Note: Descriptions are shown in the official language in which they were submitted.
1 31 ~4~
--1--
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 ~
--2--
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'-~
--3--
~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
--4--
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
--7--
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:
R4
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
--8--
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
--10--
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
-12-
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
R3
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:
R4 - N
R6
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~
-14-
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~
-16-
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
P3H2
-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:
PO3H2 6
R5 - C - N ~
CoR7
P3H2
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:
P3H2
R - C - 0
P3H2
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
-20-
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
-21-
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
-23-
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
-24-
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:
--27--
1 3 1 ~4 2~
,,
a
.¢ o
~r~
C, ~ ~ ~ ~ ~ ~ ~ ~ ~
~P ~ I ~ ~ O
u~ O O O ~r
N ~ OLtltr~ O I O
a~ --,_1. . . . . . Lt~
~ O-1 0 0 t~ ~ t~ O N _I
~ ~ E~
C ~ ~ ~ ~ ~ Z
O ~ ~ ~ ~ ~ ~ ~ ~,~
c., ~ e ~
.r~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 4
4^ I Ln O ~ O
U _I N~ OU I O ~ ~ O
O O .,1 . . . . . . , ~fl O ~ ~!
æ ~ O ,,~O Ou~ ~ N ~ O 1~
¢ ~ ~ O
O
~i
~ ~ X O
.,1 El J U ~_t
~ .~ ~ a
O O
.,1 1 4
4 _
:r J~
1: ~a ~
~ .,1 ~ tll J ~
4 --` ~ (D 4 Ul
~ ~ o c ~
~ a~ eO a ~ c~ Oe ~ 4
~ ~ w o o o ~e ~
o ~ ~ .,,.~.rl C::
~1 ~ ~o a~ ~ ~
o ~ ~ C
o U o o o~ W r~
~ N O O O.e I
-- _ c ~ ~e r~
O ~ c ~ e ~ o~
c Ln ~ ~ ~e ~
O d ~ w rl ~o o , n ~ ~ ~~-,, ~ .,
C r-l U 2 3 3 ~
e . _f O ~1 .C PC X ~ ~ .C
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~
.~ o o ~f~a~ f l~J
I ~ r~ ZJ~ --~ ¢f J~ f.
1.,l 4 ~ O O ~Of ~l ~ O 1 ~f t'J~ ~ 1~
~-f f':~ æ fL~ fll fi~f ~) 0.1 CL~ ~~ ~ ~ ~ _
Ll~ O LS~ O
1--l ~f C~f
-28- 1 31 ~42/-~
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.
