processed by immersing in an aqueous color developer for about 30 seconds at F. and thereafter squeegeed together with a mordanted receiving sheet of the type described in Example 1 for three minutes at 75 F. The receiving sheets were then stripped away from the films. The color developer utilized had the following composition:

G. 4-amino-N-ethyl-N- B-hydroxyethyl aniline 10 Sodium carbonate (anhydrous) 20 Sodium thiosulfate 4 Sodium sulfite (anhydrous) 2 Potassium thiocyanate 3 Water to make one liter.

Reversal color images were obtained from all coatings except coatings 1 and 2, the latter containing no diffusible black-and-white developer. When the nondiffusible black-and-white auxiliary developer is omitted from coatings 10 to 15 which contained 3-pyrazolidone developers, substantially no reversal images were obtained. Similarly, no reversal images were obtained when hydroquinone or N-methyl-p-aminophenol sulfate were used as the incorporated black-and-White developers.

Example 3 A color film having the structure substantially as shown in .FIG. 2 of the drawings was prepared by coating on a subbed cellulose acetate film support successively the following layers:

(1) Light-sensitive layer (e.g., layer No. 21, FIG. 2). A coating of a developing-out, negative gelatino-silver chlonobromide (2% chloride, 98% bromide) emulsion containing .15 mg. per square foot of colloidal sliver, 300 mg. per square foot of gelatin, mg. per square foot of 1 hydroxy 4 (3-n-octadecy1carbamylphenylthio-N- ethyl-3',5'-dicarboxy-Z-naphthanilide, 100 mg. per square foot of 2,5 bis[N,N-bis(/3-hydroxethyl)aminomethyl1- hydroquinone and silver halide at a coverage of 45 mg. per square foot of silver. The emulsion was unsensitized but inherently sensitive to blue light.

(2) Color developer layer (e.g., layer N0. 23, FIG. 2). A gelatin coating containing 300 mg. per square foot of gelatin and a sulfur dioxide salt of the color developing agent, 4-{3-[3 (4-ti-amyl x sulfophenoxy)benzamido] 5 benzylideneamino} N ethyl-(fi-hydroxyethynaniline 21 from the film. The activator solution had the following composition:

G. Sodium carbonate (anhydrous) 20 Sodium thiosulfate 4 Sodium sulfite (anhydrous) 2 Potassium thiocyanate 3 Water to make one liter.

A positive cyan image was transferred to the receiving sheet. Similar results were obtained with a photographic element wherein the color developer-containing layer (layer No. 2 above) was coated below the light-sensitive layer (layer No. 1 above).

Example 4 Several single-coating films were prepared containing a nondilfusible color coupler that forms a nondiffusible dye on reaction with oxidized color developing agents. The various films were of the general type illustrated by FIG. 1 of the drawings. On cellulose acetate film supports were coated developing-out, negative-type, gelatinosilver chlorobromide (2% chloride, 98% bromide) emulsions containing 300 mg. per square foot of gelatin, .15 mg. per square foot of colloidal silver, the color coupler, 5 [a (2,4-di-t.-amylphenxy)butyramido] 2 butyr amidophenol, dissolved in di-n-butylphthalate and coated at 70 mg. per square foot of coupler and 70 mg. per square foot of solvent, the silver halide at a coverage of 45 mg. per square foot of silver, and various black-and-white developers at various coverages as indicated below. The emulsion was unsensitized but inherently sensitive to blue light. The black-and-white developers were 2,5-bis[N,N-bis(flhydroxyethyl)aminomethyl]hydroquinone at a coverage of 100 mg. per square foot, and 2-[N,N-bis( 8-hydroxyethyl)aminomethyl] methylhydroquinone methomethanesulfonate at coverages of 50, 84, and 100 mg. per square foot. The prepared films were exposed through a neutral density step tablet in an Eastman Ib sensitometer, color developed for four minutes at about 72 F. in a tank containing a color developer, the development stopped by immersing the films for one minute in a 5% acetic acid stop bath, washed for three minutes in water, bleached for three minutes, washed for 30 seconds in water, fixed for two minutes, and thereafter washed and dried. Positive cyan images remain on the cellulose acetate film supports in each instance. The color developer employed had the following composition:

4-amino-N-ethyl-N-(fl-hydroxyethyl) aniline g 5.0 Sodium sulfite (anhydrous) g 2.0 Sodium metaborate octahydrate g 20.0 Potassium thiocyanate g 4.0 Potassium bromide g 4.0 Ascorbic acid g 0.2 Benzyl alcohol cc 10.0 N,N-diethyl-1,3-propanediamine cc 10.0 Sodium hydroxide g 2.75 Water to make one liter.

The bleach utilized had the following composition:

Sodium hexametaphosphate g 1.0 Potassium ferricyanide g 100.0 Sodium bromide g 34.4 Water to make one liter.

The fixing bath had the following composition:

Sodium thiosulfate g 240.0 Sodium sulfite (anhydrous) g 15.0 Acetic acid, 28% cc 48.0 Boric acid g 7.5 Potassium alum g 15.0

Water to make one liter.

Example 5 Several single-layer coatings were made wherein the black-and-white developer was dissolved in a high-boiling solvent and dispersed in finely-divided droplets in the emulsion. The various films were of the general type illustrated by FIG. 1 of the drawings and were utilized to prepare direct-positive color transfer prints by diifusion transfer of positive images to receiving sheets. The films were prepared by coating on subbed cellulose acetate film supports a developing-out, gelatino-silver chlorobromide (2% chloride, 98% bromide) emulsion containing 350 mg. per square foot of gelatin, .15 mg. per square foot of colloidal silver, mg. per square foot of 1-hydroxy-4- (3-n-octadecylcarbamylphenylthio) N ethyl-3,5-dicarboxy-Z-naphthanilide, a silver halide at a coverage of 45 mg. per square foot of silver, and the black-and-white developer, 2,5 bis(N,N-dimethylaminomethyl)hydroquinone, at a coverage of 54 mg. per square foot dissolved in a high-boiling organic solvent at a ratio of one part by weight of the black-and-white developer to three parts by Weight of the organic solvent. The emulsion was unsensitized but inherently sensitive to blue light. The following high-boiling organic solvents were utilized separately to dissolve the coupler and form the dispersion of droplets in the emulsion: di-n-octylphthalate, tetrahydrofurfurylphthalate, and N-amyl succinimide. The prepared coatings were exposed through a neutral density step tablet in an Eastman Ib sensitometer, immersed for about 30 seconds at 72 F. in the color developer described in Example 2, and thereafter squeegeed in contact for three minutes at 72 F. with the mordanted receiving sheet described in Example 1. The receiving sheets were thereafter stripped away from the films to give positive transfer cyan images on the receiving sheets.

The incorporated color developing agent utilized in the photographic element of Example III was prepared as follows:

Intermediate 1-2-(m-nitr0phenyl) 1,3 di0x0lane. A mixture of 680 g. of m-nitrobenzaldehyde, 307 g. of ethylene glycol, and 1.2 ml. of 85% phosphoric acid in 600 ml. of xylene was heated to reflux for 4 hours, during which time va total of 84 ml. of water distilled from the mixture. At the end of the reflux period, the xylene Was removed under vacuo. The residue was poured into a mixture of 1200 ml. of ethyl alcohol, 5 g. of sodium carbonate, and 50 ml. of water. The resultant clear solution was cooled to 0 C. with stirring, whereupon the solid which separated was collected :and dried to yield 818 g. of product.

Intermediate 22-(m-aminophenyl) 1,3-di0x0lane. A solution of intermediate 1 in ml. of ethyl acetate was shaken in a Parr hydrogenation apparatus using Raney nickel as -a reducing catalyst under a hydrogen atmosphere at 45 p.s.i. for one hour. The mixture was filtered and the clear ethyl acetate solution was concentrated in vacuo. The clear residual liquid was distilled (B.P. l63167 C. at 5-6 mm. (Hg) pressure) yielding 22.5 g. of product (76%).

Intermediate 3-3- [3-(4-tamyl X chlorosulfonylphenoxy)benzamido]benzaldehyde.-To a solution of 20 g. of anhydrous sodium acetate and 20 g. of intermediate 2 in 200 ml. of acetic acid was added 50 g. of 3-(4-t-amyl- X-ohlorosulfonylphenoxy)benzoyl chloride with stirring at a temperature of 27 C. The reaction was stirred for 30 minutes, after which time the mixture was diluted with 450 ml. of water, whereupon an oily precipitate separated. The oily residue which solidified on standing was recrystallized from 350 ml. of acetonitrile, yielding 42 g. of product, M.P. 188l90 C.

Intermediate 43-[3-(4-t-amyl-X-sulfophen0xy)benzamido1benzaldehyde sodium salt.A solution of 159 g. of intermediate 3 in 2 liters of methyl alcohol was refluxed for 2 hours, after which time it was concentrated in vacuo. The residual solid was then dissolved in a solution of 14 g. of sodium hydroxide in 200 ml. of water. To this solution was added saturated sodium chloride solution, and the solid which separated was collected, recrystallized from a mixture of ethyl ether and absolute 23 ethyl alcohol toyield 83 g. of product, M.P. 244-245 C.

Preparation developing agent salt.To a solution of 105 g. of intermediate 4 in a mixture of 60 ml. of water and 400 ml. of ethyl alcohol was added a solution of 46 g. of 4-amino-N-ethyl-N-(fl-hydroxyethyl)aniline sulfate in 160 ml. of water and 33 g. of sodium carbonate in 260 ml. of water with stirring. The resultant solution was stirred for one hour at room temperature, after which time it was diluted with 500 ml. of absolute ethyl alcohol, filtered, and the clear filtrate concentrated in vacuo. The dark red residue was recrystallized from absolute alcohol to yield 90 g. of product. To a solution of 1 gram of the resulting product in ml. of ethanol was added 2 moles of sulfur dioxide gas. The resulting solution was incorporated into a gelatin composition and coated on the photographic element without isolation with the resulting salt.

The ditfusible hydroquinone and catechol black-andwhite developing agents containing amino-substituted lower alkyl groups can be prepared by methods known in the art. Such compounds can be prepared from the Mannich-reaction product of a hydroquinone or catechol, formaldehyde and an amine by alkylation. Reference is made to Photographic Science and Engineering, vol. 4, N0. 2, March-April 1960, pages 101-109; Hellmann and Opitz, a-Aminoalkylierung, Verlag Chemie GrnbH, Weinheim/Bergstr., Germany (1960); and Reichert, die Mannich-Reaction, Springer-Verlog OHG, Berlin, Gottingen and Heidelberg, Germany (1959) for suitable methods for preparing such developing agents.

The invention has been described in considerable detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

I claim:

1. A photographic direct positive color process for treating an image-exposed photographic element having a support and a light-sensitive silver halide emulsion layer coated thereon, said emulsion layer containing (A) physical development nuclei addenda,

(B) a nonditfusible color coupler that reacts with oxidized aromatic primary amino color developing agents to form a dye, and

(C) a black-and-white developing agent selected from the group consisting of (1) a dilfusible hydroquinone having at least one amino-substituted lower alkyl group, (2) a diifusible catechol having at least one aminosubstituted lower alkyl group, and (3) a combination of (a) a ditlusible 3-pyrazolidone, and (b) a nondiffusible hydroquinone containing a photographically inert organic ballasting group of such molecular size and configuration as to render the hydroquinone nondiifusible, which comprises treating said emulsion layer with an aqueous alkaline composition containing a silver halide solvent in the presence of an aromatic primary amino color developing agent, chemically developing the silver halide in regions of exposure and forming a negative silver image without the formation of a color image, and there after physically developing the remaining unexposed and undeveloped silver halide with said color developing agent, said color coupler reacting with resulting oxidized color developing agent to form a positive dye image.

2. A photographic process as described in claim 1 wherein the aqueous alkaline composition contains the color developing agent.

3. A photographic process as described in claim 1 wherein the photographic element contains the color developing agent.

4. A photographic process as described in claim 1 V 24 Y Y wherein the photographic element is a multilayer element containing a plurality of light-sensitive silver halide emulsion layers that are sensitive to different regions of the spectrum and contain color couplers that form dyes that are substantially complementary in color to the spectral sensitivity of the respective emulsion layers.

52 A photographic process as described in claim 1 wherein the color coupler forms a diffusible dye image during the physical development, and which dye image is permitted to diffuse to a receiving sheet juxtaposed on the photographic element.

6. A photographic process as described in claim 1 wherein the color coupler forms a nondiffusible dye image during the physical development, and wherein the silver on the support after formation of said dye images is bleached and fixed to leave a positive dye image on the support.

7. A photographic direct positive color process for treating an image exposed photographic element having a support with superposed red, green and blue lightsensitive silver halide emulsion layers containing a cyanforming coupler, a magenta-forming coupler and a yellow-forming coupler respectively, as well as physical development nuclei addenda and a black-and-white developing agent selected from the group consisting of (a) a ditfusible hydroquinone having at least one amino-substituted lower alkyl group, (b) a diffusible catechol having at least one aminosubstituted lower alkyl group, and (c) a combination of (1) a diflusible 3-pyrazolidone, and (2) a nonditfusible hydroquinone containing a photographically inert organic ballasting group of such molecular size and configuration as to render the hydroquinone nonditfusible, said couplers being nondiilusible, capable of forming difiusible dyes on reaction with oxidized aromatic primary amino color developing agent, and having a formula selected from the group consisting of DYELINK-(COUPBALL) n and BALLLINK (COUP-SOL) n wherein:

(1) DYE is a 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 azo radical, a mercuri radical, an oxy radical, an alkylidene radical, a monothio radical, a dithio radical and an azoxy radical;

(3) COUP is coupler radical selected from the group consisting of a 5-pyrazolone 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 couplers nondiifusable during de velopment in said alkaline color developing solution;

(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

(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 azo radical, a mercuri radical, an oxy radical, a monothio radical,'a dithioradical and an azoxy radical;

which comprises treating the said silver halide emulsion layers with an aqueous alkaline composition containing a silver halide solvent in the presence of an aromatic primary amino color developing agent, chemically developing the said silver halide layers in regions of exposure with said black-and-white developing agent to form a negative silver image, and thereafter physically developing the remaining unexposed and undeveloped silver halide corresponding to positive image areas, resulting oxidation product of said color developing agent reacting with said couplers to release dilrusible dye images in regions of physical development, and said dye images diffusing imagewise in register to a juxtaposed reception layer for said dye images.

8. A photographic direct positive color process for treating an image exposed photographic element having a support with superposed red, green and blue light-sensitive silver halide emulsion layers containing a cyanforming coupler, a magenta-forming coupler and a yellow-forming coupler respectively, as well as physical development nuclei addenda and a black-and-white developing agent having the formula wherein:

(1) R is an amino-substituted lower alkyl radical; (2) R is selected from the group consisting of an amino-substituted lower alkyl radical, a hydrogen atom, a lower alkyl radical and a lower alkoxy radical; and (3) R and R are each selected from the group consisting of a hydrogen atom and a carbonyl masking radical that hydrolyzes off in the presence of aqueous alkaline processing compositions: said couplers being nondiffusible, capable of forming diffusible dyes on reaction with oxidized aromatic primary amino color developing agent, and having a formula selected from the group consisting of DYE-LINK-(COUPBALL) n and BALLLIN]K---(COUPSOL) wherein:

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

(4) BALL is photographically inert organic ballasting radical of such molecular size and configuration as to render said couplers nondiffusable during development in said alkaline color developing solution;

(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 azo radical, a mercuri radical, an oxy radical, a monothio radical, a dithio radical and an azoxy radical;

which comprises treating the said silver halide emulsion layers with an aqueous alkaline composition containing a silver halide solvent in the presence of an aromatic primary amino color developing agent, chemically developing the said silver halide layers in regions of exposure with said black-and-white developing agent to form a negative silver image, and thereafter physically developing the remaining unexposed and undeveloped silver halide corresponding to positive image areas, resulting oxidation product of said color developing agent reacting with said couplers to release diffusible dye images in regions of physical development, and said dye images difiusing imagewise in register to a juxtaposed reception layer for said dye images.

9 A photographic direct positive color process for treating an image exposed photographic element having a support with superposed red, green and blue light-sensitive silver halide emulsion layers containing a cyan-forming coupler, a magenta-forming coupler and a yellowforming coupler respectively, as well as physical development nuclei adenda and a black-and-white developing agent having the formula wherein:

(1) R is an amino-substituted lower alkyl radical;

(2) R is selected from the group consisting of an amino-substituted lower alkyl radical, a hydrogen atom, a lower alkyl radical and a lower alkoxy radical; and

(3) R and R are each selected from the group consisting of a hydrogen atom, a carbonyl masking radical and a sulfonyl masking radical, said masking radicals being capable of hydrolyzing ed in the presence of aqueous alkaline processing compositions;

said couplers being nondiffusible, capable of forming dilfusible dyes on reaction with oxidized aromatic primary amino color developing agent, and having a formula selected from the group consisting of DYELINK COUPBALL) n and BALLLINK(COUPSOL) wherein:

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

(3) COUP is coupler radical selected from the group consisting of a S-pyrazolone 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 couplers nondiffusible during development in said alkaline color developing solution;

which comprises treating the said silver halide emulsion layers with an aqueous alkaline composition containing a silver halide solvent in the presence of an aromatic primary amino color developing agent, chemically developing the said silver halide layers in regions of exposure with said black-and-white developing agent to form a negative silver image, and thereafter physically develop ing the remaining unexposed and undeveloped silver halide corresponding to positive image areas, resulting oxidation product of said color developing agent reacting with said couplers to release ditfusible dye images in regions of physical development, and said dye images diffusing imagewise in register to a juxtaposed reception layer for said dye images,

10. A photographic direct positive color process for treating an image exposed photographic element having a support with superposed red, green and blue light-sensitive silver halide emulsion layers containing a cyan-forming coupler, a magenta-forming coupler and a yellowforming coupler respectively, as well as physical development nuclei addenda and a black-and-white developing agent comprising a combination of a 3-pyrazolidone and a ballasted hydroquinone, said 3-pyrazolidone having a formula selected from the group consisting of and said ballasted hydroquinone having the formula wherein:

(1) R R R R and R are each selected from the group consisting of a lower alkyl radical, a hydrogen atom and a phenyl radical;

(2) R is selected from the group consisting of a hydrogen atom and a carbonyl masking radical that hydrolyzes off in the presence of aqueous alkaline processing compositions;

(3) R is a carbonyl masking radical that hydrolyzes off in the presence of aqueous alkaline processing compositions;

(4) R is photographically inert organic ballasting radical of such molecular size and configuration as to render said ballasted hydroquinone nondiffusible; and

(5) R is selected from the group consisting of a photographically inert organic ballasting radical of such molecular size and configuration as to render said ballasted hydroquinone nondiffusible and an acidic solubilizing radical;

said couplers being nondiffusible, capable of forming diffusible dyes on reaction with oxidized aromatic primary 6 amino color developing agent, and having a formula selected from the group consisting of (2) LINK is a connecting radical selected from the group consisting of an azo radical, a mercuri radical, an oxy radical, an alkylidene radical, a monothio radical, a dithio radical and an azoxy radical;

(4) BALL is a photographically inert organic ballasting radical of such molecular size and configuration as to render said couplers nondilfusible during development in said alkaline color developing solution;

(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 azo radical, a mercuri radical, an oxy radical, a monothio radical, a dithio radical and an azoxy radical;

which comprises treating the said silver halide emulsion layers with an aqueous alkaline composition containing a silver halide solvent in the presence of an aromatic primary amino color developing agent, chemically developing the said silver halide layers in regions of exposure with said black-and-white developing agent to form a negative silver image, and thereafter physically developing the remaining unexposed and undeveloped silver halide corresponding to positive image areas, resulting oxidation product of said color developing agent reacting with said couplers to release diffusible dye images in regions of physical development, and said dye images dilfusing imagewise in register to a juxtaposed reception layer for said dye images. i

11. A photographic process as described in claim 7 wherein the silver halide solvent is selected from the group consisting of an alkali metal thiosulfate, an alkali metal thiocyanate and N,N-diethyl-1,3-propanediamine.

12. A photographic element comprising a support having coated thereon a light-sensitive silver halide emulsion layer containing (A) physical development nuclei addenda,

(B) a nondiffusible color coupler that reacts with oxidized aromatic primary amino color developing agents to form a dye, and

(C) a black-and-white developing agent selected from the group consisting of (1) a difiusible hydroquinone having at least one amino-substituted lower alkyl radical, (2) a diifusible catechol having at least one aminosubstituted lower alkyl radical, and (3) a combination of (a) a diffusible 3-pyrazolidone, and (b) a nondiffusible hydroquinone containing a photographically inert organic bal lasting radical of such molecular size and configuration as to render the hydroquinone nondiffusible.

13. A photographic element as described in claim 12 containing an aromatic primary amino color developing agent.

14. A photographic element as described in claim 12 wherein the color coupler forms a diffusible dye when reacted with oxidized aromatic primary amino color developing agent.

15. A photographic element as described in claim 12 wherein the color coupler forms a nondiffusible dye when reacted with oxidized aromatic primary amino color developing agent.

16. A photographic element comprising a support with a plurality of light-sensitive silver halide emulsion layers coated thereon that are sensitive to different regions of the spectrum, each of said silver halide emulsion layers containing (A) physical development nuclei addenda,

(B) a nondiffusible color coupler that reacts with oxidized aromatic primary amino color developing agents to form a dye that is substantially complementary in color to the light recorded by the said emulsion, and

(C) a black-and-white developing agent selected from the group consisting of (1) a diflFusible hydroquinone having at least one amino-substituted lower alkyl radical, (2) a difiusible catechol having at least one amino substituted lower alkyl radical, and (3) a combination of (a) a diffusible 3-pyrazolidone, and (b) a photographically inert organic ballasting radical of such molecular size and configuration as to render the hydroquinone nonditlusible.

17. A photographic element comprising a support with superposed red, green and blue light-sensitive silver halide emulsion layers containing a cyan-forming coupler, a magneta-forming coupler and a yellow-forming coupler respectively, as well as physical development nuclei addenda and a black-and-white developing agent selected from the group consisting of (1) a ditfusible hydroquinone having at least one amino-substituted lower alkyl group,

(2) a diffusible catechol having at least one aminosubstituted lower alkyl group, and

(3) a combination of (a) a diffusible 3-pyrazolid0ne, and (b) a photographically inert organic ballasting radical of such molecular size and configuration as to render the hydroquinone nondifiusible; said couplers being nondiffusible, capable of forming diffusible dyes on reaction with oxidized aromatic primary amino color developing agent, and having a formula selected from the group consisting of DYELINK-(COUPBALL) and BALL-LINK(COUPSOL) wherein:

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

(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 azo radical, a mercuri radical, an oxy radical, a monothio radical, a dithio radical and an azoxy radical.

18. A photographic element as described in claim 17 wherein the physical development nuclei addenda are selected from the group consisting of colloidal silver and zinc sulfide.

19. A photographic element comprising a support with superposed red, green and blue light-sensitive silver halide emulsion layers containing a cyan-forming coupler, a magenta-forming coupler and a yellow-forming coupler respectively, as well as physical development nuclei addenda and a black-and-white developing agent having the formula wherein (l) R is an amino-substituted lower alkyl radical; (2) R is selected from the group consisting of an amino-substituted lower alkyl radical, a hydrogen atom, a lower alkyl radical and a lower alkoXy radical; and (3) R and R are each selected from the group consisting of a hydrogen atom and a carbonyl masking radical that hydrolyzes off in the presence of aqueous alkaline processing compositions;

said couplers being nondiffusible, capable of forming diffusible dyes on reaction with oxidized aromatic primary amino color developing agent, and having a formula selected from the group consisting of DYELINK-(COUPBALL),, and

BALI-LINK--(COUPSOL) wherein:

(3) COUP is a coupler radical selected from the group consisting of a S-pyr-azolone coupler radical, a phenolic coupler radical and an openchain ketomethylene coupler radical, said COUP being substituted in the coupling position with said LINK;

(4) BALL is .a photographically inert organic ballastin-g radical of such molecular size and configuration as to render said couple-rs nondiff-usible during development in said alkaline color developing solution;

20. A photographic element comprising a support with superposed red, green and blue light-sensitive silver halide emulsion layers containing a cyan-forming coupler, a magenta-forming coupler and a yellow-forming coupler respectively, as well as physical development nuclei addenda and a black-and-white developing agent having the formula wherein:

(1) R is an amino-substituted lower alkyl radical;

(2) R is selected irom the group consisting of an amino-substituted lower alkyl radical, a hydrogen atom, a lower alkyl radical and a lower alkoxy radical; and

(3) R and R are each selected from the group consisting of a hydrogen atom, a carbonyl masking radical and a sulfonyl masking radical, said masking radicals being capable of hydrolyzing olf in the presence of aqueous alkaline processing compositions;

said couplers being nondiffusible, capable of forming diffusible dyes on reaction with oxidized aromatic primary amino color developing agent, and having a formula selected from the group consisting of DYELINK COUP-BALL) n and BALL LINK(COUPSOL) wherein (1) DYE is a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group;

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

(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 azo radical, a mercuri radical, an oXy radical, a mono thio radical, a dithio radical and an azoxy radical.

21. A photographic element comprising a support with superposed red, green and blue light-sensitive silver halide emulsion layers containing a cyan-forming coupler, a magenta-forming coupler and a yellow-forming coupler respectively, as well as physical development nuclei addenda and a black-and-white developing agent comprising a combination of a 3-pyrazolidone and a ballasted hydroquinone, said S-pyrazolidone having a formula selected from the group consisting of and said ballasted hydroquiso fie having the formula wherein:

(2) R is selected from the group consisting of a hydrogen atom and a carbonyl masking radical that hydrolyzes olf in the presence of aqueous alkaline proc essing compositions;

(3) R is a carbonyl masking radical that hydrolyzes oil? in the presence of aqueous alkaline processing compositions;

(4) R is photographically inert organic ballasting radical of such molecular size and configuration as to render said ballasted hydroquinone nondifiusible; and

(5) R is selected from the group consisting of a photographically inert organic ballasting radical of such molecular size and configuration as to render said ballasted hydroquinone nondiffusble and an acidic solubilizing radical;

said couplers being nondiffusible, capable of forming diffusible dyes on reaction with oxidized aromatic primary amino color developing agent, and having a formula selected firom the group consisting of DYELINK(COUPBALL) and BALLLINK COUPSOL wherein:

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

(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 azo radical, a mercuri radical, an oxy radical, a mono thio radical, a dithio radical and an azoxy radical.

22. A photographic element as described in claim 21 wherein at least about mole of ballasted hydroquinone for each mole of 3-pyrazolidone is utilized in the silver halide emulsions.

23. A photographic element comprising a support with superposed layers of a red-sensitive, developing-out, negative-type gelatino-silver halide emulsion containing the cyan-forming coupler, 1-hydroxy-4-(3-n-octadecylcarbamylphenylthio)-N-ethyl-3',5-dicarboxy-2-naphthanilide, a green-sensitive, developing-out, negative-type, gelatino-silver halide emulsion containing the magenta-forming coupler, 1-phenyl-3-(3,5-disulfobenzamido)-4-(2 hydroxy-4- 33 pentadecylp-henylazo)-5-pyrazolone, a blue-sensitive, developing-out, negative-type gelatino-silver halide emulsion containing the yellow-forming coupler, u-b6I1ZOyl-a-(3-I1- actadecylcarbamylphenylthio)-3,5 dicarboxyacetanilide, each of said gelatino-silver halide emulsions containing colloidal silver as physical development nuclei addenda and at least /2 mole per mole of silver halide of the black and white developer, 2-[N,N-bis(fl-hydroxyethyl)aminoethyl] -5 methylhydroquinone metho-methanesulfonate.

References Cited by the Examiner UNITED STATES PATENTS 2,865,747 '12/ 1958 Madem- 9666 937,086 5/1960 Yutzy et al. 96-95 3,148,062 9/ 1964 Whitmore et -al 9695 3,192,046 6/1965 Kennard et al. 9695 NORMAN G. TORCHIN, Primary Examiner.

I. T. BROWN, Assistant Examiner.

Claims

7. A PHOTOGRAPHIC DIRECT POSITIVE COLOR PROCESS FOR TREATING AN IMAGE EXPOSED PHOTOGRAPHIC ELEMENT HAVING A SUPPORT WITH SUPERPOSED RED, GREEN AND BLUE LIGHTSENSITIVE SILVER HALIDE EMULSION LAYERS CONTAINING A CYANFORMING COUPLER, A MAGENTA-FORMING COUPLER AND A YELLOW-FORMING COUPLER RESPECTIVELY, AS WELL AS PHYSICAL DEVELOPMENT NUCLEI ADDENDA AND A BLACK-AND-WHITE DEVELOPING AGENT SELECTED FROM THE GROUP CONSISTING OF (A) AA DIFFUSIBLE HYDROQUINONE HAVING AT LEAST ONE AMINO-SUBSTITUTED LOWER ALKYL GROUP, (B) A DIFFUSIBLE CATECHOL HAVING AT LEAST ONE AMINOISUBSTITUTED LOWER ALKYL GROUP, AND (C) A COMBINATION OF (1) A DIFFUSIBLE 3-PYRAZOLIDONE, AND (2) A NONDIFFUSIBLE HYDROQUINONE CONTAINING A PHOTOGRAPHICALLY INERT ORGANIC BALLASTING GROUP OF SUCH MOLECULAR SIZE AND CONFIGURATION AS TO RENDER THE HYDROQUINONE NONDIFFUSIBLE, SAID COUPLERS BEING NONDIFFUSIBLE, CAPABLE OF FORMING DIFFUSIBLE DYES ON REACTION WITH OXIDIZED AROMATIC PRIMARY AMINO COLOR DEVELOPING AGENT, AND HAVING A FORMULA SELECTED FROM THE GROUP CONSISTING OF