Photographic elements containing particular color couplers in combination with hydroquinone type stabilizers

A photographic element having at least one photosensitive silver halide layer and associated therewith both a particular type of color coupler and a particular type of stabilizer. The color coupler is of the general formula (1) or (2): ##STR1## wherein A and B represent the same or different electron-withdrawing group, PA1 X is H or a group which splits off on coupling with oxidized color developer, PA1 R is an alkyl, cycloalkyl, aryl or heterocyclic which may be substituted, --COR.sup.1, --CSR.sup.1, SOR.sup.1, SO.sub.2 R.sup.1, --NHCOR.sup.1, --CONHR.sup.1, --COOR.sup.1, --COSR.sup.1, --NHSO.sub.2 R.sup.1 wherein R.sup.1 is an alkyl, cycloalkyl, or aryl group any of which are optionally substituted, and wherein two or more of A, B, R, and X optionally form part of a ring, PA1 Link is a linking group and PA1 n is 0, 1 or 2. The stabilizer is of the general formula: ##STR2## wherein: E.sup.1, E.sup.2, W.sup.2 and W.sup.3 may independently be a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, an acylamino group, a mono or dialkylamino group, an aliphatic or aromatic thio group, an aliphatic or aromatic oxycarbonyl group, or W.sup.2 and W.sup.3 in combination with the benzene ring may independently represent the atoms necessary to complete a fused ring system, or E.sup.1 and W.sup.3 together, and E.sup.2 and W.sup.2 together, may independently form a heterocyclic ring with an O.

FIELD OF THE INVENTION 
This invention relates to photographic elements containing both a 
particular class of color couplers and stabilizers that are particularly 
effective with the foregoing class. 
BACKGROUND OF THE INVENTION 
Color photographic elements typically contain several records each with 
silver halide sensitized to a different region of the visible light 
spectrum. Generally, one record is sensitized to red light, another green 
light and another, blue light. Each of the foregoing records also contains 
a color coupler which reacts with oxidized developer during processing of 
the element, to produce a dye in a pattern corresponding to the image to 
which the element was exposed. In a typical element the red, green and 
blue sensitive records respectively contain a cyan dye forming coupler, a 
magenta dye forming coupler and a yellow dye forming coupler. 
As to the colour couplers, these are known to belong to a number of 
classes, for example magenta dye-forming couplers can be pyrazolones, 
pyrazolotriazoles and pyrazolobenzimidazoles while yellow dye-forming 
couplers can be acetanilides. European Patent Specification 0 431 374 A 
describes .beta.,.gamma.-unsaturated nitriles as cyan colour couplers of 
the general formula: 
EQU R.sub.2 --V.dbd.C(R.sub.1)--CH(W)--CN 
wherein 
W is hydrogen or an atom or group capable of being released when the 
compound is subjected to a coupling reaction with oxidised product of an 
aromatic primary amine derivative and is attached to a carbon atom having 
an sp.sup.3 electronic configuration, 
R.sub.1 is a substituent, 
V is nitrogen or --C(R.sub.3).dbd., 
if V represents nitrogen, R.sub.2 represents a substituent, 
if V represents --C(R.sub.3).dbd., R.sub.2 and R.sub.3 each represent a 
substituent, provided that at least one of R.sub.2 and R.sub.3 represent 
an electron attractive substituent, and provided that if R.sub.2 or 
R.sub.3 represents an aliphatic group or an aromatic group, the other does 
not represent an acyl group, and 
R.sub.1 and R.sub.2 may bond together to form a ring.

The color couplers used in the photographic elements of the present 
invention, as described below, are distinct from those of European 
Specification 0 431 374A because, inter alia, the coupling position is a 
carbon atom having an sp.sup.2 electronic configuration and the compounds 
are .alpha.,.beta.-unsaturated. No examples of them appear in EP 0 431 
374A, nor is any method of making them disclosed. 
"Preparation and Reactions of 1,2-dicyano-1,2-disulfonylethylenes" by E. L. 
Martin, Journal of the American Chemical Society, Aug. 20, 1963 at page 
2449, describes compounds of the formula: 
EQU RNH--C(CN).dbd.C(CN)--SO.sub.2 R. 
The method of preparation means that only compounds having the --SO.sub.2 R 
can be prepared. In addition there is no disclosure of ballasted 
compounds. 
The dyes that are formed by any color coupler during processing have a 
tendency to fade over time particularly as a result of exposure to light. 
As all three image dyes of a typical color element fade, this 0 results in 
overall fading of the image over time. In addition, since the three image 
dyes may not fade at the same rate, an apparent change in image color also 
results. Stabilizers are classes of compounds which reduce the foregoing 
image dye fading problem. Such stabilizers include phenols, bis-phenols, 
blocked phenols, blocked bis-phenols, metal and other organic complexes 
and other compounds used in conjunction with many different color 
couplers. Photographic elements containing the foreogoing color coupler 
and stabilizer combinations are described, for example, in EP 0 298 321; 
EP 0 231 832; EP 0 161 577; EP 0 218 266; U.S. Pat. No. 3,043,697; U.S. 
Pat. No. 3,700,455; Kokai JP 62043-641, JP 01137-258, JP 01144-048; U.S. 
Pat. No. 4,782,011 and U.S. Pat. No. 4,748,100. 
It is desirable then, to provide photographic elements which incorporate a 
color coupler with advantageous properties, and which elements also 
incorporate a stabilizer which is effective at stabilizing image dyes 
formed from such a color coupler. 
SUMMARY OF THE INVENTION 
The present invention provides photographic elements containing a 
particular class of couplers in combination with a particularly effective 
class of stabilizers. As to the color couplers, these are capable of 
forming dyes having good spectral characteristics such as maximum 
wavelength (.lambda..sub.max) and half-band width, little unwanted 
absorption of blue light and good fastness properties. Both magenta and 
yellow dye formation has been observed. 
According to the present invention there are provided photographic elements 
comprising at least one photosensitive silver halide layer and in or 
adjacent said silver halide layer a colour coupler of the class described 
below. The elements also have, in the same layer as the color coupler, a 
stabilizer of the class described below. 
As to the color coupler, these are of the general formulae: 
##STR3## 
wherein A and B represent the same or different electron-withdrawing 
group, 
X is H or a group which splits off on coupling with oxidised colour 
developer, 
R is an alkyl, cycloalkyl, aryl or heterocyclic group any of which may be 
substituted, --COR.sup.1, --CSR.sup.1, SOR.sup.1, SO.sub.2 R.sub.1, 
--NHCOR.sup.1, --CONHR.sup.1, --COOR.sup.1, --COSR.sup.1, --NHSO.sub.2 
R.sub.1 wherein R.sup.1 is an alkyl, cycloalkyl, or aryl group any of 
which are optionally substituted, and wherein two or more of A, B, R, and 
X optionally form part of a ring, 
Link is a linking group and 
n is 0, 1 or 2. 
It is noted that formulae (1) and (2) represent geometric isomers (cis and 
trans versions) of the same compound. 
As to the stabilizers these are of general formula (I) below: 
##STR4## 
wherein: 
E.sup.1, E.sup.2, W.sup.2 and W.sup.3 may independently be a hydrogen atom, 
a substituted or unsubstituted aliphatic group, a substituted or 
unsubstituted aromatic group, an acylamino group, a mono or dialkylamino 
group, an aliphatic or aromatic thio group, an aliphatic or aromatic 
oxycarbonyl group, or W.sup.2 and W.sup.3 in combination with the benzene 
ring may independently represent the atoms necessary to complete a fused 
ring system, or E.sup.1 and W.sup.3 together, and E.sup.2 and W.sup.2 
together, may independently form a heterocyclic ring with an O. 
The advantages of the present invention include the provision of couplers 
of good activity capable of forming dyes having good spectral 
characteristics such as maximum wavelength (.lambda..sub.max) and 
half-band width, little unwanted absorption of blue light, good fastness 
properties, .lambda..sub.max selectable under the influence of coupler 
solvents, and easy bleaching giving retouchability. 
EMBODIMENTS OF THE INVENTION 
Particular embodiments of first, the color couplers used in the 
photographic elements of the present invention, and then the stabilizers, 
will now be described. Further details of embodiments of the elements are 
then provided. 
First, with regard to the color couplers used in the elements of the 
present invention, in one embodiment A and B of the above formulae (1) and 
(2) together may complete an electron-withdrawing heterocycle which may be 
substituted. In another embodiment R and X together complete a 
heterocyclic ring which is optionally substituted. 
In one embodiment of the present invention the couplers contain a 
ballasting group of such size and configuration to render the coupler 
non-diffusible in the photographic material. 
A and B may each individually represent an electron attractive group 
wherein the value of the Hammett substituent constant .sigma..sub.p 
(SIGMA.sub.p as defined by Hansch et al, J. Med. Chem.,1973, 16, 1207; and 
ibid. 1977, 20, 304) is 0.03 or greater, preferably 0.35 or greater and 
more preferably 0.5 or above. 
A substituent or atom wherein the value of the .sigma..sub.p (SIGMA.sub.p) 
is 0.03 or above includes a fluorine atom, a chlorine atom, a bromine 
atom, an iodine atom, a substituted alkyl group (eg. trichloromethyl, 
trifluormethyl, chloromethyl and perfluorobutyl), a nitrile group, an acyl 
group (eg. formyl, acetyl and benzoyl), a carboxyl group, a substituted or 
unsubstituted carbamoyl group (eg. methylcarbamoyl) an aromatic group 
substituted by another electron attractive group (eg pentachlorophenyl, 
pentafluorophenyl), a heterocyclic group (eg. 2-thienyl, 2-benzoxazolyl, 
2-benzthiazolyl, 1-otetrazolyl and 1-phenyl-2-benzimidazolyl), a nitro 
group, an azo group (eg. phenylazo), an amino group substituted by another 
electron attractive group (eg. ditrifluoromethylamino), an alkoxy group 
substituted by another electron attractive group (eg. trifluoromethoxy), 
an alkylsulphonyloxy group (eg. methanesulphonyloxy), an acyloxy group 
(eg. acetyloxy, benzoyloxy), an arylsulphonyloxy group (eg. 
benzenesulphonyloxy), a phosphoryl group (eg. dimethoxyphosphoryl and 
diphenylphosphoryl), a thioalkyl group substituted by another electron 
attractive group (eg. trifluoromethyl), a sulphamoyl group, a sulphonamide 
group, a sulphonyl group (eg. methanesulphonyl, benzenesulphonyl), a 
thiocyanate group and a sulphoxide group. 
Examples of electron-withdrawing groups which A and B may represent are 
hydrogen, halogen, --CN, --NO.sub.2, --OR.sup.4, --SR.sup.4, --SO.sub.2 
R.sub.1, --OSO.sub.2 R.sub.1, --SOR.sup.1, --NHCOR.sup.1, --CONHR.sup.1, 
--OCONHR.sup.1, --NHCO--OR.sup.1, --SO.sub.2 NH--R.sup.1, --NHSO.sub.2 
R.sub.1, --NHSO.sub.2 NHR.sup.1, --NHNH--SO.sub.2 --R.sup.1, --COOH, 
--COOR.sup.1, --O--COR.sup.1, --COR.sup.1, --CSR.sup.1, --CONHNHR.sup.1, 
--CF.sub.3, --NH.sub.2, --NHR.sup.1, --NHR.sub.1 R.sup.1', silyloxy, aryl, 
aralkyl, alkyl, cycloalkyl, ureido, imido, or a heterocycle, 
wherein 
R.sup.1 is as defined above, 
R.sup.1' has the same definition as R.sup.1 and may be the same or 
different to R.sup.1, and 
R.sup.4 is an alkyl, cycloalkyl, aryl or heterocyclic group any of which 
are optionally substituted, 
and wherein the nature of the groups R.sup.1, R.sup.1' and R.sup.4 and the 
substituents thereon are such that the group is electron-withdrawing. 
The groups A and B may be also be any of the above groups joined by way of 
a group that will extend the conjugated path from A or B to the --NH--R 
group while leaving the whole group electron-withdrawing. Such a group may 
have the formula: 
##STR5## 
wherein R.sup.8 and R.sup.9 are each hydrogen, halogen, or an alkyl or 
aryl group that may be substituted, 
or R.sup.8 and R.sup.9 may complete a carbocyclic or heterocyclic ring, and 
m is 1 or 2. 
The ballast group may be located as part of A, B, X or R. Preferably the 
ballast group is part of R. 
A preferred class of groups R have the general formula: 
##STR6## 
wherein p is 0, 1, 2, 3 or 4 and each R.sup.3 is preferably in a meta or 
para position with respect to R.sup.2 (if vacant); 
each R.sup.3 is individually a halogen atom or an alkyl, alkoxy, aryloxy, 
carbonamido, carbamoyl, sulphonamido, sulfamoyl, alkylsulphoxyl, 
arylsulphoxyl, alkylsulphonyl, arylsulphonyl, alkoxycarbonyl, 
aryloxycarbonyl, acyloxy, ureido, imido, carbamate, cyano, nitro, acyl, 
trifluoromethyl, alkylthio, carboxyl or heterocylic group; and 
R.sup.2 is a hydrogen or halogen atom or an alkyl, alkoxy, aryloxy, 
alkylthio, arylthio, carbonamido, carbamoyl, sulphonamido, sulphamoyl, 
alkylsulphonyl, arylsulphonyl, alkoxycarbonyl, acyloxy, acyl, cyano, 
nitro, or trifluoromethyl group. 
Specific groups which R may represent are listed in the following table 
(Table 1). 
TABLE 1 
__________________________________________________________________________ 
##STR7## 
##STR8## 
##STR9## 
##STR10## 
##STR11## 
##STR12## 
##STR13## 
##STR14## 
##STR15## 
##STR16## 
##STR17## 
##STR18## 
##STR19## 
##STR20## 
##STR21## 
##STR22## 
##STR23## 
##STR24## 
##STR25## 
##STR26## 
##STR27## 
##STR28## 
##STR29## 
##STR30## 
##STR31## 
##STR32## 
##STR33## 
##STR34## 
##STR35## 
##STR36## 
##STR37## 
##STR38## 
##STR39## 
##STR40## 
##STR41## 
##STR42## 
##STR43## 
##STR44## 
##STR45## 
##STR46## 
##STR47## 
##STR48## 
##STR49## 
##STR50## 
##STR51## 
##STR52## 
##STR53## 
##STR54## 
##STR55## 
##STR56## 
##STR57## 
##STR58## 
##STR59## 
##STR60## 
##STR61## 
##STR62## 
##STR63## 
##STR64## 
##STR65## 
##STR66## 
##STR67## 
##STR68## 
__________________________________________________________________________ 
In the above groups the groups R.sub.1 to R.sub.5 are substituents not 
incompatible with the function of the compound. Examples of such 
substituents are those listed above for R.sup.2 and R.sup.3. 
The ballast group or X may have water-solubilising substituents thereon 
and, in particular, those groups which will increase the activity of the 
coupler. 
Examples of coupling-off groups which X may represent are shown in Table 3 
below (a listing of compounds useful in the present invention). 
The coupling-off group X may comprises the radical of a photographically 
useful group, for example a developer inhibitor or accelerator, a bleach 
accelerator, etc. Such groups are referred to in the Research Disclosure 
article referred to below. 
Link may be a timing group which can be used to speed or slow release of a 
photographically useful group. Two timing groups may be used in 
circumstances where staged release is required. 
The timing groups may have one of the following formulae shown in Table 2 
in which they are shown attached to a photographically useful group (PUG): 
TABLE 2 
______________________________________ 
OCH.sub.2PUG 
##STR69## 
##STR70## 
##STR71## 
##STR72## 
##STR73## 
##STR74## 
##STR75## 
______________________________________ 
Specific examples of groups which R.sup.3 may represent are given in the 
list of compounds useful in the present invention listed in Table 3 below. 
Examples of groups which split off on coupling include halogen, carboxy, 
heterocyclyl joined via a ring carbon or hetero atom in the heterocyclic 
nucleus, --OR.sup.4, --SR.sup.4, arylazo or heterocyclylazo. Chloro is a 
particularly preferred coupling-off group as it gives the coupler superior 
activity. The group which splits off may provide a photographically useful 
compound. Many such groups are often known as photographically useful 
groups and they provide developer inhibitors, bleach accelerators, 
developer accelerators, antifoggants, competing couplers, etc. Many 
examples are listed in Research Disclosure Item 308119, December 1989 
published by Kenneth Mason Publications, Emsworth, Hants, United Kingdom. 
The color couplers used in the elements of the present invention may 
further be of the general formulae: 
##STR76## 
wherein A and B represent the same or different electron-withdrawing 
group, 
X is H or a group which splits off on coupling with oxidised colour 
developer, 
R is an alkyl, cycloalkyl, aryl or heterocyclic group any of which may be 
substituted, --COR.sup.1, --CSR.sup.1, SOR.sup.1, SO.sub.2 R.sup.1, 
--NHCOR.sup.1, --CONHR.sup.1, --COOR.sup.1, --COSR.sup.1, --NHSO.sub.2 
R.sub.1 wherein R.sup.1 is an alkyl, cycloalkyl, or aryl group any of 
which are optionally substituted and wherein two or more of A, B, R, and X 
optionally form part of a ring, 
Link is a linking group and 
n is 0, 1 or 2. 
Examples of couplers of the foregoing type which are useful in the elements 
of the present invention are listed in Table 3 below. 
TABLE 3 
______________________________________ 
##STR77## (C-1) 
##STR78## (C-2) 
##STR79## (C-3) 
##STR80## (C-4) 
##STR81## (C-5) 
##STR82## (C-6) 
##STR83## (C-7) 
##STR84## (C-8) 
##STR85## (C-9) 
##STR86## (C-10) 
##STR87## (C-11) 
##STR88## (C-12) 
##STR89## (C-13) 
##STR90## (C-14) 
##STR91## (C-15) 
##STR92## (C-16) 
##STR93## (C-17) 
##STR94## (C-18) 
##STR95## (C-19) 
##STR96## (C-20) 
##STR97## (C-21) 
##STR98## (C-22) 
##STR99## (C-23) 
##STR100## (C-24) 
##STR101## (C-25) 
##STR102## (C-26) 
##STR103## (C-27) 
##STR104## (C-28) 
##STR105## (C-29) 
##STR106## (C-30) 
##STR107## (C-31) 
##STR108## (C-32) 
##STR109## (C-33) 
##STR110## (C-34) 
##STR111## (C-35) 
##STR112## (C-36) 
##STR113## (C-37) 
##STR114## (C-38) 
##STR115## (C-39) 
##STR116## (C-40) 
##STR117## (C-41) 
##STR118## (C-42) 
##STR119## (C-43) 
##STR120## (C-44) 
##STR121## (C-45) 
##STR122## (C-46) 
##STR123## (C-47) 
##STR124## (C-48) 
##STR125## (C-49) 
##STR126## (C-50) 
##STR127## (C-51) 
##STR128## (C-52) 
##STR129## (C-53) 
##STR130## (C-54) 
##STR131## (C-55) 
##STR132## 
______________________________________ 
Where X is: 
__________________________________________________________________________ 
C-56 C-57 C-58 C-59 
##STR133## 
##STR134## 
##STR135## 
##STR136## 
C-60 C-61 C-62 C-63 
##STR137## 
##STR138## 
##STR139## 
##STR140## 
C-64 C-65 C-66 C-67 
##STR141## 
##STR142## 
##STR143## 
##STR144## 
C-68 C-69 C-70 C-71 
##STR145## 
##STR146## 
##STR147## 
##STR148## 
C-72 C-73 C-74 C-75 
##STR149## 
##STR150## 
##STR151## 
##STR152## 
C-76 C-77 C-78 
##STR153## 
##STR154## 
##STR155## 
__________________________________________________________________________ 
##STR156## 
Where X is: 
__________________________________________________________________________ 
C-79 C-80 C-81 C-82 
##STR157## 
##STR158## 
##STR159## 
##STR160## 
C-83 C-84 C-85 C-86 
##STR161## 
##STR162## 
##STR163## 
##STR164## 
C-87 C-88 C-89 C-90 
##STR165## 
##STR166## 
##STR167## 
##STR168## 
C-91 C-92 C-93 C-94 
##STR169## 
##STR170## 
##STR171## 
##STR172## 
C-95 C-96 C-97 C-98 
##STR173## 
##STR174## 
##STR175## 
##STR176## 
C-99 C-100 C-101 
##STR177## 
##STR178## 
##STR179## 
__________________________________________________________________________ 
##STR180## 
Where X is: 
__________________________________________________________________________ 
C-102 C-103 C-104 C-105 
##STR181## 
##STR182## 
##STR183## 
##STR184## 
C-106 C-107 C-108 C-109 
##STR185## 
##STR186## 
##STR187## 
##STR188## 
C-110 C-111 C-112 C-113 
##STR189## 
##STR190## 
##STR191## 
##STR192## 
C-114 C-115 C-116 C-117 
##STR193## 
##STR194## 
##STR195## 
##STR196## 
C-118 C-119 C-120 C-121 
##STR197## 
##STR198## 
##STR199## 
##STR200## 
C-122 C-123 C-124 
##STR201## 
##STR202## 
##STR203## 
C-125 
##STR204## 
C-126 
##STR205## 
C-127 C-128 
##STR206## 
##STR207## 
C-129 C-130 
##STR208## 
##STR209## 
C-131 C-132 
##STR210## 
##STR211## 
C-133 C-134 
##STR212## 
##STR213## 
C-135 
##STR214## 
C-136 
##STR215## 
C-137 C-138 
##STR216## 
##STR217## 
C-139 C-140 
##STR218## 
##STR219## 
C-141 C-142 
##STR220## 
##STR221## 
C-143 C-144 
##STR222## 
##STR223## 
C-145 C-146 
##STR224## 
##STR225## 
C-147 C-148 
##STR226## 
##STR227## 
C-149 C-150 
##STR228## 
##STR229## 
C-151 C-152 
##STR230## 
##STR231## 
C-153 C-154 
##STR232## 
##STR233## 
C-155 C-156 
##STR234## 
##STR235## 
C-157 C-158 
##STR236## 
##STR237## 
C-159 C-160 
##STR238## 
##STR239## 
C-161 C-162 
##STR240## 
##STR241## 
C-163 C-164 
##STR242## 
##STR243## 
##STR244## (C-165) 
##STR245## (C-166) 
##STR246## (C-167) 
##STR247## (C-168) 
##STR248## (C-169) 
##STR249## (C-170) 
##STR250## (C-171) 
##STR251## (C-172) 
##STR252## (C-173) 
##STR253## (C-174) 
##STR254## (C-175) 
##STR255## (C-176) 
##STR256## (C-177) 
##STR257## (C-178) 
##STR258## (C-179) 
C-180 C-181 
##STR259## 
##STR260## 
C-182 C-183 
##STR261## 
##STR262## 
C-184 C-185 
##STR263## 
##STR264## 
__________________________________________________________________________ 
Couplers 53 to 55 above form yellow image dyes whereas the rest all form 
magenta image dyes. 
The present colour couplers may be prepared by the following general 
scheme: 
##STR265## 
in which B' may be an anionic or neutral species and X' may be an anionic, 
neutral or cationic species. 
The color couplers described above which are used in the elements of this 
invention, can be used in any of the ways and in any of the combinations 
in which couplers are used in the photographic art. Typically, the coupler 
is incorporated in a silver halide emulsion and the emulsion coated on a 
support to form part of a photographic element. Alternatively, the coupler 
can be incorporated at a location adjacent to the silver halide emulsion 
where, during development, the coupler will be in reactive association 
with development products such as oxidized color developing agent. Thus, 
as used herein, the term "associated" signifies that the coupler is in the 
silver halide emulsion layer or in an adjacent location where, during 
processing, the coupler is capable of reacting with silver halide 
development products. 
For example, the magenta coupler used in the elements of the invention may 
be used to replace all or part of the magenta layer image coupler or may 
be added to one or more of the other layers in a color negative 
photographic element comprising a support bearing the following layers 
from top to bottom: 
(1) one or more overcoat layers containing ultraviolet absorber(s); 
(2) a two-coat yellow pack with a fast yellow layer containing "Coupler 1": 
Benzoic acid, 
4-chloro-3-((2-(4-ethoxy-2,5-dioxo-3-(phenylmethyl)-1-imidazolidinyl)-3-(4 
-methoxyphenyl)-1,3-dioxopropyl)amino)-, dodecyl ester and a slow yellow 
layer containing the same compound together with "Coupler 2": Propanoic 
acid, 
2-[[5-[[4-[2-[[[2,4-bis(1,1-dimethylpropyl)phenoxy]acetyl]amino]-5-[(2,2,3 
,3,4,4,4-heptafluoro-1-oxobutyl)amino]-4-hydroxyphenoxy]-2,3-dihydroxy-6-[( 
propylamino)carbonyl phenyl]thio]-1,3,4-thiadiazol-2-yl]thio]-, methyl 
ester and "Coupler 3": 1-((dodecyloxy)carbonyl) 
ethyl(3-chloro-4-((3-(2-chloro-4-((1-tridecanoylethoxy) 
carbonyl)anilino)-3-oxo-2-((4)(5)(6)-(phenoxycarbonyl)-1H-benzotriazol-1-y 
l)propanoyl)amino))benzoate; 
(3) an interlayer containing fine metallic silver; 
(4) a triple-coat magenta pack with a fast magenta layer containing 
"Coupler 4": Benzamide, 
3-((2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-N-(4,5-dihydr 
o-5-oxo-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-yl)-, "Coupler 5": 
Benzamide, 3-((2-(2,4 
-bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-N-(4',5'-dihydro-5'-oxo 
-1'-(2,4,6-trichlorophenyl) (1,4'-bi-1H-pyrazol)-3'-yl)-, "Coupler 6": 
Carbamic acid, (6-(((3-(dodecyloxy)propyl) 
amino)carbonyl)-5-hydroxy-1-naphthalenyl)-, 2-methylpropyl ester , 
"Coupler 7": Acetic acid, ((2-((3-(((3-(dodecyloxy)propyl)amino) 
carbonyl)-4-hydroxy-8-(((2-methylpropoxy)carbonyl) 
amino)-1-naphthalenyl)oxy)ethyl)thio)-, and "Coupler 8" Benzamide, 
3-((2-(2,4-bis(1,1-dimethylpropyl) 0 
phenoxy)-1-oxobutyl)amino)-N-(4,5-dihydro-4-((4methoxyphenyl) 
azo)-5-oxo-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-yl)-; a mid-magenta 
layer and a slow magenta layer each containing "Coupler 9": 2-Propenoic 
acid , butyl ester, styrene , 2:1:1 polymer with 
(N[1-(2,4,6-trichlorophenyl)-4,5-dihydro-5-oxo-1H-pyrazol-3-yl]-2-methyl-2 
-propenamide).sub.2 and "Coupler 10": Tetradecanamide, 
N-(4-chloro-3-((4-((4-((2,2-dimethyl1-oxopropyl) 
amino)phenyl)azo)-4,5-dihydro-5-oxo-1(2,4,6-trichlorophenyl)-1H-pyrazol-3- 
yl)amino)phenyl)-, in addition to Couplers 3 and 8; 
(5) an interlayer; 
(6) a triple-coat cyan pack with a fast cyan layer containing Couplers 6 
and 7; a mid-cyan containing Coupler 6 and "Coupler 11": 
2,7-Naphthalenedisulfonic acid, 
5-(acetylamino)-3-((4-(2-((3-(((3-(2,4-bis(1,1-dimethylpropyl)phenoxy) 
propyl)amino)carbonyl)-4-hydroxy-1-naphthalenyl) 
oxy)ethoxy)phenyl)azo)-4-hydroxy-, disodium salt; and a slow cyan layer 
containing Couplers 2 and 6; 
(7) an undercoat layer containing Coupler 8; and 
(8) an antihalation layer. 
In a color paper format, the magenta coupler used in the elements of the 
invention may suitably be used to replace all or a part of the magenta 
coupler in a photographic element such as one comprising a support bearing 
the following from top to bottom: 
(1) one or more overcoats; 
(2) a cyan layer containing "Coupler 1": Butanamide, 2-(2,4-bis ( 
1,1-dimethylpropyl ) phenoxy) -N-(3,5 -dichloro-2 -hydroxy-4-methylphenyl) 
-, "Coupler 2": Acetamide, 2- (2,4-bis (1,1-dimethylpropyl)phenoxy) 
-N-(3,5-dichloro-2-hydroxy-4-, and UV Stabilizers: Phenol, 2- 
(5-chloro-2H-benzotriazol-2-yl) -4,6-bis(1,1-dimethylethyl)-; Phenol, 
2-(2H-benzotriazol-2-yl) -4-(1,1-dimethylethyl)-; Phenol, 
2-(2H-benzotriazol-2-yl)-4-(1,1-dimethylethyl)-6-(1-methylpropyl)-; and 
Phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl) and a 
poly(t-butylacrylamide) dye stabilizer; 
(3) an interlayer; 
(4) a magenta layer containing "Coupler 3": Octanamide, 
2-[2,4-bis(1,1-dimethylpropyl)phenoxy]-N-[2-(7-chloro-6-methyl-1H-pyrazolo 
[1,5-b][1,2,4]-triazol-2-yl) propyl]-together with 1,1'-Spirobi 
(1H-indene), 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-5,5',6,6'-tetrapro 
poxy-; 
(5 ) an interlayer; and 
(6) a yellow layer sontaining "Coupler 4": 1-Imidazolidineacetamide, 
N-(5-((2-(2,4-bis 
(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-2-chlorophenyl)-. 
alpha.-(2,2-dimethyl-1-oxopropyl)-4-ethoxy-2,5-dioxo-3-(phenylmethyl) -. 
In a reversal medium, the magenta coupler used in the elements of the 
invention could be used to replace all or part of the magenta coupler in a 
photographic element such as one comprising a support and bearing the 
following layers from top to bottom: 
(1) one or more overcoat layers; 
(2) a nonsensitized silver halide containing layer; 
(3) a triple-coat yellow layer pack with a fast yellow layer containing 
"Coupler 1": Benzoic acid, 
4-(1-(((2-chloro-5-((dodecylsulfonyl)amino)phenyl) 
amino)carbonyl)-3,3-dimethyl-2-oxobutoxy)-, 1methylethyl ester; a mid 
yellow layer containing Coupler 1 and "Coupler 2": Benzoic acid, 
4-chloro-3-[[2-[4-ethoxy-2,5-dioxo-3-(phenylmethyl)-1-imidazolidinyl]-4,4- 
dimethyl-1,3-dioxopentyl]amino]-, dodecylester; and a slow yellow layer 
also containing Coupler 2; 
(4) an interlayer; 
(5) a layer of fine-grained silver; 
(6) an interlayer; 
(7) a triple-coated magenta pack with a fast magenta layer containing 
"Coupler 3": 2-Propenoic acid, butyl ester, polymer with 
N-[1-(2,5-dichlorophenyl)4,5-dihydro-5-oxo-1H-pyrazol-3-yl]-2-methyl-2prop 
enamide; "Coupler 4": Benzamide, 
3-((2-(2,4bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-N(4,5-dihydro- 
5-oxo-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-yl)-; and "Coupler 5": 
Benzamide, 
3-(((2,4bis(1,1-dimethylpropyl)phenoxy)acetyl)amino)-N-(4,5-dihydro-5-oxo- 
1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-yl)-; and containing the stabilizer 
1,1'-Spirobi(1H-indene), 
2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-5,5',6,6'-tetrapropoxy-; and in 
the slow magenta layer Couplers 4 and 5 with the same stabilizer; 
(8) one or more interlayers possibly including fine-grained nonsensitized 
silver halide; 
(9) a triple-coated cyan pack with a fast cyan layer containing "Coupler 
6": Tetradecanamide, 
2-(2-cyanophenoxy)-N-(4-((2,2,3,3,4,4,4-heptafluoro-1-oxobutyl)amino)-3-hy 
droxyphenyl)-; a mid cyan containing "Coupler 7": Butanamide, 
N-(4-((2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-2-hydroxyp 
henyl)-2,2,3,3,4,4,4-heptafluoro- and "Coupler 8": Hexanamide, 
2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-N-(4-((2,2,3,3,4,4,4-heptafluoro-1- 
oxobutyl)amino)-3-hydroxyphenyl)-; 
(10) one or more interlayers possibly including fine-grained nonsensitized 
silver halide; and 
(11) an antihalation layer. 
It is common to include ballast or "BALL" substituents in the coupler. 
Representative BALL groups are of such size and configuration as to confer 
on the coupler molecule sufficient bulk to render the coupler 
substantially non-diffusible from the layer in which it is coated in the 
described photographic recording material. 
Representative ballast groups include substituted or unsubstituted alkyl or 
aryl groups containing 8 to 40 carbon atoms. 
Representative substituents on such groups include alkyl, aryl, alkoxy, 
aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxcarbonyl, 
carboxy, acyl, acyloxy, amino, anilino, carbonamido, carbamoyl, 
alkylsulfonyl, arysulfonyl, sulfonamido, and sulfamyl groups wherein the 
substituents typically contain 1 to 40 carbon atoms. Such substituents can 
also be further substituted. 
As to the stabilizer, one or more of the stabilizers of the type of 
formulae (I) may be incorporated into the element in the same layer as the 
color coupler of formulae (1) or (2). Any of the particular embodiments of 
the stabilizer described below, may be used with any of the embodiments of 
the color coupler described above. 
With regard to the stabilizer, it is preferred, but not necessary, that 
E.sup.1 and E.sup.2 are the same, and W.sup.2 and W.sup.3 are the same. 
Further, as to particular E.sup.1 and E.sup.2, they may preferably be are 
selected from hydrogen or substituted or unsubstituted C.sub.1 -C.sub.30 
alkyl groups; a substituted or unsubstituted trialkysilyl group each alkyl 
group being C.sub.1 -C.sub.30 ; a substituted or unsubstituted cycloalkyl 
group; a substituted or unsubstituted alkenyl or alkynyl group; a 
substituted or unsubstituted aryl group; a substituted or unsubstituted 
acyl group; a substituted or unsubstituted aroyl group; a substituted or 
unsubstituted alkyl sulfonyl or aryl sulfonyl group; or a phosphate ester 
group. Any of the foreoging groups particularly may have from 1 to 20, or 
even from 1 to 10 carbon atoms. 
As to particular W.sup.2 and W.sup.3, they may be, independently, a 
substituted or unsubstituted alkyl group, substituted or unsubstituted 
alkenyl group, substituted or unsubstituted cycloalkyl group, or 
substituted or unsubstituted aryl group, or W.sup.2 and W.sup.3 in 
combination with the benzene ring may independently represent the atoms 
necessary to complet a fused ring system, or E.sup.1 and W.sup.3 together, 
and E.sup.2 and W.sup.2 together, may independently form a heterocyclic 
ring with an O. Any of the foregoing groups may particularly have from 1 
to 20, or even from 1 to 10 carbon atoms. 
The stabilizer may particularly be of formula (IA): 
##STR266## 
wherein W.sup.2 and W.sup.3 each independently represent a hydrogen or a 
substituted or unsubstitued linear or branched alky group of from 1 to 12 
carbon atoms, or a substituted or unsubstituted alkyl chain with a 
terminal ester group and between 4 to 15 carbon atoms. 
The total amount of stabilizer which may be used is typically from about 
0.1 to about 2.0 moles per mole of coupler, and more preferably from 0.2 
to about 1.0 mole per mole of the coupler used in the present invention. 
Examples of stabilizers of formula (I) are: 
##STR267## 
Further examples of stabilizers of the type of formula (I) above, include 
those disclosed in EP 0 18 266, EP 0 298 321, and US 4,748,100, all of 
which are incorporated herein by reference. It will be appreciated that 
the stabilizers used in the elements of the present invention can, if 
desired, be used in conjunction with other stabilizers. Particularly, 
other stabilizers which may be used are those described in U.S. patent 
applications: PHOTOGRAPHIC ELEMENTS CONTAINING TICULAR COLOR COUPLERS 
IN COMBINATION WITH POLYMERIC STABILIZERS, Attorney Docket Number 7,329; 
PHOTOGRAPHIC ELEMENTS CONTAINING TICULAR COLOR COUPLERS IN COMBINATION 
WITH TICULAR STABILIZERS, Attorney Docket Number 65,254; PHOTOGRAPHIC 
ELEMENTS CONTAINING TICULAR COLOR COUPLERS IN COMBINATION WITH METAL 
COMPLEX STABILIZERS, Attorney Docket No. 65,270; all by Jain et al. and 
all filed on the same date as the present application. The foregoing 
applications are incorporated herein by reference. 
The photographic elements can be single color elements or multicolor 
elements. Multicolor elements contain dye image-forming units sensitive to 
each of the three primary regions of the spectrum. Each unit can be 
comprised of a single emulsion layer or of multiple emulsion layers 
sensitive to a given region of the spectrum. The layers of the element, 
including the layers of the image-forming units, can be arranged in 
various orders as known in the art. In a alternative format, the emulsions 
sensitive to each of the three primary regions of the spectrum can be 
disposed as a single segmented layer. 
A typical multicolor photographic element comprises a support bearing a 
cyan dye image-forming unit comprised of at least one red-sensitive silver 
halide emulsion layer having associated therewith at least one cyan 
dye-forming coupler, a magenta dye image-forming unit comprising at least 
one green-sensitive silver halide emulsion layer having associated 
therewith at least one magenta dye-forming coupler, and a yellow dye 
image-forming unit comprising at least one blue-sensitive silver halide 
emulsion layer having associated therewith at least one yellow dye-forming 
coupler, at least one of the couplers in the element being a coupler of 
the type described above for elements of this invention. The element can 
contain additional layers, such as filter layers, interlayers, overcoat 
layers, subbing layers, and the like. 
In the following discussion of suitable materials for use in elements of 
this invention, reference will be made to Research Disclosure, December 
1989, Item 308119, published by Kenneth Mason Publications, Ltd., Dudley 
Annex, 12a North Street, Emsworth, Hampshire P010 7DQ, ENGLAND, which will 
be identified hereafter by the term "Research Disclosure." The contents of 
the Research Disclosure, including the patents and publications referenced 
therein, are incorporated herein by reference, and the Sections hereafter 
referred to are Sections of the Research Disclosure. 
The silver halide emulsions employed in the elements of this invention can 
be either negative-working or positive-working. Suitable emulsions and 
their preparation as well as methods of chemical and spectral 
sensitization are described in Sections I through IV. Color materials and 
development modifiers are described in Sections V and XXI. Vehicles are 
described in Section IX, and various additives such as brighteners, 
antifoggants, stabilizers, light absorbing and scattering materials, 
hardeners, coating aids, plasticizers, lubricants and matting agents are 
described , for example, in Sections V, VI, VIII, X, XI, XII, and XVI. 
Manufacturing methods are described in Sections XIV and XV, other layers 
and supports in Sections XIII and XVII, processing methods and agents in 
Sections XIX and XX, and exposure alternatives in Section XVIII. 
Preferred color developing agents are p-phenylenediamines. Especially 
preferred are: 
4-amino N,N-diethylaniline hydrochloride, 
4-amino-3-methyl-N,N-diethylaniline hydrochloride, 
4-amino-3-methyl-N-ethyl-N-(b-(methanesulfonamido) ethyl)aniline 
sesquisulfate hydrate, 
4-amino-3-methyl-N-ethyl-N-(b-hydroxyethyl)aniline sulfate, 
4-amino-3-b-(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride and 
4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonic acid. 
With negative working silver halide a negative image can be formed. 
Optionally positive (or reversal) image can be formed. 
The magenta coupler described herein may be used in combination with other 
classes of magenta image couplers such as 3-acylamino-5-pyrazolones and 
heterocyclic couplers (e.g. pyrazoloazoles) such as those described in EP 
285,274; U.S. Pat. No. 4,540,654; EP 119,860, or with other 5-pyrazolone 
couplers containing different ballasts or coupling-off groups such as 
those described in U.S. Pat. No. 4,301,235; U.S. Pat. No. 4,853,319 and 
U.S. Pat. No. 4,351,897. The coupler may also be used in association with 
yellow or cyan colored couplers (e.g. to adjust levels of interlayer 
correction) and with masking couplers such as those described in EP 
213.490; Japanese Published Application 58-172,647; U.S. Pat. No. 
2,983,608; German Application DE 2,706,117C; U.K. Patent 1,530,272; 
Japanese Application A-113935; U.S. Pat. No. 4,070,191 and German 
Application DE 2,643,965. The masking couplers may be shifted or blocked. 
The couplers may also be used in association with materials that accelerate 
or otherwise modify the processing steps e.g. of bleaching or fixing to 
improve the quality of the image. Bleach accelerators described in EP 
193,389; EP 301,477; U.S. Pat. No. 4,163,669; U.S. Pat. No. 4,865,956; and 
U.S. Pat. No. 4,923,784 are particularly useful. Also contemplated is use 
of the coupler in association with nucleating agents, development 
accelerators or their precursors (UK Patent 2,097,140; U.K. Patent 
2,131,188); electron transfer agents (U.S. Pat. No. 4,859,578; U.S. Pat. 
No. 4,912,025); antifogging and anti color-mixing agents such as 
derivatives of hydroquinones, aminophenols, amines, gallic acid; catechol; 
ascorbic acid; hydrazides; sulfonamidophenols; and non color-forming 
couplers. 
The couplers may also be used in combination with filter dye layers 
comprising colloidal silver sol or yellow and/or magenta filter dyes, 
either as oil-in-water dispersions, latex dispersions or as solid particle 
dispersions. Additionally, they may be used with "smearing" couplers (e.g. 
as described in U.S. Pat. No. 4,366,237; EP 96,570; U.S. Pat. No. 
4,420,556; and U.S. Pat. No. 4,543,323.) Also, the couplers may be blocked 
or coated in protected form as described, for example, in Japanese 
Application 61/258,249 or U.S. Pat. No. 5,019,492. 
The coupler may further be used in combination with image-modifying 
compounds such as "Developer Inhibitor-Releasing" compounds (DIR's). DIR's 
useful in conjunction with the color couplers useful in the invention, are 
known in the art and examples are described in U.S. Pat. Nos. 3,137,578; 
3,148,022; 3,148,062; 3,227,554; 3,384,657; 3,379,529; 3,615,506; 
3,617,291; 3,620,746; 3,701,783; 3,733,201; 4,049,455; 4,095,984; 
4,126,459; 4,149,886; 4,150,228; 4,211,562; 4,248,962; 4,259,437; 
4,362,878; 4,409,323; 4,477,563; 4,782,012; 4,962,018; 4,500,634; 
4,579,816; 4,607,004; 4,618,571; 4,678,739; 4,746,600; 4,746,601; 
4,791,049; 4,857,447; 4,865,959; 4,880,342; 4,886,736; 4,937,179; 
4,946,767; 4,948,716; 4,952,485; 4,956,269; 4,959,299; 4,966,835; 
4,985,336 as well as in patent publications GB 1,560,240; GB 2,007,662; GB 
2,032,914; GB 2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824; DE 
3,644,416 as well as the following European Patent Publications: 272,573; 
335,319; 336,411; 346, 899; 362, 870; 365,252; 365,346; 373,382; 376,212; 
377,463; 378,236; 384,670; 396,486; 401,612; 401,613. 
Such compounds are also disclosed in "Developer-Inhibitor-Releasing (DIR) 
Couplers for Color Photography," C. R. Barr, J. R. Thirtle and P. W. 
Vittum in Photographic Science and Engineering, Vol. 13, p. 174 (1969), 
incorporated herein by reference. Generally, the developer 
inhibitor-releasing (DIR) couplers include a coupler moiety and an 
inhibitor coupling-off moiety (IN). The inhibitor-releasing couplers may 
be of the time-delayed type (DIAR couplers) which also include a timing 
moiety or chemical switch which produces a delayed release of inhibitor. 
Examples of typical inhibitor moieties are: oxazoles, thiazoles, diazoles, 
triazoles, oxadiazoles, thiadiazoles, oxathiazoles, thiatriazoles, 
benzotriazoles, tetrazoles, benzimidazoles, indazoles, isoindazoles, 
mercaptotetrazoles, selenotetrazoles, mercaptobenzothiazoles, 
selenobenzothiazoles, mercaptobenzoxazoles, selenobenzoxazoles, 
mercaptobenzimidazoles, selenobenzimidazoles, benzodiazoles, 
mercaptooxazoles, mercaptothiadiazoles, mercaptothiazoles, 
mercaptotriazoles, mercaptooxadiazoles, mercaptodiazoles, 
mercaptooxathiazoles, telleurotetrazoles or benzisodiazoles. In a 
preferred embodiment, the inhibitor moiety or group is selected from the 
following formulas: 
##STR268## 
wherein R.sub.I is selected from the group consisting of straight and 
branched alkyls of from 1 to about 8 carbon atoms, benzyl and phenyl 
groups and said groups containing at least one alkoxy substituent; 
R.sub.II is selected from R.sub.I and --SR.sub.I ; R.sub.III is a straight 
or branched alkyl group of from 1 to about 5 carbon atoms and m is from 1 
to 3; and R.sub.IV is selected from the group consisting of hydrogen, 
halogens and alkoxy, phenyl and carbonamido groups, --COOR.sub.V and 
--NHCOOR.sub.V wherein R.sub.V is selected from substituted and 
unsubstituted alkyl and aryl groups. 
Although it is typical that the coupler moiety included in the developer 
inhibitor-releasing coupler forms an image dye corresponding to the layer 
in which it is located, it may also form a different color as one 
associated with a different film layer. It may also be useful that the 
coupler moiety included in the developer inhibitor-releasing coupler forms 
colorless products and/or products that wash out of the photographic 
material during processing (so-called "universal" couplers). 
As mentioned, the developer inhibitor-releasing coupler may include a 
timing group which produces the time-delayed release of the inhibitor 
group such as groups utilizing the cleavage reaction of a hemiacetal (U.S. 
Pat. No. 4,146,396, Japanese Applications 60-249148; 60-249149); groups 
using an intramolecular nucleophilic substitution reaction (U.S. Pat. No. 
4,248,962); groups utilizing an electron transfer reaction along a 
conjugated system (U.S. Pat. Nos. 4,409,323; 4,421,845; Japanese 
Applications 57-188035; 58-98728; 58-209736; 58-209738) groups utilizing 
ester hydrolysis (German Patent Application (OLS) No. 2,626,315; groups 
utilizing the cleavage of imino ketals (U.S. Pat. No. 4,546,073); groups 
that function as a coupler or reducing agent after the coupler reaction 
(U.S. Pat. No. 4,438,193; U.S. Pat. No. 4,618,571) and groups that combine 
the features describe above. It is typical that the timing group or moiety 
is of one of the formulas: 
##STR269## 
wherein IN is the inhibitor moiety, Z is selected from the group 
consisting of nitro, cyano, alkylsulfonyl; sulfamoyl (--SO.sub.2 
NR.sub.2); and sulfonamido (--NRSO.sub.2 R) groups; n is 0 or 1; and 
R.sub.VI is selected from the group consisting of substituted and 
unsubstituted alkyl and phenyl groups. The oxygen atom of each timing 
group is bonded to the coupling-off position of the respective coupler 
moiety of the DIAR. 
Suitable developer inhibitor-releasing couplers for use in the elements of 
the present invention include, but are not limited to, the following: 
##STR270## 
It is also contemplated that the concepts of the present invention may be 
employed to obtain reflection color prints as described in Research 
Disclosure, November 1979, Item 18716, available from Kenneth Mason 
Publications, Ltd, Dudley Annex, 12a North Street, Emsworth, Hampshire 
P0101 7DQ, England, incorporated herein by reference. The emulsions and 
materials to form elements of the present invention, may be coated on pH 
adjusted support as described in U.S. Pat. No. 4,917,994; with epoxy 
solvents (EP 0 164 961); with nickel complex stabilizers (U.S. Pat. No. 
4,346,165; U.S. Pat. No. 4,540,653 and U.S. Pat. No. 4,906,559 for 
example); with ballasted chelating agents such as those in U.S. Pat. No. 
4,994,359 to reduce sensitivity to polyvalent cations such as calcium; and 
with stain reducing compounds such as described in U.S. Pat. No. 5,068,171 
and U.S. Pat. No. 5,096,805. Other compounds useful in the elements of the 
invention are disclosed in Japanese Published Applications 83-09,959; 
83-62,586; 90-072,629, 90-072,630; 90-072,632; -072,633; 90 -072,634; 
90-077,822; 90-078,229; 90-078,230; 90-079,336; 90-079,338; 90-079,690; 90 
-79,691; 90-080,487; 90-080,489; 90-080,490; 90-80,491; 90-080,492; 
90-080,494; 90-085,928; 90-86,669; 90-086,670; 90-087,361; 90-087,362; 
90-87,363; 90-087,364; 90-088,096; 90-088,097; 90-93,662; 90-093,663; 
90-093,664; 90-093,665; 90-93,666; 90-093,668; 90-094,055; 90-094,056; 
90-01,937; 90-103,409; 90-151,577. 
Especially useful in this invention are tabular grain silver halide 
emulsions. Specifically contemplated tabular grain emulsions are those in 
which greater than 50 percent of the total projected area of the emulsion 
grains are accounted for by tabular grains having a thickness of less than 
0.3 micron (0.5 micron for blue sensitive emulsion) and an average 
tabularity (T) of greater than 25 (preferably greater than 100), where the 
term "tabularity" is employed in its art recognized usage as 
EQU T=ECD/t.sup.2 
where 
ECD is the average equivalent circular diameter of the tabular grains in 
microns and 
t is the average thickness in microns of the tabular grains. 
The average useful ECD of photographic emulsions can range up to about 10 
microns, although in practice emulsion ECD's seldom exceed about 4 
microns. Since both photographic speed and granularity increase with 
increasing ECD's, it is generally preferred to employ the smallest tabular 
grain ECD's compatible with achieving aim speed requirements. 
Emulsion tabularity increases markedly with reductions in tabular grain 
thickness. It is generally preferred that aim tabular grain projected 
areas be satisfied by thin (t&lt;0.2 micron) tabular grains. To achieve the 
lowest levels of granularity it is preferred to that aim tabular grain 
projected areas be satisfied with ultrathin (t&lt;0.06 micron) tabular 
grains. Tabular grain thicknesses typically range down to about 0.02 
micron. However, still lower tabular grain thicknesses are contemplated. 
For example, Daubendiek et al U.S. Pat. No. 4,672,027 reports a 3 mole 
percent iodide tabular grain silver bromoiodide emulsion having a grain 
thickness of 0.017 micron. 
As noted above tabular grains of less than the specified thickness account 
for at least 50 percent of the total grain projected area of the emulsion. 
To maximize the advantages of high tabularity it is generally preferred 
that tabular grains satisfying the stated thickness criterion account for 
the highest conveniently attainable percentage of the total grain 
projected area of the emulsion. For example, in preferred emulsions 
tabular grains satisfying the stated thickness criteria above account for 
at least 70 percent of the total grain projected area. In the highest 
performance tabular grain emulsions tabular grains satisfying the 
thickness criteria above account for at least 90 percent of total grain 
projected area. 
Suitable tabular grain emulsions can be selected from among a variety of 
conventional teachings, such as those of the following: Research 
Disclosure, Item 22534, January 1983, published by Kenneth Mason 
Publications, Ltd., Emsworth, Hampshire P010 7DD, England; U.S. Pat. Nos. 
4,439,520; 4,414,310; 4,433,048; 4,643,966; 4,647,528; 4,665,012; 
4,672,027; 4,678,745; 4,693,964; 4,713,320; 4,722,886; 4,755,456; 
4,775,617; 4,797,354; 4,801,522; 4,806,461; 4,835,095; 4,853,322; 
4,914,014; 4,962,015; 4,985,350; 5,061,069 and 5,061,616. 
The photographic elements can be single colour elements or multicolour 
elements. In a multicolour element, the dye-forming color couplers used in 
this invention which provide magenta dyes, would usually be associated 
with a green-sensitive emulsion, although they could be associated with an 
emulsion sensitised to a different region of the spectrum, or with a 
panchromatically sensitised, orthochromatically sensitised or unsensitised 
emulsion. Multicolour elements contain dye image-forming units sensitive 
to each of the three primary regions of the spectrum. Each unit can be 
comprised of a single emulsion layer or of multiple emulsion layers 
sensitive to a given region of the spectrum. The layers of the element, 
including the layers of the image-forming units, can be arranged in 
various orders as known in the art. 
A typical multicolour photographic element comprises a support bearing 
yellow, magenta and cyan dye image-forming units comprising at least one 
blue-, green- or red-sensitive silver halide emulsion layer having 
associated therewith at least one yellow, magenta or cyan dye-forming 
coupler respectively, at least one of the dye-forming couplers being a 
coupler of the type described above as useful in this invention. The 
element can contain additional layers, such as filter and barrier layers. 
Photographic elements of the present invention may also usefully include a 
magnetic recording material as described in Research Disclosure, Item 
34390, November 1992. 
The following Preparative Examples 1 and 2 illustrate preparation of color 
couplers as used in photographic elements of the present invention. 
Examples 1 to 5 below illustrate the beneficial properties of such color 
couplers. The examples after Example 5 illustrate elements of the present 
invention and show the advantageous stabilization provided by the class of 
stabilizers described above in combination with the class of color 
couplers described above. 
PREATIVE EXAMPLE 1 
Compound C-1 of Table 1 is prepared by a four-step synthesis and synthetic 
details for it and all intermediates are provided below. The preparation 
is illustrated by the following sequence. 
##STR271## 
Methyl Cyanoacetimidate Hydrochloride (7) 
A solution of malononitrile (66 g; 1 mole) in diethyl ether (500 ml) and 
methanol (44 g; 1.38mole) was cooled to 0.degree. C. by means of an 
ice-salt bath. The solution was well stirred and hydrogen chloride bubbled 
through it for 1 h. On standing at 0.degree. C. overnight the product 
crystallised as a white solid. This was filtered, washed with diethyl 
ether and allowed to dry to afford the imidate hydrochloride as white 
crystals (100.6 g; 75% yield). The product was used without 
characterisation in the preparation of trimethyl ortho-cyanoacetate. 
Trimethyl Ortho-cyanoacetate (8) 
The methyl imidate ester hydrochloride salt was added to methanol (1.01) 
and stirred at room temperature for 18 h. Precipitated ammonium chloride 
was removed by filtration and the filtrate evaporated to dryness. The 
residue was partitioned between ether (900 ml) and a saturated sodium 
carbonate solution (300 ml). The organic layer was separated, dried over 
magnesium sulphate and filtered. Removal of the ether in vacuo gave the 
orthoester as a pale yellow oil (75 g; 69%). The product was shown to be 
pure by NMR spectroscopy [2.86 (2H, s, NC--CH2) and 3.36 (9H, s, OMe)] and 
used without further characterisation. 
Compound (9) 
Trimethyl ortho-cyanoacetate (14.5 g; 100 mmole) and the aniline (33.3 g; 
75mmole) were mixed together in a round-bottom flask and heated by means 
of an oil bath at a temperature of 130-140 C. When all of the aniline had 
melted so that the reaction comprised a mobile liquid, a catalytic amount 
of p-toluene sulphonic acid was added. This caused the reaction mixture to 
bubble and methanol to distill from the open flask. Heating was continued 
for a further 40 minutes then suction was applied to the reaction vessel 
by means of a water pump for 5 minutes more. The reaction mixture was 
opened to the air and allowed to cool to room temperature to leave a brown 
gum which was then dissolved in hot methanol (100 ml). On stirring the 
solution at ice-bath temperature, a cream coloured solid crystallised. 
This was filtered and dried under suction to give the pure imidate product 
as an amorphous solid (30.34 g; 77%). 
______________________________________ 
% 
C.sub.30 H.sub.40 ClN.sub.3 O.sub.3 
C H Cl N 
______________________________________ 
requires: 68.5 7.6 6.8 8.0 
found: 68.4 7.7 6.75 8.0 
______________________________________ 
Compound C-1 
To a solution of 5.3 g (10 mmole) compound 9 obtained above in water (5 ml) 
and DMF (75 ml) was added sodium cyanide (1 g; 20 mmole). The mixture was 
allowed to stir at room temperature for 4 hours then it was warmed gently 
by means of a steam bath for 2 hours. The solution was then allowed to 
cool before being poured onto 1.51 of brine into which had been dissolved 
15 ml of concentrated hydrochloric acid. The brown precipitate was 
extracted into ethyl acetate and washed with brine. The organic layer was 
separated, dried with anhydrous magnesium sulphate, and filtered. The 
solvents were removed under reduced pressure to leave a brown gum. Column 
chromatography using ethyl acetate: 60-80 petrol in the ratio of 1:3 gave 
impure product as a pale yellow solid (4.8 g). Pure product was obtained 
as a cream coloured solid (4 g; 77%) by trituration with a mixture of 
ethyl acetate and 60-80 petrol. The product exhibited satisfactory mass 
and proton NMR spectra. 
______________________________________ 
% 
C.sub.30 H.sub.37 ClN.sub.4 O.sub.2 
C H Cl N 
______________________________________ 
requires: 69.1 7.2 6.8 10.75 
found: 69.1 7.5 6.8 10.6 
______________________________________ 
PREATIVE EXAMPLE 2 
Compound C-50 of Table 1 is prepared from compound C-1 by a two step 
synthesis and synthetic details for it are provided below. 
Compound C-50 
Sulphuryl chloride (1.61 g; 12 mmol) was added dropwise to a solution of 
1-phenyl-1H-tetrazole-5-thiol (1.96 g; 11 mmol) in dry dichloromethane 
(100 ml) and the resulting mixture stirred at room temperature for 3 
hours. After this time the solvents were removed under reduced pressure to 
leave a brown oil. This was dissolved in dry dimethylformamide (10 ml) 
then added rapidly to a solution of compound C-1 (5.21 g; 10mmol) in 
dimethylformamide (50 ml). The resulting solution was stirred at room 
temperature for 18 hours before being poured onto dilute hydrochloric acid 
(40 ml of c.HCl in 31 of water) to precipitate a pale yellow solid. The 
solid was extracted into ethyl acetate and washed with brine; the organic 
layer was separated, dried with anhydrous magnesium sulphate, filtered 
then the solvents were removed under reduced pressure to leave the crude 
product as a yellow solid (6.96 g). Pure product (5.2 g, 75%) was obtained 
from this as a pale yellow solid by column chromatography using silica-gel 
(63-200 mesh) as the solid support and ethyl acetate and 60-80 petroleum, 
in the ratio of 1:2, as eluent. The product exhibited satisfactory mass 
and proton NMR spectroscopy. 
______________________________________ 
% 
C.sub.37 H.sub.41 ClN.sub.8 O.sub.2 S 
C H Cl N S 
______________________________________ 
requires: 63.7 5.9 5.0 16.1 4.6 
found: 63.1 6.0 4.7 16.1 4.4 
______________________________________ 
Compound C-52 
Compound C-52 of Table 1 was prepared from C-51 in a one-step synthesis and 
the synthetic details are provided below. 
A solution of sulphuryl chloride (2.43 g; 18 mmol) in dichloromethane (50 
ml) was added to a solution of compound C-51 (7.83 g; 18mmol) in 
dichloromethane (100 ml) over 30 minutes. The resulting pale yellow 
solution was stirred at room temperature for 1 hour before the solvents 
were removed under reduced pressure to leave the crude product as a yellow 
oil. Trituration of this with ethyl acetate and 60-80 petroleum in the 
ratio of 1:100 afforded pure product as a cream coloured solid (4.59 g; 
54%). The product exhibited satisfactory mass and proton NMR spectra. 
______________________________________ 
% 
C.sub.22 H.sub.29 C.sub.12 N.sub.3 O.sub.2 S 
C H Cl N S 
______________________________________ 
Requires: 56.2 6.2 15.1 8.9 6.8 
Found: 56.2 6.3 15.0 8.9 6.55 
______________________________________ 
EXAMPLE 1 
Dye Image Properties 
The compounds C-1 to C-6 useful in elements of the present invention, and 
control compounds 1-3 were incorporated into a photographic silver 
bromoiodide emulsion and coated in the following format: 
______________________________________ 
Gel Supercoat gelatin 1.50 g/m.sup.2 
Emulsion Silver bromoiodide 
1.60 g/m.sup.2 
Layer 
Coupler 1.04 mmol/m.sup.2 
Gelatin 2.42 g/m.sup.2 
Bis (vinylsulphonyl)-methane 0.06 g/m.sup.2 
(hardener) 
Support Cellulose acetate 
______________________________________ 
Control compounds 1-3 had the following formulae: 
##STR272## 
The coupler dispersion used contained 6% w/w gelatin, 8.8% coupler and 
coupler solvents in the ratio:- coupler: tricresyl phosphate: 
2-(2-butoxyethoxy) ethyl acetate 1:0.5:1.5. 
The experimental photographic coatings prepared in this way are slit and 
chopped into 35 mm test strips. These are exposed through a 0 - 4.0 
neutral density step wedge (0.2 ND step increments) and Daylight V, 
Wratten 9 filters then processed through the following the C-41 process 
described in British Journal of Photography (1988) 196-198: 
______________________________________ 
Developer 2.5 minutes 
Bleach 4.0 minutes 
Wash 2.0 minutes 
Fix 4.0 minutes 
Wash 2.0 minutes 
______________________________________ 
For each test strip, step-wedge densities are measured using a Macbeth 
TD/504/Hewlett Packard 85 automatic transmission densitometer. 
Measurements of minimum density (Dmin), maximum density (Dmax) and 
contrast (gamma) are calculated from the D log E curves. 
The results are shown in Table 4 below. 
TABLE 4 
______________________________________ 
Compound D.sub.min 
D.sub.max .lambda..sub.max nm 
HBW nm 
______________________________________ 
Control 1 0.18 2.52 555.5 96.0 
Control 2 0.30 2.75 547.5 94.5 
Control 3 0.15 2.68 553.3 90.5 
C-1 0.19 2.22 549.0 92.0 
C-2 0.31 3.36 550.0 95.0 
C-3 0.40 2.93 555.0 100.0 
C-4 0.22 2.48 552.5 92.0 
C-5 0.27 1.85 549.0 101.0 
C-6 0.22 1.14 552.0 106.0 
C-45 0.16 2.64 546.0 87.0 
______________________________________ 
The results presented in Table 4 for the .lambda..sub.max and half-band 
width values show that compounds C-1 to C-6 produce dyes of similarly 
desirable absorption characteristics as each of the control couplers. 
However the dyes from compounds C-1 to C-6 show much less secondary 
absorption in the blue region of the 0 spectrum than the dyes from control 
pyrazolone couplers or 2. This is similar to control compound 3 (a 
pyrazolotriazole). It is well recognised that a secondary absorption in 
the blue region is undesirable as it has an adverse effect on colour 
reproduction. Accordingly the use of compounds C-1 to C-6 in a 
photographic system offers advantages over the use of the control couplers 
1 or 2. 
The dye formed from coupler C-9 has an extinction coefficient of 50,000 in 
ethyl acetate and 52,000 in tricresyl phosphate. This is similar or higher 
than dyes formed from known magenta couplers. 
FIG. 1 is a plot of absorbance vs wavelength for the dyes obtained from 
coupler C-3 and Control 1 (dotted line). It can be seen that the unwanted 
absorption of Control 1 in the 400-450 nm region is not present in the dye 
formed from coupler C-3. 
The dyes from C-1 to C-6 show good light fastness and keeping properties 
when compared with the control couplers 1-3. 
As judged by the values presented for D.sub.max, the couplers C-1 to C-6 
show a range of photographic activity which may be less than, equal to or 
greater than the activity shown by the control couplers. The availability 
of such a range of coupler activity implies that a coupler may be selected 
to best comply with the requirements of any particular photographic 
system. 
The preparation of control 3 involves difficult methods of synthesis in a 
multi-step sequence within which product yields are often low. By 
contrast, the compounds C-1 to C-6 are easily obtained in high yield from 
readily available starting materials in a four-step sequence. 
EXAMPLE 2 
Fastness Properties 
The dye sample patches (density .dbd.1.0) are tested for light stability 
using the EDIE fadeometer for fade times of 100 h and 200 h accumulated 
fade. The spectrophotometric curves are remeasured after each fade period 
and the degree of fade quoted as the fractional decrease in density prior 
to fading. 
Dark/wet stability is tested by incubating the yellow dye samples in a dark 
oven for periods of 1, 3 and 6 weeks at a constant 60.degree. C. and 70% 
relative humidity. The spectrophotometric curves of the samples are then 
remeasured and once again the degree of fade is quoted as the fractional 
decrease in density at the absorption maximum (.DELTA.D) relative to the 
initial density prior to fading. A positive value for dye fade indicates 
an increase in dye density. 
Spectrophotometry has been chosen to monitor dye fade so that any subtle 
changes in curve shape as the dye fades will be apparent. 
Typical EDIE fade results are shown below: 
TABLE 5 
______________________________________ 
Compound 100 hrs 200 hrs 
______________________________________ 
C-6 -0.34 -0.58 
Control 3 -0.43 -0.65 
______________________________________ 
Typical dark/wet fade results are shown below: 
TABLE 6 
______________________________________ 
Compound 1 week 2 weeks 3 weeks 
______________________________________ 
C-6 -0.05 -0.14 -0.23 
Control 1 -0.34 -0.36 -0.38 
______________________________________ 
In both tables the dyes formed from the color couplers of the described 
type for the invention, are shown to have light fastness as good as or 
better than Control 3 and dark/wet fade considerably better than Control 
1. 
EXAMPLE 3 
Variable .lambda..sub.max in Coupler Solvents 
The dye obtained from coupler C-9 was dissolved in a number of solvent 
mixtures. The .lambda.max and bandwidth of each solution was measured and 
the results recorded in the table below. 
TABLE 7 
______________________________________ 
.lambda..sub.max 
Bandwidth 
Solvent System Ratio nm nm 
______________________________________ 
Cyclohexane:ethyl acetate 
9:1 520 73 
Diethyl ether:ethyl acetate 
9:1 525 72 
Methanol:ethyl acetate 
9:1 535 77 
Acetone:ethyl acetate 
9:1 537 77 
Dimethyl Sulphoxide 553 83 
Diethy lauramide:tricresyl phosphate 
9:1 544 73 
p-Dodecylphenol:tricresyl phosphate 
9:1 547 78 
______________________________________ 
As can be seen, the .lambda..sub.max can be varied by choice of solvent 
while the bandwidth stays comparatively constant. 
EXAMPLE 4 
Retouchability 
The dye image of a number of the coatings described above was treated with 
a reducing solution to convert the dye to its leuco form which is 
relatively uncoloured. This is often the first step in the hand retouching 
of a photographic image. All samples showed considerable bleaching. 
The reducing solution has the following composition: 
______________________________________ 
Stannous chloride 10 g 
Ethylenediamine tetraacetic acid.2Na 
1 g 
Acetic acid 20 ml 
Water to 200 ml 
______________________________________ 
EXAMPLE 5 
Formaldehyde Sensitivity 
In-film resistance of the coupler to formaldehyde is measured by hanging 
unexposed test strips in a closed container in an atmosphere of 
formaldehyde generated from 10 g of paraformaldehyde. A controlled 
relative humidity is achieved using a water/glycerol mixture. Control 
strips are prepared by hanging similar strips in an identical closed 
container with the same humidity control but without the paraformaldehyde. 
After 48 hours the strips are removed from the respective containers, 
exposed and processed through the C-41 process as described above. The 
resistance of the coupler to formaldehyde is then calculated as a 
percentage density loss relative to the unfumed control. The results are 
shown in Table 8 below. 
TABLE 8 
______________________________________ 
Dye from Coupler 
% Density Loss 
______________________________________ 
Control 1 90 
Control 2 97 
Control 3 0.5 
C-1 (4-equivalent) 
32.5 
C-45 (2-equivalent) 
0.5 
______________________________________ 
The color couplers useful for the invention both show resistance to fading 
compared to two of the prior art dyes while the 2-equivalent coupler C-45 
and Control 3 (a pyrazolotriazole coupler) show substantial immunity to 
fading by formaldehyde. 
The compounds of formula Control 1 and C-50 were together incorporated into 
a photographic silver bromoiodide emulsion and coated in the following 
format: 
______________________________________ 
Gel Supercoat gelatin 1.5 g/m.sup.2 
Emulsion Silver 0.8 g/m.sup.2 
Layer bromoiodide 
Control 1 1.265 mmol/m.sup.2 
Coupler C-50 (See Table 9 
below) 
Gelatin 2.42 g/m.sup.2 
Bis (vinylsulphonyl)-methane 0.06 g/m.sup.2 
(hardener) 
Support Cellulose acetate 
______________________________________ 
The coupler dispersion used for Control 1 contained 6% w/w gelatin, 8.8% 
coupler and coupler solvents in the ratio:- coupler: tricresyl phosphate: 
2-(2-butoxyethoxy)ethyl acetate 1:0.5:1.5. 
The coupler dispersion used for C-50 contained 12.5% w/w gelatin, 2.2% 
coupler and coupler solvents in the ratio:- C-50: tricresyl phosphate: 
2-(2-butoxyethoxy)ethyl acetate 1:2:3. 
The experimental photographic coatings prepared in this way are slit and 
chopped into 35 mm test strips. These are exposed through a 0-4.0 neutral 
density step wedge (0.2 ND step increments) and Daylight V, Wratten 9 
filters then processed through the the C-41 process described in British 
Journal of Photography (1988) 196-198 as used above. 
For each test strip, step-wedge densities are measured using a Macbeth 
TD/504/Hewlett Packard 85 automatic transmission densitometer. 
Measurements of maximum density (Dmax) and contrast (gamma) are calculated 
from the D log E curves. The results from these measurements are shown in 
Table 9 below. 
TABLE 9 
______________________________________ 
C-50 Laydown 
(mmol/m2) D-max Gamma 
______________________________________ 
0 2.22 1.51 
0.06 2.07 1.19 
0.12 1.89 1.11 
0.24 1.63 0.97 
0.36 1.47 0.91 
______________________________________ 
The results show that both the D.sub.max and gamma of Control 1 are reduced 
as the level of C-50 within the emulsion layer is increased. Such a 
reduction in gamma and the corresponding loss in dye density clearly 
demonstrates that compound C-50 acts as a development inhibitor releasing 
coupler. 
EXAMPLE 6 
Dispersions of the couplers were prepared in the following manner. In one 
vessel, 657 mg of a coupler COUP-1 of the type used in the present 
invention (compound C-1 described above), 657 mg of a coupler solvent 
2-ethylhexylphosphate, 130 mg of STAB-3 stabilizer, and ethyl acetate were 
combined and warmed to dissolve. In a second vessel, gelatin, Alkanol 
XC.TM. (E. I. dupont Co.) and water were combined and passed three times 
through a Gaulin colloid mill. The ethyl acetate was removed by 
evaporation and water was added to restore the original weight after 
milling. 
The photographic element of sample 2 was prepared by coating the following 
layers in the order listed below on a resin-coated paper support. The 
elements of the remainder of the sample were prepared in the same manner 
except that the amount of compound used as stabilizer was varied to obtain 
the level indicated in Tables 10 and 11. 
______________________________________ 
1st layer 
Gelatin 300 mg/ft.sup.2 
2nd layer 
Gelatin 150 mg/ft.sup.2 
Coupler C-1 22 mg/ft.sup.2 
Coupler solvent 22 mg/ft.sup.2 
Stabilizer 4.4 mg/ft.sup.2 
(except as noted in Tables) 
Green sensitized AgCl emulsion 
26.5 mg/ft.sup.2 
3rd layer 
Gelatin 124 mg/ft.sup.2 
2-(2H-benzotriazol-2-yl)-4,6-bis- 
68 mg/ft.sup.2 
(1,1-dimethylpropyl)phenol 
Tinuvin 326 .TM. (Ciba-Geigy) 
12 mg/ft.sup.2 
4th layer 
Gelatin 130 mg/ft.sup.2 
Bis(vinylsulfonylmethyl) ether 
12.6 mg/ft.sup.2 
______________________________________ 
All of the photographic elements of the samples in Tables 10 and 11 were 
given stepwise exposures to green light to provide image dye densities 
including those listed in Tables 10 and 11, and were processed follows at 
35.degree. C.: 
______________________________________ 
Developer 45 seconds 
Bleach-Fix 45 seconds 
Wash (running water) 
1.5 minutes 
______________________________________ 
The developer and bleach-fix were of the following compositions: 
______________________________________ 
Developer 
Water 700.00 mL 
Triethanolamine 12.41 g 
Blankophor REU .TM. (Mobay Corp.) 
2.30 g 
Lithium polystyrene sulfonate (30%) 
0.30 g 
N,N-Diethylhydroxylamine (85%) 
5.40 g 
Lithium sulfate 2.70 g 
N-{2-[(4-amino-3-methylphenyl) 
5.00 g 
ethylamino]ethyl}methanesulfonamide 
sesquisulfate 
1-Hydroxyethyl-1,1-diphosphonic 
0.81 g 
acid (60%) 
Potassium carbonate, anhydrous 
21.16 g 
Potassium chloride 1.60 g 
Potassium bromide 7.00 mg 
Water to make 1.00 L 
pH @ 26.7.degree. C. adjusted to 10.04 .+-. 0.05 
Bleach-Fix 
Water 700.00 mL 
Solution of ammonium thiosulfate 
127.40 g 
(54.4%) + ammonium sulfite (4%) 
Sodium metabisulfite 10.00 g 
Acetic acid (glacial) 10.20 g 
Solution of ammonium ferric 
110.40 g 
ethylenediaminetetraacetate (44%) + 
ethylenediaminetetraacetic acid (3.5%) 
Water to make 1.00 L 
pH @ 26.7.degree. C. adjusted to 5.5 .+-. 0.1 
______________________________________ 
Magenta dyes were formed from coupler C-1 each of the samples upon 
processing. The following photographic characteristics were determined: 
Dmax (the maximum density to green light); Speed (the relative log 
exposure required to yield a density to green light of 1.0); and Contrast 
(the ratio (S-T)/0.6, where S is the density at a log exposure 0.3 units 
greater than the Speed value and T is the density at a log exposure 0.3 
units less than the Speed value. In each of the inventive samples in 
Tables 10 and 11, no significant change in the foregoing parameteres was 
seen between the same elements with or without stabilizer present. 
Each of the samples of Tables 10 and 11 following exposure and processing 
as outlined above, were tested for fading. In each case the test was done 
by irradiating the sample with a light from a high 5 intensity Xenon light 
source. All samples of Table 10 received the same exposure with intensity 
at the sample plane of 5.4 klux. All samples of Table 11 received the same 
time of exposure (which was a shorter time than the Table 10 samples) to a 
50 klux light source. The change in status A green density from an initial 
density of 0.5, 1.0 and 1.7, as a result of exposure to radiation was then 
measured. The results are shown in Tables 10 and 11 below. In both Tables 
0.5, 1.0 and 1.7 indicate initial green densities while the figures within 
the columns represent the density decrease mulitplied by 100 (for example, 
0.15 is the density decrease for Table 10, sample 1 with an initial 
density of 0.5). The formulae for STAB-3 is above. Formulae for various of 
the other compounds are listed below Table 11. (I) indicates an element of 
the present invention while (C) indicates a comparative element (since the 
stabilizer is not one of those required by the present invention). Samples 
7-9 were from a coating set different from that of the remainder of the 
samples. 
TABLE 10 
______________________________________ 
Sample Stabilizer D = 0.5 D = 1.0 
D = 1.7 
______________________________________ 
1 (C) none 15 27 41 
2 (I) STAB-3 (4.4mg/ft.sup.2) 
12 23 31 
3 (C) polystyrene 15 27 43 
______________________________________ 
TABLE 11 
______________________________________ 
Sample 
Stabilizer D = 0.5 D = 1.0 
D = 1.7 
______________________________________ 
4 (C) none 12 23 36 
5.sup. (I) 
STAB-3 (4.4 mg/ft.sup.2) 
11 21 30 
6 (C) polystyrene (11 mg/ft.sup.2) 
10 19 30 
7 (C) CST-1 (22 mg/ft.sup.2) 
20 42 64 
8 (C) CST-2 (22 mg/ft.sup.2) 
22 37 48 
9 (C) none 13 24 33 
______________________________________ 
##STR273## 
##STR274## 
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.