CA1169691A - Color-forming para-sulfonamidodiphenylamine dye precursor and sulfonimide dye in photographic material and process - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A color-forming para-sulfonamidodiphenylamine dye precursor in a photographic material and process enables formation of a dye image by means of cross-oxidation with-out the need for a coupling reaction. The color-forming para-sulfonamidodiphenylamine dye precursor is useful in a photographic silver halide material for producing (i) a dye image, or (ii) a dye image and silver image. The exposed photographic material is processes to produce (a) a positive dye image, (b) a negative dye and negative silver image, (c) a negative dye image or (d) a positive dye image and a positive silver image.

Description

1 ~;.'3691 COLOR-FORMING PARA-SULFONAMIDODIPHENYLAMINE
DYE PRECURSOR AND SULFONIMIDE DYE IN
PHOTOGRAPHIC MATERIAL AND PROCESS
Field of the Invention Thi& invention relate6 to a photographic material and proce6s for producing images by means of photosensi-tive silver halide and a color-forming para-sulfonamidodi-phenylamine dye precuræor. One aspect of the invention relates to a photographic element for producing such images. Another aspect relates to a photographic composi-tion comprising the dye precursor according to the inven-tion. A further aspect relates to processes for producing images in an imagewise expo6ed photographic material comprising a color-forming para-sulfonamidodiphenylamine dye precursor.
Description of the State cf the Art Photographic materials for producing silver images and dye images are known. The dye image in such materiale is generally produced by a coupling reaction in which a developing agent is oxidized upon development of photosensitive 6ilver halide in the material, followed by reaction of the resulting oxidized form of the developing agent with a coupling agent to produce a dye image. It has been desirable to provide alternative means for producing a dye image, e~pecially a dye image that enhances a silver image, other than by a coupling reac-tion. The formation of dye images according to the inven-tion by means of a dye precursor doe6 not involve a coupling reaction.
Production of reversal color images, al60 known as positive dye images, by developing a silver image in an imagewise exposed photographic material is also known.
Such reversal color images and proce6se6 for producing such images are described in, for example, U.S. Patent 4,035,184 and U.S. Patent 3,938,995. These patents describe production of a negative dye image by means of a ~ 3~

leuco dye comprising the reaction product of a color-form-ing coupler and an N,N-dialkyl-~-phenylenedismine.
Neither of these patents relate to the formation of a dye image and silver image in which the dye is produced from a color-forming para-sulfonamidodiphenylamine dye precur-sor. The present invention also avoids the need for a coupling reaction to produce a dye described in these patents.
The term "photographic material" herein means photographic elements and photographic compositions. For instance, photographic material herein includes photo-graphic elements and photographic compositions comprising photosensitive silver halide and a color-forming para-sulfonamidodiphenylamine dye precursor according to the invention.
SUMMARY OF THE INVENTION
It has been found according to the invention that a stable dye image, especially a dye image that enhances a silver image, is produced by means of a photographic material comprising, in reactive association, in binder:
(a) photosensitive silver halide, and (b) a color-forming dye precursor which is imagewise converted upon expo~ure and proces6ing of the photographic material to a dye by cross-oxidation, preferably by means of a cross-oxidizing silver halide developing agent. The color-forming dye precursor according to the invention is a color-forming para-sulfonamidodiphenylamine dye precursor.
An e6pecially useful color-forming sulfonamidodi-phenylamine dye precursor according to the invention is one that comprises a stabilizer group. The stabilizer group provides increased light stability to the resulting dye upon processing of the photographic material contain-ing the color-forming sulfonamidodiphenylamine dye precur-sor. The term stabilizer group herein means such 8 group that provides increased light stability to the resulting dye from the sulfonamidodiphenylamine upon processing of ~ 3~ ~1 the photographic material. Many stabilizer groups are u~eful a~ a component of the sulfonamidodiphenylamine according to the invention. An especially useful stabi-lizer group is a 2,4,6-triisopropylbenzene 6tabilizing S group bonded to a sulfonamido group of the para-sulfon-amidodiphenylamine. A combination of stabilizer groups is also useful.
It has also been found that a positive dye image is provided in a photographic material according to the invention by a process comprising (a) developing the exposed photographic material in an alkaline photographic developer in the absence of a cross-oxidizing silver halide developing agent; then, (b) fogging the resulting element, such as by uniformly exposing the resulting element to a flash exposure of light or, alternatively, a chemical fogging agent; followed by (c) developing the photographic element in an alkaline cross-oxidizing devel-oper, such as a 3-pyrazolidone cross-oxidizing developer;
and, then (d) bleaching and fixing the photographic material in a silver halide bleaching and fixing compo6i-tion to produce a positive dye image in the photographic material. After step (a) and before step (b), optionally the photographic process for producing a positive dye image includes a stop bath treatment. This enable6 a tesirable lowering of the pH of the development to a point at which development of a negative silver image stops quickly. This produces an improved dye image upon processing .
A negative dye image and a negative ~ilver image are produced in an imagewise exposed photographic material comprising, in reactive association, in binder, (8) photo-sensitive silver halide, and (b) a color-forming para-sul-fonamidodiphenylamine dye precursor by developing the photographic material in an alkaline, cross-oxidizing, photographic 6ilver halide developer composition, prefer-ably such a composition comprising a 3-pyrazolidone silver 3tj9 halide developing agent. The negative dye i~age prefer-ably enhances the negative silver image. Thi6 enables a lower concentration of silver in the photographic material before exposure than otherwise might be necessary to form a similar developed image from silver halide alone. When the negative, developed silver image is removed from the photographic material, such as by means of a bleaching and fixing composition, a negative dye image remains in the proce~sed photographic material.
A positive dye image and a positive silver image are produced in an imagewise exposed photographic material according to the invention by means of direct-positive photographic silver halide. A process for producing a positive, dye image and a positive, silver image in an imagewise exposed photographic material comprising, in reactive association, in binder, (a) direct-positive photographic silver halide, and (b) a color-forming para-sulfonamidodiphenylamine dye precursor comprises (A) developing the photographic element by means of an alka-line, cross-oxidizing photographic silver halide develop-ing composltion; then (B) fixing the resulting photogra-phic element to produce a positive dye image and a po6i-tive silver image.
In each of the photographic materials and processes, the resulting dye in the image areas has increased stability. The dyes according to the invention containing a ~tabilizer group exhibit better stability than dyes that do not contain a stabilizer group.
DETAILED DESCRIPTION OF THE INVENTION
Many para-sulfonamidodiphenylamines are useful color-forming sulfonamidodiphenylamine dye precursors in photographic materials and processes according to the invention. Combinations of color-forming para-sulfon-amidodiphenylamine dye precursors are also useful, if desired. The color-forming para-sulfonamidodiphenylamine dye precursor is selected to provide a dye image by means of a cross-oxidizing photographic silver halide developing agent after imagewise exposure.
The term "para-sulfonamidodiphenylamine" herein alternatively means 4'-sulfonamidodiphenylamine.
One illustrative class of color-forming para-sul-fonamidodiphenylamine dye precursors is represented by the formula:
Rl R3 y O / -NH--/ O \--NHSO2Rs ~herein:
R is in the meta or para position and is an electron donating substituent selected from amino groups represented by the formula:
~R
N
~R7 alkoxy containing 1 to 20 carbon atoms, such as methoxy, ethoxy, propoxy, hexyloxy and octadecyl-oxyj sulfonamido, such as R5ASo2NH; aryloxy containing 6 to 20 carbon atoms, such as phenoxy, 3,4,5-trimethylphenoxy, 2,4-di-t-amylphenoxy and halophenoxy; and carboxamido groups, such as acetamido, N-methylacetamido and propionamido;
is in the ortho or meta position and is hydrogen, alkyl containing 1 to 3 carbon atoms, such as methyl, ethyl and propyl, carbamoyl, alkoxy containing 1 to 3 carbon atoms, such as methoxy, ethoxy and propoxy, sulfonylalkyl containing 1 to 3 carbon atoms, such as sulfonylmethyl, sulfonyl-ethyl, and sulfonylpropyl, sulfonylaryl contain-ing 6 to 12 carbon atoms, such as sulfonylphenyl and sulfonyl methylphenyl, chlorine, bromine, iodine or fluorine; R2 is hydrogen, alkyl containing l to 3 carbon atoms, such as methyl, ethyl and propyl, carba-moyl, alkoxy containing 1 to 20 carbon atoms, such as methoxy, ethoxy and propoxy, sulfonyl-alkyl containing 1 to S carbon atoms, such as sulfonylmethyl, sulfonylethyl, and sulfonyl-propyl, sulfonylaryl containing 6 to 12 carbon atoms, such as sulfonylphenyl and sulfonyl methylphenyl, chlorine, bromine, iodine or fluorine; S R3 is hydrogen, alkyl containing 1 to 20 carbon atoms, such as methyl, ethyl and propyl, halo-alkyl containing 1 to 3 carbon atoms, such as tribromomethyl, trifluoromethyl, 2,2,2-trichloro-ethyl, and 3,3,3-trichloropropyl, alkoxy contain-ing 1 to 20 carbon atoms, such as methoxy, ethoxy, propoxy and decyloxy, an ester containing 1 to 20 carbon atoms, such as formoxy, acetoxy, butyroxy and stearoxy, carboxy, carboxamido, such as acetamido, N-methylacetamido and propionamido, chlorine, bromine, iodine, fluorine, carbamoyl, sulfonic acid, sulfamyl, sulfonylalkyl containing 1 to 5 carbon atoms, such as sulfonylmethyl, sulfonylethyl and sulfonylpropyl, ureido, or a carbocyclic group containing 5 to 12 carbon `
atoms, such as cyclohexyl, cyclopentyl and dimethylcyclohexyl;
R4 is hydrogen, alkyl containing 1 to 20 carbon atoms, alkoxy containing 1 to 20 carbon atoms, such as methoxy, ethoxy and propoxy, an ester represented by the formula:

~ ~3~

carboxy, carboxamido, chlorine, bromine, iodine, fluorine, carbamoyl, sulfonic acid, sulfamyl, sulfonylalkyl containing 1 to 3 carbon atoms, such as sulfonylmethyl, sulfonylethyl and sulfon-ylpropyl, ureido, and a carbocyclic group containing 5 to 12 carbon atoms, such as cyclo-pentyl, cyclohexyl and dimethylcyclohexyl; or atoms necessary to complete a naphthyl ring with the ad;oining phenyl ring containing NHSo2R5;
Rs and R5A are individually alkyl containing 1 to 20 carbon atoms, such as methyl, ethyl, propyl, decyl, eicosyl and benzyl, aryl containing 6 to 20 carbon atoms, such as phenyl, naphthyl, halo-phenyl, 2,4,6-triisopropylphenyl, 2,6-di-methyl-phenyl, p-tolyl, 2,4,6-trimethylphenyl and

2,6-diisopropylphenyl;
R6 is hydrogen, alkyl containing 1 to 20 carbon atom8, 8uch a8 methyl, ethyl, propyl, hexyl, decyl, and eicosyl, O

or aryl containing 6 to 20 carbon atom6, such as phenyl, tolyl and trimethylphenyl, or represents, with R7, atoms 6uch as carbon, oxygen, 6ulfur and nitrogen atoms completing a heterocyclic group, including a 5- or 6-member heterocyclic group, such as a pyridino, morpholino or piper-idino group;
R7 is alkyl containing 1 to 20 carbon atoms, 6uch a6 methyl, ethyl, propyl and decyl, carbamoyl, '3~gl carboxamido, or represents, wi~h R6, atoms ~uch as carbon, oxygen, sulfur and nitrogen atomæ
completing a heterocyclic group, including a 5- or 6-member heterocyclic group;
R~ is alkyl containing 1 to 4 carbon atoms, such as methyl, ethyl, propyl and butyl; and R6A i8 alkyl containing 1 to 20 carbon atoms, such as ethyl, octyl and decyl.
The terms "alkyl" and "aryl" herein mean un6ub-stituted alkyl and unsubstituted aryl. The terms "alkyl"
and "aryl" herein also mean ~ubstituted alkyl and substi-tuted aryl wherein the alkyl and aryl are substituted by groups which do not adversely affect the sulfonamidodi-phenylamines or the corresponding sulfonimide dyes accord-ing to the invention. Example~ of suitable substitutedalkyl groups include alkyl contsining a sulfonamido group, such as CH3S02NHCHzCH2-, a carboxamido group, an alkoxy group, such as methoxy or ethoxy, a carboxyl t-COOH), an aryl group, such as a benzyl group, and carbonyl. An alkyl group containing an aryl substituent is also known as an aralkyl group. Examples of suitable substltuted aryl groups include phenyl containing an alkoxy group, such as methoxy and ethoxy, carboxyl, alkyl such as methyl, ethyl, propyl and butyl, and hydroxy. An especially useful substituted aryl group is an alkyl substituted aryl group, such as tolyl, Z,4,6-triisopropyl-phenyl and t-butylphenyl. An alkyl substituted aryl group is also known as an alkaryl group.
Especially useful para-sulfonamidodiphenylamines and corresponding sulfonimide dyes in imaging materials and processes are those which comprise a stabilizer group. The term stabilizer group herein means a group that is substituted on the sulfonamidodiphenylamine to provide increased stability to the sulfonamidodiphenyl-amine and the corresponding sulfonimide dye. A partic-ularly useful stabilizer group is a 2,4,6-triisopropyl-phenyl group represented by the formula:

~ .3æ~

~'\ 0 /-CH
t This group is alternatively herein repre~ented by the formula:

\._.
_ / 0 /-_\

While a 2,4,6-triisopropylphenyl group is a particularly useful stabilizer group, other stabilizer group6 are also useful .
Examples of useful color-forming para-sulfon-amidodiphenylamine dye precursors according to the inven-tion include:
4-Dihexylamino-4'-(2,4,6-trii60propylbenzenesulfona mido) diphenylamine represented by the formula:

C 3 ( ) ~ 0\- -NH--\ 0 \--NHS0 2 --~O~-CH

3~

4-Hexyloxy-3'-methyl-4'-(2,4,6-triisopropylben-zenesulfonamido) diphenylamine represented by the formula:

CH3(CH2)sO--\ 0 /--NH--/ 0 /--NHS02--/ Q /--CH

4-N,N-diethylamino-4'-(2,4,6-triisopropylbenzene-sulfonamido)diphenylamine represented by the formula:

--/ 0 /--NH--\ 0 /--NHSO2--\ 0 /--CH

4-N,N-dihexylamino-2'-methylsulfonyl-4'-~2,4,6-triisopropylbenzenesulfonamido) diphenylamine represented by the formula:

C ( ) ~ 0~--NH-~0~--NHSO2-/0~-CH

l~t;9~1 An especially useful embodiment iB a photographic element comprising a support having thereon, in reactive association, in a gelatino binder: (a) photosensitive silver halide gelatino emulsion; and (b) a color-forming S dye precursor which is imagewise converted upon exposure and processing of the element to a dye by cross-oxidation by means of a cross-oxidizing developing agent wherein the color-forming dye precursor is a para-sulfonamidodiphenyl-amine consisting essentially of 4-dihexylamino-4'-(2,4,6-triisopropylbenzenesulfonamido) diphenylamine.
Another illustrative class of color-forming para-sulfonamidodiphenylamine dye precursor6 that are useful in a photographic material is the class of color-forming para-sulfonamidodiphenylamines represented by the formula:

I o R R' 2 20~~~\~ ~ ~--NH--\ O /-NHSO2RI 4 Rl I Rl 3 wherein:
R9 is in the meta or para position and is an elec-25tron donating substituent selected from ~Rl s \Rl 6 alkoxy containing 1 to 20 carbon atom~, such aR
methoxy, ethoxy, propoxy and hexyloxy, aryloxy containing 6 to 12 carbon atoms, such as phenoxy and naphthoxy, sulfonamido, and carboxamido groups such as acetamido, butyramido, N-methyl-acetamido and n-octylureido;

Rl is in the ortho or meta position and is hydro~en, alkyl containing 1 to 3 carbon atoms, such as methyl, ethyl and propyl, carbamoyl, alkoxy containing 1 to 3 carbon atoms, such as methoxy, ethoxy and propoxy, sulfonylalkyl containing 1 to 3 carbon atoms, such as sulfonylmethyl, sulfonyl-ethyl and sulfonylpropyl, sulfonylaryl containing 6 to 12 carbon atoms, such as sulfonylphenyl and sulfonylmethylphenyl, chlorine, bromine, iodine or fluorine~ or in the meta position is sulfon-amido;
Rll is hydrogen, alkyl containing 1 to 3 carbon atoms, such as methyl, ethyl and propyl, carbamoyl, alkoxy containing 1 to 3 carbon atoms, such as methoxy, ethoxy and propoxy, sulfonyl-alkyl containing 1 to 3 carbon atoms, such as sulfonylmethyl, sulfonylethyl and sulfonylpropyl, sulfonylaryl containing 6 to 12 carbon atoms, such as sulfonylphenyl and sulfonylmethylphenyl, chlorine, bromine, iodine or fluorine;
Rl2 is hydrogen, alkoxy containing 1 to 20 carbon atoms, or carboxamido, such as acetamido, propionamido, pivalamido and ureido;
Rl 3 iS hydrogen, alkoxy containing 1 to 20 carbon atoms, or carboxamido, such as acetamido, propionamido, pivalamido and ureido;
Rl 4 iS alkyl containing 1 to 20 carbon atoms, such as methyl, ethyl, propyl, decyl and eicosyl, aryl containing 6 to 20 carbon atoms, such as phenyl tolyl, 2,4,6-triisopropylphenyl and 2,4,6-trimethylphenyl;
Rl 5 iS hydrogen or alkyl containing 1 to 20 carbon atoms, such as methyl, ethyl, propyl, decyl and eicosyl; and, ~ 1~i9~ ~1 Rl 6 iS hydrogen, alkyl containing l to 20 carbon atoms, such aæ methyl, ethyl, propyl, decyl and eicosyl, or aryl containing 6 to 12 carbon atoms, such as phenyl and tolyl.
Particularly useful compounds are those within the above formula wherein when Rl3 is carboxamido, then Rl2 is carboxamido.
The term "sulfonamido" herein means a substituent group represented by the formula:
-NHS02Rl 7 wherein Rl 7 iS a substituent which does not adver~ely affect the diphenylamine compound or imide dye according to the invention. Rl 7 iS, for example, alkyl containing 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, decyl, and eicosyl, or aryl containing 6 to 20 carbon atoms, æuch as phenyl, tolyl and 2,4,6-triiso-propylphenyl. Examples of such groups include 2,4,6-tri-isopropylsulfonamido, methylsulfonamido and tolyl6ulfon-amido.
Examples of us~ful color-forming para-sulfon-amidodiphenylamine dye precursors within the above formula containing carboxamido groups include:
4-[N-ethyl-N-(~-methanesulfonamidoethyl)amino]-2-methyl-2',5'-dipivalamido-4'-(2,4,6-triisopropylbenzene-sulfonamido) diphenylamine repre6ented by the formula:

il I
/CH3 HNCC(CH3)3 CH3-CH CH3 /N--\ 0 /--NH--\ 0 /--NHS02--~ 0 /--CH
CH3S02NHCH2CH2 t t--(CH3)3CCNH H3C-CH CH3 Il I

;9 4-n-Hexyloxy-2',5'-dipivalamido-4'-(2,4,6-triiso-propylbenzenesulfonamido)diphenylamine repre6ented by the formula:

Il I
HNCC(CH3)3 H3C-CH CH3 1 . .
n-C6H13O-/ ~ ~--NH-/ Q ~- NHSO2--/ O \--CH

C(CH3)3 A further illustrative clas~ of color-forming para-~ulfonamidodiphenylamine dye precur~ors is repre-sented by the formula:

R2~S02 ~ NHCRI9 CH3-CH CH3 -NH--~ O /--NHS02~/ O ~--CH
-- -T T--wherein:
Rl 8 i6 alkyl containing 1 to 20 carbon atoms, such as methyl, ethyl, propyl, decyl and eicosyl, alkoxy containing 1 to 20 carbon atom6, such a6 methoxy, ethoxy and dodecyloxy, or an appropriate amino group, such as N\R2 3 Rl9 is alkyl containing 1 to 20 carbon atoms, such ~æ
methyl, ethyl, propyl, decyl and eico6yl, aryl containing 6 to 12 carbon atoms, such a6 phenyl and tolyl, alkoxy containing 1 to 4 carbon atom6, such as methoxy, ethoxy, and butoxy, aryloxy containing 6 to 12 carbon atoms, such a6 phenoxy and 3,4,5-trimethylphenoxy, or NH-R2 4;
R20 i6 hydrogen or o R2 1 i8 alkyl containing 1 to 12 carbon atom6, such as methyl, ethyl, propyl and dodecyl;
R2 2 i8 hydrogen or alkyl containing 1 to 2~ carbon atoms, such as methyl, ethyl, propyl and decyl;
R2 3 iB hydrogen, alkyl containing 1 to 20 carbon atoms, such as methyl, ethyl, propyl and hexyl, or aryl containing 6 to 12 carbon atoms, such as phenyl and tolyl;
R2 4 iB alkyl containing 1 to 20 carbon atoms, such as methyl, ethyl and decyl, aryl containing 6 to 12 carbon atoms, such as phenyl and tolyl, alkoxy containing 1 to 4 carbon atoms, such as methoxy, ethoxy and butoxy, or aryloxy containing 6 to 12 carbon atoms, such a6 phenoxy and 3,4,5-tri-methylphenoxy;
R2s is alkyl containing 1 to 20 carbon atoms, such as methyl, ethyl, propyl and decyl, aryl containing 6 to 12 carbon atoms, such as phenyl and tolyl, alkoxy containing 1 to 4 carbon atoms, such as methoxy and butoxy, or aryloxy containing 6 to 12 carbon atoms, such as phenoxy and 3,4,5-tri-methylphenoxy.
Examples of suitable color-forming para-sulfon-amidodiphenylamine dye precursors within this formula include:

~ 3 3-Methanesulfonamido-4-methyl-2'-palmitamido-4'-(2,4,6-triisopropylbenzene~ulfonamido)diphenylamine repre-sented by the formula:

Il l NHS02CH3 NHCClsH3l CH3-CH CH3 ! . !_. ! .
H3C--\ 0 /- NH - \ 0 /. NHS02 / Q \--CH

3-Methanesulfonamido-4-methoxy-2'-pivalamido-4'-(2,4,6-triisopropylbenzenesulfonamido) diphenylamine represented by the formula:

Il I
NHS02CH3 NHCC(CH3)3 CH3-CH CH3 CH30--/ 0 \--NH--/ 0 /- NHS02 - / 0 \--CH

The color-forming para-sulfonamidodiphenylamine dye precursors are prepared generally by one of four methods. The first method (Method 1) involves condensa-tion of a phenylenediamine compound or ether-substituted aniline with a sub~tituted halonitrobenzene wherein the nitro group is ortho or para with respect to a halogen atom on the benzene ring, followed by reduction of the nitro group and subsequent sulfonylation of the inter-35 . mediate amine.

The second method (Method 2) involves condensa-tion of a halonitroaniline with 6ulfonyl chloride, followed by condensation with a phenylenediamine or aniline. The resulting intermediate i8 then reduced, S followed by acylation of the intermediate amine to yield a carboxamido-sub6tituted sulfonamidodiphenylamine. The sulfonylation step is avoidable by using a halonitro6ul-fonamidobenzene that condenses directly with the phenyl-enediamine or aniline.
The third method of preparation (Method 3) involves condensation of a 6ubstituted aniline with a sulfonyl chloride, followed by oxidative coupling. Thiæ
oxidative coupling is with a phenylenediamine in the pre6ence of ferricyanide and base to yield a dye that is subsequently reduced, such as by hydrogenation in the presence of a suitable palladium-charcoal catalyst, to form the corresponding leuco form of the compound.
Carboxamido groups are introduced prior to oxidative coupling.
The fourth method of preparation (Method 4) involves a Smlles rearrangement method for those cases in which the direct nucleophilic condensation, such as in Method 1, is not entirely satisfactory.
An illustrative preparation for preparing a compound by Method 1 is the preparation of 4-dihexyl-amino-4'-benzenesulfonamidodiphenylamine. This illustra-tive preparation i8 as follows:
A Rample of N,N-dihexyl-~-phenylenediamine-di-~-eoluenesulfonic acid salt (30.8 grams, 0.05 mole) in dimethylformamide (150 ml) is stirred under nitrogen atmosphere as succes6ive additions of sodium bicarbonate (16.8 grams) and para-fluoronitrobenzene (7.05 grams, 0.05 mole) are made. After stirring overnight at 90 to lOO~C, the reaction mixture is poured into ice water and extracted with ethyl acetate. The extract is washed with water, dr~ed and freed of solvent. The filtrate residue ~ 3 ~ ~ ~

i~ then chromatographed from an appropriate 6ilica gel, using benzene as eluent, to provide 4-dihexylamino-4'-nitrodiphenylamine that is characterized by nuclear magnetic resonance. This nitro intermediate is reduced to the corresponding amine by hydrogenation over palladium-charcoal catalyst in a suitable hydrogenation apparatu6.
The corre~ponding amine is converted to its benzenesulfon-amide derivative by means of benezenesulfonyl chloride.
The resulting color-forming sulfonamidodiphenylamine dye precursor is purified by methods known in the organic synthesi~ art, such a6 by recrystallization from an appro-priate solvent, such as methanol.
Another illustrative preparation is the prepara-tion of 4-diethylamino-4'-benzenesulfonamidodiphenylamine according to Method 1. This method is as follows:
A solution of N,N-dimethyl-~-phenylenediamine (16.4 gramR, 0.18 mole) and ~-fluoronitrobenzene (14.1 grams, 0.10 mole) in 200 ml of dimethylformamide i~
stirred overnight with sodium bicarbonate (16.8 grams, 0.20 mole) at 85 to 90~C under a nitrogen atmosphere.
This reaction mixture i5 poured into ice water and extracted with ethyl acetate. Evaporation of the 601vent provides 4-diethylamino-4'-nitrodiphenylamine which is recrystallized from ethanol to provide red violet leaflets having a melting point of 139 to 141~C. This nitro inter-mediate (5.7 grams) in tetrahydrofuran (100 ml) is hydro-genated over a palladium-charcoal catalyst (1.2 gram6) in a 6uitable hydrogenation apparatus (40 pBi hydrogen pressure). The corresponding amine is converted to the desired benezenesulfonamide compound by means of reaction with benzenesulfonyl chloride. The product is recry6tal-lized from methanol to provide a gray 601id having a melt-ing point of 145 to 146C.
A further preparation that illu6trate6 the Method 1 is the preparation of 4-methoxy-4'-benzene6ulfon-amidodiphenylamine. Thi6 preparation i6 a6 follow6:

A solution of ~-anisidine (49.2 grams, 0.4 mole) and ~-fluoronitrobenzene (28.2 grams, 0.2 mole) in dimethylsulfoxide was stirred for 24 hours on a steam bath. The resulting red reaction mixture was poured into water (500 ml) and extracted with ethyl acetate. The extract wa6 washed with water, dried over magnesium sulfate and evaporated to dryness. The residue was slurried in ligroin and filtered to provide a brick red solid. This was di6601ved in ethyl acetate, warmed with charcoal, and the filtrate filtered. The filtrate was evaporated and the re6idue recrystallized from ethyl acetate to provide 4-methoxy-4'-nitrodiphenylamine having a melting point of 149 to 151C. A solution of the resulting nitro compound (24.4 grams, 0.1 mole) in ethyl acetate (250 ml) is converted to the corresponding amine by hydrogenation over a palladium-charcoal catalyst at 60 psi hydrogen pressure. After filtration, the solvent i6 removed under vacuum and the light purple solid dis601ved in pyridine (150 ml). This i6 reacted with benzenesul-fonyl chloride (17.7 grams, 0.1 mole) by stirring for 3hours under a nitrogen atmosphere at 25C. After dilution with water (500 ml), the organic phase is washed with water, dried over magne6ium sulfate and freed of solvent.
The red oil resulting is dissolved in chloroform and filtered through an appropriate filtering composition.
The filtrate residue is purified, 6uch as by recrystalli-zation three time6 from chloroform-ligroin, to provide a desired white powder having a melting point of 133 to 135~C.
A further example of a method of preparing a compound according to Method 1 is the preparation of 4-dihexylamino-4'-(2,4,6-triisopropylbenzenesulfonamido)-diphenylamine. This method is carried out as follows:
A sample (5.24 grams, 0.013 mole) of the compound 4-dihexylamino-4'-nitrodiphenylamine is reduced by hydro-genation in a suitable hydrogenation apparatus in try tetrahydrofuran (100 ml) containing palladium-charcoal catalyst (1.2 grams). The resulting filtrate i6 freed of solvent under vacuum, and the resulting 4'-amino deriva-tive di6solved in dry pyridine (25 ml) and reacted at 5C
with 2,4,6-triisopropylbenzenesulfonyl chloride (4.5 gram6, 0.015 mole). After stirring for three hours at 25C, the reaction mixture is poured into chloroform (200 ml) and ice water. The organic phase iB waehed five times with water, dried, concentrated to about 50 ml volume and chromatographed on an appropriate silica gel. The chloro-form eluate i6 freed of solvent, and the filtrate residue recrystallized from methanol. The crystalline product i6 purified by washing with an appropriate 601vent, 6uch as a methanol-water mixture, and dried to provide the de6ired product having a melting point of 127 to 129C.
An illustrative preparation according to Method 2 i6 the preparation of 4-[N-ethyl-N-(~-methane6ulfon-amidoethyl)amino]-2-methyl-2'-octanamido-4'-(2,4,6-tri-isopropylbenzene6ulfonamido)diphenylamine. This prepara-tlon is as follows:
The following preparation of a desired inter-mediate i6 carried out:

F S02Cl F
i/ + \i/o~ \ Pyridine i/O\i~
\ . / . I \
NH2 / \ NHS02--~ O /---\
_ --A 601ution of 4~fluoro-3-nitroaniline (15.6 gram6, 0.1 mole) in pyridine (400 ml) is 6tirred at room temperature and 2,4,6-triisopropylbenzenesulfonyl chloride (30.2 grams, 0.1 mole) is added in bulk. The resulting j,t~

æolution is 6toppered tightly and 6tirred at room tempera-ture (about 20C) overnight (about 18 hour6). The reac-tion mixture i6 then poured over an ice hydrochloric acid (aqueou6) mixture (500 gram6 of ice and 500 ml of concen-trated aqueou6 hydrogen chloride). An oily solidseparates and i6 removed by filtration. Repeated recry6-tallization from methanol and water provides light golden cry6tal6 having a melting point of 151 to 152C. The desired intermediate product i6 identified by methods known in the chemical analytical art, such as by elemental analy6is.
The following reaction is then carried out:

F C2HsNCH2CH2NHSO2CH3 1S I o ,/NO2 i CH3 -J~
i~0,i /i~

iOi ~ \CH 3 NH
/ \ /NO2 i,O l~
NHSO2 \ O ,---, This reaction iB carried out as follow6:
42.2 grams ~0.1 mole) of 2-fluoro-5-(2,4,6-tri-isopropylbenzenesulfonamido)nitrobenzene in 275 ml of l-picoline is stirred at reflux under nitrogen for three days with 40.6 grams (0.15 mole) of 4-amino-3-methyl-N-ethyl-N-(~-methanesulfonamidoethyl) aniline (in the form of a free base). The reaction solution is allowed to cool to room temperature and i6 poured over an ice water mixture (1.5 liters). The mixture is allowed to stand until a red-brown oil separates. The aqueous layer is decanted from the oil. The oil is di~solved in CH2Cl2 (about 400 ml). The methylene chloride solution is then washed with vigorous agitation with 5 percent hydrochloric acid (50 ml concentrated HCl plus 380.5 ml of water) four times (500 ml), then with 5 percent NaHCO3 (four times, 500 ml) and finally with 500 ml of water (four times). The methylene chloride layer is dried by means of sodium sulfate and then swirled with a filtering composition (Florisil) to remove a purple residue. Evaporation of the solvent provides a red oil which is taken up in about 150 ml of boiling methsnol.
The methanol solution is allowed to cool to room tempera-ture (about 20C) overnight. A yellow-orange crystalline product having a melting point of 164 to 166C is produced. Thin layer chromatography on silica gel-glass and recrystallization from ethyl acetate provide~ the desired pure product which is identified by methods known in the chemical analytical art, such as by elemental analysis.

The following reaction iB then carried out:

C2HsNCH2CH2NHSO2CH3 C2HsNCH2CH2NHSO2CH3 i/O\i i O`i I \CH3 \T/ ~ H3 NH NH
/ \ /N02 H2 ~ H 2 i O i Pd/C i O I + C7Hl5CCl+Ca(OH)2 \./ THF
NH NH

_J ' ,!_ i~o,i C2HsNCH2CH2NHSO2CH3 i`O i ~/ \CH3 ~ !NH o i o i-NHCC7Hl 5 -n \./
NH

! ! !
i O i ~ /
/ \

6.7 grams (0.01 mole) of the nitro compound in 35 about 75 ml of tetrahydrofuran is reduced over 10 percent palladium on charcosl at 40 pounds psi in a hydrogen - .

(3 atmosphere until the hydrogen uptake ceases (within about 2.5 hours). The reaction mixture is blanketed with nitro-gen and removed from the hydrogen atmosphere. No attempt i~ made to remove the catalyst at this point. The calcium S hydroxide (0.41 grams, 0.055 mole), used as an HCl 6cavenger, i~ added in bulk to the reaction mixture.
Next, octanoyl chloride (1.8 grams, 0.011 mole) i6 added in bulk to the reduction mixture. The resulting reaction mixture is stoppered tightly and allowed to be fitirred at room temperature (about 21C) for three hours. No exothermic properties are observed. The catalyst and calcium salts are removed by filtration. The solvent is evaporated to yield a brown oil. The oil iB taken up in boiling ether. The oil is dissolved and a precipitate begins to form. Filtering provides a colorless solid with a strong octanoyl chloride odor. The solid is re-6us-pended in boiling ether (100 ml), then filtered and vacuum dried at room temperature (about 21C) to yield 6.0 grams of a very faintly yellow-tinted 601id having a melting point of 98 to 100C. Thin layer chromatogrsphy with silica gel on glass shows one component with a variety of solvents (ethyl acetate, methylene chloride, acetone and acetonitrile). The compound i8 further characterized by methods known in the chemical anslytical art, such as infrared analysis, nuclear magnetic resonance, mass spectrography and elemental analysi~. Oxidation with aqueous potassium ferricyanide yield6 a green dye.
Another illustrative preparation according to Method 2 is the preparation of 3-methanesulfonamido-2'-octanamido-4'-(2,4,6-triisopropylbenzenesulfonamido)di-phenylamine. This preparation is carried out a8 follows:

~ ~ ~ 9~ 9 NHS02CH3 N02 ~!
/ 0 \--NH2+ F--/ 0 /--NHS02--\ 0 / - \ (heat) NHS02CH3 N02 _!
! . ! . \. .
. ~ Q, . -NH- . ~ Q, . -NHso 2 - ~ Q, - ~

H2 l Pd/C

n-C7Hl5CCl THF

NHS02CH 3 NHCC7Hs 1 . 1 . \. .
/O ~--NH- ~0 ~--NHSO2- ,Q ,-- , .

A mixture of meta-methanesulfonamidoaniline (1.86 gram6, 0.01 mole) and 2-fluoro-5-(2,4,6-triisopropylben-zenesulfonamido)nitrobenzene (4.2g grams, 0.01 mole) in 25 ml of a-picoline i8 refluxed for 29 hours. Thi6 mixture is poured into a mixture of 100 gram6 of ice and 100 ml of lN hydrochloric acid, and the 6eparated oil extracted with 100 ml of ethyl acetate. The extract i8 washed with water, dried by means of anhydrou6 60dium 8ul fate, and freed of solvent. The re6ulting oil is chrom~tographed on Woelm'6 6ilica gel using methylene chloride as the eluent. The column held material is eluted w~th 1:1 parts by volume methylene chlorideethyl acetate, freed of 601vent, and character$zed as 3-methanesulfonamido-2'-nitro-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenyl-emine. Thi6 compound is identified by, for example,nuclear magnetic re60nance. 2.9 grams of the oily product i6 di6601ved in 150 ml of 1:1 methanoltetrahydrofuran and reduced by hydrogen over a palladium-charcoal catalyst.
After removal of catalyst and 601vent, the 601id product is characterized, 6uch as by nuclear magnetic resonance, a6 3-methane6ulfonamido-2'-amino-4'-(2,4,6-trii60propyl-benzenesulfonamido)diphenylamine. 1.5 gram6 (0.003 mole) of this compound are then dis601ved in 20 ml of dry pyri-dine and reacted at 5uC with 6.5 gram6 of octanoyl chloride in 20 ml of dry tetrahydrofuran. After 18 hours at 25C, the reaction mixture i6 poured into ice and 20 ml of concentrated hydrochloric acid, and the separated oil extracted with methylene chloride. The extract is washed with 10 percent 60dium bicarbonate in water, tried, and freed of solvent. The resulting oil i6 purified by high pressure liquid chromatography to yield 1.3 grams of a glass that is recrystallized from etherhexane to give white leaflets. The desired product is characterized, such a6 by nuclear magnetic resonance, and ha6 a melting point of 146 to 148~C. A sample of thi6 compound i6 oxidized in butyl acetate with potassium ferricyanide in pH 10 buffer, yielding a yellow dye possessing a maximum absorption of 429 nm.
A preparation which illustrates preparation of a compound by Method 3 is the preparation of 4-~N-ethyl-N-(~-methanesulfonamidoethyl)amino]-2-methyl-2',5'-di-pivalamido-4'-(2,4,6-trii60propyl-benzenesulfonamido)di-phenylamine. This preparation according to Method 3 is as follows:

~ 3~ ~ 1 NH2 S02Cl 5l 0 1 + I 0 i Pyridine \j/ \./

101, /NHS02 \ 0 /---!,0,! ./
.

\ -NHS02 -~Q,-- ~

20i 0 i 2 ~./
N0z 15.3 grams (0.1 mole) of the 4-nitro-o-phenylene-diamine are dissolved in 200 ml of pyridine snd the solu-tion cooled in an ice bath. After one hour, a solution of 31.2 grams (0.1 mole) of 2,4,6-triisopropylbenzenesulfonyl chloride in 100 ml of tetrahydrofuran are added to the amine solution. The resulting mixture is stirred over-night at room temperature and is next poured over ice (400 grams) plus 300 ml of glacial acetic acid. An oil sepa-rates and solidifies upon standing. The crude solid is removed by filtration. The resulting solid is recrystal-lized twice from methanol-water to yield a yellow crystal-line solid (27.6 grams) having a melting point of 187 to 3~9 191C. Thin layer chromatography on 6ilica gel (hexane:-ethyl acetate; 3:2 by volume) indlcates a major ~nd minor component mixture, a~ indicated by the 6tructure~ above.
The de6ired intermediate i6 identified by elemental S analysi6-The following reaction is then carried out:

NH2 \._. NHSO2- ~ O /--~/
~NHS02- ~Ø~ - \ I ~ \ 11 N(CH3)2 NHCC(CH3)3 \ /

i/0 i TN~ i i-NHso2 \- /

21.0 gram6 (0.05 mole) of the crude amine mixture are dis601ved in 250 ml of tetrahydrofuran and 6.6 gram~
(0.05 mole) of the acid scavenger, N,N-dimethylaniline, are added in bulk. To this 601ution is added, dropwise in 15 minutes, 6.6 grams (0.05 mole) of the pivaloyl chloride. After stirring at room temperature overnight (at about 20UC), thin layer chromatography indicates an incomplete reaction. Thu6, an additional 5 millimoles of acid chloride and base are added, and the mixture is stirred overnight again. The mixture is diluted with methanol (100 ml), then quenched in one liter of water.
An oil separates and solidifies. The solid obtained is recry6tallized from methanol-water to provide 24.6 grams of 601id having a melting point of 160 to 162~C. Thi6 material contain6 a small amount (less than 2 percent) of the following i~omeric compound:

!
0 lNHS02 \ 0 ~.0~

The de6ired product i6 identified by elemental analy~is.
The following reaction i6 then carried out:

NHCC(CH 3 ) 3 _ / 10% Pd/C

NHCC(CH 3 ) 3 o i/0 i- NHS02--/ 0 ~---/ + (CH3)3CCCl +

1~;9t~

N(CH3)3 NHCC(cH3)3_ i/O\i ~ i\O i~lS2 ~.0/--~

NHCC(CH3)3 10.1 grams (0.02 mole) of the nitro compound is reduced 8t room temperature in 125 ml of tetrahydrofuran over 10 percent palladium on charcoal at 40 psi hydrogen preæ~ure until hydrogen uptake cea6eæ (1.5 hours). The 15 catalyst is then removed by filtration. 2.5 grams (0.021 mole) of the acid scavenger, N,N-dimethylaniline, ig added in bulk; followed by bulk addition of 2.5 grams (0.021 mole) of pivaloyl chloride. The mixture iæ stoppered and stirred overnight at room temperature. Solvent is then 20 evsporated to yield an amber oil. The oil is crystsllized irom ethanol-water to yield 10.2 grams of colorle~s solid having a melting point of 196C. This desired inter-mediate iB identified, such as by elemental analy6is.
The structure of the intermediate is confirmed by 25 making the same compound by an alternate synthetic route:

NH2 0 NHCC(CH3) 2 ! ~02 ll ! N02 30 t/O j (CH3)3CCCl t/O\t' H2 Et3N \./ Pd/C, THF
NH2 NHCC(CH3)3 O

3~1 \ NHCC(CH3) /o i - NHS0 i \ /---\ NHCC(CH3)3 /---\ O /--S02Cl 0 \._ CH3 11 NHS02- ~Q `- ~ C2Hs~NCH2CH2NHS02CH3 +H i\/l 0 CH \I/ \CH
NHC + CH 3 NH2 (A) (B) i O i --' '1' '--+ K3Fe(CN)6 ~ K2C03 ~ S02 0 ~ HC + CH3 CH31l i1 i1 CH3 CH3 ¦ CNH/ ~i1/

i /0~ i /
\./
C2HsNCH2CH2NHS02CH3 ~ 6 9 ~

10.5 grams (0.02 mole) of the coupler (A) and 5.4 grams (0.02 mole) of the reducing agent (B) are dissolved in 200 ml of tetrahydrofuran. With rapid stirring, the aqueous potassium carbonate 601ution (11.0 grams, 0.08 mole in 50 ml of water) is added to the tetrahydrofuran solution of (A) and (B). Finally, the aqueous potassium ferricyanide solution (26.3 grams, 0.08 mole in 150 ml of water) is added dropwise to the above solution. A green dye began to form during the addition. Following the addition, the reaction mixture is stirred for 45 minutes and then is quenched in one liter of water. The dye is extracted into methylene chloride, washed well with water, and dried by means of sodlum sulfate. It is then evapo-rated to yield a green oil. The oil is chromatographed in Woelm'~ silica gel with an ethyl acetate-hexane (8:2 parts by volume) eluent to yield 12.0 grams of green dye as a 8reen glass (maximum absorption in butyl acetate of 672 nm). The gla6s is used directly without further purification.
The following reaction is carried out:

/- I \ H2 S02 0 10% Pd/C, U ~ C ¦ CH3 Il / \ / CH3 30CH3 ¦ CNH il /~ /CH3 ~0-1 \./
C2HsNCH2CH2NHSOzCH3 ;'3ti~

i'O`I
s /'' 't ~
S02 o NHC ~ H 3 Il / \O/ CH3 CH3 ¦ CNH t ,!, /CH3 \/-C2HsNCH2CH2NHS02CH3 The glass obtained above i~ dissolved in tetra-hytrofuran and reduced over 10 percent palladium on char-coal at room temperature (sbout 20~C) and 40 p8i hydrogenpressure until hytrogen uptake cea6es (about 5 minutes).
The catalyst is removed by filtration and the solvent i6 evaporated at reduced pressure to yield a light blue oil.
The oil is recrystallized from ether-hexane (2:5:1 parts by volume) to yield 8 grams of colorless solid having a melting point of 166 to 168C. The desired product i~
identified, such as by elemental analysis.
A further preparation illustrating preparation of a compound according to Method 3 is the preparation of 4-diethylamino-2-methyl-2'-methoxy-5'-pivalamido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine. This method is carried out as follows:

/l~ /NHCC(C~3)3 /J\ /NHcc(cH3)3 CH30 ~-/ 10% Pd/C CH30/ ~-/

$02Cl _J J l_ l \i/o\i/ Pyridine I O~i / \ S02 o NH "
/o\ /NHCC(CH3)3 CH30/ \-/

13.3 grams (O.OS mole) of the nitro compound in 150 ml of tetrahydrofuran is reduced at 40 pBi hydrogen lS pressure over 10 percent palladium on charcoal at room temperature (about 20C) until hydrogen uptake ceases (1.5 hours). The catalyst is removed by filtration, and the solvent by evaporation, to yield a colorless crystalline solid which is the desired amine. This amine is used directly. The colorle~s solid is dissolved in 250 ml of pyridine, and the resulting solution cooled in an ice bath. Next, triisopropylbenzenesulfonyl chloride (15.1 grams, O.OS mole) i8 added portion-wise to yield a bright-yellow solution which is allowed to warm to room temperature and is stirred overnight (about 18 hours).
The mixture is poured into a mixture of ice (400 grams) and concentrated hydrogen chloride (300 ml) to produce a colorless solid. Filtration and recrystallizAtion from acetonitrile produce~ 18.6 grams of a colorless crystal-line solid having a melting point of 177 to 178~C. Thisdesired intermediate is identified, such as by elemental analysis.

~6~91 Then the following reaction is carried out:

CH30 NHSO2 - '\ 0 /-~-\ N(C2Hs)2 CH3~cNH~i/o\i ~ + i O i +

\-/ \OCH3 \t/ \CH
NH2 HCl K3Fe(CN)s+K2CO3 '/Oi -t !I~ /NHC +
I.l Ii H2 CH30/ \iI/ 10% Pd/C
N THF

i\o/i N(C2Hs)2 ti 91 i O 1 - T i t -NH 1l !, ,NHC +

o ,! O !
NH
,CH3 iOi \./
N(C2Hs)2 The designation l herein means - C - CH3 The following solution~ are prepared:
Solution A: 10.0 grams (0.02 mole) of the start-ing intermediate in 150 ml of tetrahydrofursn;
Solution B: 4.2 grams (0.02 mole) of N,N-di-ethyl-3-methyl-~-phenylenediamine hydrochloride in 60 ml of water;
Solution C: 26.3 gram6 (0.08 mole) of potassium ferricyanide in 125 ml of water; and, Solution D: 11.0 gram6 (0.08 mole) of potassium carbonate in 25 ml of water.
Addition of Solution A and then Solution B to Solution D produces no color change. Next, Solution C i6 added to the previous mixture dropwise in 15 minutes. A

~ 3~ 9 green dye is formed. The mixture is stirred for two hours following the addition and then diluted to one liter with water. The dye is extracted into methylene chloride, washed well with water, dried by means of sodium sulfate and evaporated under reduced pressure to yield the crude green dye as a thick oil (approximately 15 grams). The crude dye is dissolved in tetrahydrofuran and reduced over 10 percent palladium on charcoal at 40 psi hydrogen pressure, at room temperature ~about 20C), until hydrogen uptake ceases (30 minutes). Filtration provides a brown-magenta solution. Solvent i6 evaporated and replaced with methylene chloride (about 300 ml). The magenta-brown solution is 61urried with a filtering composition (Florisil) (10 grams) and filtered to yield a pale green solution. The solvent is evaporated to yield a crude pale green solid. Recrystallization from methanol-water fails to remove the trace of dye present. The sample i6 repeatedly recrystallized from ether- hexane until constant melting point i6 reached. The melting point of the desired product is 201 to 202UC.
The color-forming para-sulfonamidodiphenylamine dye precursor~ and their corresponding sulfonimide dyes are pre6ent in a photographic material and process accord-ing to the invention in their ~alt form or non-salt form.
The color-forming sulfona~idodiphenylamine dye precursors and their corresponding dyes herein include either of the appropriate forms. Examples of suitable salt6 of the color-forming para-sulfonamidodiphenylamine dye precursor6 include para-toluenesulfonate, 1,5-naphthalenedisulfonate and benzenesulfonate salts.
The color-forming para-sulfonamidodiphenylamine dye precursors are useful in a photographic material and process according to the invention in a range of concen-trations. Selection of an optimum concentration of color-forming para-sulfonamidodiphenylamine dye precursor or combination of 6uch dye precursor6 depends upon the desired image, the particular photographic material, processing steps and conditions, other components in the photographic material, and the particular para-sulfon-amidodiphenylamine. A useful concentration of para-sul-fonamidodiphenylamine is generally within the range ofabout 0.1 to about 0.6 mole of para-6ulfonamidodiphenyl-amine per mole of photosensitive silver halide in the photographic material. An especially useful concentration of para-sulfonamidodiphenylamine is within the range of about 0.1 to about 0.2 mole of para-sulfonamidodiphenyl-amine per mole of silver halide in the photographic material. In a photographic element, a useful concentra-tion of color-forming para-sulfonamidodiphenylamine dye precursor is within the range of about 0.5 to about 22 mg Of color-forming para-sulfonamidodiphenylamine dye precur-sor per square decimeter of support, such as a concentra-tion within the range of about S to about 11 mg per square decimeter of support.
The hue of the dye produced from the color-form-ing para-sulfonamidodiphenylamine dye precursor will vary, depending upon such factors as the particular groups on the color-forming para-sulfonamidodiphenylamine dye precursor, processing conditions, other components in the photographic material such as disper6ion solvent6, and whether a combination of dyes is present in the photogra-phic material or not. The color-forming para-sulfonamido-diphenylamine dye precursor in the photographic material is preferably colorless prior to exposure and processing.
Some of the suitable color-forming para-sulfonamidodi-phenylamine dye precursor~ have a slight color, such as aslight yellow color, in the photographic material. This slight color is not considered unacceptable.
The term "colorless" herein means that the color-forming para-sulfonamidodiphenylamine dye precursor in the photographic material does not absorb radiation to an unde6ired degree in the visible region of the electro-magnetic 6pectrum. In some photographic materials, the color-forming para-sulfonamidodiphenylamine dye precursor absorbs radi~tion in certain areas of the electromagnetic ~pectrum which do not adversely affect the desired properties or the desired image formed upon proces6ing.
The color-forming para-sulfonamidodiphenylamine dye precursor generally absorbs electromagnetic radiation outside the visible region of the electromagnetic spectrum before imagewise expo6ure and proces6ing of the photogra-phic material. The nature of the absorption and degree ofabsorption of the color-forming pars-sulfonamidodiphenyl-amine dye precursor depend6 upon the nature, for the mo6t part, of the substituent group~ on the para-sulfonamidodi-phenylamine.
The photographic materials according to the invention comprise a photosensitive component which consists essentially of photographic silver halide.
Examples of useful photographic silver halides are silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide, silver iodide and mixtures thereof.
The photographic silver halide is generally present in the photographic material in the form of an emulsion which is a dispersion of the photographic silver halide in a suitable binder. The photographic silver halide is present in a range of grain sizes from fine grain to coarse grain. A compo6ition containing the photographic silver halide is prepared by any of the well known procedures in the photographic art, such as described in Research Disclosure, December 1978, Item No. 17643.
The photographic material according to the inven-tion contains addenda commonly found to be useful in silver halide photographic materials. These addenda include chemical 6ensitizers, brighteners, antifoggants, emul6ion stabilizers, light absorbing and scattering materials, hardener6, coating aid6, pla6ticizer6, lubri-cants, antistatic materials, matting agents, and develop-ment modifiers, as described in esearch Disclosure, December 1978, Item No. 17643.
The photographic silver halide is generally spectrally senæitized by means of spectral sensitizing dyes, a6 described in, for example, Research Disclosure, December 1978, Item No. 17643. Useful spectrsl sensitiz-ing dyes in photographic materials according to the inven-tion include such dyes as polymethine dyes which include the cyanines, merocyanines, complex cyanines and mero-cyanines (including tri, tetra and polynuclear cyanines and merocyanines), as well as oxonols, hemioxonols, styryls, merostyryls and streptocyanines. Combinations of spectral sensitizing dyes are also useful in photographic materials according to the invention.
The photographic silver halide is useful in A
range of concentrations in a photographic material sccord-ing to the invention. An optimum concentration of photo-graphic silver halide depends upon such factors as the de8ired image, processing conditions, particular sulfon-amidodiphenylamine dye precursor, other components of the photographic material and particular photographic silver halide. A useful concentration of photographic 6ilver halide in the photographic material ~ccording to the invention is generally within the range of about 2 to about 7 moles of photographic silver halide per mole of color-forming sulfonamidodiphenylamine dye precursor in the photographic material. The coverage of photographic silver halide is less than otherwise might be useful, due to the enhancing properties of the dye produced upon processing of the photographic material according to the invention.
The color-forming para-sulfonamidodiphenylamine dye precurBor iB in any suitable location in a photogra-phic material according to the invention which produces the desired dye upon processing. The color-forming para-sulfonamidodiphenylamine dye precursor is, if desired, in a layer contiguous to the layer comprising the photosensi-tive ~ilver halide. The term "in reactive association"
herein means that the photo~ensitive silver halide and the color-forming sulfonamidodiphenylamine dye precursor are in a location with respect to each other which enable~ the photographic material according to the invention upon processing to produce a desired dye image and a desired silver image.
Many developing agent6 are useful for developing an image in a photographic material according to the invention. Any ~ilver halide developing agent is useful according to the invention, provided it comprise6 a cross-oxidizing developing agent which will cross-oxidize with the color-forming para-sulfonamidodiphenylamine dye precursor. Such a silver halide developer, called herein a cros6-oxidizing developing agent, becomes oxidized during development by reducing exposed silver halide to silver metal. The oxidized developer then cross-oxidizes the color-forming para-sulfonamidodiphenylamine dye precursor to form the deslred dye.
A cross-oxidizing developing agent (COD) enables the color-forming para-sulfonamidodiphenylamine dye precursor to become oxidized without the color-forming para-sulfonamidodiphenylamine dye precursor itself developing ~ilver. The color-forming sulfonamidodiphenyl-amine dye precursor is viewed alternatively as an electron transfer agent which shuttles electrons between the developing silver halide and the para-sulfonamidodiphenyl-amine dye precursor.
The color-forming para-sulfonamidodiphenylamine dye precursor is frequently immobilized in an oil phase in the photographic material. This enables the dye precursor to be dispersed satisfactorily. Alternatively, the color-forming para-sulfonamidodiphenylamine dye precursor is dispersed in a dispersion solvent to produce a desired photographic material. Coupler solvent~ known in the photographic art are useful for aiding di~persion of the color-forming para-sulfonamidodiphenylamine dye precur-sor. Examples of useful coupler solvents include ~-n-butylacetanilide, diethyl lauramide, di-n-butyl phthalate and 2,4-di-tertiaryamylphenol. The color-form-ing para-sulfonamidodiphenylamine dye precursor is also usefully loaded into a latex or a non-solvent dispersion is prepared, if desired.
The requirementæ for a cro6s-oxidizing developing agents generally are: (a) the developing agent must have sufficient electrochemical potential under the conditions of use to develop exposed silver halide, (b) in its oxidized form, the developing agent must be of such electrochemical potential as to oxidize the color-forming para-sulfonamidodiphenylamine dye precursor, and (c) in its oxidized form, the developing agent must be stable to decomposition by other chemical reactions for a sufficient period to undergo the redox reaction with the color-form-ing para-sulfonamidodiphenylamine dye precursor. Whether a developing agent is a cross-oxidizing developing agent or not depend~ upon whether the oxidized form is sufficiently stable and the oxidizing potential is such that an effective transferral of electrons occurs through whatever phase barriers exist during cross-oxidizing development. Whether a particular developing agent meets these requirements depends upon the conditions under which development occurs. Other fsctors influence whether a particular developing agent is a cross-oxidizing developer, including the pH of the developing composition, the temperature of the development process and the length of development time. Examples of developing agents which are useful as cross-oxidizing developing agents include 3-pyrazolidone developers, such as 1-phenyl-3-pyrazoli-done, l-phenyl-4,4-dimethyl-3-pyrazolidone and 4-hydroxy-methyl-4-methyl-1-phenyl-3-pyrazolidone. Such cross-oxidizing developing agents are described in, for example, U.S. Patent 3,938,995. Combinations of non-cross-oxidizing developing agents and cros~-oxidizing developing agent6 are useful, provided a minor proportion of the non-cros~-oxidizing developing agent i6 pre6ent, 6uch as less than about 10 percent of the total combina-~ion is non-cro6s-oxidizing developing agent. Examples of combinations of a non-cross-oxidizing developing agent and a cross-oxidizing developing agent include 4-hydroxy-methyl-4-methyl-1-phenyl-3-pyrazolidone with a minor proportion of at least one of the following non-cross-oxidizing developing agent~:ascorbic acid, hydroquinoneand pyrimidine. Selection of an optimum cross-oxidizing silver halide developing agent or developing agent combi-nation will depend upon such factors as the desired image, the particular photosensitive silver halide, processing conditions, and the particular color-forming para-sulfon-amidodiphenylamine dye precursor.
A silver halide developing agent or silver halide developing agent combination i8 incorporated in the photo-graphic material according to the invention, if desired.
Generally, the silver halide developing agent i8 mo6t useful in a processing solution in which the photographic material according to the invention i6 processed after exposure .
The developing agent is useful in a range of concentration in the photographic material or in a proces~ing compo~ition in which the photographic material according to the invention is proce6sed. A concentration of developing agent in the photographic material is generally within the range of about 0.01 to about 1.0 mole of developing agent per mole of color-forming para-sulfon-amidodiphenylamine dye precursor in the photographic material. A useful concentration of developing agent in a process~ng solution for proces6ing a photographic material containing a color-forming para-sulfonamidodiphenylamine dy~ precursor is within the range of about 0.5 to about 2 grams of developing agent per liter of processing solution 3~:i91 The term "developing agent" herein includes compound~ which are developing agents or developing agent precursors. That i6, those compound~ are included which are not developing agent~ in the photographic material until a condition occurs, such a~ contact with A suitable activator for the photographic material.
The tone of the silver image and dye image produced in a photographic material according to the invention will vary, depending upon such factors a~ the silver morphology of the developed silver image, the covering power of the 6ilver materials, the particular dye formed, the particular developing agent, processing condi-tions, and other components in the photographic material.
In photographic materials according to the invention that provide a brown silver image, a dye produced iR especially useful which i~ complementary in hue to the silver image.
A combination of dyes and a ~ilver image that produce a neutral-appearing image are generally most useful.
The photographic materials according to the invention comprise a varlety of binders alone or in combi-nation. The binders include both naturally occurring substances, such as proteins, for example, gelatin, gelatin derivatives, cellulose derivativeR, polysaccha-rides, such as dextran, and gum arabic; but also include synthetic polymeric materials, such as water-soluble poly-vinyl compounds, like poly(vinylpyrrolidone) and acryl-amide polymer~. Examples of useful binders include tho6e de~cribed in, for instance, Research DiscloRure, December 1978, Item No. 17643.
The photographic elements according to the inven-tion generally contain an overcoat layer, and/or inter-layer, and/or ~ubbing layer to provide de~ired properties. The overcoat layer, for example, increases resi6tance to abrasion and other markings on the element.
The overcoat layer, interlayer or Rubbing layer contain, alone or in combination, the described binders.

i..~ 3~1 A photographic element according to the invention comprises a variety of ~upports. Useful supports include those that are resistant to adver6e changes in structure due to proces6ing conditions and which do not adversely affect the desired sen6itometric properties of the photo-graphic materials. Examples of useful supports include cellulose ester, poly(vinylacetal), poly(ethylene tere-phthalate) and polycarbonate films, as well as related films and resinous materials. Glass, paper and metal supports are also useful. A flexible support is generally most useful.
Photographic materials according to the invention are generally coated on a suitable support by procedures known in the photographic art. Such procedures include, for example, immersion or dip coating, roller coating, reversal roll coating, airknife coating, doctor blade coating, spray coating, extrusion coating, bead coating, stretch flow coating and curtain coating.
Photographic elements according to the invention are imagewise exposed by means of vsrious forms of energy to produce a developable image. Such orms of energy include those to which the photo6ensitive 8ilver halide is sensitive, and encompass ultraviolet, visible and infrared regions of the electromagnetic 6pectrum, as well as electron beam and beta radiation, gamma ray, X-ray, alpha particle, neutron radiation and other forms of corpuscular wave-like radiant energy in either coherent or non-coherent forms. Lasers are useful, for example.
Exposures are monochromatic, orthochromatic or panchro-matic, depending on the spectral sensitization of thephotosensitive silver halide. Imagewise exposure is generslly for a sufficient time and intensity to produce a developable latent image in the photographic material.
A photographic element according to the invention is processed in (a) a process which produces a positive dye image, (b) in a process which produces a negative dye image and negative silver image, (c) in a process which produces a negative dye image, or (d) in a process which processes a po~itive dye image and a positive silver image. The light-sensitive silver halide in the photogra-phic material according to the invention i~ processedfollowing exposure to form a visible image. This is done, for example, by associating the silver halide at one stage of the process with an aqueous alkaline medium in the presence of a cross-oxidizing developing agent contained in the medium and/or in the photographic material.
To produce a positive dye image, also known as a rever~al dye image, according to the invention, it is generally desirable to process the exposed photographic material by means of a non-cros~-oxidizing developing composition as a first development step. During this step, the exposed silver halide is reduced to elemental silver by the non-cross-oxitizing developing composition.
The non-cross-oxidizing developing composition does not, when oxidized, oxidize the color-forming para-sulfonamido-diphenylamine dye precursor to its corresponding dye.
The non-cross-oxidizing developer composition useful in this step 18 generally an alkaline solution, preferably an aqueous solution comprising a non-cross-oxidizing developing agent. Non-cross-oxidizing develop-ing agents are known in the photographic art and includemany silver halide developing agents which will reduce exposed photosensitive silver halide to silver, but will not oxidize the color-forming para-sulfonamidodiphenyl-amine dye precursor to a corresponding dye. Examples of useful non-cross-oxidizing developing agents are described in, for example, Research Disclosure, December 1978, Item No. 17643. Useful non-cross-oxidizing developers include developer compositions comprising ascorbic acid, hydro-quinone, pyrimidine developing agents and a combination of hydroquinone and N-methyl-~-aminophenol.

~ 91 In a 6econd step of a proce6s for forming a posi-tive dye im~ge according to the invention, fogging of the photographic material i8 accomplished by expo6ing the photographic material to light or by chemical fogging by mean6 of chemical fogging agent6 known in the photographic art.
Following the described fogging step, a second silver halide developing 6tep i6 carried out. Thi6 i6 carried out by means of a cross-oxidizing developing compo6ition. It i6 in this 6tep that the color-forming para-sulfonamidodiphenylamine dye precursor is converted to a dye in the image areas. Any silver halide developing composition is useful in thi6 6tep, provided that it cross-oxidizes the color-forming para-sulfonamidodiphenyl-amine dye precur60r to a de6ired dye. Such silver halidedeveloping compo6itions include alkaline 601ution6 comprising a cross-oxidizing silver halide developing agent, preferably a 3-pyrazolidone cros6-oxidizing silver halide developing agent. Thi6 cross-oxidizing developing agent becomes oxidized during development by reducing exposed or fogged silver halide to 6ilver metal. The oxidized developing agent then cros6-oxidizes the color-forming para-sulfonamidodiphenylamine dye precursor to a desired dye. The photographic material, upon processing, contains a concentration of dye in inverse proportion to the amount of exposure of the photographic element. That is, a positive dye image, also described herein a6 a rever6al dye image, is formed.
An especially useful process for producing a positive dye image in an imagewise exposed photographic element according to the invention compri6es: (a) develop-ing the exposed photographic element in an alkaline photo-graphic developer in the absence of a cross-oxidizing silver halide developing agent, and then (b) uniformly exposing the resulting element to a flash exposure of light, followed by (c) developing the photographic element in an alkaline, cross-oxidizing developer, comprising an aqueous, alkaline solution of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, and (d) bleaching and fixing the photographic element in a silver haiid~ bleaching and fixing 601ution to produce a positive dye image in a photographic element. It iB generally useful to treat the photographic element by mean6 of a development stop bath after step (a) and before step (b).
Photographic elements according to the invention are also useful for producing negative dye images. Such negative dye images are produced in an expoæed photogra-phic element comprising a support having thereon, in reactive as60ciation, in binder, (a) photosen6itive silver halide, and (b) a color-forming para-6ulfonamidodiphenyl-amine dye precursor by ~A) developing the photographicelement in an alkaline, cro6s-oxidizing photographic silver halide developer composition to produce a negative dye image and silver image; then (B) removing at least part of the silver image from the photographic element, such as by bleaching and fixing the silver from the element. Removal of the silver is accompllshed by means of bleaching and fixing compositions known in the photo-graphic art. The optimùm bleaching and fixing composi-tions are selected to provide the desired dye image.
Suitable bleaching and fixing composition6 are described in Grant Haist, Modern Photographic Processing, Vol. 2, Chapter 10 (1979).
Photographic elements according to the invention compri6ing direct-po6itive photographic silver halide are useful for forming positive, dye images and positive, silver images. A process of producing a positive, dye image and a positive, silver image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in binder, (a) direct-positive photographic silver halide, and (b) a color-forming para-sulfonamidodiphenylamine dye precursor, comprising (A) developing the photographic element in an alkaline, cross-oxidizing photographic silver halide developing composition; then (B) fixing the resulting photographic element to produce a positive, dye image and a positive, 6ilver image. Useful direct-positive silver halide is described in, for example, Research Disclosure, December 1978, Item No. 17643, page6 22 through 31. Fixing the photographic element is accomplished by means of fixing compositions known in the photographic art, such as a sodium thiosulfate fixing composition.
An advantage of the photographic material and process according to the invention is that the dye images produced upon processing po6sess de6ired stability to post-processing conditions and visible light expoRure. A
simple test is useful for establishing the degree of stability which is desired for a dye image produced from a color-forming sulfonamidodiphenylamine dye precursor according to the invention. One such test is a test well known ln the photographic art in which a processed photo-graphic element is exposed to a Simulated Average North American Skylight (SANS) with continuous 5400 LUX of exposure at an average temperature of 21~C at 45 percent relative humidity. A comparison of the stability of the tested dye is then observed. This test is described with respect to specific compounds in the following examples.
When a cross-oxidizing silver halide developing agent is present in the photographic material according to the invention, a developed image is produced after image-wise exposure of the photographic material by contacting the material with an alkaline activator solution which enables development of the exposed silver halide, as well as production of the desired dye. Many alkaline activators are useful for developing an image in a photo-graphic material according to the invention compri6ing an incorporated cross-oxidizing silver halide developing agent. Alkaline activators which are known to be useful in the photographic art, such as in stabilization process-ing, are useful for developing an image in the de6cribed gl - so -photographic material according to the invention.
Examples of useful alkaline activator~ include ~odium hydroxide, potassium hydroxide, tri60dium phos-phate l2H20 (pH 12), 60dium metabora~e (pH 12), di60dium phosphate and monosodium phosphate. An optimum alkaline activator will depend upon such factor6 a6 the desired image, the particular cross-oxidizing developing agent, proce66ing condition6 and the particular color-forming para-sulfonamidodiphenylamine dye precursor. An e6pecially u6eful alkaline activator compri6es trisodium pho6phate (pH 12).
The alkaline activator is useful in a range of concentrations. A generally u6eful concentration of alka-line activator is within the range of about 10 to about 50 grams per liter of activator solution which produces a pH
within the range of about 11 to about 12. An optimum concentration of alkaline activator will depend upon such factor6 as the de6ired image, the particular activator, proces6ing condition6, particular cro6~-oxidizing developing agent, particular photosen6itive silver halide and particular color-forming para-sulfonamidodiphenylamine dye precursor.
After exposure and processing of the photographic material according to the invention, the photographic material comprise6 a 6ulfonimide dye image or, alternatively, a 6ulfonimide dye image and a silver image. The 6ulfonimide dye image con6i6t~ e66entially of a 6ulfonimide dye repre6ented by the formula:
Rl ~3 n -~ o ~ -N~-\ /--NS02Rs t ~

t;~6 wherein R, Rl, R2, R3, R4 and Rs are as defined. Preferably, R5 in this dye is a stabil-izer group, 6uch as a 2,4,6-trlisopropylphenyl group.
Examples of useful sulfonimide dyes in ex-posed and processed photographic materials according to the invention are as follows:
N-(4-dihexylaminophenyl)-N'-(2,4,6-triisopro-pylbenzenesulfonyl)-p-benzoquinonediimine repre-sented by the formula:

CH3 (CH2) 5 ! -. I
~N - . /0 ~. -N-. / \. 5NS02 - . / O \ . - CH

N-(4-hexyloxyphenyl)-N'-(2,4,6-triisopropylben-zenesulfonyl)-3-methyl-~-benzoquinonediimine represented by the formula:

~C~3 CH3-CH CH3 CH3 ( CH2 ) s O - . / O / . -N~ . 5NSO2 - . ~ O ~ . - CH

C~13 N-dihexylaminophenyl)-N'-(2,4,6-triisopropylben-zene6ulfonyl)-3-methyl-~-benzoquinonediimine represented by the formula:

3~91 CH3 CH3-CH ~H3 CH3(CH2) /N- \ 0 /--N--\ /--NS02--/ 0 \ CH

N-S4-dihexylaminophenyl)-N'-(2,4,6-triisopropyl-benzenesulfonyl)-2-methylsulfonyl-p-benzoquinonediimine represented by the formula:

CH3(CH2)s\ /---\
/N--\ 0 /--N=-\ /-=NS02--~ 0 /--CH

N-(4-dihexylaminophenyl)-N'-(2,4,6-triisopropyl-benzenesulfonyl)-2-pivalamido-~-benzoquinonediimine represented by the formula:

Il l 30(CH3)3CCNH CH3-CH CH3 N-.\ 0 /--N=., ~-~NS02--/ 0 /--CH

11~'3~91 - s3 -N-(4-hexyloxyphenyl)-N'-(2,4,6-trii60propylben-zenesulfonyl)-~-benzoquinonediimine represented by the formula:

CH3(CH2)sO--/ O /--N=-\ /-=NSO2--/ Q /--CH

N-[4-N-ethyl-N-(~-methane6ulfonamidomethyl)- amin o]-N'-(2,4,6-triisopropylbenzenesulfonyl)-2,5-dipival-amido-~-benzoquinonediimine represented by the formula:

Il I
C2Hs /CH3 HNCC(CH3)3 CH3;cH CH
~N--~ O /-~N''-~ /-~-NS02- ~ O / CH
CH3SO2NHCH2CH2 -- ~ I_- CH
(CH3)3CCNH H3C-CH 3 Il I

~'3~ 9 N-(4-n-hexyloxyphenyl)-N'-t2,4,6-trii60propyl-benzenesulfonyl)-2,5-dipivalamido-~-benzoquinonediimine repre6ented by the formula:

Il I
HNCC(CH3)3 H3C-CH CH3 n-C6HI30--\ 0 /--N==-~ NS02--\ 0 /--CH

C ~ CH3 C(CH3)3 N-(4-methyl-3-methane6ulfonamidophenyl)-N'-(2,4,6-trii60propylbenzene6ulfonyl)-2-palmitamido-~-benzo-quinonediimine repre6ented by the formula:

NHS02CH3 NHCClsH3l CH3-CH CH
1 . ~............... 1 . , H3C-- ~Q `._ N ~NS02 - / 0 /--CH
CHs-CH CH3 N-(4-methoxy-3-methanesulfonamidophenyl) -N ' -(2,4,6-triisopropylbenzenesulfonyl)-2-pivalamido-~-benzenequinonediimine represented by the formula:

CH3S02HN Nycc(cH3) 3 CH3-CH CH3 CH3 0- - / O \- -N ~ NS0 2 - ,O, - -CH

The following examples are included for a further understanding of the invention.

l.~t;~1i5~1 Example 1 -- Reversal Proce~sing to Produce a Positive Dye Image Thi6 illustrates the invention.
A silver bromide gelatino photographic emulsion was prepared containing a dispersion of the following S color-forming sulfonamidodiphenylamine dye precursor which iB 4-diethyl~mino-4'-(2,4,6-triisopropylbenzenesulfon-amido)diphenylamine:

H3C\ CH3 o C~ CH3 (C2Hs)2N--\ 0 \--N--\ 0 /--NHS--/ 0 /--CH

CH3 ~H3 (Dye Number le) dispersed in N-n-butylacetanilide. The emulsion was coated on a film support at a silver (Ag+) coverage of 104 mg/ft2 (corresponding to 11.2 mg/dm2), 45 mg/ft2 of Compound le and 90 mg/ft2 of N-n-butylacetanilide (corresponding to 4.9 and 9.7 mg/dm2, respectively). A
sample of the resulting photographic film was imagewise exposed to light in a commercial sensitometer for 10-4 seconds through a 1.0 neutral density filter to produce a developable latent image in the film. Processing of the exposed film was carried out as follows:
1. Develop for 60 seconds in the following developer solution:
(a) sodium hexametaphosphate2.0 g (b) N-methyl-~-aminophenol sulfate 6.0 g (c) sodium sulfite (anhydrous) 50.0 g (d) sodium carbonate (anhydrous) 30.0 g (e) hydroquinone 6.0 g (f) potassium bromide 2.0 g (g) sodium thiocyanate 1.3 g (h) sodium hydroxide 2.0 g (i) potas6ium iodide (0.1 percent solution) 6.0 ml (j) water to 1 li,ter (pH 10.1 to 10.3) 2. Wash in water for 60 second6.
3. Re-expose by means of a uniform flash to light.
4. Develop 30 seconds in a pH 12 buffered developer containing:
(a) 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (cross-oxidizing developing agent) l g/Q
(b) pota6sium bromide l g/Q
(c) benzyl alcohol 10 m1/Q
(d) water to 1 liter

5. Wash in water for 60 seconds.

6. Soak in the following bleaching and fixing compo-sition (composition B-F~ for 60 seconds:
(a) (NaFe or NH4Fe) ethylene-diaminetetraacetic acid 40.0 g (b) ethylenediaminetetraacetic acid (EDTA) 4.0 g (c) potassium iodide 1 g (d) ammonia (20 percent aqueous solution) 10 ml (e) ammonium thiosulfate, crystalline 100 g (f) sodium sulfite, anhydrous 2 g (g) sodium or ammonium thio-cyanate (20 percent aqueous solution) 50 ml (h) water to 1 liter (pH 6.2 to 6.5)

7. Wash 120 seconds in water, and

8. Dry at 22C in room air.
A dye only image which was a cyan po6itive image was produced in the photographic film. The cyan dye image had a maximum density of 1.41 and a minimum density of ;9~

0.17. The dye image had a maximum absorption at 680 nm.
Examples 2 through 11 Dye images were also produced by the procedure of Example 1, with the exception that some of the color-forming sulfonamidodiphenylamine dye precursors from the following Table I were used in place of Dye Number le in Example 1.
The absorptions of the resulting dyes are given in the follow-ing Table I. These values were obtained by the following procedure:
A sample of the proposed color-forming sulfon-amidodiphenylamine dye precursor (3 to 18 mg, based on anticipated value of 1.0 for optical density of a solution) was dissolved in butyl acetate (50 ml) or a similar solvent for the dye precursor. This was mixed vigorously with a solution of excess K3Fe(CN)6 in pH 12 phosphate buffer.
The organic phase was washed three times with water and then diluted to 100 ml with butyl acetate for spectrophoto-metric assay. This procedure ls useful for pre-screening color-forming sulfonamidodiphenylamine dye precursors, because the hue, ~-max (wavelength of maximum absorption) and molar extinction (~) values obtained are comparable to the properties of the image dye produced in a photographic element. It is not probable that a proposed color-forming sulfonamidodiphenylamine dye precursor is useful in a photo-graphic element to form an image dye if the procedure of reaction with K3Fe(CN)6 produces no suitable dye.

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The color-forming ~-sulfonamidodiphenyl~mine dye precursors from which the dyes in Table I are derived are named as follows:

Color-Forming Sulfonamidodiphenylamine Dye Dye Precursors Correspondi.ng to Noted Dyes in Number Table I:
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la 4-Dihexylamino-4' (2,4,6-triisopropylbenzene-sulfonamido)diphenylamine lb 4-Dihexylamino-3'-methyl-4'-~2,4~6 tr~iso-propylbenzenesulfonamido)diphenylamine lc 4-Dihexylamino-2'-methylsulfonyl-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine ld 4-Dihexylamino-2'-[~-(2,4-di-tert-amyl-phenoxy)butylsulfamyl]-4'-benzenesulfonamido-diphenylamine lf 4-Diethylamino-4 7 - (4-n-dodecyloxybenzenesul-fonamido)diphenylamine lg 4-Hexyloxy-4'-(2,4,6-triisopropylbenzenesul-fonamido)diphenylemine lh 4-Hexyloxy-3'-methyl-4'-(2,4~6-triisopropyl-benzenesulfonamido)diphenylamine li 4-Dihexylamino-4'-(2,4,6-triisopropylbenzene-sulfonamido)diphenylamine lj 4-Dihexylamino-3l-methyl-4'-benzenesulfon-amidodiphenylamine lk 4-Hexyloxy-4'-benzenesulfonamidodiphenylamlDe Examples 12 ~hrou~h 21 -- Fixing of .lements Comprising Dyes of Sulfonamido_~phenylamines Film strips (I) prepared as described in Example 1 containing photographic silver halide and containing the color-forming sulfonamldodiphenylamine dye precursors described in the following Table II were processed as follows:

3~;91 1. Fixed in the following liquid fix 601ution (fix composition A) for 30 seconds:
(a) 60dium thiosulfate (cry6talline) (or ammonium thiosulfate at 120.0 g) 160.0 g (b) potassium metabisulfite 20.0 g (c) water to 1 liter, 2. Wa~hed well in water for 120 6econds, 3. The color-forming 6ulfonamidodiphenylamine dye precur~or wa6 oxidized by immer6ing the film into the following composition:
(a) K3Fe(CN)6 (one percent by weight in benzyl alcohol) 20 g (b) Water to 1 liter (buffered to pH 12), and 4. Washed 120 æecond6 in water.
A æecond æet of comp~rative film 6trip6 (II) containing the same color-forming æulfonamidodiphenylamine dye precur~or6 were processed in the same way a6 described for film 6trips (I), with the exception that the strips were also reflxed in fix composltion A for 30 second6 following step 4, and then washed in water for 120 seconds.
The percentage den6ity 1088 on fixing for the dyes waæ calculated aæ follow6:
% Denæity Lo6æ on Fixing ~ I D II x 100 where DI and DII were densities to complementary light of film strip6 I and II, reæpectively.

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Table II demonstrates that only a 6 to 9 percent dye density loss occurs for the 4'-triisopropylbenzene ~ulfonamido cyan dye formers la and lb relative to the 46 to 100 percent losses experienced for the non-ballasted homologs. Comparison of the re~pective los6es (16 versu6 ~6 percent) for Compounds le and lf demonstrate the importance of a 4'-ballast with isopropyl groups in both ortho positions of the benzene ring. The excellent stability of Compound ld (4 percent loss~ demonstrates that a bulky sub~tituent in the 2'-ring position conveys stabilization of the image dye after fixing. Furthermore, comparisons of the respective den6ity losses (O versus 33 percent) for the magenta dye precursor lh and the dye precursor 2b show the value of the introduction of a tri-isopropylbenzene sulfonamido ballast at the 4'-position.
Examples 22 through 29 -- Processing of Photographic Elements A. Film strips prepared as in Example 1 containing photographic silver halide and containing the color-forming sulfonsmidodiphenylamine dye precursor descrlbed in the following Table III-A
were chemically processed at 22.2C according to the sequence:
(l) 30-second fix in fix composition A, (2) 60-second water wash, (3) 30 seconds in pH 12.0 Na ~04 buffer containing 10 g/liter K3Fe(CN)6, 10 ml/liter benzyl alcohol, 1 g/liter KBr and water to l liter, (4) 5-minute wash in water, and ~
3 (5) lO seconds in Kodak Photo-Fl~ , followed by distilled water wash for 120 seconds.
The processed strips were then mounted on aperture cards and exposed (emulsion side to light source) at 21~C and 45 percent relative humidity in a SANS test a6 described ~Ising 5400 ~UX irradiation for one, three and seven days.
Percentage fade of the dyes was calculated as follows:

3~i91 % Fade D
initial where D is the density to complementary light after n days. The term SANS herein means Simulated Aver~ge Northern American Skylight.
B. Film 6trips prepared as in Example 1 containing photographic silver halide and containing the color-forming sulfonamidodiphenylamine dye precur60rs described in Table III-B were photo-graphically processed at 22.2C according to the sequence:
(1) Imagewise expo6e to provide developable latent image, (2) Activate in the following developer:
pH 12 Na3P04 buffer containing 1 gram 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolido ne, 10 ml benzyl alcohol, 1 gram K8r, water to 1 liter, for 30 seconds, (3) 2-minute wash in water, (4) 30-second fix in fix composition A, (5) 2-minute wash in water~ and (6) dry in room air.
The dried strip6 were mounted and exposed to SANS irradia-tion, as described above.

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The SANS fade results summarized in Table III-A
(for coatings chemically oxidized without development) demonstrate the advantage of the triisopropylbenzenesul-fonamido ballast. The respective seven-day dye loss for la was about 23 percent, compared to almost complete fading (83 to 100 percent) for the non-bsllasted dye6.
Similarly, the seven-day loss for lb was 9 percent versus 59 percent for the non-ballasted 1~ cyan dye; and, again, a 19 percent loss for Compound le as contrasted to 100 percent destruction of the dye of Example 20. The ballasted magenta dye-former lh faded 4.5 percent in seven-day SANS, whereas the unballasted compound of Example 22 showed 58 percent dye fade.
Density values of the images produced for the listed dyes are as follows (see Table III-B):

Density Example Number Dye Silver (Ag)Silver ~Ag) with Dye lb 0.42 1.56 20 36 la 0.43 1.68 37 ld 0.45 1.03 38 lh 0.37 1.40 39 lg 0.47 1.03 Example 40 A disper~ion of a color-forming para-sulfonamido-d1phenylamine dye precursor, as designated in the follow-ing Table IV-A, was prepared by dissolving one part of the dye precursor in two parts of ethyl acetate and two parts of N-n-butylacetanilide (coupler solvent~. This organic mixture was combined with an aqueous gelatin solut~on and passed through a colloid mill five times. The resulting disper6ion was mixed with a gelatino photographic silver halide emulsion and coated at about 11.7 mgs of ~ilver per dm2 on a clear poly(ethylene terephthalate) film ~l t;~ ;'31 ~upport. The resulting photographic element was lmagewise expo6ed to light through a 1.0 neutral density filter in a commercial sensitometer to provide a developable latent image in the element.
The exposed photographic element was proce6sed for 30 seconds at 22C in a developer composition comprising:
4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone (cross-oxidizing develop-0 ing agent) 1 g Na3P0412H 2 47 . 52 g KBr 1 g Water to 1 liter The photographic element was then fixed for two 15 minute6 in an aqueou6 solution of 5-(2-hydroxyethyl)tetra-hydro-S-triazine-2(lH)-thione represented by the formula:

-N
Ho-cH2cH2-N~ N/ ~S
H

The photographic element was then washed in water for five minutes. The following Table IV-A identifies the color-5 forming sulfonamidodiphenylamine dye precursor, a8 well asthe maximum absorption of the corresponding dye produced upon proces 8 ~ng.

TABLE IV-A

Example Dye Absorption:
NumberNumber Dmax DminAmax, nm Control None 0.19 0.14 (black) 40a 0.59 0.08 460 41a 0.53 0.07 535 42 42A 1.16 0.20 720 43 43a 0.48 0.08 430 ~6!~6~3 Example Dye Color-Forming Number Number Dye Precursor 1-methoxy-4'-benzenesulfonamido-diphenylamine 41 41a 4-hexyloxy-3'-methyl-4'-benzene-8ul fonamidodiphenylamine 42 42a 4-dihexylamino-4'-benzenesulfon-amidodiphenylamine 43 43a 4-methyl-4'-~-tolylsulfonamido-diphenylamine Example 44 -- Use in Direct Positive Photographic Silver Halide Material A photographic element was prepared by coating the following composition on a poly(ethylene terephtha-late) film support:
Silver chloroiodide gelatino emulsion (0.4 mole percent I, 0.24 micron cubic grsins, surface chemically sensitized, internally doped) 9.7 mg/dm2 (as Ag) gelatin ~hardened by means of bis(vinylsulfonylmethyl)ether]43.2 mg/dm2 color-forming dye precursor:
(dispersed in di-n-butylphthalate~ 5.4 mg/dm 2 CH3 _.
CH3CH2~ / 0 \--NH--/ 0 /--NHS02--~ 0 / -CH3S02NH(CH2)2 -- t NHCC7HIs-n .

~ 9f;91 The resulting emulsion layer was overcoated with 10.8 mg/dm2 of gelatin hardened with bis(vinylsulfonylmethyl) ether. The resulting photographic element according to the invention was imagewise exposed to light in a commer-cial senæitometer to produce a developable image in the emulsion layer. Then the exposed photographic element was processed as follows:
(1) 30 seconds activation in the following composition:
0 phosphate buffer (pH 12) 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1 g/L.
benzyl alcohol (1 percent by volume), (2) 60-second wash in water, (3) 30-second fix (pH 10) in a fixing composition; snd (4) 120-second wash in water.
This produced a dye image and silver image in the emulæion layer. The processed element w~s permitted to dry in air. The density of the resulting image was (read through B red filter): Dmax 1.57, Dmin 0.41. A reversal image was produced.
A second sample of the imagewise exposed photo-graphic element was fixed and oxidized by means of potas-sium ferricyanide to produce a maximum density of 1.40.
Example 45 -- Illustrative Developeræ
A. The following photographic composition was coated on a poly(ethylene terephthalate) film support:
AgBr octahedral grains)9.4 mg/dm2 gelatin (binder) 43.2 mg/dm2 bis(vinylæulfonylmethyl) ether (hardener) 0.4 mg/dm2 di-n-butyl phthalate (coupler ~olvent) 5.4 mg/dm2 ~ ~6'36~:~

color-formlng para-sulfonamidodi-phenylamine dye precursor: 5.4 mg/dm2 NHCC7HIs _./

CH3SO2NH(CH2) ~ ~.0 ~ NH- \ 0 ~--NHSO2 -/ 0 \---~

(Compound 45A) (Cyan) potas6ium nitrate 0.6 mg/dm2 The resulting emul6ion layer was then overcoated by means of gelatin (10.8 mg/dm2) hardened by bis(vinylsulfonyl-methyl) ether (0.108 mg/dm2). The re6ulting photo-graphic element was imagewise exposed to light through a conventional step tablet in a commercial sensitometer to produce a developable latent image in the emulsion layer.
Processing was carried out at 22C as follows with agita-tion oi the processing solutions:

(a) Development for 30 seconds in the following developer solution:
Na3P04-12H20 47.5 g Na2S3 5.0 g N,N-diethylhydroxylamine (85 percent in H20) 1.0 ml 4,4-dimethyl-1-phenyl-3-pyrazolidone 5 mM

KBr 1~0 g Water (to one liter) (pH 12.0);

1~6'3691 (b) Rinse for 60 second~ in water;
(c) Fix for 30 seconds in the following compo~ition:

Na2S2o3 5H20 248 g Na2C03-H20 30.0 g NaHC03 g Water to one liter (pH 10.0);

(d) Wash for five minutes in water; and (e) air dry.
A cyan image was produced.
The procedure was repeated, with the exception that the following color-forming sulfonamidodiphenylamine dye precursor was used in place of Compound 45A:

11 NHCC(CH 3 ) 3 . /
! . \. .
C6Hl30--/ 0 /--NH--\ ~ ~ - -NHSO 2 - ~0 (Compound 45B) (Magenta) Compound 45B was coated in the emulsion layer at 9.6 mg/dm2 with 9.6 mg/dm2 of the coupler solvent.
The image produced with the Compound 45B had a maximum density of 1.25 to green light and a density of 0.41 in the eleventh step of the image. The image produced with the Compound 45A had a maximum den~ity of 1.12 to red light and a density of 0.80 in the eleventh step of the image.

1:~L6'3~91 B. The procedure in A. was repeated, with the excep-tion that N-(p-hydroxyphenyl) pyrrolidine waæ used in place of 4,4-dimethyl-1-phenyl-3-pyrazolidone. The image produced with Compound 45B had a maximum den6ity of 1.41 and an eleventh step density of 0.43. The image produced with Compound 45A had a maximum density of 1.56 and an eleventh step density of O.S9.
C. The procedure in A. was repeated, with the excep-tion that ~-N,N-dimethyl-~-aminophenol was used in place of 4,4-dimethyl-1-phenyl-3-pyrazolidone. The image produced with Compound 45B had a maximum density of 0.80 and an eleventh step density of 0.21. The image produced with Compound 45A had a maximum den6ity of 1.42 and an eleventh 6tep density of 0.28.
D. The procedure in A. was repeated, with the excep-tion that N,N,N',N'-tetramethyl-~-phenylenediamine dihydrochloride wa6 used in place of 4,4-dimethyl-1-phenyl-3-pyrazolidone. The image produced with Compound 45B had a maximum density of 1.30 and an eleventh step den~ity of 0.38. The image produced with Compound 45A h~d a maximum density of 1.34 and an eleventh step denslty of 0.72.
E. The procedure in A. wa~ repeated, with the exception that 6-amino-1-hydroxyethyl-2,2,4-trimethyl-tetrahydroquinoline dihydrochloride wa6 u6ed in place of4,4-dimethyl-1-phenyl-3-pyrazolidone. The image produced with Compound 45B had a maximum density of 1.23 and an eleventh step den6ity of 0.22. The image produced with Compound 45A had a maximum den6ity of 1.32 and an eleventh step density of 0.40.
The maximum density valuefi for each of the images produced in Examples 45A, B, C, D and E comprised about 0.40 neutral metallic silver den6ity.
Example 46 -- Mixed Dye Precursor6 A dispersion of 4-dihexylamino-4'-(2,4,6-triiso-propylbenzenesulfonamido)diphenylamine (see Dye la in Example 1) was prepared by di~æolving 3.0 gram6 of this fir6t color-forming dye precur60r in 8.0 gram6 of N-n-butylacetanilide. The re6ulting di6per6ion was designated Di6persion 46A. A dispersion of 4-hexyloxy-3'-methyl-4'-(2,4,6-trii60propylbenzenesulfonamido)diphenyla mine (6ee Dye lh in Example 1) wa6 prepared by dis601ving 4.0 gram6 of this 6econd color-forming dye precur60r in 8.0 grams of N-n-butylacetanilide and 8.0 gram6 of ethyl acetate. The resulting dispersion wa6 designated Disper6ion 46B.
The following fir6t photographic 6ilver bromide composition was coated on a poly(e~hylene terephthalate) film 6upport:
red-sen6itized gelatino photo-graphic 6ilver bromide emul6ion 9.7 mg/dm2 Disper6ion 46A:
4-dihexylamino-4'-(2,4,6-tri-isopropylbenzene-sulfonamido)diphenylamine (dye precursor) 4.1 mg/dm 2 N-n-butylacetanilide 1008 mg/dm 2 gelatin (binder) 43.2 mg/dm 2 bis(vinylsulfonylmethyl) ether (hardener) 0.4 mg/dm2 The following interlayer was coated on the resulting fir6t layer:
2,5-di-s-dodecyl-1,4-dihydroxy-benzene 12.9 mg/dm 2 gelatin (binder) 16.8 mg/dm2 bis(vinylsulfonylmethyl)ether (hardener) 0.17 mgldm 2 ~ 3 Then the following second photographic silver bromide compo~i~ion was coated on the re6ulting interlayer:
green-sensitized gelatino photo-graphic silver bromide emulsion 9.7 mg/dm2 Di6persion 46B:
4-hexyloxy-3'-methyl-4'-(2,4,6-triisopropylbenzene-sulfonamido)diphenylamine (dye precur60r) 5.4 mg/dm2 N-n-butylacetanilide 10.8 mg/dm2 gelatin (binder) 43.2 mg/dm 2 bis(vinylsulfonylmethyl) ether0.4 mg/dm The re6ulting photographic element was de6ignated a6 Element 46I. A 6imilar photographic element wa6 prepared, with the exception that 2,5-dl-s-dodecyl-1,4-dihydroxy-benzene was omitted. This photographic element was designated a6 Element 46II. Each of the photographic element6 wa6 imagewi6e exposed to light by mean6 of a commercial wedge 6pectrograph to produce a developable latent image in the element6. Then the element6 were proces6ed at 22~C. a6 follows:
(1) Activated 30 seconds in the following composition:
Na3P04 (pH 12) (buffer) 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1 g benzyl alcohol 10 ml KBr 1 g Water to 1 liter;

1~9~9~

(2) Wa6hed two minutes in water;
(3) Fixed for 30 second6 in the following fixing composition:
Sodium thiosulfate (or ammonium thio6ulfate 120.0 g) 160.0 g Pot~sium metabisulfite 20.0 g Water to 1 liter (pH 4.7);
(4) Wa6~ed two minute6 in water; and (5) Air dried.
The photographic element6 produced a developed silver and dye image. The following tran6mi6sion maximum and minimum dye den6ities (negative) were ob6erved for the image~
produced in each e}ement when read by white, red and green light:

Element 46I. Dmax Dmin White 1.47 0.23 Red 1.66 0.39 Green 0.31 0.09 Element 46II: Dmax Dmin White 1.47 0.10 Red 1.62 0.17 Green 0.74 0.09 The data demon6trateæ that the photographic Elements 46I and 46II provide an overall blue dye-enhanced silver image.
Compari60n of the maximum density values for green light indicates color contamination occurred for Element 46II which was a consequence of wandering of the oxidized form of the 3-pyrazolidone developing agent between layers of the element. In Element 46I, pure color separation was ob6erved with no evidence of interlayer oxidized 3-pyrazolidone developing agent wandering.

Example 47 -- Comparison of Stability in Photogrsphic Material The following color-forming 6ulfonamidodiphenyl-amine dye precursors were compared regarding the 6tability 5 of the corresponding 6ulfonimide dyes formed in a silver halide photographic material according to the invention:
47A 4-Hexyloxy-4'-(2,4,6-triisopropylbenzene6ul-fonamido)diphenylamine 47B 4-n-Hexyloxy-2'-pivalamido-4'-(2,4~6-triisopropyl-benzene6ulfonamido)diphenylamine 47C 4-Hexyloxy-3'-pivalamido-4'-(2,4,6-trii60propyl-benzenesulfonamido)diphenylamine 47D 2',5'-Dipivalamido-4-n-hexyloxy-4'-(2,4,6-trii60-propylbenzene6ulfonamido)diphenylamine 15 Each one of these dye precur60rs wa6 incorporated in a photographic 6ilver halide element compri6ing a subbed poly(ethylene terephthalate) film support having thereon a layer comprising:
(1) 6ilver bromide (0.8 micron grain size, octahedral grains, chemlcally sensitized by means of 8ulfur and gold sensitizers) (9.7 mg/dm2) (90 mg/ft2), and (2) gelatin (400 mg/ft2) (43.2 mg/dm2) hardened with bi6(vinyleulfonylmethylether) (one percent by weight) (binder).
The color-forming para-~ulfonamidodiphenylamine dye precur- 60r was di6per6ed in 601vent (1:1 to 1:2 part6 by weight) in the layer at 35 to 150 mg/ft 2 (3.0 to 16.2 mg/dm2). Each of the photographic element6 wa6 30 uniformly exposed to light in a commercial 6en6itometer to produce a developable image in the element. Then each photographic element wa6 proce~6ed at 22C a6 follow6:
(a) Activated for 30 seconds in the following composition:
4-methyl-4-hydroxymethyl-l-phenyl-3-pyrazolidone 1 g ~ 9 potassium bromide 1 g benzyl alcohol 10 ml Na3P04-12H20 47.5 g H20 to one liter pH ad~u6ted to 12.0 (b) Washed for 30 6econds in water;
(c) Fixed for 30 6econds in the following composition:
Na2S203-5~ 0 248 g Na2C03-H20 30.0 g NaHC03 5.0 g Water to 1 liter (pH 10.0); and (d) Wa6hed for two minute6 in water.
A dye image and a silver image were formed in each of the photographic elements. The developed images had the following maximum and minimum density values:

Dmax Dmin (Measured at(Derived from Maximum Unexpo6ed Dye AbsorptionPhotographic Precur60r Wavelength)Element at ~max of dye) 47A 1.03 0.08 47B 0.72 0.08 47C 1.49 0.07 47D 1.71 0.08 Each of the photographic elements after processing was exposed to light in a SANS test. After seven days, the percentage fade of the dye image wa6 observed. The following result6 were obtained:

;969 Dye Precur60r Percent Fade 47A 13.3 47B 5.6 47C 26.2 This illustrates the degree of stability to light exhibited by dye image6 according to the invention.
A separate sample of each of the photogr&phic elements after processing was exposed to a "wet oven test"
in which the photographic element was placed in an oven at 60C and 70 percent humidity. After 6even days, the percentage fade of the dye image was observed. The following re6ults were obtained:

Dye Precursor Percent Fade 20 47A 100.0 47B 6.3 47C 100.0 47D +1.9 (The dye image for 47D
increased in density.) This illustrates that the sulfonimide dye images produced from dye precursors 47B and 47D are more stable than the sulfonimide dye~ produced from Compound6 47A and 47C.
The foll~wing dye precursors were also found to produce corresponding 6ulfonimide dyes according to the invention:
Example 48 4-[N-ethyl-N-(~-methanesulfonamidoethyl)amino~-2-methyl-2~,5~-pivalamido-4~-(2,4,6-trii60propylbenzenesul-fonamido)diphenylamine l~i9~

Example 49 4-[N-ethyl-N-(~-methanesulfonamidoethyl)amino]-2-methyl-3'-pivalamido~4'-(2,4,6-triisopropylbenzenesul-fonamido)diphenylamine Example 50 4-[N-ethyl-N-(~-methanesulfonamidoethyl)amino]-2-methyl-2',5'-dipivalamido-4'-(2,4,6-trii60propylbenzene-sulfonamido)diphenylamine Example 51 4-[N-ethyl-N-(~-methanesulfonamidoethyl)amino]-2-methyl-2'-octanamido-4'-(2,4,6-triisopropylbenzenesul-fonamido)diphenylamine Example 52 4-Diethylamino-2-methyl-2'-methoxy-5'-pival-amido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenyl-amine Example 53 4-Hexyloxy-2'-(N-methyl)acetamido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine Example 54 4-Methoxy-2-methyl-2'-octanamido-4'-(2,4,6-tri-isopropylbenzene6ulfonamido)diphenylamine Example 55 4-Methoxy-2-methyl-2'-n-hexylureido-4'-(2,4,6-triisopropylbenzene6ulfonamido)diphenylamineExample 56 4-Hexyloxy-2'-[~-(2,4-di-t-amylphenoxy)hexan-amido]-4'-(2,4,6-triisopropylbenzene6ulfonamido)di-phenylamine Example 57 4-Dihexylamino-3'-pivalamido-4'-(2,4,6-triiæo-propylbenzenesulfonamido)diphenylamine Example 58 4-[N-ethyl-N-(~-methanesulfonamidoethyl)amino~-2-methyl-2',5'-didodecyloxy-4'-(2,4,6-triisopropylbenzene-sulfonamido)diphenylamine Example 59 The following photographic ~ilver halide compo~i-tion was prepared and coated on a poly(ethylenetere-phthalate) film support:
photographic silver bromide gelatino 9.7 mg/dm2 emulsion (0.8 micron grain, octa-hedral grains, sulfur and gold chemically sensitized) gelatin 43.2 mg/dm2 bis(vinylsulfonylmethyl) ether0.43 mg/dm 2 (hardener) N-n-butylacetanilide (coupler6.5 mg/dm2 solvent) 3-methanesulfonamido-2'-octan-6.5 mg/dm2 amido-4'-(2,4,6-triisopropyl-benzenesulfonamido)diphenylamine (dye precursor) The resulting photographic element was imagewise exposed to light through a step tablet and a neutral density filter in a commercial sensitometer to provide a develop-able latent image in the photographic silver bromide layer. The exposed element was then processed at 22~C as fcllows:
(1) Activated for 30 seconds in the following composition:
4-hydroxymethyl-4-methyl-l-phenyl-3-pyràzolidone 1 g benzyl alcohol 10 ml pH 12, Na3P04 buffered water to 1 liter;

(2) Fixed until cleared in the following fixing composition:
NaHC03 0.5 g Na2C3 40 g Na2S23 100 g Water to 1 liter This provided a developed 6ilver image and dye image having a maximum density of 0.92. The maximum absorption (~ max) was 435 nm. The procedure was repeated, with the exception that in place of fixing the developed photo-graphic element in the noted fixing composition, the photographic element was treated in a bleach-fix composition.
lS This removed the silver image. The resulting dye image had a maximum density of 0.3 at 435 nm.
Examples 60 through 78 The following color-forming para-sulfonamidodi-phenylamlne dye precursors also provided corresponding sulfonimide dyes similar to the dye image produced in Example 59. In each case, the dye precursor was prepared as a dispersion in N-n-butylacetanilide (weight ratio of 1:1 to 1:2) and coated in the photographic silver halide layer at 3.8 to 16.2 mg/dm2 at the appropriate concen-tration to produce a dye and silver image density of about2Ø The development step was carried out at 26 to 27C
in an aqueous proces~ing solution (buffered to pH 12.2) containing 1 gram per liter of 4-hydroxymethyl-4-methyl-l-phenyl-3-pyrazolidone (cross-oxidizing developing agent). The maximum absorption wavelength of each of the corresponding sulfonimide dyes formed is given for each of the dye precursors. Many of the ionizable 3-sulfonamido sub6tituted dye precursors gave improved reactivity.
Example 60 3-Methanesulfonamido-4-methoxy-2'-octanamido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine (475 nm) Example 61 3-(N-methyl)methaneæulfonamido-4-methoxy-2'-octanamido-4'-(2,4,6-triisopropylbenzene6ulfonamido)-dlphenylamine (472 nm) _xample 62 3-Methanesulfonamido-4-methoxy-2'-pivalamido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine (478 nm) Example 63 4-Methyl-2~-palmitamido-4'-(2,4,6-triisopropyl-benzenesulfon~mido)diphenylamine (489 nm) Example 64 3-Methanesulfonamido-2'-octanamido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine (429 nm) Example 65 3-(N-methyl)methanesulfonamido-2'-octanamido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine (430 nm) Example 66 3-Methane~ulfonamido-2'-palmitamido-4'-(2,4,6-triisopropylbenzene~ulfonamido)dlphenylamine (429 nm) Example 67 3-Methanesulfonamido-4-methyl-2'-palmitamido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine (438 nm) Example 68 3-Methanesulfonamido-4,6-dimethyl-2'-palmitamido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine (433 nm) Example 69 3-Methanesulfonamido-6-methoxy-2'-octanamido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine (419 nm) Example 70 3-Acetamido-2'-octanamido-4~-(2,4,6-triisopropyl-benzenesulfonamido)diphenylamine (429 nm) 1~ ~ 9~ 9 _xample 71 4-[N-(~-methylsulfonamido)ethyl-N-ethyl~-amino-2-methyl-2'-octanamido-4'-(2,4,6-trii60propyl-benzenesulfonamido)diphenylamine (641 nm) Example 72 4-~N-(g-N'-methylmethylsulfonamido)ethyl-N-ethyl]amino-2-methyl-2'-octanam~do-4'-(2,4,6-tri-isopropylbenzenesulfonamido)diphenylamine (642 nm) Example 7_ 3-(4-Dodecyloxybenzene)sulfonamido-4~-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine (484 nm) Example 74 3-(2,4-Ditert-amylphenoxy)acetamido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine (479 nm) Example 75 4-Methoxy-2-methyl-2'-octanamido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine (515 nm) Example 76 4-n-Hexyloxy-2'-L~-dodecyl-a-(3-tertbutyl-4-acetoxyphenoxy)acetamido]-4'-(2,4,6-trli80propylben-zenesulfonamido)diphenylamine ~505 nm) Example 77 4-n-Hexyloxy-2'-[~-dodecyl--(3-tertbutyl-4-hydroxyphenoxy)acetamido]-4'-(2,4,6-triisopropylben-zenesulfonamido)diphenylamine (504 nm)Example 78 2,4-Dimethoxy-2'-octanamido-4'-(2,4,6-triiso-propylbenzenesulfonamido)diphenylamine (533 nm) Other color-forming para-6ulfonamidodi-phenyl~mine dye precursors that are useful for form-ing sulfonimide dyes are described in copending Canadian Application Serial No. 403,954, of R. S.
Gabrielsen, P. A. Graham, J. E. Kli~anowicz and M. H.
Stern, filed May 28, 1982 entitled "Color-Forming Sulfonamidodiphenylamine6 and Corresponding Sulfonimide Dyes".
<

.~

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

Claims (55)

WHAT IS CLAIMED IS:

1. In a photographic element comprising a support having thereon, in reactive association, in binder, (a) photosensitive silver halide; and (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
the improvement comprising as said dye precursor, a color-forming parasulfon-amidodiphenylamine.

2. A photographic element as in Claim 1 wherein said color-forming para-sulfonamidodiphenylamin is repre-sented by the formula:

wherein:
R is in the meta or para position and is an electron donating substituent selected from alkoxy containing 1 to 20 carbon atoms, aryloxy containing 6 to 20 carbon atoms, sulfonamido and carboxamido groups;
R1 is in the ortho or meta position and is hydrogen, alkyl containing 1 to 3 carbon atoms, carbamoyl, alkoxy containing 1 to 3 carbon atoms, sulfonyl-alkyl containing 1 to 3 carbon atoms, sulfonylaryl containing 6 to 12 carbon atoms, chlorine, bromine, iodine or fluorine;

R2 is hydrogen, alkyl containing 1 to 3 carbon atoms, carbomoyl, alkoxy containing 1 to 20 carbon atoms, sulfonylalkyl containing 1 to 5 carbon atoms, sulfonylaryl containing 6 to 12 carbon atoms, chlorine, bromine, iodine or fluorine;
R3 is hydrogen, alkyl containing 1 to 20 carbon atoms, haloalkyl containing 1 to 20 carbon atoms, alkoxy containing 1 to 20 carbon atoms, an ester containing 1 to 20 carbon atoms, carboxy, carbox-amido, chlorine, bromine, iodine, fluorine, carbamoyl, sulfonic acid, sulfamyl, sulfonylalkyl containing 1 to 5 carbon atoms, ureido or a carbo-cyclic group containing 5 to 12 carbon atoms;
R4 is hydrogen, alkyl containing 1 to 20 carbon atoms, alkoxy containing 1 to 20 carbon atoms, an ester represented by the formula , carboxy, carboxamido, chlorine, bromine, iodine, fluorine, carbamoyl, sulfonic acid, sulfamyl, sulfonylakyl containing 1 to 3 carbon atoms, ureido and a carbocyclic group containing 5 to 12 carbon atoms;
R5 is individually alkyl containing 1 to 20 carbon atoms or aryl containing 6 to 20 carbon atoms;
R6 is hydrogen, alkyl containing 1 to 20 carbon atoms, , aryl containing 6 to 20 carbon atoms, or repre-sents, with R7, atoms completing a 5- or 6-member heterocyclic group;

R7 is alkyl containing 1 to 20 carbon atoms, carbamoyl, carboxamido, or represents, with R6, atoms completing a 5- or 6-member heterocyclic group;
R8 is alkyl containing 1 to 4 carbon atoms; and R6A is alkyl containing 1 to 20 carbon atoms.

3. A photographic element as in Claim 2 wherein R5 is 2,4,6-triisopropylphenyl.

4. A photgraphic element as in Claim 1 wherein said color-forming para-sulfonamidodiphenylamine consists essentially of 4-dihexylamino-4'-(2,4,6-triisopropyl-benzenesulfonamido)diphenylamine represented by the formula:

5. A photographic element as in Claim 1 wherein said color-forming para-sulfonamidodiphenylamine consists essentially of 4-hexyloxy-3'-methyl-4'-(2,4,6-triisopropyl-benzenesulfonamido)diphenylamine represented by the formula:

6. A photographic element as in Claim 1 wherein said color-forming para-sulfonamidodiphenylamine consists essentially of 4-dihexylamino-3'-methyl-4'-(2,4,6-triiso-propylbenzenesulfonamido)diphenylamine represented by the formula:

7. A photographic element as in Claim 1 wherein said color-forming para-sulfonamidodiphenylamine consists essentially of 4-dihexylamino-2'-methylsulfonyl-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine repre-sented by the formula:

8. A photographic element as in Claim 1 wherein said color-forming para-sulfonamidodiphenylamine consists essentially of 3-methanesulfonamido-4-methoxy-2'-pival-amido-4'-(2,4,6-triisopropylbenzenesulfonamido) diphenyl-amine represented by the formula:

9. A photographic element as in Claim 1 wherein said color-forming para-sulfonamidodiphenylamine consists essentially of 4-[N-ethyl-N-(.beta.-methanesulfonamido-ethyl)amino]-2-methyl-2',5'-dipivalamido-4'-(2,4,6-tri-isopropylbenzenesulfonamido) diphenylamine represented by the formula:

10. A photographic element as in Claim 1 also comprising (c) a cross-oxidizing photographic silver halide developing agent.

11. A photographic element as in Claim 1 wherein said binder is a gelatino binder.

12. In a photographic element comprising a support having thereon, in reactive association, in a gelatino binder, (a) photosensitive silver halide; and (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
the improvement comprising as said dye precurso, a para-sulfonamidodi-phenylamine consisting essentially of 4-dihexyl-amino-4'-(2,4,6-triisopropylbenzenesulfonamido)-diphenylamine.

13. In a photographic element comprising a support having thereon, in reactive association, in a gelatine binder, (a) photosensitive silver halide; and (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
the improvement comprising as said dye precursor, a color-forming parasulfon-amidodiphenylamine consisting essentially of 4-hexyloxy-3'-methyl-4'-(2,4,6-triisopropyl-benzenesulfonamido)diphenylamine.

14. In a photographic element comprising a support having thereon, in reactive association, in a gelatino binder, (a) photosensitive silver halide; and (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
the improvement comprising as said dye precursor, a color-forming sulfon-amidodiphenylamine consisting essentially of 4-[N-ethyl-N-(.beta.-methanesulfonamidoethyl)-amino]-2-methyl-2',5'-dipivalamido-4'-(2,4,6-triisopropylbenzenesulfonamido) diphenylamine represented by the formula:

15. In a photographic element comprising a support having thereon, in reactive association, in a gelatino binder, (a) photosensitive silver halide; and (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
the improvement comprising as said dye precursor, a color-forming sulfon-amidodiphenylamine consisting essentially of 4-n-hexyloxy-2',5'-dipivalamido-4'-(2,4,6-tri-isopropylbenzenesulfonamido) diphenylamine represented by the formula:

16. In a photographic composition comprising:
(a) photosensitive silver halide; and (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said composition to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
the improvement comprising as said dye precursor, a color-forming parasulfon-amidodiphenylamine.

17. A photographic composition as in Claim 16 also comprising a binder.

18. A photographic composition as in Claim 16 also comprising (c) a cross-oxidizing silver halide developing agent.

19. A photographic composition as in Claim 16 also comprising (c) a 3-pyrazolidone cross-oxidizing silver halide developing agent.

20. A photographic composition as in Claim 16 wherein said color-forming para-sulfonamidodiphenylamine is represented by the formula:

wherein:
R is in the meta or para position and is an electron donating substituent selected from , alkoxy containing 1 to 20 carbon atoms, aryloxy containing 6 to 20 carbon atoms, sulfonamido and carboxamido groups;
R1 is in the ortho or meta position and is hydrogen, alkyl containing 1 to 3 carbon atoms, carbamoyl, alkoxy containing 1 to 3 carbon atoms, sulfonyl-alkyl containing 1 to 3 carbon atoms, sulfonylaryl containing 6 to 12 carbon atoms, chlorine, bromine, iodine or fluorine;
R2 is hydrogen, alkyl containing 1 to 3 carbon atoms, carbamoyl, alkoxy containing 1 to 3 carbon atoms, sulfonylalkyl containing 1 to 5 carbon atoms, sulfonylaryl containing 6 to 12 carbon atoms, chlorine, bromine, iodine or fluorine;
R3 is hydrogen, alkyl containing 1 to 20 carbon atoms, haloalkyl containing 1 to 3 carbon atoms, alkoxy containing 1 to 20 carbon atoms, an ester containing 1 to 20 carbon atoms, carboxy, carbox-amido, chlorine, bromine, iodine, fluorine, carbamoyl, sulfonic acid, sulfamyl, sulfonylalkyl containing 1 to 5 carbon atoms, ureido or a carbo-cyclic group containing 5 to 12 carbon atoms;
R4 is hydrogen, alkyl containing 1 to 3 carbon atoms, alkoxy containing 1 to 20 carbon atoms, an ester represented by the formula:

- ? - O -R8 , carboxy, carboxamido, chlorine, bromine, iodine, fluorine, carbamoyl, sulfonic acid, sulfamyl, sulfonylalkyl containing 1 to 3 carbon atoms, ureido and a carbocyclic group containing 5 to 12 carbon atoms;
R5 is alkyl containing 1 to 20 carbon atoms or aryl containing 6 to 20 carbon atoms;

R6 is hydrogen, alkyl containing 1 to 20 carbon atoms, , aryl containing 6 to 20 carbon atoms, or repre-sents, with R7, atoms completing a 5- or 6-membered heterocyclic group;
R7 is alkyl containing 1 to 20 carbon atoms, carbamoyl, carboxamido, or represents, with R6, atoms completing a 5- or 6-membered heterocyclic group;
R8 is alkyl containing 1 to 4 carbon atoms; and R6A is alkyl containing 1 to 20 carbon atoms.

21. A photographic composition as in Claim 16 wherein R5 is 2,4,6-triisopropylphenyl.

22. A photographic composition as in Claim 16 wherein said para-sulfonamidodiphenylamine consists essen-tially of 4-dihexylamino-4'-(2,4,6-triisopropylbenzene-sulfonamido)diphenylamine represented by the formula:

23. A photographic composition as in Claim 16 wherein said para-sulfonamidodiphenylamine consists essen-tially of 4-hexyloxy-3'-methyl-4'-(2,4,6-triisopropyl-benzenesulfonamido)diphenylamine represented by the formula:

24. A photographic composition as in Claim 16 wherein said para-sulfonamidodiphenylamine consists essen-tially of 4-dihexylamino-3'-methyl-4'-(2,4,6-triiso-propylbenzesulfonamido)diphenylamine represented by the formula:

25. A photographic composition as in Claim 16 wherein said para-sulfonamidodiphenylamine consists essen-tially of 4-dihexylamino-2'-methylsulfonyl-4'-(2,4,6-tri-isopropylbenzenesulfonamido)diphenylamine represented by the formula:

26. In a photographic composition comprising, in a gelatino binder, (a) photosensitive silver halide; and (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
the improvement comprising as said dye precursor, a para-sulfonamidodi-phenylamine consisting essentially of 4-dihexyl-amino-4'-(2,4,6-triisopropylbenzenesulfonamido)-diphenylamine.

27. In a photographic composition comprising, in a gelatino binder, (a) photosensitive silver halide; and (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
the improvement comprising as said dye precursor, a para-sulfonamidodiphenyl-amine consisting essentially of 4-hexyloxy-3'-methyl-4'-(2,4,6-triisopropylbenzenesulfonamido)-diphenylamine.

28. In a photographic composition comprising:
(a) photosensitive silver halide; and (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said composition to a dye by cross-oxidation by means of a cross-oxidation silver halide developing agent;
the improvement comprising as said dye precursor, a para-sulfonamidodiphenyl-amine consiting essentially of 4-[N-ethyl-N-(.beta.-methanesulfonamidoethyl)amino]-2-methyl-2',5'-dipivalamido-4'-(2,4,6-triisopropyl-benzenesulfonamido) diphenylamine represented by the formula:

29. In a photographic composition comprising:
(a) photosensitive silver halide; and (b) a color-forming dye precursor which is imagewise converted upon exposure and processing of said composition to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
the improvement comprising as said dye precursor, a a para-sulfonamidodi-phenylamine consisting essentially of 4-n-hexyloxy-2',5'-dipivalamido-4'-(2,4,6-triiso-propylbenzenesulfonamido) diphenylamine repre-sented by the formula:

30. A process of producing a negative dye image and a negative silver image in an imagewise exposed photo-graphic element comprising a support having thereon, in reactive association, in binder, (a) photosensitive silver halide, and (b) a color-forming para-sulfonamidodiphenylamine dye precursor which is converted upon processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
said process comprising:
(A) developing said photographic element in an alkaline, cross-oxidizing, photographic silver halide developer composition to produce a negative dye image and silver image.

31. A process as in Claim 30 wherein said alka-line, cross-oxidizing developer composition comprises a 1-phenyl-3-pyrazolidone, cross-oxidizing, photographic silver halide developing agent.

32. A process of producing a negative dye image and a silver image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in a gelatino binder, (a) photosensitive silver halide; and (b) a color-forming para-sulfonamidodiphenylamine dye precursor consisting essentially of 4-dihexyl-amino-4'-(2,4,6-triisopropylbenzenesulfonamido)-diphenylamine;
said process comprising:
(A) developing said photographic element in an aqueous, alkaline, cross-oxidizing, photogra-phic silver halide developer solution comprising a cross-oxidizing photographic silver halide developing agent consisting essentially of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone.

33. A process of producing a negative dye image and a silver image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in a gelatino binder, (a) photosensitive silver halide;
(b) a color-forming para-sulfonamidodiphenylamine dye precursor consisting essentially of 4-hexyl-oxy-3'-methyl-4'-(2,4,6-triisopropylbenzene-sulfonamido)diphenylamine;
said process comprising:
(A) developing said photographic element in an aqueous, alkaline, cross-oxidizing, photogra-phic silver halide developer solution comprising a cross-oxidizing photographic silver halide developing agent consisting essentially of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone.

34. A process of producing a positive dye image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in binder, (a) photosensitive silver halide; and (b) a color-forming para-sulfonamidodiphenylamine dye precursor which is converted upon processing of said element to a dye by cross-oxidation by means of a cross-oxidizing photographic sllver halide developing agent;
said process comprising the steps:
(A) developing a silver image in said photogra-phic element by means of an alkaline, photo-graphic silver halide developer in the absence of a cross-oxidizing, photographic silver halide developing agent;
(B) fogging the resulting element;
(C) producing a dye image in the photographic element by means of an alkaline, cross-oxidizing, photographic silver halide developer; and (D) bleaching and fixing the photographic element by means of a silver halide bleaching and fixing solution;
to produce a positive dye image in the photographic element.

35. A process as in Claim 34 wherein said fogging is performed by means of a uniform flash exposure.

36. A process as in Claim 34 wherein ssid photo-graphic element after step (A) and before step (B) is treated by means of a photographic development stop bath.

37. A process of producing a positive dye image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in a gelatino binder, (a) photosensitive silver halide gelatino emulsion; and (b) a color-forming sulfonamidodiphenylamine dye precursor consisting essentially of 4-hexyl-oxy-3'-methyl-4'-(2,4,6-triisopropylbenzene-sulfonamido)diphenylamine;
said process comprising the steps:

(A) developing said photographic element in an alkaline, photographic developer in the absence of a cross-oxidizing, photographic silver halide developing agent;
(B) treating the photographic element by means of a photographic development stop bath;
(C) fogging the resulting element;
(D) producing a dye image in the photographic element by means of an alkaline, cross-oxidizing, photographic silver halide developer comprising an alkaline solution of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyra-zolidone, and then (E) bleaching and fixing the photographic element in a silver halide bleaching and fixing solution;
to produce a positive dye image in the photographic element.

38. A process of producing a positive dye image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in a gelatino binder, (a) photosensitive silver halide gelatino emulsion; and (b) a color-forming sulfonamidodiphenylamine dye precursor consisting essentially of 4-dihexyl-amino-4'-(2,4,6-triisopropylbenzenesulfonamido)-diphenylamine;
said process comprising the steps:
(A) developing said photographic element in an alkaline, photographic silver halide developer in the absence of a cross-oxidiz-ing, photographic silver halide developing agent;
(B) treating the photographic element by means of a photographic development stop bath;
(C) fogging the resulting element;

(D) producing a dye image in the photographic element by means of an alkaline, cross-oxidizing, photographic silver halide developer comprising an alkaline solution of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyra-zolidone, and then (E) bleaching and fixing the photographic element in a silver halide bleaching and fixing solution;
to produce a positive dye image in the photographic element.

39. A process of producing a negative dye image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in binder, (a) photosensitive silver halide, and (b) a color-forming para-sulfonamidodiphenylamine dye precursor which is converted upon processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halite developing agent;
said process comprising:
(A) developing said photographic element in an alkaline, cross-oxidizing, photographic silver halide developer composition to produce a negative dye image and silver image; then (B) removing at least part of the silver image from the photographic element.

40. A process of producing a negative dye image as in Claim 39 wherein said alkaline, cross-oxidizing developer composition comprises a 1-phenyl-3-pyrazolidone, cross-oxidizing, photographic silver halide developlng agent.

41. A process of producing a negative dye image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in a gelatino binder, (a) photosensitive silver halide, and (b) a color-forming para-sulfonamidodiphenylamine dye precursor consisting essentially of 4-dihexyl-amino-4'-(2,4,6-triisopropylbenzenesulfonamido)-diphenylamine;
said processing comprising:
(A) developing said photographic element in an aqueous, alkaline, cross-oxidizing, photogra-phic silver halide developer solution comprising a cross-oxidizing photographic silver halide developing agent consisting essentially of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone; then (B) removing at least part of the silver image from the photographic element.

42. A process of producing a negative dye image in an imagewise exposed photographic element comprising a support having thereon, in reactive association, in a gelatino binder, (a) photosensitive silver halide, and (b) a color-forming para-sulfonamidodiphenylamine dye precursor consisting essentially of 4-hexyloxy-3'-methyl-4'-(2,4,6-triisopropylbenzenesulfon-amido)diphenylamine;
said process comprising:
(A) developing said photographic element in an aqueous, alkaline, cross-oxidizing photogra-phic silver halide developing solution comprising a cross-oxidizing photographic silver halide developing agent consisting essentially of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone; then (B) removing at least part of the silver image from the photographic element.

43. A process of producing a positive dye image and a positive silver image in an imagewise exposed photo-graphic element comprising a support having thereon, in reactive association, in binder, (a) direct-positive photographic silver halide t and (b) a color-forming para-sulfonamidodiphenylamine dye precursor which is converted upon processing of said element to a dye by cross-oxidation by means of a cross-oxidizing silver halide developing agent;
said process comprising:
(A) developing said photographic element in an alkaline, cross-oxidizing photographic silver halide developing composition; then (B) fixing the resulting photographic element to produce a positive dye image and a positive silver image.

44. A process of producing a positive dye image and a positive silver image in an imagewise exposed photo-graphic element comprising a support having thereon, in reactive association, in a gelatino binder, (a) direct-positive photographic silver halide, and (b) a color-forming para-sulfonamidodiphenylamine dye precursor consisting essentially of 3-methane-sulfonamido-4-methoxy-2'-pivalamido-4'-(2,4,6-triisopropylbenzenesulfonamido) diphenylamine;
said process comprising:
(A) developing said photographic element in an alkaline, cross-oxidizing photographic silver halide developing composition comprising a 3-pyrazolidone silver halide developing agent; then (B) fixing the resulting photographic element to produce a positive dye image and a positive silver image.

45. In an exposed and processed photographic element comprising a support having thereon a dye image, the improvement comprising:
as said dye image, a dye consisting essentially of a sulfonimide dye represented by the formula:

wherein:
R is in the meta or para position and is an electron donating substituent selected from , alkoxy containing 1 to 20 carbon atoms, aryloxy containing 6 to 20 carbon atoms, sulfonamido and carboxamido groups;
R1 is in the ortho or meta position and is hydrogen, alkyl containing 1 to 3 carbon atoms, carbamoyl, alkoxy containing 1 to 3 carbon atoms, sulfonyl-alkyl containing 1 to 3 carbon atoms, sulfonylaryl containing 6 to 12 carbon atoms, chlorine, bromine, iodine or fluorine;
R2 is hydrogen, alkyl containing 1 to 3 carbon atoms, carbamoyl, alkoxy containing 1 to 3 carbon atoms, sulfonylalkyl containing 1 to 5 carbon atoms, sulfonylaryl containing 6 to 12 carbon atoms, chlorine, bromine, iodine or fluorine;

R3 is hydrogen, alkyl containing 1 to 20 carbon atoms, haloalkyl containing 1 to 3 carbon atoms, alkoxy containing 1 to 20 carbon atoms, an ester containing 1 to 20 carbon atoms, carboxy, carbox-amido, chlorine, bromine, iodine, fluorine, carbamoyl, sulfonic acid, sulfamyl, sulfonylalkyl containing 1 to 5 carbon atoms, ureido or a carbo-cyclic group containing 5 to 12 carbon atoms;
R4 is hydrogen, alkyl containing 1 to 3 carbon atoms, alkoxy containing 1 to 20 carbon atoms, an ester represented by the formula , carboxy, carboxamido, chlorine, bromine, iodine, fluorine, carbamoyl, sulfonic acid, sulfamyl, sulfonylalkyl containing 1 to 3 carbon atoms, ureido and a carbocyclic group containing 3 to 6 carbon atoms;
R5 is alkyl containing 1 to 20 carbon atoms or aryl containing 6 to 20 carbon atoms;
R6 is hydrogen, alkyl containing 1 to 20 carbon atoms, , or aryl containing 6 to 20 carbon atoms, or represents, with R7, atoms completing a 5- or 6-member heterocyclic group;
R7 is alkyl containing 1 to 20 carbon atoms carbamoyl, carboxamido, or represents, with R6, atoms completing a 5- or 6-member heterocyclic group;
R8 is alkyl containing 1 to 4 carbon atoms; and R6A is alkyl containing 1 to 20 carbon atoms.

46. An exposed and processed photographic element as in Claim 45 wherein R5 is 2,4,6-triisopropyl-phenyl.

47. An exposed and processed photographic element as in Claim 45 wherein said sulfonimide dye consists essentially of 4-dihexylamino-4'-(2,4,6-triiso-propyl benzenesulfonamido)diphenylamine represented by the formula:

48. An exposed and processed photographic element as in Claim 45 wherein said sulfonimide dye consists essen-tially of 4-hexyloxy-3'-methyl-4'-(2,4,6-triisopropyl-benzenesulfonamido)diphenylamine represented by the formula:

49. An exposed and processed photographic element as in Claim 45 wherein said sulfonimide dye consists essentially of 4-dihexylamino-3'-methyl-4'-(2,4,6-triiso-propylbenzenesulfonamido)diphenylamine represented by the formula:

50. An exposed and processed photographic element as in Claim 45 wherein said sulfonimide dye consists essen-tially of 4-dihexylamino-2'-methylsulfonyl-4'-(2,4,6-tri-isopropylbenzenesulfonamido)diphenylamine represented by the formula:

51. An exposed and processed photographic element as in Claim 45 wherein said sulfonimide dye consists essen-tially of 4-[N-ethyl-N-(.beta.-methanesulfonamidoethyl)-amino]-2-methyl-2',5'-dipivalamido-4'-(2,4,6-triiso-propylenzenesulfonamido) diphenylamine represented by the formula:

52. An exposed and processed photographic element as in Claim 45 wherein said sulfonimide dye consists essen-tially of 4-n-hexyloxy-2',5'-dipivalamido-4'-(2,4,6- tri-isopropylbenzenesulfonamido) diphenylamine represented by the formula:

53. An exposed and processed photographic element as in Claim 45 also comprising a silver image.

54. An exposed and processed photographic element comprising a support having thereon, in reactive associa-tion, in binder, developed silver image enhanced by a sulfonimide dye image wherein said dye image consists essentially of 4-dihexylamino-4'-(2,4,6-triisopropyl-benzenesulfonamido)diphenylamine represented by the formula:

55. An exposed and processed photographic element comprising a support having thereon, in binder, a developed silver image enhanced by a sulfonimide dye image wherein said dye image consists essentially of 4-hexyloxy-3'-methyl-4'-(2,4,6-triisopropylbenzenesulfonamido)di-phenylamine represented by the formula: