ilat-‘iterated July 22, 1947 2,424,256 UNITED STATES PATENT" OFFICE COLOR DEVELQPEBS COMPRISING‘ ARYL SULFONHYDRAZIDES METHODS OF DEVELOPING SAME Willy A. Schmidt‘ a'ii'd" Joseph A, Sprungl Eastqn, Pa., assignors to Generalv Aniline‘ &_Film ‘Cor porati'on, New York, N. Y-., a corporation or Delaware No Drawing, Application January 23, 1945, Serial N0. 574,810‘ 1 21 Claims‘; (CI. 954-88‘) 2 The present invention relates to color ph‘ol' not produced from the iii-aromatic sulfonhy tography and particularly to the product-ion'of azo dyestu? images by the utilization of color de'# drazide during the development with an azo dye stu? coupling component. It appears that the” velopers which during development are condi oxidation‘ conditions which prevail ‘during such tioned for reaction with an aim dyestuff coupling‘ 3 development convert said “(i-aromatic sulfonhy component to produce an azo dyestu?. drazide to ‘an aromatic'diaz'o sul'fone; The latter Considerable attention has been given by‘ the‘ compound is capable ofr'eactihg with a coupling component the same as any true diazoniiim salt. inpther words; during the reduction of‘ the sn'ver art to the employment of azo 'dye‘st‘u?s for the formation of color images in color photography. It is known that the azo dyestuffs are more stable than the azo methine and quinon'eimine ‘dyes salt‘, the" Biarolnatic suirsnhyurazide is condi tioned for‘ reaction with the az‘o coupling com ponent; as a consequence of which an aZo' d'y'e which constitute the dyestu? images produced in color ?lm by the color forming development method devised by Fischer and described‘ in" U. S. P. 1,102,028. Furthermore, the'azodvyeistu?‘s“ give brilliant images and because of the great‘ number of components which may be reacted to produce such dyes, they provide a greater 'n'unr ber of alternates for forming the dyest'uff images. Many methods have been proposed by which 20 azo dyestu? images'are formed'in color ?lm. ‘One method, known as the silver d'ye‘ bleaching’ images" are to be understood as those obtained method, involves the pre~dy6ing of a silver halide by rebonvers'ibnof a} negative or positive silver emulsion, the exposure and development of the stuff image is formed in situ with the silver image- . . w. , .. It is to be pointed out that by “prints’f‘we mean latent images which have been obtainedby ex posing a sensitive photographic emulsion of higher contrast than is ordinarily used for nega tl‘irv'e', material, fora longer period‘ of time than is customarily used for negative eiiposu'r'e‘ in a camera; On the‘ other hand; “bleached silver image into a silver salt image after treatment same and a bleaching of the dyestu? at the places with an: oxidizing agent in the presence oi‘ an of the silver image. anion capable of forming a'nins'olub'le silver salt. nate‘ an imageresintm'gnan-the development an originallatent image to a silver image and consists’of the silver halide un'a?écte‘d'b'y origi Thi’s'method is disadvan The ?eriii- “residual silver saltiimagéfismtodesig} tageous for the reason that the colored emulsions act as ?lters requiring long exposures to give bal anced images in the various emulsion layers. Another method takes advantage of the fact that diazonium compounds are capable of form ing silver antidiazotates. According to this pro sarexpashre It is-a'ccordiii‘gly and‘ ?rst an-o'bjectiof development. the present 'invenf _ cedure a silver image is bleached and treated with an alkali antidiazotate to convert the bleached non-memorials by the utilizationlasl azo'dyes'tu? a developing imagesagent ‘in color of a [3' silver image lntc a silver antidiazotate. The treated emulsion is then subjected to the action a'romatic sulfonhydr‘azide.” of a coupling compound in the presence of an acid medium to produce the dyestuff image. Still another method proposes to'incorporate in an emulsion a coupling component, to expose, develop and fix the emulsion and to couple the coupling component with a diazonium compound in the presence of a heavy metal salt. Through the agency of such salt, the dyestuff is formed in the areas free from metallic silver. H i H _ ' It is" ailirtlierfrobjectiof thisinve'ntioni t'o'_'proé duce and dressing images in color‘?l’m by the'utri liza?on as a- developing agent: of a p-aromatic sul'fyoiihydrajzide in'wjhich‘t-he sulfur atom is subj stituted' by hydroxyl true corresponding alkali pi‘smiiipmum salts,v or by an alkyl or an aromatic 45: radical. v V ‘ a V _ I > It is'a further‘object'lof this invention to pro duce az'o'v dyést‘u’ff images‘ by reacting a'couplin'g component with’ the‘ product resulting rrqmjt-he _ . . . . These latter methods, a study'reveals, have oxidation of an aforesaid ?-aromat'ic sulfonhyi many shortcomings ‘which have militated against drazi'de‘ ‘during the'development of a‘ print; ‘a their general adoption for practical purposes and bleached1 silver image or a‘ residual silver salt have been applied only to a limited extent. We have now discovered’ that azo dyestuif 50: It is‘ajfurth'er obl'e'ctof this invention to ping; images can be prepared by the simple method of imfelgé. developing latent silver halide images, particu- ' larly prints, bleached silver images and residual 1,, .. . a H _ ‘containing esssilve‘r halide‘ azo‘ ‘dyestuff emulsions‘ images leading by developing’ to vcolor a‘ ‘print; a'b'leachecl silver image or a residual silver salt-image with an aforesaid p-aromatidsulfom drazide and the subsequent coupling of the prod- 6B: hydrazide" andreacting the oxidation product of silver salt images with a ,s-aromatic sulfonhy 2,424,256 3 4. therefore be more speci?cally de?ned by the fol lowing formula: said c-aromatic sulfonhydrazide with an azodye stuif coupling component. It is a further object of this invention to pro vide a color developer comprising an aforesaid c-aromatic sulfonhydrazide and an azo dyestuff 5 wherein X1 is an aromatic hydrocarbon such as phenyl, naphthyl, diphenyl and the like, and such coupling component, radicals substituted by a neutral or electroposi tive radical such as alkoxy i. e. methoxy, ethoxy, It is a further object of this invention to de velop a silver halide emulsion containing an azo propoxy and the like, aryloxy i. e. phenoxy and means of an aforesaid ?-aromatic sulfonhydra 10 the like, primary amino, substituted amino such as alkylamino i. e. methylamino, dimethylamino, zide by which an azo dyestuff is produced in situ ethylamino, diethylamino, propylamino, butyl with the silver image. amino and the like, arylamino such as phenyl It is a further object of this invention to facili amino and the like, acylamido such as alkyl car tate the aforesaid coupling reaction by the utili 15 bonamido i, e. acetamido, propionamido, butyr zation of a nitrogenous base. amido and the like, arylcarbonamido such as Other and further important objects of the in benzamido and the like, sulfonamido such as vention will be apparent as the description pro. alkyl sulfonamido i. e. methylsulfonamido, ethyl ceeds. sulfonamido and the like, and arylsulfonamido The p-aromatic sulfonhydrazides which we employ according to the present invention are 20 such as phenylsulfonamido and the like, R is OH or the corresponding alkali metal and am embraced by the following general formula: monium salt groups, alkyl such as ethyl, methyl, dyestu? coupling component fast to diffusion by propyl, butyl, hexyl, decyl, dodecyl, stearyl and the like, or such radicals containing a water in which X is an aromatic radical such as phenyl, solubilizing group such as sulfo, carboxy, hy naphthyl and the like, R is hydroxy or the cor 25 droxy ethenoxy and the like, or an aromatic responding alkali metal or ammonium salt radi radical such as phenyl, naphthyl, diphenyl, chlor cal, alkyl or an aromatic radical. While the phenyl, nitrophenyl, chlornaphthyl, hydroxy invention can be effected with compounds of this phenyl, hydroxy naphthyl, alkylphenyl, alkoxy formula, it has been ascertained that certain properties of the aromatic sulfonhydrazides must 30 phenyl, hydroxy diphenyl, aminophenyl, alkyl aminophenyl, arylaminophenyl and amidophenyl, be taken into consideration in selecting those the alkoxy, amino, alkylamino, arylamino, amido which will give the best results. Among these and alkyl groups having the values stated pre factors are viously, and n being 1 or 2. While it is true 35 that the aromatic radical represented by R may bear negative substituents, it is advisable when (1) Stability of the compounds, (2) Speed of development, and (3) Speed of coupling. employing such groups to limit the substitution of the aromatic ring to one such group since otherwise the stability of the compound may It has been further ascertained, and this is an important aspect of the invention, that these factors are greatly affected by the substituents 40 suffer. Examples of compounds which fall within this on the aromatic ring joined to the [fl-nitrogen general classi?cation are listed below: atom on the one hand and on the aromatic radical joined to the sulfur atom on the other hand. Thus experiments have shown that where 0 0 O O 0 O 2) CH: the aromatic ring joined to the nitrogen atom 45 Sodium salt of phenyl hydrazine sulionic acid on the one hand and the aromatic radical repre sented by R on the other hand are substituted by electropositive groups or substituents, the rate of development is most rapid. The stability of the compounds is decreased considerably when the aromatic radical joined to a sulfur atom is substituted by an electronegative substituent. The rate of coupling of the diazo sulfones lead ing to the azo dye is more rapid when the sub stituent on said aromatic ring joined to a nitro gen atom is neutral or weakly electropositive. An electronegative substituent on said aromatic radi cal represented by R is found in many cases to increase the speed of coupling. From these ex periments the conclusions have been reached that in the preferred compounds the substituents on the aromatic radical joined to the p-nitr'ogen atom should be either electropositive or neutral, whereas the substituents on the aromatic radical represented by B may be neutral, electropositive or electronegative. NH-NHS OYSNHL Ammonium salt of phenyl hydrazine sulfonic acid 50 ?-phenyl-ethanesulfonhydrazide 55 ?-phenyl-methanesulionhydrazide 60 ?-phenyl-dodecancsulionhydrazide NH-NHSOiCHa 65 _ B-(3'-methoxy-pbenyl) methanesulfonhydrazide By electropositive radicals is meant those radi cals which are electron donating in character, such as the acylamido and alkoxyl radicals. Neutral radicals or groups are hydrogen and alkyl 70 groups. The electronegative radicals are those which possess electron attracting properties, such as halogen, nitro, sulfo, carboxy and the like. The ?-aromatic sulfonhydrazides which have been found most suitable for my purposes may 75 @ B-(p'-octadccyl-phenyl)-methanesulionhydrazidc 0 - H3701 NH-NHSOzCHs (C2115) 2N NH-—-NHS 0202115 ?-(4’-diethylamino-phenyl)~etl1anesulfonhydrazide ‘2,424,253 2;? . sotic acid, 2-hydroxy-3-naphthoic acid anilide, acetoacetanilide, I-phenyI-S-pyrazolone and the ing acetoacetanilide to form the azo dye with elimination of a sul?nic acid group; ‘ like. . . The process of ‘producing azo dyestuif images by the utilization of said B-a‘romatic sulfonhy drazides may be effected in various ways. For instance, a ?lm may be exposed and developed in a black and white developer, ?xed, the image II Ar——N=NSOzR '+ OHaCOCHzCONHO __-> bleached to a silver salt image and re-developed O O CH: + RSOzH, ArN=NCH with said ,B-aromatic sulfonhydrazide in the pres ence of an azo coupling component. \CONHO Or a silver halide emulsion‘may be exposed, developed in a black and white developer, re-exposed and devel oped with the p-aromatic sulfonhydrazide in the presence of the coupling component. Again, a Similar reactions takeplace when the coupler is a phenol or the like. - silver halide emulsion containing a coupling com I1; has been stated above that‘the sulfonhy ponent fast to diffusion may be processed as above. drazides may contain an electronegative group in The color developing solutions are generally the aromatic radical represented by R. It is pre alkaline in nature and the alkalinity may be sup ferred, however, that such radical either be un substituted or be substituted by a-neutral group -. 20 plied by means of an alkali metal carbonate such as sodium carbonate, potassium carbonate and such as alkyl or by an electropositive group such the like, or an alkali metal hydroxide such as as an alkoxy, amino, acylamido or the like group, sodium hydroxide, potassium hydroxide, etc. The since it has been found that any sacri?ce in cou said ,B-aromatic' sulfonhydrazide is ‘dissolved or pling speed due to the presence‘ of such a group is more than compensated for byv an increase in v25 dispersed in the alkaline solution. Generally the --NHSO2R group ofthe hydrazide is sufficiently the stability of the compounds.v Should it tran acidic to make the compound soluble in the alka spire that the compounds selected have a low line solution. ‘ In the event, however, that such rate of coupling, coupling may be facilitated by grouping does not ‘render the compound sul? the utilization of small quantities of a ni trogenous base incapable of coupling with‘ a di 3.0 cientiy soluble, a water-solubilizing group such as a sulfonic acid or carboxylic acid group should azonium compound to form an azo dye such as be incorporated into the alkyl or aryl radical ammonium hydroxide, an aliphatic amine, i. e., linked to the sulfur atom. It is of course evident meth'ylamine, dimethylamine, ethylamine, di that where R in the above formula stands for OH ethylamine, trimethylamine, ethanolamine, di ethanolamine, triethanolamine, propanolamine, or the corresponding alkali metal or ammonium salt group, ‘the compound will be soluble in an butylamine and the like or heterocyclic ni alkaline solution.‘ trogenous base such as pyridine, quinoline and As is evident, the gradation of the dyestuif the like. The aromatic amines are of course ca images .will vary with the particular p-aromatic pable of coupling and consequently are-excluded. sulfonhydrazide selected. Should a sulfonhydra Best results are secured while employing the 40 zldebe employed which gives poor gradation, the heterocyclic nitrogenous bases and the's'e'are ac selection however being dictated because of ad cordingly recommended for use. vantages resulting from stability of the developer, The p-aromatic sulfonhydrazides are best speed of development, speed of coupling or the suited for reducing an undeveloped print, a production of a particular dyestuff shade, the bleached silver image or a residual silver salt im-e. gradation may be improved by the utilization of age to give, with coupling ‘components, azo dye small amounts of an aliphatic aldehyde such as images of excellent density and gradation, It. ‘formaldehyde or acetaldehyde which may be may be noted however, that theymay also be incorporated'inthe developing bath. Good re used to reduce normal latent'negative images sults have been obtained when utilizing amounts particularly when the emulsion is one of extreme "50 of the aldehyde ranging from 1 to 5 parts for each contrast which has been given ‘sufficient ex liter of developer. posure in the camera. , Where R in the above for mula is 01-1 or a corresponding alkali. metal or > As previouslyv indicated, the process may be effected while utilizing the coupling components ammonium salt group the coupling reaction oc curs satisfactorily only in the presence of ultra- ‘ in the silver halide emulsion provided that the coupling components are rendered fast to diffu sion. This result may be accomplished by includ ing in the molecule of the coupling component a violet radiation. Any coupling component utilizedin the azo dyestuff art may be employed for reaction with substantive group such as benzidine, stilbene or a like radical, or by the introduction of a'molec the diazosulfone compounds. These components, as is known, are aromatic compounds which con 60 ular enlarging group such as a natural resin, a tain a phenolic hydroxyl group, an amino group, synthetic resin, a sterol, a carbohydrate, a terpene, an alkylamino group such‘ as, methylamino, or a long fatty chain. The means by which fast ethylamino and the like, an arylamino group ness to diffusion may be effected are described such as phenylamino and the like, said com pounds having replaceable hydrogen atoms or groups in the 0-. or p-positions thereto. They may also be compounds which contain a reactive methylene group such as acetoacetic acid deriva tives, pyrazolones, and- the like. ; ‘ . . f Examplesof such compounds are .—naphtho1, N- (p-naph‘thyl), -3,-hydr_oXy-2 - naphthamide, .-N (o-tolyl) -3-hydroxy-2- —. ,anthramide, ,N ‘- ,(1'-.an. .1 65 in United States Patents 2,178,612, 2,179,228, 2,179,238, 2,179,239, 2,179,244, 2,186,685, 2,186,719, 2,186,732, 2,186,733, 2,186,734, 2,186,849, 2,186,851, 2,186,852, 2,280,722, etc. Thepreferred method for rendering the vcoupling components fast to . diffusion is by the introduction of a long fatty chain and good results have been securediwhen using as such chain a decyl, dodecyl, stearyl and similar radicals. The coupling components may be located inemulsion layers of a three-layer ?lm, _acid,.J_.acid, chromotropic acid-R salt, resorcinol, diacetoaceticeo-tolidide,: .salicyclic ; acid, _ o-cre :75 a bi-pack or the like, or in a gelatin layer super thryl) glycine,- G salt, _H_ acid, K acid, gamma 2,424,256 9 imposed on the emulsion layer. 10 The coupling. components are selected so that. subtractively colored dyestu?‘ images are obtained in- each of the layers. Said ?-aromatic sulfonhydrazides may be pro duced by methods already described in the liter After. development, the ?lm is then bleached I withableaching solution of the following com Position: Parts Water ______________________________ __ 1000 ature. Such methods involve condensation of an Potassium ferricyanide ________________ __ Disodium phosphate __________________ __ arylhydrazine with a sulionyl chloride, reduction Monopotassium phosphate ____________ __ 100 4.3. 5.8 of a diazo sulfone with zinc dust or sulfur‘dioxide, condensation of an arylhydrazine with a sul?nic 10 The ?lm isthen thoroughly washed andl?xed in anaacid hardening hypo bath. After removal of acid, and reduction of a diazonium salt with sulfur the hypo by washing, and drying of the ?lm, dioxide or sodium hydrosul?te. there remainsablue azo dye image having the The following examples are illustrative of the following constitution: invention but it is to be understood that the inven O C2135 tion is not restricted thereto. The parts are by 15' Weight unless otherwise stated. Example 1 A solution of 2,5-diethoxy-4-benzamido-ben zene-diazonium chloride prepared from 30 parts 20 of 2,5-diethoxy-4-benzamidoaniline in_500 parts W of water is added to a cold solution ofv 22 parts of p-acetamidobenzene'sul?nic'acid and 13.8 parts Example 2 of potassium carbonate in 500 parts of water. The An exposed strip ?lm bearing a silver bromide combined solution is slowly acidi?ed with. cold 4-N-hydrochloric acid to a pH of- 2. After the 25" emulsion is processed as in Example 1 through the second exposure and is then developed in a mixture has remained at room temperature for one-half hour, the orange-colored diazo sulfone is removed by ?ltration- and washed Well withv water. The material after drying in a’ vacuum 30 desiccator over phosphoruspentoxide amounted to 33 parts, representing a yield of 65 per cent. It melted at 110° C. with decomposition. The product is 2,5-diethoxy-4-benzamidobenzenedi azo- (p-acetamidophenyl) ~sulfone, 35 A solution of 25.5 parts of the above diazo color developer having the following composition: 0.2 part of p43’-(p-di-acetamidobenzenesulfon yl(-3.3’-dimethyl-4.4’-dihydrazinobiphenyl dis solved in Parts Ethanol ____ ___ 10 N -(o-tolyl) -3-hydroxy-2-anthramide ____ __ 0.2 Aqueous potassium hydroxide ___________ __ l0 Pyridine __ 5.0 37% aqueous formaldehyde solution ______ __ 0.2 sulfone in a mixture of 500 cc. of acetone, 7.5 Water ____ __ ____ _ 85 parts of glacial acetic acid and 10 parts of H20 is slowly treated at room temperature under vigor The emulsion is bleached and ?xed, yielding. a ous stirring with zinc dust until the solution 40 ?lm strip containing a green azo dyestu? image turns from a deep orange to a faint yellow color. having the following constitution: CH3 CH3 HO CH: The zinc compounds are removed by ?ltration, and the cooled ?ltrate is diluted with 250 parts of water. The sulfonhydrazide, which separates, is The pp’-(p-di-acetamidobenzenesulfonyl)-3.3' removed by ?ltration and dried in a’ vacuum‘ sulfonhydrazide of Example 1. Example 3 desiccator over phosphorus pentoxide. The yield 55 is 16 parts or 62%. The material when recrystals lized from dilute ethanol melted at 166° C. with dimethyl-4.4'-dihydrazinobipheny1 is obtained by a method similar to that utilized in preparing the To a solution of 43 parts of phenylhydrazine in 180 parts of ether chilled in an ice bath, there is slowly added with stirring A photographic ?lm containing a light-sensi 60 tive silver bromide emulsion is exposed and. de 44.3 parts of'3-chlorosulfonyl benzoic acid in 180 veloped in a metol-hydroquinone developer. The parts of ether. ?lm after. washing is re-exposed to light and: After the mixture has remained at room tem processedfor 15 minutesv at 15<to 20° C; in a'colori perature for one hour, 25000. of a low boiling developer of- the following composition: 65 petroleum ether is added and the solid material 0.2 part of ,B-(2.5-diethoxy-4-benzamidophen is removed by ?ltration and washed with petro yl). -p.-acetamidobenzenesulfonhydrazid'e;dissolved leum ether. The product is digested with one in. liter of dilute hydrochloric acid to remove the Parts‘ phenylhydrazine hydrochloride and the residue Ethanol _______________________________ __ 10 is recrystallized from dilute ethanol. 44 parts of N- (p-naphthyl) -3-hydroxy-2-naphthamide- 0.2 a product are obtained representing a yield of 10% aqueous potassium hydroxidesolution__ 10 75%‘. The product is p-phenyl-B-carboxyben Pyridine ___________________________ __g____ 1.0_ zenesulfonhydrazide which has a melting point of decomposition. 37% aqueous formaldehyde _____________ __ Water 02- ____ __ 85 178910: with decomposition. A photographic ?lm containing a silver halide 2,424,256 11 V . , tion: in the patent, however, do not contain an alkyl or aryl sulfonyl group or sulfo salt groups as in Tithe compounds of our invention. Accordingly, ‘the reaction by which the dyestuffs are formed is different. In addition, as previously pointed out, it is possible with our color developers to vary the properties by suitable selection of the .substituents on the various aryl groups present ' 0.2 part of ,8-phenyl-3-carboxybenzenesulfon hydrazide dissolved in Parts Ethanol ____ ____ p-naphthol _________ _'_ _________________ __ 10 0.2 Aqueous potassium carbonate ____________ .._. >10 Pyridine ______________________________ __ 1.0 37% aqueous formaldehyde solution ______ __ 0.2 Water _____ __ _ 10 in the molecule. Inasmuch as said properties have a direct bearing upon the processing of the ?lm, as previously explained, the processing can be better regulated when using the sulfonhydra ‘_ ‘zides in lieu of the phenyl hydrazines of the pat 85 After development, the ?lm is washed and bleached for 5 minutes in a bath as described in Example 1. The washed ?lm strip is then ?xed in a bath of 20% aqueous sodium thiosulfate. The resulting ?lm contains an orange azo dye image of the following constitution: 12 emulsions. The aromatic hydrazines employed emulsion is exposed and developed in a metol hydroquinone developer. The ?lm is washed, re-g exposed to light and developed for 15 minutes at 15 to 20° C. in a bath of the following composi 15 - ent. Various modi?cations of our invention will oc - our to persons skilled in the art and we there fore do not intend to be limited in the patent granted except as necessitated by the prior art 20 and the appended claims. We claim: 1. The process for the production of azo dye stuff images in an exposed silver halide emul M3 sion layer which comprises subjecting said emul 25 sion to development with a solution of a B-aro matic sulfonhydrazide in the presence of an azo do‘ OH dye coupling component. 2. The process as de?ned in claim 1 wherein Example 4 the azo dye coupling component is located in the A multilayer ?lm sold under the trade name 30 solution of the ,B-aromatic sulfonhydrazide. 3. The process as de?ned in claim 1 wherein the solution of the ,B-aromatic sulfonhydrazide and white as in Example 1 and after re-expo is an aqueous alkaline solution. sure is color developed for 20 minutes in a bath 4. The process of producing an azo dyestuff of the following composition: , 0.2 part of ,8-phenyl-3-carboxybenzenesul 35 image in a photographic element bearing a sil ver halide emulsion containing an exposed sil fonhydrazide dissolved in ver halide image which comprises subjecting said Parts emulsion to development with a B-aromatic sul Ethanol _______________________________ __ 10 “Ansco Color” is exposed, developed to black Potassium carbonate solution ___________ __ 10 Pyridine _______________________________ __ 2.0 37% aqueous formaldehyde solution _____ __ 0.2 Water _________________________________ __ 85 The ?lm is then bleached and ?xed as in Example 1, thereby yielding a yellow-green azo dye image in the ?rst layer, a yellow azo dye image in the second layer, and a red azo dye image in the third fonhydrazide whereby said image is converted 40 into a silver image and said sulfonhydrazide is simultaneously converted into a diazosulfone, and coupling said diazosulfone with an azo dye coupling component, in the presence of a nitrog enous base incapable of coupling to form an 45 azo dye, to facilitate the coupling reaction. 5. The process as de?ned in claim 1 wherein the solution of the B-aromatic sulfonhydrazide layer. contains a small quantity of an aliphatic alde Example 5 hyde for the purpose of improving the gradation 4 parts of N-(3-octadecamidobenzyl) H-acid 60 of the azo dyestu? image. 6. The process as de?ned in claim 1 wherein are dissolved in 5 cc. of sodium carbonate of 20% the coupling takes place in the presence of a strength and 50 parts of water. The resulting small quantity of an aliphatic aldehyde to im solution is added to 1000 parts of a photographic prove the gradation of the azo dyestu? image. silver bromide emulsion. The emulsion is coat 55 7. The process of producing an azo dyestu?f ed, exposed, developed in a black and white de image in a photographic element bearing a silver veloper as in Example 1 and then developed with halide emulsion, said element containing an azo the sulfonhydrazide developer described in Ex dyestuif coupling component fast to di?usion and ample 3. After further processing the ?lm as in said emulsion an exposed silver halide image in Example 1, there is obtained a magenta dye 60 vwhich comprises subjecting said element to the stu? image of the following constitution: action of a solution of a p-aromatic sulfonhy drazide whereby said image is developed to a silver image, and an azo dyestu? is formed in situ with the silver image by coupling of the 65 coupling component with the oxidation product of said hydrazide. . ‘8. The process as de?ned in claim 1 where said p-aromatic sulfonhydrazide has the follow- . 'ing formula: ‘ N803S some I am aware of the existence of U. S. P. 2,339,213, 70 X being an aromatic radical, R being a member of the class consisting of OH, O-alkali metal, which discloses the employment of aromatic hy O-N'H4, alkyl and an aromatic radical. drazines with suitable coupling agents for the production of azo dyestu? images in silver halide 75. 9. The process as de?ned in claim 4. wherein. 2,424,256 13 14 said ,B-aromatic sulfonhydrazide has the follow ing formula: of OH, O-alkali metal, O—NH4, alkyl and an aromatic radical and X1 is a member of the class consisting of aryl, alkoxyaryl, aryloxyaryl, aminoaryl and acylaminoaryl radicals, an azo wherein R is a member of the class consisting of CI dye coupling component, and a small amount of OH, O-alkali metal, O—NH4, alkyl and an arc a nitrogenous base incapable of coupling to form matic radical and X1 is a member of the class an azo dye and serving to facilitate the coupling consisting of aryl, alkoxyaryl, aryloxyaryl, aminoaryl and acylaminoaryl radicals. of the azo dye coupling component with the oxidation products of the p-aromatic sulfonhy 10. The process as de?ned in claim 7 wherein 10 drazide. 18. The composition as de?ned in claim 14 in which there is present a small amount of an ali said Iii-aromatic sulfonhydrazide has the follow— ing formula: phatic aldehyde to improve the gradation of the B. being a member of the class consisting of OH, O-alkali metal, O—NI-I4|, alkyl and an aromatic radical and X1 being a member of the class con sisting of aryl, alkoxyaryl, aryloxyaryl, amino aryl and acylaminoaryl radicals. 11. A color developer comprising a solution of a B-aromatic sulfonhydrazide and an azo dyestuff coupling component. 12. A color developer comprising a solution of a ?-aromatic sulfonhydrazide, an azo dye cou pling component and a small amount of a nitrog enous base incapable of coupling to produce an azo dye and operating to facilitate coupling of the azo dye coupling component with the oxida tion products of the ?-aromatic sulfonhydrazide. azo dye formed by the color developer. 19. The process of producing a reversed azo dyestu? image in a photographic silver halide emulsion which comprises exposing a silver halide emulsion, developing the same in a black and white developer, re-exposing the emulsion, and developing the same in an aqueous alkaline solu tion of ?-phenyl-3-carboxybenzene sulphonhy drazide and p-naphthol. 20. The process of producing an azo dyestuif image in a photographic silver halide emulsion which comprises exposing the emulsion, develop ing the same in a black and white developer, re exposing the emulsion, and developing the same in an aqueous alkaline solution of ?-(2.5-di ethoxy - 4 - benzamidophenyl) -p-acetamido-ben 13. The composition as de?ned in claim 11 zenesulfonhydrazide and N-(?-naphthyl) -3-hy wherein the solution is an aqueous alkaline solu 30 droxy-2-naphthamide. tion. 21. The process of producing an azo dyestu? image in a photographic silver halide emulsion 14. A color developer comprising a solution of a ,B-aromatic sulfonhydrazide having the follow ing constitution: which comprises exposing the emulsion, develop in which R is a member of the class consisting in an aqueous alkaline solution of ,6.,6'-(p-di of OH, O-alkali metal, O—-NH4, alkyl and an dihydrazinobiphenyl and N(o-tolyl)-3-hydroxy 2-anthramide. ing the same in a black and white developer, re expcsing the emulsion and developing the same aromatic radical, and X is an aromatic radical and an azo dye coupling component. 15. The composition as de?ned in claim 14 wherein the solution is an aqueous alkaline solu tion. 16. A color developer comprising a solution of a B-aromatic sulfonhydrazide having the follow ing constitution: acetamidobenzenesulfonyl) - 3.3’ - dimethyl-4.4’ WILLY A. SCHMIDT. JOSEPH A. SPRUNG. REFERENCES CITED The following references are of record in the ?le of this patent: UNITED STATES PATENTS in which R is a member of the class consisting of OH, O-alkali metal, O——NI-I4, alkyl and an aromatic radical, and X1 is a member of the class Number Name Date aryloxyaryl, 1,934,011 2,191,037 2,304,025 Schmidt et a1. ____ __ Nov. 7, 1933 Mannes et al. ____ __ Feb. 20, 1940 Schneider et al _____ __ Dec. 1, 1942 aminoaryl and acylaminoaryl radicals and an 2,339,213 Woodward et al. ___ Jan. 11, 1944 azo dye coupling component. 2,196,734 Marriage ________ __ Apr. 9, 1940 17. A color developer comprising a solution of 55 a p-aromatic sulfonhydrazide having the follow ing constitution: 2,266,442 Schinzel _________ __ Dec. 16, 1941 consisting of aryl, alkoxyaryl, ‘ 2,276,254 X1—NH--NHSO2R Number in which R is a member of the class consisting 60 462,140 Schinzel _________ __ Mar. 10, 1942 FOREIGN PATENTS Country 1 Date Great Britain ______ __ Mar. 3, 1937 ' Certi?cate of Correction Patent No. 2,424,256. July 22, 1947. WILLY A. SCHMIDT ET AL. It is hereby certi?ed that error appears in the printed speci?cation of the above numbered patent requiring correction as follows: Column 5, next to the last formula, for that portion reading CH I (IJHI MG MG and that the said Letters Patent should be read with this correction therein that the " ' same may conform to the record of the case in the Patent Of?ce. Signed and sealed this 14th day of October, A. D. 1947, [am] THOMAS F. MURPHY, Assistant Gammz'ssz'oner of Patents.