CA1314424C

CA1314424C - Photographic color developing compositions which are especially useful with high chloride photographic elements

Info

Publication number: CA1314424C
Application number: CA000523217A
Authority: CA
Inventors: Sheridan E. Vincent; Richard W. Berls
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1986-01-24
Filing date: 1986-11-18
Publication date: 1993-03-16
Anticipated expiration: 2010-03-16
Also published as: JPH06100807B2; EP0258288A1; WO1987004534A3; WO1987004534A2; JPS63502222A; EP0258288B1

Abstract

-i-PHOTOGRAPHIC COLOR DEVELOPING
COMPOSITIONS WHICH ARE ESPECIALLY USEFUL
WITH HIGH CHLORIDE PHOTOGRAPHIC ELEMENTS

ABSTRACT OF THE DISCLOSURE
Photographic color developing compositions which are especially useful in the processing of high chloride silver halide photographic elements are free, or at least substantially free, of bromides:
optionally contain a small amount of sulfite; and comprise (1) a primary aromatic amino color develop-ing agent, (2) an N,N-dialkylhydroxylamine, (3) at least one sequestering agent which functions to sequester iron and (4) at least one sequestering agent which functions to sequester calcium. The developing compositions exhibit excellent stability.
They also provide minimal development restraint which permits the use of very short development times, as needed for rapid access processing.

Description

1 31 ~4~

PHOTOGRAPHIC COLOR DEVELOPING COMPOSITIONS
WHICH ARE ESPECIALLY USEFUL ~ITH HIGH
CHLORIDE PHOTOGRAPHIC ELEMæNTS

_IELD OF THE INVENTION
5This invention relates in general to photography and in pa~icular to novel compositions and method~ for processing photog~aphic color elements. More specifically, thi~ invention relates to novel photographic color developing compositions and to a novel method of rapid access proces6ing of high chloride photographic elements utilizing such developing compositions.
BACKGROUND OF THE INVENTION
The formation of color photographic image~
by the image-wi6e coupling of oxidized primary a~omatic amino developing agents with color forming or coupling compound6 to form indoaniline~
indophenol, and azomethine dye6 i~ well known. In the~e processe~, the subtractive proce6s of color formation i6 ordinarily used, and the image dye~
customarily formed are cyan, magenta, and yellow, the colors that aLe complementary to the primary colors, red, green, and blue, respectively. Usually phenol or naphthol coupler~ are used to form the cyan dye image: pyrazolone or cyanoacetyl derivative coupler~ are used to ~orm the magenta dye image: and acylacetamide coupleLs are used to form the yellow dye image.
In these color photographic sy~tem~, the 3 color-forming coupler may be eithe~ in the develope~
solution or incorporated in the light-6en~i~ive photographic emulsion layer ~o that, during development, it i8 available in the emul~ion layer to react with ~he color developing agent tha~ i~
oxidized by silver image development. DiffuEible 1 3 ~

couple~s are used in color developer ~olutions.
Nondiffusing coupler6 are incorporated in photog~a-phic emul~ion layers. When the dye image formed i6 to be u~ed in situ, couplers are selected which form non-diffusing dyes. ~or image transfer color proces~e~, couplers are u~ed which will produce diffu6ible dyes capable of heing msrdanted or fixed in the receiYing 6heet.
Photographic color elements often utilize silver halide emulsions of the high bromide type, including 6ilver b~omide, ~ilver bromoiodide and ~ilver chlorobromide em~lsions. ~oweveL, as explained in Atwell, United States paten~ 4,269,927, issued May 26, 1981, high chloride silver halide photographic element6 -- that i6, elements in which the silver halide grain~ are at least 80 mole percent ~ilver chloride -- po~e~s a number of highly advantageous characteristics. For example, silver chloride possesse~ less native ~ensitivity in the visible region of the spectrum than silver bromide, thereby permitting yellow filter layers to be omitted from multicolor photographic element6. Fu~thermore, high chlocide silver halides are more soluble than high bromide silver hal~des, thereby permitting development to be achieved in shorter times.
Photographic color developing compositions used heretofore have typically been adapted for use with high bromide ~ilver halide photographic elements. These conventional developing compo6itions can be used with high chloride ~ilveL halide photo-gcaphic elemen~s, but, in general, they tend to give less than ~ati~fac~ory re~ults. For example, they typically contai~ ~e6training a~ent~ such as potas~ium bromide, which exert too great a retarda-tion effect on development for sati6factory use withhigh chloride silver halide element~. Mo~eover, they 1314~2'-~

~ypically contain hydroxylamine, or a water-soluble acid ~alt thereof, which func~ions a6 an anti-o~idant and thereby serve~ to protect the primary aromatic amino colo~ developing agent againxt oxidation. Use of hydroxylamine, or a water-soluble acid salt thereof, i6 disadvantageou~, however, since it tend~
to act as a scavenger whi~h reduces oxidized color developing agent ~efore it can react with coupler to form dye. It also ac~s as a develoæing agent which compete~ with the color developing agen~ unle6~ it is adequately restcained by b~omide. In addition to hydroxylamine, or a water-~oluble acid salt thereof, developing compo6itions heletofore u~ed with high bromide silver halide element6 often contain substan-tial concentrations of xulfite to al~o provideprotection again6t oxidation of the developing agent.
The sulfite~ which ifi typically utilized in the fo~m of an alkali metal sulfite or bisul~ite, function~ to sulfonate oxidized color developing agent and, when used in sufficient concentration, its competition with coupler foe oxidized colo~ developing agent ~e~iou~ly a~fect~ dye fo~mation.
IncluAed among the numerous patentfi which describe photographic color deYeloping composition6, of the type typically u~ed with high bromide silver halide element6, are the follow;ng:
Kridel, U. S. paten~ 2,875,049, i6~ued February 24, 1959, Tassone, U. S. patent 3~462,269, i~sued August 19, 1969, Anselm, U. S. patent 3,489,566, i~ued January 13, 1970, ~eilmann, U. S. patent 3,746,544, i66ued July 17, 1973, Brown, U. S. patent 3,839,0~5, ixsued Octobe~ 1, 1974, 1 3 1 ~424 Frank, V. 5. patent 3,994,730, is~ued Novembe~ 30, 1976, Sh;mamura et al, U. S. patent 4,083,723, i~fiued April 11, 1978, Ca~e et al, U. 5. patent 4,170,478, issued 4ctober 9, 1979~
Ca~e, U. S. patent 4,252,892, i~ued February 24, 1981, Vincent et al, U. S. patent 4,264~716, is~ued April 28, 1981, Cappel, U. SO patent 4,394,440, i~ued July 19, 19~3, Kapecki et al, U. S. patent 4,414,307, issued November 8, 1983, Twist et al, U. S. patent 4,482,626, is~ued November 13, 1984.
In light of the above, it is clear that there is a need in the art to provide photographic color developing compositions and photographic processes which are especially adapted for use with high chloride ~ilver halide elements if the inherent advantages of such elements are to be mo~t fully realized. It is toward the objective of filling 6uch need that the present invention is directed.
SUMMARY OF THE INVENTION
The novel photographic color developing compositions of this invention are e~pecially useful with high chloLide 6ilver halide emul~ions. They are free, or at least substantially f~ee, of b~omide6, ~ince bromide~ in significant quanti~ies can unduly restrain the dsvelopmen~ reaction. They a~e free of sulfite, or contain only a low concentration of ~ulfite, to minimize comp~tition with the dye-forming reaceions. They co~ta;n the following ingredienes:
(1) a primary aromatic amino color developing agent, _5_ 1314424 (2) an N,N-dialkylhydroxylamine, (3) at lea6~. one seque6~Qring agent which function6 to sequeRter iron, and 14~ at least one seque~tering agent which functions to ~equester calcium.
In a p eferIed embodiment of the invention, the aforesaid photographic color developing compo6i-tion i6 free of benzyl alcohol and is u~ed in a rapid acces6 proce~s for proce66ing high chloride silver halide photographic color element~ which employ6 the step6 of color developing, bleach-fixing without washing between the color developing and bleach-~ixing step6, and stabilizing without washing between the bleach-fixing and ~tabilizing ~teps. Elimination o~ the benzyl alcohol from the developing composition allow6 the bleach-fix to be utiliæed at a lowe~ pH
than i6 otherwise permis6ible, without the ri~k of producing leuco cyan dye. The low pH increase6 the rate of bleach-fix reactions, thereby enabling the use of a 6hort bleach-fix time as i6 needed for a rapid access process.
DESCRIPTlON OF THE PREFERRED EMBODIMENTS
The primary aromatic amino color de~eloping agent6 that are utilized in the composition6 and method6 of this invention are well known and widely used in a variety of color ~hotographic proces~e~.
They include aminophenols and p-ehenylenedia~ine6~
They are u6ually used in the 6alt form, such as the hydrochloride or ~ulfate, a~ the 6alt form i~ ~ore stable than the free amine, and a~e geneLally employed in concentra~ion~ of from about O.l to about 20 grams per liter of developing solution and ~ore preferably from about 0.5 to about lO sram6 Rer liter of developing ~olu~îon.
Example~ of aminophenol develo2ing agents include o-aminophenol, p-aminophenol, 5-amino-2-hydroxy-toluene, 2-amino-3-hydcoxy-toluene, -6- 1 31 4a 2d 2-hydroxy-3-amino-1,4-dimethylbenzene, ~nd the like.
Particularly u6eful primary aromatic amino color developing agent6 are the p-phenylenediamines and e~pecially the N,N-dialkyl-p-phenylenediamine6 in which She alkyl groups or the aroma~ic nucleu~ can be ~ub~tituted or un6ub~tituted. Example6 of useful p~phenylenediamine color developing agents include:
N,N-diethyl-p-phenylenediamine ~onohydro-chloride, 4-N,N-diethyl~2-methylphenylenediamine monohydrochloride, 4-(N-ethyl-N-2-methanesulfonylaminoethyl)-2-methylphenylenediamine ~esqui6ulfate monohydrate, 4-(N-ethyl-N-2-hydroxyethyl)-2-me~hylphenyl-enedia~n;ne sulfate, ~-N,N-diethyl-2,2'-methanesulfonylaminoethyl-phenylenediamine hydrochloride, and the like.
An especially preferred class of p-phenyl-enediamine developing agents are tho~e containing at lea6t one alkylsulfonamîdoalkyl sub6titutent attached to the aromatic nucleu~ or to an amino nitrogen.
Other especially preferred cla6se& of p-phenylene-diamines are the 3-alkyl-N-alkyl-N-alkoxyalkyl-p-phenylenediamine~ and the 3-alkoxy-N-alkyl-N-alkoxy-alkyl-p-phenylenediamine~. The6e develo~ing agents are de~cribed in United States Patents 3,656,959 and 3,658,525, and can be represented by the formula:
3 CH3 - CH2 - ~ ~ ~CH2)n ~L
NE~2 whelein n i8 an integer having a value of fLom 2 to 4, R i~ an alkyl group of from 1 to 4 carbon atoms, 1 3t ~424 and Rl is an alkyl group of from 1 to 4 carbon atoms or an alkoxy group of from 1 to 4 carbon atoms.
Illustrative examples of these deYeloping agents include the following compounds:

N-ethyl-N-methoxybutyl-3-methyl-p-phenylene-diamine, N-ethyl-N-ethoxyethyl-3-methyl-p-phenylene-diamine N-e~hyl-N-methoxyethyl-3-n-propyl-p-phenyl-enedia~ine, N-athyl-N-metho~ysthyl-3-methoxy-p-phenylene-diamine, N-ethyl-N-butoxyethyl-3-me~hyl-p-phenylene-diamine, and the like.

In addition to the primary aromatic amino color developing agent, the developing compositions of thi~ invention contain an N,N-dialkylhydroxyl-amine. The N,N-dial~ylhydroxylamine can be used in the color developing comeosition in the form of the free amine, but is more typically employed in the form of a water-soluble acid salt. Typical examples of such salts are sulfates, oxalates, chlorides, pho6phates, carbonates, acetates, and the like.
The N,N-dialkylhydroxylamine is preferably of the formula:

R - N - OH
wherein R3 and R4 cepresent the same or dif~erent alkyl groups of 1 to 4 carbon atoms.

1 3 1 4 ~lï 2 lL

Typical examples of N,N-dialkylhydroxyl-amines include:
N,N-diethylhydroxylamine, N-e~hyl-N-methylhydroxylamins, N-ethyl-N-propylhyd~oxylamine, N,N-dipropylhydroxylamine, N-methyl-N-butylhydroxylamine, and the like.
Using the N,N-dialkylhydroxylamine in the photographic color developing compo~itions of this invention provides fully adequate ~tability against oxidation, without the unwanted developmant and unwanted reaction with oxidized color develo~ing agent that occur8 with the use of un~ubstituted hydroxylamines or mono-alkyl ~ub~tituted hydroxylamines. This i8 believed to be a re6ult of the two alkyl group6 at~ached to the nitrogen atom ~erving to block the site at which reaction could otherwise take place.
N,N-dialkylhydcoxylamine~ have been u~ed hecetofore in photographic color developing composi-tions. Thus, for example, they are USQd in the magenta color developing solutions described in An6elm, United State~ eatent 3,48~,566, is6ued 25 January 13, 1970. However, in these magenta develop-ing 601utions, they are employed in combination with an un~ub~tituted or mono-alkylsub~tituted hydroxyl-amine, and they serve as balancing developing agent~.
A~ de~cribed hereinabove, the novel color 3 developing composition6 of thi~ invention contain at least one seque6tering agent which function6 to ~equestec iron. The prefer~ed ~equestering agent for this pu~pose is an aromatic polyhydroxy compound that forms a complex with ferric ion in alkaline solution in which the molar ratio of ~he feLric ion to the 9 131 4h24 aromatic polyhydroxy compound iB 1 to 3. Preferably, the aromatic polyhydroxy compound is a compound having at least two hydroxy groups in ortho-position in relation to each other on an aromatic ring. ~06t preferably, it i~ a compound which has at lea~t two hydroxy groups ;n ortho-position in relation to each other on an aromatic carbocyclic ring and which i6 free of exocyclic unsaturation. Included within ~he bLoad class of aromatic polyhydroxy compound~ which are useful in thi~ invention are, for example, com-pounds of the benzene ~eries and of the naphthalene series, which can be represented by the formula:
, C - OH
/ C - OH
X "
`C ' where X represents the carbon atoms nece6sary to complete the benzene or naphthalene aromatic ring structure. In addition to the hydroxyl substituent~, the acomatic ring structure can be ~ubstituted with groups such as sulfo radicals, carboxy radicals, or halogen atoms. Typical examples of aromatic ~olyhydroxy compounds u~eul in this invention include the following comeounds:
eyrocatechol, 4,5-dihydroxy-m-benzene disulfonic acid, 4,5-dihydcoxy-m-benzene disulfonic acid disodium salt, ~etcabromopyrocatechol, pyrogallol, gallic acid, methyl gallate, propyl gallate, 2,3-dihydroxynaphthalene-6-sulfonic acid, 2,3,8-trihydroxynaphthalene-6-~ulfonic acid, and the like.

1 31 4~2A

In a pceferred embodiment of this invention, the aromatic polyhyd~oxy compound i8 5, 6-dihydlOXy-1,2,4-benzenetri~ulfonic acid or a 5,6-dihydroxy-1,~,4-benzenetrisulfonate (also known a~ a catechol tri6ulfonate or pyrocatechol trisulfona~e). These compounds can be represented by the formula:

OH
~03S ~ OH
M03S ~ S03M
wherein M is hydrogen or a monovalent cation such as sodium or potassium. The most preferred compound of this class is s~6-dihydroxy-l~2~4-benzenetri6ulfonic acid trisodium ~alt.
The 5,6-dihydroxy-1,2,4-benzenetrisulfonic acid trisodium ~alt is advantageously employed in photographic color developing compositions in com-parison with other ~imilar aromatic polyhydroxycompounds, ~uch as 4,5-dihydroxy-m-benzene disulfonic acid disodium salt in that it is more stable to aerial oxidation and has much less tendency to exhibit adverse sen6itomet~ic effects. It can be prepared by oxidation of 4,5-dihydroxy-m-benzene disulfonic acid disodium salt in an alkaline solution containing sulfite. Oxidation can be accompli~hed by bubbling air through the solution or by reaction with a persulfate.
Aromatic polyhydroxy compounds have been used heretofore in photographic color developing compo~itions. Thus, for example, they a~e used in Heilmann, U. S. patent 3,746,544, issued July 17, 1973, in combination with aminopolycarboxylic acid sequestering agents and in Vincent et al, U. S.
patent 4,264,716, issued April 28, 1981, in combina-tion ~ith aminopolyphosphonic acid ~equestering agents.

1 3 1 ~ /1 2 '-1-The primary function of the aromatic poly-hydroxy compound in the photograpllic color developing compositions of this invention i6 to ~eque~ter iron but it can al~o function to 6equester other heavy me~als which can al~o catalyze the auto-oxidation of the N,N-dialkylhydroxylamine. Thus, the aromatic polyhydroxy compound ~tabilizes ~he developing compo-sition and enable6 the N,N-dialkylhydroxylamine to effectively perform it~ function as an anti-oxidant which protects the primary aLomatic amino color developing agent.
As described hereinabove, the novel color developing composi~ions of this invention contain at least one seque6tering agent which function6 to sequester calcium and thereby prevent the formation of unwanted precipitates. The p~eferred sequestering agent for this purpose i~ an aminopolycarboxylic acid seque~tering agent.
The aminopolycarboxylic acid sequestering agents are well known and widely u~ed in photo-graphic proces6ing. Typical examples of the aminopolycarboxylic acid 6equestering agents include:
nitrilotriacetic acid, (NTA), ethylenediamine~et~aacetic acid, (EDTA), 1,3-diamino-2-propanol-M,N,N',N'-tetra-acetic acid, (DPTA), diethylenetciaminepentaacetic acid (DTPA), N,N'-bis(2-hydcoxybenzyl) ethylenediamine-N,N'-diacetic acid (HBED), hydroxyethylethylenediaminetriacetic acid, cyclohexanediaminotetraacetic acid, aminomalonic acid, and the like~
The photographic color developing compo6itions o~ this inven~ion ace employed in the form of aqueous alkaline working solu~ion~ having a 131~42'1 pH of above 7 and mo6t ~ypically in the range of f~om abou~ 9 to abou~ 13. To provide the necessacy pH, they contain one or more of the well known and widely u6ed pH buffering agents, 6uch as She alkali metal carbonates o~ pho62hates. Potassium carbonate i8 e~pecially useful as a pH buffering agent.
A6 indicated above, the four e~sential component~ of the novel photographic coloc developing compo6itions of thi~ invention are the primary aromatic amino color developing agen~, the N,~-dialkylhydroxylamine, the 6eque6tering agent which function6 to ~eque~ter iron and the seque6ter-ing agent which functions to ~eque6ter calcium~ The N,N-dialkylhydroxylamine i~ preferably employed in an amount of ~rom about 1.5 to about 6.0 mole~ per mole of the developing agent, the seque~tering agent which functions to sequester iron is preferably employed in an amount of from about 0.04 to about 0.25 moles per mole of the developing agent, and the ~equestering agent which function~ to 6equester calcium i8 preferably employed in an amount of from about 0.3 to about 1.7 moles per mole of the develoeing agent.
A small amount of ~ulfite can optionally be incorporated in the developing compositions of thi~
invention to pLovide additional protection against oxidation. In view of the fact that sulfite compete6 with coupler for oxidized developing agent, it i6 pEeferred that the amount of sulfite be very 6mall, fo~ example in the range of from zero to about 0.2 30 mole6 per mole of primary aromatic amino color developing agent. The use of a ~mall amount of ~ulfite i~ especially desirable when the color developing compo6ition is packaged in the form of a concentrated 601ution, 6ince 6uch concentrate~ are 35 e6pecially ~u6ceptible to o~idation.

-13- 1 31 ~4 2l-A further ingredient which can optionally be included in the color developing compo~ition i6 an alkanolamins. The alkanolamine6 are primarily useful in providing additional protectio~ again t oxidation. As described in Cafie et al, U. S. patent 4,170,47~, is6ued October 9, 1979, preferred alkanolamines for u~e in photographic color develop-ing composition~ are compounds of the formula:

Rz /

Rl - N

wherein Rl i~ an hydroxyalkyl group of 2 to 6 carbon atoms and each of R2 and R3 i~ a hydrogen atom, an alkyl group of 1 to 6 carbon atom~, an hydroxyalkyl group of 2 to 6 carbon a~oms, a benzyl cadical, or a CnH2n N \ geoup y wherein n iB an integer of from 1 to 6 and each of X
and Y is a hydrogen atom, an alkyl group of 1 to 6 carbon atom~ or an hydroxylalkyl group of 2 to 6 carbon atoms~ Alkanolamines which are especially preferred are compounds of the formula:

wherein R4 is an hydroxyalkyl group of 2 to ~
arbon atoms and each of R and R is an alkyl group of 1 to 4 carbon atom~ or an hydroxyalkyl 1 31 442~

group of 2 to 4 carbon atoms. Typical examples of alkanolamine~ which can be used in the coloc develop;ng compo6itions of this invention include:
e~hanolamine diethanolamine ~riethanolamine di-isopropanolamine Z-methylaminoethanol 2-ethylaminoethanol 2-dimethylaminoethanol 2-diethylaminoethanol l-diethylamino-2-propanol 3-diethylamino-1-propanol 3-dimethylamino-1-propanol isopropylaminoethanol 3-amino-1-peopanol Z-amino-2-methyl-1,3-propanediol ethylenediamine tetraisopeopanol benzyldiethanolamine 2-amino-~-thydroxymethy~ ,3-propanediol and the like.
To improve the claLity of the working developing solution and reduce the tendency for tarring to take place, it is preferred to incorporate therein a small amount of a water-soluble sulfonated polystyrene. The sulfonated polystyrene can be used in the f~ee acid form or in the ~alt form. The free acid form of ~he sulfonated polystyrene i8 comprised of units having the formula:

3 r H H
_ -C-C- _ _ ~ S03~ _ ~

1 31 ar4 2~!

where X ifi an integer repre6enting the number of repeating unit6 in the polymer chain and i~ typically in the range from about 10 to about 3,000 and more preferably in the range from about 100 to about l,ooo, The salt form of the ~ulfonated poly~tyrene i6 comprised of units having the formula:
H H
~ - C C -- ~ S020-l!q~ - X

where X is as defined above and ~ is a monovalent cation, 6uch as, for example, an alkali metal ion.
The ~ulfonated polystyrenes utilized in the developing compositions of this invention can be sub6tituted with sub~tituents such as halogen atoms, hydroxy g~oups, and alkyl groups. For example, they can be sulfonated decivatives of chlorostyrene, alpha methyl styrene, vinyl toluene, and the like. Neither the molecular weight noc the degree of sulfonation are critical, except that the molecula~ weight should not be 80 high nor the degree of sulfonation 80 low as to render the 6ulfonated polystyrene insoluble in aqueou6 alkaline photographic colo~
developing ~olutions. Typically, the average degree of ~ulfonation, that i~ the number of sulfonic acid groups per ~epeating ~tyrene unit, i~ in the range from about 0.5 to 4 and more pceferably in the range from about 1 to about 2.5. A variety of ~alts of the ~ulfonated polrstyrene can be employed, i~clud-ing, in addition to alkali ~etal ~alt6, the amine salts such as ~alt6 of monoethanolam;ne, diethanol-amine, triethanolamine, morpholine, pyridine,picoline, quinoline, and ehe like.

1 31 ~42~

The 6ulfonated polys~yrene can be used in the working developer ~olution in any effective amount. Typically, it is employed in amounts of from about 0.05 ~o about 30 gram6 per liter of developer solution, more u~ually in amounts of from about 0.1 to about 15 grams per liter, and preferably in amount6 of from about 0.2 to abcut 5 gram~ per liter.
In addi~ion ~o or in place of the aminopoly-carboxylic acid 6equestering agent, the photographic color devaloping compositions of this invention can contain an aminopolyphosphonic acid ~equestering agent. The aminopolyphosphonic acid ~squestering agent can be utilized in the form of a free acid or in the form of a water-soluble ~alt. Among the useful aminopolyphos~honic acid sequestering agents are the following:
(1) amino-N,N-dimethylenephosphonic acids of the focmula:
R3 - N(CH2Po3M2)2 wherein M is a hydrogen atom o~ a monovalent cation and R is an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alicyclic group or a heterocyclic radical, and R3 can be further substituted with substituents such as hydroxyl, halogen, an alkoxy group, a - P03M2 group, a -CH2P03M2 group, or an -N(CH2P03M2)2 group;
(2) aminodiphosphonic acids of the formula:
P3Hz R ~ C - ~H2 -17- 1 31 ~4 2l in which R4 i8 an alkyl group, p~efelably of one to five ca~bon atoms, and (3) N-acylaminodipho6phonic acids of the formula:

R5 - C - N ~
CoR7 where R5, R6 and R7 a~e hydrogen or an alkyl group, preferably alkyl of one to five ca~bon atoms.
Typical examples of the aminopolyphosphonic acid 6eques~ering agent~ u6eful in the novel color developing compo~itions of thi6 invention include:
l-aminoethane-l,l-diphosphonic acid, l-aminopropane-l,l-dipho6phonic acid, N-acetyl-l-aminoethane-l,l-diphosphonic acid, ethylenediamine-N,N,N',N'-tetramethylene-phosphonic acid, nitlilo-N,N,N-trimethylenepho6phonic acid, 1,2-cyclohexanediamine-N,N,N',N'-tetra-methylenepho6phonic acid, o-ca~boxyanilino-N,N-dimethylenepho~honic acid, propylamino-N,N-dimethylenephosphonic acid, 4-(N-py~rolidino)butylamine-N,N-bi6tmethyl-ene pho~phonic acid, 1,3-diaminop~opanol-N,N,N',N'-tetramethylene-pho phonic acid, 1,3-propanediamine-N,N,NI,N'-tetrame~hylene-phosphoni~ acid, 1,6-hexanediamine-N,N,N',N'-tetramethylene-phosphonic acid, -18- 1314~24 o-acetamidobenzylamino-N,~-dimethylenepho~-phonic acid, o-toluidine-N,N-dimethylenepho~phonic acid, 2-pyridylamino-N',N'-dime~hylenGphosphonic acid, diethylenetriamine pentamethylenephosphonic acid, and the like.
Othe~ particularly u6eful seque~tering agents for photographic color developing composition~ are the hyd~oxyalkylidenedipho6phonic acid sequestering agent~ oP the formula:

where R i6 alkyl of 1 to 5 carbon atoms.
The hydroxyalkylidenedipho6phonic acid 6eque6tering agent6 can ~e~ve a6 both the ~eque~tel-ing agent which function~ to ~eque6ter iron and the sequestering agent which function6 to ~eque6ter calcium, as they have the ability to effectively 6eque6tec both iron and calcium. A8 de6cLibed in Brown, V. S. Patent 3,839,045 i6sued October 1, 1974, they are preferably utilized in combination with small amount~ of lithium 6alt6, ~uch a~ lithium sulfate.
~dditional ingcedients which can optionally be included in the photographic color developing compo6ition~ of this invention include thickening agent~, bLightening agent~, wetting agents, ~tain reducing agents, and so forth.
3 The photographi~ color developing compo~i-tion~ of thi~ invention are prefe~ably ~ree, or at -19- 131~!2~, lea~t ~ubstantially free, of bromide6. By the term "6ubstantially free" is meant a concentration of bLomide of not more than about 0.01 mole~ per mole of primary aromatic amino color developing agent. As i~ well known, bromide6 are very active development re6trainer~. To achieve the objective of a very short development time, it i6 nece~6ary to have little or no bromide in the developing 601ution.
~here the emul~ions u6ed are all-chloride emulsion6, then there will not be any b~omide present in ~he developing ~olution a6 a result of leaching from the element. A~ previou~ly explained herein, high chloride 6ilver halide elements are elements in which the silver halide grains are at lea~t 80 mole percent ~ilvec chloride. Thus, while high ~hloride 6ilver halide ele~lent6 can contain 6mall amount~ of 6ilver bromide or ~ilver bromoiodide, the amount6 are low enough that the concentration of bromide in the developing solution thae re6ults from leaching is low, and the restraining effect i6 not pronounced.
Chloride will, of cour~e, be leached from high chloride silver halide element6, but chloride i~
not nearly as active a development restrainer a6 bromide. An important objective of the preferred embodiment6 of this invention i6 to have minimal development restraint from either developing compo6i-tion component6 or from 6ea~0ning product~ that leach ~rom the photographic element. Thu6, while the wocking 601ution may contain chloride that has leached from the element, typically no chlo~ide i6 incorporated in the ~epleni~hec solution.
It i~ particularly pcefe~red that the photo-graphic color developing compositions of this invention be free of benzyl alcohol. In the past, benzyl alcohol ha~ typically been u6ed in the proce~ing of color pIint papers to function as a 1 3 1 ~ 2/-1 coupling accelerator. Since the developing compo~itions of ~his invention are designed to have minimal development restraint -- and 6ince oxidation protection i~ provided by u~e of an N,N-dialkyl-hyd~oxylamine, optionally with the additional use ofa small amount of ~ulfite, and therefore without introducing significant compe~ition with coupler fo~
oxidized developing agent -- ~hey do not require the u~e of benzyl alcohol. Elimination of benzyl alcohol has ~everal benefits. For example, it p~ovides impLoved mixability of the developing compo6ition component6 and it provides the environmental improve-ment of reduced biological oxygen demand. A furth~r advan~age i~ that for those proces6e6 in which a bleach-fix i6 u~ilized, the elimination of benzyl alcohol from the developer enable~ the pH of the bleach-fix to be ceduced without the risk of produc-ing leuco cyan dye. The reduced pH increase6 the rate of bleach-~ix reactionsl and thereby allow6 a very short bleach-fix time and, accordingly, facilitate6 accompli~hment of the goal of a very 6hort total eroces6ing time. Yet another advantage of eliminating benzyl alcohol from the color develop-ing compo&ition i6 that thi6 will help in avoiding or minimizing edge staining of the photog~aphic print, as de~cribed for example in Tamagawa et al, United States Patene 4,433,030, i6sued February 21, 1984.
ln the production of color photogeaphic image6, it i~ nece~6ary to remove the silver image which i~ formed coincident wi~h the dye image. This can be done by oxidizing the ~ilver by mean~ of a 6uitable oxidizing agent, commonly referred to a6 a bleaching agent, in the presence of halide ion followed by dissolving the silver halide ~o formed in a 6ilver halide ~olvent, commonly referred to as a 131442'1 fixing agent. Altecnatively, the bleaching agent and fixing agent can be combined in a bleach-fixing ~olution and the silve~ {emoved i~ one step by use of ~uch ~olution.
Color p~int paper6 are most commonly proce66ed by uae of a bleach-fixing 601ution. The bleaching agent i~ typically a fe~ric complex of an aminopolycarboxylic acid, mo6t usually the fe~ric complex of ethylenediaminetetraacetic acid (EDTA).
The fixing agen~ i~ typically a thiosul~ate 6uch a6 sodium thiosulfate or ammonium thio6ulfate.
In p~oce6siny color p~int pape~, the bleach-fixing step can be followed by a ~tabilizing ~tep in whi~h ~he print i6 proces6ed in a ~tabilizing bath to reduce fading of the dye image~
and staining of the print that can result from exposure to high humiditie6 and/or high temperatu~es.
The stabilizing bath will typically contain an aldehyde, such as focmaldehyde, which i6 known to ~eact with the active methylene group6 on ~esidual color-forming couplers, and thufi p~event them from reacting with the image dye6. In addition to the aldehyde, the stabilizing bath can contain a variety of other agent~ 6uch a6 6equestering agent6, buffering agents, and biocides. Particularly effective 6tabilizing bath6 for u6e in the p~oces6 of thi6 invention are described in Mowrey, U. S.
patent 3,676,136, is~ued July 11, 1972.
The novel color developing ~ompositio~ of 3 thi6 inventio~ are e6pe~ially u~eful in the process-ing of color print pape~ utilizing high chloride 6ilvel halide emul~ion layer~ and particula~ly in the proces6ing of ~uch papers in a rapid acce~s proce6s compri~ing the step~ of ~olor developing, bleach-fixing without a wash ~tep betveen the step~ of colordeveloping and blea~h-fixing, and fitabilizing without ~2 1 31 ~4 2 a wash 8tep between the step6 of bleach-fixing and stabilizing. The bleach-fixing compo~ition i8 compri6ed of a thiosulfate fixing agent and a ferric ~omplex of an aminopolycarboxylic acid, which acts a~ a bleaching agent, while the stabilizing composi-tion contains an aldehyde a~ the 6tabilizing agent.
Such a proce6s involve~ only ~he three ~teps of colsr developing, bleach-fixing and ~tabilizing -- followed by a short drying 6tep -- 80 it i6 especially well adapted to the very short total proces~ing ~ime that is needed in ~o-called "mini-lab" processing facili-ties. The wash steps are omitted in the interest of achieving the shorte~t po~sible total processing time and reducing the total amount of effluent.
In a particularly preferred embodiment, the present invention provides a method of rapid access proce~ing of a high chloride silver halide photogra-phic color print paper, which compri6e6 the step6 of:
tl) developing for a period of about 30 to about 60 ~econds at a temperature of about 30 to about 40C in a color developing composition having a pH in the range of from about 9 to about 13 and comprising (a) a primary aromatic amino color developing agent, (b) an N,N-dialkylhyd~oxylamine, (c) at least one seque6tering agent which functions to sequester iron, and (d) at lea~t one sequestering agent which functions ~o sequester calcium, (2) bleach-fixing, without washing be~ween the developing and bleach-fixing s~ee~, foI a pe~iod of about 30 to about 60 seconds at a temperature of abou~ 25~C to about 40 C in a bleach-fix composition having a pH in the cange of from about 5 to about 8 and more preferably in ~he range of from about 6 to about 7 and compri~ing a thiosulfate fixing agent and a bleaching agent which i~ a ferric complex of an a~inopolycarboxylic acid;

1 3 1 4 ~. 2l-r and (3~ stabilizing, without wa6hing between the bleach-fixing and 6tabilizing step~, for a period of about 60 to absut 120 second6 at a temperature of about 25 to about 40 C in a ~tabilizing compoEi-tion having a pH in the range from about 5 to about8 and comprising an aldehyde that function6 a6 a stabilizing agent.
Following comple~ion of the stabilizing step, the print i8 dried for a brief ~eriod. Drying for about one ~inute at a temperature of about 60C is usually adequate.
5ince, in the preferrQd proces~ of this invention, no wa~hing step~ are utilized, there is carry-over of bleach-fixing composition into the stabilizing bath. The thio&ulfate which i8 thereby carried into the ~tabilizing bath can undergo 6ulfurization. However, the tendency for 6ul~uriza-tion to occur can be eliminated, or at least reduced, by u~e of a stabilizing bath containing an aldehyde bi6ulfite adduct, such as those de6cribed in Mowrey, U. S. patent 3,676,136. In addition to the aldehyde bisulfite adduct, the 6tabilizing bath advantageously comprise~ an aminopolycarboxylis acid seque6tering agent, of the type hereinbefore described, and an 25 aminopolyphosphonic acid seque6tering agent or hydroxyalkylidenedipho6phonic acid sequestering agent of the types hereinbefsre de6cribed. The aminopoly-carboxylic acid 6equesters calcium, and thereby prevents the formation of unwanted precipitatec, and 30 also protects the ~ulfite again~ oxidation. The aminopoly~hosphonic acid or hydroxyalkylidenedipho6-phonic acid ~eque6ter~ heavy metal~, such a~ copper and iron, and thereby prevent~ such ~etal~ from cataly~ing the oxidation of sulfite. It also 35 provides protection against yellowing of photographic prin~& cau~ed by retained iron. Another u6eful 1 3 1 ~4 2l-1 ingredient in a ~tabilizing bath of thi~ typ~ i~ a biocide. Examples of particulally useful biocides are ~hiazoles ~uch as 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one.
The individual ingredient6 employed in the photographic color developing compositions of this invention have been employed heretofo~e in one o~
other of the photographic color developing compo~i-tions de6cribed in the United States patents listed hereinabove. However, the particular combination of ingredients utilized in the ~olor developing composi-tions of this invention is a novel combination, and is unexpectedly advantageous in providing a develop-ing composition which i6 especially adapted for u~e with high chloride silver halide element6, and i~
particularly well adapted for u6e in the rapid acce~s proces6 described herein in which total wet proces6ing time i~ a6 little a~ three minutes.
It should be particularly noted that 5,6-dihydroxy-1,2,4-benzenetri6ulfonic acid has not been employed heretofore in photographic color developing compo~itions, and that its use (in either acid or salt form) repre~ents an impor~ant feature of ~he most preferred embodiment of the present inven~ion.
25 A~ compared with 6imilaL compounds which have previou~ly been used in color developing compositions -- such as the 4,5-dihydroxy-m-benzenedi6ulfonic acid described in United States patent 3,746,544 --it provides several important advantages. Thus, for 3o example, it has improved stability in alkaline ~olutions and i~ more s~able to aerial oxidation.
Moreover, it ha6 much less of a tendency to e~ert adver~e sensitomet~ic effec~s.
It fihould also be noted that the N,N-35 dialkylhydroxylamine i6 utilized in the developing compoRition of thi6 invention as an anti-oxidant.

-25- 1 31 ~42ll, This i~ in contra~t ~ith i~s typical u~e in the prior art, for example, in United States patent 3,489,566, in which it is used pri~arily a6 a balancing developing agent, that is as an agent which react~
5 with exposed 6ilver halide ~o as to function as an auxiliary developing agent.
In U. S. patents 4,170,478 and 4,Z64,716, the hydLoxylamine~ which are used in the color developing compositions de~cribed are hyd~oxylamines of the formula:
H

~ - N - OH
where R i8 hydrogen or alkyl, and wateL-soluble acid salts thereof. Thus, the hydroxylamine6 in these patent6 are un~ub~tituted hydroxylamines or mono-15 alkyl-sub~tituted hydroxylamines. In the present invention, dialkyl-substituted hydroxylamines are utilized rather than un~ub6tituted hydroxylamines or mono-alkyl-~ub6tituted hydroxylamines. The dialkyl-sub6tituted hydroxylamine~ have been unexpectedly 20 found to provide sati6factory protection against oxidation, while having the advantage that they do not reduce oxidized developer before it can react to form dye, and the further advantage that they are much slower developing agents than un~ubstitu~ed 25 hydroxylamine~ oc mono-alkyl-6ubstituted hydroxyl-amine6. Thu6, by using the dialkyl-sub~tituted hydroxylamine and no sulfite, or a very low level of sulfite, competition with couplers in the dye-forming reactions is effectively avoided.
3 The invention is further illustrated by the following example of it~ prac~ice:
A photographic color print paper of the high chloride type, as described in Atwell, U. S. patent 4,269,927 issued May 26, 1981, wa~ proce~sed in a -26- ~ 3~f~-12~,1 three-step process cons;sting of a 45 ~econd develop-ment ~tep, a 45 second bleach-fix step and a 90 second stabilization step. Each of the three s~eps wa~
carried out at a temperature of 35C and the print was dried for one minute at 60C. No washing steps were u~ed in the pcoces~. ~he developing compo6ition exhibited excellent ~tability and the ~roce~s provided excellent re6ult6, even ~hough the total wet time was only three minutes, and thu6 achieved the objective of high quality rapid-acce6s p~oce~ing, which is especially useful in a "mini-lab" facility. The color developing, bleach-fixing and stabilizing compo~ition6 used in the proces~ were as follow6:

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tlt O .e fE~ e z ¢ c ~ ~ z ~ :1 ~ ~ oP-- u, f3 ~f~1)r-l ~11 U rl N J ~ O In1') 1 I.r~ u C~
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Bleach-Fixinq Composition The bleach-fixing composition had a pH of 6.2 and was comprised of ammonium thio~ulfate, sodium bi~ulfite, and an ammonium salt of the ~erric complex of ethylenediaminetetraacetic acid.

Stabilizing Com~osition The ~tabilizing composition had a pH of 7.2 and wa6 comprised of ~ormaldehyde, sodium metabi-sulfite, pota6sium hydroxide, die~hylene glycol, 5-chloro-2-methyl-~-isothiazolin-3-one, the disodium salt of ethylenediaminetetraacetic acid, and l-hydroxyethylidene-l,l~diphosphsnic acid. (In this formulation~ the diethylene glycol 6erves as a solvent for the 5-chloro-2-methyl-4-i60thiazolin-3-one).
An important feature of this invention isthat there is minimal development restraint and this permits rapid acce6s processing. ~oreover, the rapid acce6s processing does not requiLe high development temperatures and can be achieved with development temperatures of a~ low as about 15C.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims

1. A photographic color developing composition which is especially useful in the development of high chloride silver halide photographic elements, said composition being substantially free of bromides and comprising:
(1) a primary aromatic amino color developing agent, (2) an N,N-dialkylhydroxylamine.
(3) at least one sequestering agent which functions to sequester iron, and (4) at least one sequestering agent which functions to sequester calcium.

2. A photographic color developing composi-tion as claimed in claim 1 wherein said sequestering agent which functions to sequester iron is an aromatic polyhydroxy compound that forms a complex with ferric ion in alkaline solution in which the molar ratio of the ferric ion to the aromatic polyhydroxy compound is 1 to 3, and said sequestering agent which functions to sequester calcium is an aminopolycarboxylic acid sequestering agent.

3. A photographic color developing composition as claimed in claim 1 wherein an hydroxylalkylidenediphosphonic acid sequestering agent is employed as both the sequestering agent which functions to sequester iron and the sequestering agent which functions to sequester calcium.

4. A photographic color developing composition which is especially useful in the development of high chloride silver halide photographic elements, said composition being substantially free of bromides and benzyl alcohol and comprising:
(1) a primary aromatic amino color developing agent, (2) an N,N-dialkylhydroxylamine, (3) an aromatic polyhydroxy compound that forms a complex with ferric ion in alkaline solution in which the molar ratio of the ferric ion to the aromatic polyhydroxy compound is 1 to 3, (4) at least one aminopolycarboxylic acid sequestering agent, (5) at least one pH buffering agent, and (6) from zero to 0.2 moles of sulfite per mole of said primary aromatic amino color developing agent.

5. A photographic color developing composition as claimed in claim 1 additionally comprising an alkanolamine.

6. A photographic color developing composition as claimed in claim 1 additionally comprising triethanolamine.

7. A photographic color developing composition as claimed in claim 1 additionally comprising a water-soluble sulfonated polystyrene.

8. A photographic color developing composition as claimed in claim 4, additionally comprising triethanolamine and a water-soluble sulfonated polystyrene.

9. A photographic color developing composition as claimed in claim 1 wherein the primacy aromatic amino color developing agent is 4-(N-ethyl-N-2-methanesulfonylaminoethyl)-Z-methyl-phenylenediamine sesquisulfate monohydrate.

10. A photographic color developing composition as claimed in claim 1 wherein said N,N-dialkylhydroxylamine has the formula wherein R3 and R4 represent the same or different alkyl groups of 1 to 4 carbon atoms.

11. A photographic color developing composition as claimed in claim 4 wherein said aromatic polyhydroxy compound has the formula:

where X represents the caebon atoms necessary to complete a benzene or naphthalene aromatic ring structure.

12. A photogcaphic color developing composition as claimed in claim 4 wherein said N,N-dialkylhydroxylamine is N,N-diethylhydroxylamine.

13. A photographic color developing compo-sition as claimed in claim 4 wherein said aromatic polyhydroxy compound is 5,6-dihydroxy-1,2,4-benzenetrisulfonic acid trisodium salt.

14. A photographic color developing composition as claimed in claim 4 wherein said aminopolycarboxylic acid sequestering agent is ethylenediaminetetraacetic acid.

15. A photographic color developing composition which is especially useful for the development of high chloride silver halide photographic elements, said composition being substantially free of bromides and benzyl alcohol and comprising:
(1) 4-(N-ethyl-N-2-methanesulfonylamino-ethyl)-2-methylphenylenediamine sesquisulfate monohydrate, (2) N,N-diethylhydroxylamine, (3) 5,6-dihydroxy-1,2,4-benzenetri-sulfonic acid trisodium salt, (4) the disodium salt of ethylenediamine-tetraacetic acid, (5) the lithium salt of sulfonated polystyrene, (6) triethanolamines (7) potassium sulfite, and (8) potassium carbonate.

16. A method of rapid access processing of a high chloride silver halide photographic color element, said method comprising the steps of:
(1) developing said element for a period of about 30 to about 60 seconds at a temperature of about 30°C to about 40°C in a color developing composition having a pH in the range of from about 9 to about 13, said color developing composition being substantially free of bromides and comprising:
(a) a primary aromatic amino color developing agent, (b) an N,N-dialkylhydroxylamine, (c) at least one sequestering agent which functions to sequester iron, and (d) at least one sequestering agent which functions to sequester calcium:
(2) bleach-fixing said element, without washing between the developing and bleach-fixing steps, for a period of about 30 to about 60 seconds at a temperature of about 25°C to about 40°C in a bleach-fix composition having a pH in the range of from about 5 to about 8 and comprising a thiosulfate fixing agent and a ferric complex of an aminopoly-carboxylic acid that functions as a bleaching agent;
and (3) stabilizing said element, without washing between the bleach-fixing and stabilizing steps, for a period of about 60 to about 120 seconds at a temperature of from about 25°C to about 40°C in a stabilizing composition having a pH in the range of from about 5 to about 8 and comprising an aldehyde that functions as a stabilizing agent.

17. A method as claimed in claim 16 wherein said sequestering agent which functions to sequester iron is an aromatic polyhydroxy compound that forms a complex with ferric ion in alkaline solution in which the molar ratio of the ferric ion to the aromatic polyhydroxy compound is 1 to 3 and said sequestering agent which functions to sequester calcium is an aminopolycarboxylic acid sequestering agent.

18. A method as claimed in claim 16 wherein an hydroxyalkylidenediphosphonic acid sequestering agent is employed as both the sequestering agent which functions to sequester iron and the sequester-ing agent which functions to sequester calcium.

19. A method of rapid access processing of a high chloride silver halide photographic color element, said method comprising the steps of:
(1) developing said element for a period of about 30 to about 60 seconds at a temperature of about 30°C to about 40°C in a color developing composition having a pH in the range of from about 9 to about 13, said color developing composition being substantially free of bromides and benzyl alcohol and comprising:
(1) a primary aromatic amino color developing agent, (2) an N,N-dialkylhydroxylamine, (3) an aromatic polyhydroxy compound that forms a complex with ferric ion in alkaline solution in which the molar ratio of the ferric ion to the aromatic polyhydroxy compound is 1 to 3, (4) at least one aminopolycarboxylic acid sequestering agent, (5) at least one pH buffering agent, and (6) from zero to 0.2 moles of sulfite per mole of said primary aromatic amino color developing agent;
(2) bleach-fixing said element, without washing between the developing and bleach-fixing steps, for a period of about 30 to about 60 seconds at a temperature of about 25°C to about 40°C in a bleach-fix composition having a pH in the range of from about 5 to about 8 and comprising a thiosulfate fixing agent and a ferric complex of an aminopoly-carboxylic acid that functions as a bleaching agent;
and (3) stabilizing said element, without washing between the bleach-fixing and stabilizing steps, for a period of about 60 to about 120 seconds at a temperature of from about 25°C to about 40°C in a stabilizing composition having a pH in the range of from about 5 to about 8 and comprising an aldehyde that functions as a stabilizing agent.

20. A method as claimed in claim 19, wherein said color developing composition addition-ally comprisies an alkanolamine.

21. A method as claimed in claim 19, wherein said color developing composition addition-ally comprises triethanolamine and a water-soluble sulfonated polystyrene.

22. A method as claimed in claim 19, wherein said N,N-dialkylhydroxylamine has the formula:

wherein R3 and R4 represent the same or different alkyl groups of 1 to 4 carbon atoms.

23. A method as claimed in claim 19, wherein said N,N-dialkylhydroxylamine is N,N-diethylhydroxylamine.

24. A method as claimed in claim 19, wherein said aromatic polyhydroxy compound is 5,6-dihydroxy-1,2,4-benzenetrisulfonic acid trisodium salt.

25. A method as claimed in claim 19, wherein said bleach-fixing composition has a pH in the range of from about 6 to about 7.

26. A method as claimed in claim 19, wherein said stabilizing composition comprises an aldehyde bisulfite adduct.

27. A method as claimed in claim 19, wherein said stabilizing composition comprises a thiazole compound which functions as a biocide.

28. A method as claimed in claim 19, wherein said stabilizing composition comprises an aminopolycarboxylic acid sequestering agent, and a member selected from the group consisting of amino-polyphosphonic acid sequestering agents and hydroxy-alkylidene diphosphonic acid sequestering agents.

29. A method of rapid access processing of a high chloride silver halide photographic color paper, said method comprising the steps of:
(1) developing said color paper for a period of about 45 seconds at a temperature of about 35°C in a color developing composition having a pH
of about 10, said color developing composition being substantially free of bromides and benzyl alcohol and comprising:
(a) 4-(N-ethyl-N-2-methanesulfonylamino-ethyl)-2-methylphenylenediamine sesquisulfate monohydrate, (b) N,N-diethylhydroxylamine, (c) 5,6-dihydroxy-1,2,4-benzenetrisulfonic acid trisodium salt, (d) the disodium salt of ethylenediamine-tetraacetic acid, (e) the lithium salt of sulfonated polystyrene, (f) triethanolamine, (g) potassium sulfite, and (h) potassium carbonate:
(2) bleach-fixing said color paper, without washing between the developing and bleach-fixing steps, for a period of about 45 seconds at a temperature of about 35°C in a bleach-fix composition having a pH of about 6 and comprising ammonium thiosulfate and the ammonium salt of a ferric complex of ethylenediaminetetraacetic acid;
and (3) stabilizing said color paper, without washing between the bleach-fixing and stabilizing steps, for a period of about 90 seconds at a temperature of about 35°C in a stabilizing composition having a pH of about 7 and comprising formaldehyde, sodium metabisulfite, potassium hydroxide, diethylene glycol, 5-chloro-2-methyl-4-isothiazolin-3-one, the disodium salt of ethylenediaminetetraacetic acid, and 1-hydroxyethylidene-1,1-diphosphonic acid.