Photographic elements containing new magenta-dye-forming bis couplers

The invention provides new magenta-dye-forming couplers, new magenta dyes formed therefrom, and new photographic elements containing the new couplers. The new couplers have the structure (I): EQU Q--G--Q.sub.(I) wherein --G-- has the structure (II): EQU --L--NH--SO.sub.2 --R--SO.sub.2 -NH--L--.sub.(II) wherein --R-- is substituted or unsubstituted alkylene, alkoxylene, arylene, or aryloxylene, and PA1 each --L-- is independently substituted or unsubstituted alkylene, alkoxylene, arylene, aryloxylene, or aryloxyalkylene, and PA1 Q-- has the structure (III ): ##STR1## wherein: each R.sup.1 -- is independently H-- or a substituent; each X-- is independently H-- or a coupling-off group; and PA1 each of D, E, and Z is independently a substituted or unsubstituted methine group, .dbd.N--, or --NH--, with the provisos that one of either the D-E or E-Z bonds is a double bond and the other is a single bond, and when the D-E bond is a carbon-carbon double bond it may form part of an aromatic ring fused with Q--, and one of D, E, and Z is a methine group bonded to --G--.

FIELD OF THE INVENTION 
This invention relates to new dye-forming couplers and new magenta dyes 
formed therefrom and to photographic silver halide elements containing 
such new couplers. More particularly, the invention concerns new 
magenta-dye-forming bis couplers comprising two bicyclic pyrazoloazole 
coupling moieties bonded to a divalent linking group. 
BACKGROUND 
Color images are commonly obtained in the silver halide photographic art by 
reaction between the development product of a silver halide developing 
agent (e.g., oxidized aromatic primary amine developing agent) and a color 
forming compound commonly referred to as a coupler. The reaction between 
the coupler and oxidized developing agent results in coupling of the 
oxidized developing agent to the coupler at a reactive site on the 
coupler, known as the coupling position, and yields a dye. The subtractive 
process of color formation is ordinarily employed in color photographic 
elements, and the dyes produced by coupling are usually cyan, magenta, or 
yellow dyes which are formed in or adjacent to silver halide emulsion 
layers sensitive to red, green, or blue radiation, respectively. 
Couplers well known for forming magenta dyes include, e.g., pyrazolones and 
bicyclic pryrazoloazoles, as described, for example, in U.S. Pat. Nos. 
3,725,067; 3,810,761; 4,443,536; 4,540,654; and 4,621,046. 
However, such known couplers often have drawbacks. 
One such drawback of many magenta-dye-forming couplers is that they are not 
as efficiently reactive with oxidized developing agent as desired, such 
that the magenta dyes formed from such couplers in silver halide 
photographic elements yield relatively low levels of maximum density 
(Dmax) and/or contrast. 
A further common drawback of many magenta-dye-forming couplers is that the 
magenta dyes formed from such couplers have poor light stability, such 
that the dyes fade too quickly when exposed to daylight. Photographic 
elements containing such imaging dyes can exhibit an unacceptable decrease 
in absorption of green light too quickly, resulting in color images that 
appear too green. 
Another con, non drawback is the relatively high equivalent weight of many 
magenta-dye-forming couplers. The term "equivalent weight", as used herein 
is equal to the molecular weight of the coupler divided by the number of 
efficiently reactive coupling moieties in the coupler molecule. Each 
efficiently reactive coupling moiety is capable of reacting with oxidized 
developing agent to form a colored dye moiety. The higher the equivalent 
weight of the coupler is, the larger is the mass of coupler that must be 
included in a photographic element layer in order to be able to produce 
the desired amount of developed image dye optical density. The need for a 
larger mass of coupler in a layer results in a thicker layer, which 
inherently reduces the transparency and optical sharpness of the layer. 
Thus, lower equivalent weight couplers allow for thinner, more 
transparent, optically sharper layers. Unfortunately, the overall mass of 
a coupler molecule must be relatively large in order to provide sufficient 
organic ballast to properly suspend the coupler molecules in droplets of 
high boiling organic liquid, referred to as coupler solvent, which are 
dispersed in the desired layer of the photographic element, and thereby 
anchor the coupler in the layer and prevent it from diffusing to adjacent 
layers or out of the element during processing with various aqueous 
processing liquids. Thus, the needs for lower equivalent weight and 
sufficient organic ballast are at apparent cross-purposes. 
Also, some characteristics of pyrazoloazole magenta-dye-forming couplers 
are significantly affected by the nature of any particular substituents 
that may be bonded to the coupling moieties at their coupling position. 
For example, it is known that the nature of such substituents can have a 
significant effect on how quickly and efficiently a coupling moiety can 
couple with oxidized developing agent at the coupling position to form a 
dye moiety, because such substituents must detach from the coupling 
position during the coupling reaction. Furthermore, after detachment from 
the coupling position, such substituents can remain in a photographic 
element along with the dye produced by the coupling reaction, and it is 
known that the nature of such detached substituents can then significantly 
affect the stability of the dye produced and can also significantly affect 
other components or activity in the photographic element, e.g., the rate 
of further development by developing agents. 
There is therefore a continuing need for a new class of magenta-dye-forming 
couplers that can minimize the drawbacks described above, i.e., that are 
efficiently reactive with oxidized developing agent to form magenta dyes 
in silver halide photographic elements that yield relatively high levels 
of maximum density (Dmax) and contrast, that form magenta dyes having 
relatively high light stability, and that have relatively low equivalent 
weight, while at the same time having relatively high molecular weight to 
provide sufficient organic ballast for proper incorporation and anchoring 
in photographic element layers. It would also be desirable for such a new 
class of couplers to provide the flexibility to choose among various 
different substituents to have at the coupling position of the coupling 
moieties of such couplers, in order to be able to tailor the effects of 
such substitutents (effects such as described above) to meet particular 
needs in various photographic elements. Of course, the couplers should 
also exhibit all the other characteristics desirable for good photographic 
performance. 
SUMMARY OF THE INVENTION 
The present invention meets the above-noted need by providing new 
magenta-dye-forming couplers, new magenta dyes formed therefrom, and new 
photographic elements containing the new couplers. 
The new magenta-dye-forming couplers provided by the invention are bis 
coupler compounds having the structure (I): 
EQU Q--G--Q.sub.(I) 
wherein --G-- has the structure (II): 
EQU --L--NH--SO.sub.2 --R--SO.sub.2 -NH--L--.sub.(II) 
wherein --R-- is substituted or unsubstituted alkylene, alkoxylene, 
arylene, or aryloxylene, and 
each --L-- is independently substituted or unsubstituted alkylene, arylene, 
alkoxylene, aryloxylene, or aryloxyalkylene, and Q-- has the structure 
(III): 
##STR2## 
wherein: each R.sup.1 -- is independently H-- or a substitutent; each X-- 
is independently H-- or a coupling-off group; and 
each of D, E, and Z is independently a substituted or unsubstituted methine 
group, .dbd.N--, or --NH--, with the provisos that one of either the D-E 
or E-Z bonds is a double bond and the other is a single bond, and when the 
D-E bond is a carbon-carbon double bond it may form part of an aromatic 
ring fused with Q--, and one of D, E, and Z is a methine group bonded to 
--G--. 
The new magenta dyes of the invention are the dyes that are formed by 
coupling reaction of an oxidized photographic color developing agent and 
the new bis couplers of the invention. 
The photographic elements of the invention each comprise a support having 
thereon a photographic silver halide emulsion layer and one or more of the 
new bis couplers of the invention. 
The couplers, dyes, and photographic elements of the invention provide a 
number of advantages. 
The couplers of the invention are efficiently reactive with oxidized 
developing agents to form magenta dyes of the invention in silver halide 
photographic elements of the invention that yield relatively high levels 
of maximum density (Dmax) and contrast. 
The magenta dyes of the invention formed from the couplers of the invention 
have good light stability, exhibiting a relatively low rate of decrease in 
absorption of green light in developed photographic elements. 
Couplers of the invention have relatively low equivalent weight, because 
each coupler molecule contains two efficiently reactive coupling moieties 
of structure (III) bonded to a linking group of structure (II). Thus the 
equivalent weight of the couplers of the invention is only one half of 
their molecular weight, and layers in photographic elements of the 
invention containing such couplers can be made thinner and thus more 
transparent and optically sharper. 
Conversely, the two coupling moieties plus linking group in couplers of the 
invention result in the couplers' having relatively high molecular 
weights, which easily provide sufficient organic ballast to properly 
suspend the coupler molecules in coupler solvent and anchor them in layers 
of photographic elements of the invention. 
Also, because the linking group of structure (II) in couplers of the 
invention is bonded to the coupling moieties of structure (III) at a 
position other than the coupling position, the new class of 
magenta-dye-forming couplers of the invention provides the flexibility to 
choose among various different substituents (represented by X-- in 
structure (III)) to have at the coupling position of the coupling 
moieties. Thus, one is able to tailor the effects of such substituents 
(e.g., effects on coupling speed and efficiency, effects on dye stability, 
effects on other components and activity in a photographic element, etc.) 
to meet particular needs in various photographic elements of the 
invention. 
Furthermore, it was unpredictable that inclusion of the divalent linking 
group of structure (II) in the magenta-dye-forming coupler molecules would 
still yield couplers having the other characteristics necessary or 
desirable for good photographic performance. The couplers of the invention 
have been unexpectedly found to have such characteristics.

DESCRIPTION OF PREFERRED EMBODIMENTS 
All the Structure (I) couplers of the invention contain the bis linking 
group of structure (II) above. 
Each coupler molecule of the invention also contains two coupling moieties, 
each bonded to the bis linking group through a different one of each of 
the two free bonds shown in Structure (II), above. The particular coupling 
moieties employed are chosen depending upon the hue and other 
characteristics desired to be imparted to any particular photographic 
element of the invention. 
In magenta-dye-forming couplers of the invention the coupling moieties in 
the coupler molecules have the structure (III), above. 
In more preferred embodiments of magenta-dye-forming couplers of the 
invention the coupling moieties in the coupler molecules have the 
structure (IV): 
##STR3## 
wherein R.sup.1 -- and X-- are as previously defined for Structure (III), 
and the coupling moiety is bonded to the bis linking group through 
connection of the free bond shown in Structure (IV) to one of the two free 
bonds shown in Structure (II). 
As used herein, the terms "substituent" and "substituted" are meant to 
denote a wide range of various groups which can be chosen, as is well 
known in the art, depending upon the effect or lack of effect desired on 
various characteristics of the couplers, e.g., solubility, diffusion 
resistance, dye hue, dye stability, etc. Such groups include, for example: 
halo, e.g., chloro, bromo or fluoro; nitro; hydroxyl; cyano; and carboxyl 
and its salts; and groups which may be further substituted, such as alkyl, 
including straight or branched chain alkyl, such as methyl, 
trifluoromethyl, ethyl, t-butyl, 3-(2,4-di-t-amylphenoxy) propyl, and 
tetradecyl; alkenyl, such as vinyl and 2-butenyl; alkoxy, such as methoxy, 
ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec-butoxy, hexyloxy, 
2-ethylhexyloxy, tetradecyloxy 2-(2,4-di-t-pentylphenoxy) ethoxy, and 
3-dodecyloxyethoxy; aryl such as phenyl, 4-t-butylphenyl, 
2,4,6-trimethylphenyl, naphthyl; aryloxy, such as phenoxy, 
2-methylphenoxy, alpha- or beta-naphthyloxy, and 4-tolyloxy; amido, such 
as acetamido, benzamido, butyramido, tetradecanamido, 
alpha-(2,4-di-t-pentyl-phenoxy) acetamido, 
alpha-(2,4-di-t-pentylphenoxy)butyramido, alpha-(3-pentadecylphenoxy)- 
hexanamido, alpha-(4-hydroxy-3-t-butylphenoxy)- tetradecanamido, 
2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecyl-pyrrolin-1-yl, 
N-methyltetradecanamido, N-succinimido, N-phthalimido, 
2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2, 5-dioxo-1-imidazolyl, and 
N-acetyl-N-dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino, 
benzyloxycarbonylamino, hexadecyloxycarbonylamino, 
2,4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino, 
2,5-(di-t-pentylphenyl) carbonylamino, p-dodecylphenylcarbonylamino, 
p-toluylcarbonylamino, N-methylureido, N,N-dimethylureido, 
N-methyl-N-dodecylureido, N-hexadecylureido, N, N-dioctadecylureido, 
N,N-dioctyl-N'-ethylureido, N-phenylureido, N,N-diphenylureido, 
N-phenyl-N-p-toluylureido, N-(m-hexadecylphenyl)ureido, 
N,N-(2,5-di-t-pentylphenyl) --N' -ethylureido; and t-butylcarbonamido; 
sulfonamido, such as methylsulfonamido, benzenesulfonamido, 
p-toluylsulfonamido, p-dodecylbenzenesulfonamido, p-toluylsulfonamido, 
p-dodecylbenzenesulfonamido, N-methyltetradecylsulfonamido, 
N,N-dipropyl-sulfamoylamino, and hexadecylsulfonamido; sulfamyl, such as 
N-methylsulfamyl, N-ethylsulfamyl, N,N-dipropylsulfamyl, 
N-hexadecylsulfamyl, N, N-dimethylsulfamyl, 
N-[3-(dodecyloxy)propyl]sulfamyl, 
N-[4-(2,4-di-t-pentylphenoxy)butyl]sulfamyl, 
N-methyl-N-tetradecylsulfamyl, and N-dodecylsulfamyl; carbamoyl, such as 
N-methylcarbamoyl, N,N-dibutylcarbamoyl, N-octadecylcarbamoyl, 
N-[4-(2,4-di-t-pentylphenoxy)butyl]carbamoyl, 
N-methyl-N-tetradecylcarbamoyl, and N,N-dioctylcarbamoyl; acyl, such as 
acetyl, (2,4-di-t-amylphenoxy)acetyl, phenoxycarbonyl, 
p-dodecyloxyphenoxycarbonyl methoxycarbonyl, butoxycarbonyl, 
tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 
3-pentadecyloxycarbonyl, and dodecyloxycarbonyl; sulfonyl, such as 
methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl, 
2-ethylhexyloxysulfonyl, phenoxysulfonyl, 2,4-di-t-pentylphenoxysulfonyl, 
methylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, 
hexadecylsulfonyl, phenylsulfonyl, 4-nonylphenylsulfonyl, and 
p-toluylsulfonyl; sulfonyloxy, such as dodecylsulfonyloxy, and 
hexadecylsulfonyloxy; sulfinyl, such as methylsulfinyl, octylsulfinyl, 
2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl, phenylsulfinyl, 
4-nonylphenylsulfinyl, and p-toluylsulfinyl; thio, such as ethylthio, 
octylthio, benzylthio, tetradecylthio, 2-(2,4-di-t-pentylphenoxy) 
ethylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, and p-tolylthio; 
acyloxy, such as acetyloxy, benzoyloxy, octadecanoyloxy, 
p-dodecylamidobenzoyloxy, N-phenylcarbamoyloxy, N-ethylcarbamoyloxy, and 
cyclohexylcarbonyloxy; amino, such as phenylanilino, 2-chloroanilino, 
diethylamino, dodecylamino; imino, such as 1 (N-phenylimido) ethyl, 
N-succinimido or 3-benzylhydantoinyl; azo, such as phenylazo and 
naphthylazo; a heterocyclic group, heterocyclic oxy group or a 
heterocyclic thio group, each of which may be substituted and which 
contain a 3 to 7 membered heterocyclic ring composed of carbon atoms and 
at least one hetero atom selected from the group consisting of oxygen, 
nitrogen and sulfur, such as 2-furyl, 2-thienyl, 2-benzimidazolyloxy or 
2-benzothiazolyl; quaternary ammonium, such as triethylammonium; and 
siloxy, such as trimethylsiloxy. 
The particular substituents used may be selected to attain the desired 
photographic properties for a specific application and can include, for 
example, hydrophobic groups, solubilizing groups, blocking groups, etc. 
Generally, the above groups and substituents thereof may typically include 
those having 1 to 42 carbon atoms and typically less than 30 carbon atoms, 
but greater numbers are possible depending on the particular substituents 
selected. Moreover, as indicated, the substituents may themselves be 
suitably substituted with any of the above groups. 
The term "alkyl" or "alkylene" standing alone herein or as part of another 
term is meant to denote C.sub.1 -C.sub.20 alkyl or alkylene. 
The term "aryl" or "arylene" standing alone herein or as part of another 
term is meant to denote C.sub.6 -C.sub.12 aryl or arylene. 
Suitable "coupling-off groups" such as represented by "X" at the coupling 
position in Structures (III) and (IV) herein are known to those skilled in 
the art. Such groups can determine the equivalency of the coupler, can 
modify the reactivity of the coupler, or can advantageously affect the 
layer in which the coupler is coated or other layers in the element by 
performing, after release from the coupler, such functions as development 
inhibition, development acceleration, bleach inhibition, bleach 
acceleration, color correction, and the like. Representative classes of 
coupling-off groups include halo, particularly chloro, bromo, or fluoro; 
alkoxy; aryloxy; heterocyclyloxy; heterocyclic, such as hydantoin and 
pyrazolyl groups; sulfonyloxy; acyloxy; amido; imido; acyl; 
heterocyclylimido; thiocyano; alkylthio; arylthio; heterocyclylthio; 
sulfonamido; phosphonyloxy; and arylazo. They are described, for example, 
in U.S. Pat. Nos. 2,355,169; 3,227,551; 3,432,521; 3,476,563; 3,617,291; 
3,880,661; 4,052,212 and 4,134,766; the disclosures of which are hereby 
incorporated herein by reference. 
Examples of specific coupling-off groups are Cl, F, Br, --SCN, OCH.sub.3, 
--OC.sub.6 H.sub.5, --OCH.sub.2 C(.dbd.O)NHCH.sub.2 CH.sub.2 OH, 
--OCH.sub.2 C(.dbd.O)NHCH.sub.2 CH.sub.2 OCH.sub.3, --OCH.sub.2 
C(.dbd.O)NHCH.sub.2 CH.sub.2 OC(.dbd.C)OCH.sub.3, --NHSO.sub.2 CH.sub.3, 
--OC(.dbd.O)C.sub.6 H.sub.5, --NHC(.dbd.O)C.sub.6 H.sub.5, OSO.sub.2 
CH.sub.3, --P(.dbd.O) (OC.sub.2 H.sub.5).sub.2, --S(CH.sub.2).sub.2 
CO.sub.2 H, 
##STR4## 
In particularly preferred embodiments of magenta-dye-forming couplers of 
the invention containing two coupling moieties of Structure (III) above, 
bonded to a bis linking group of Structure (II) above: each --R-- is 
independently tetramethylene, biphenylene, or ethylethoxylene; each --L-- 
is independently propylene or phenoxytrimethylene; each R.sup.1 -- is 
independently substituted or unsubstituted alkyl, with particularly 
preferred specific examples being methyl, t-butyl, or 
##STR5## 
and each X-- is independently H--, halo or a substituted or unsubstituted 
aryloxy, arythio, or nitrogen-containing heterocyclic group, with 
particularly preferred specific examples being H--, chloro, 1-pyrazolyl, 
phenoxy, or phenylthio. 
Some specific examples of magenta-dye-forming couplers of the invention are 
illustrated in Table I, showing the bis linking group of Structure (II) 
and the two coupling moieties of Structure (IV) which together comprise 
each coupler molecule. 
3 TABLE I 
Coupler Bis Linking Group Coupling Moieties 
M-1 
##STR6## 
##STR7## 
M-2 
##STR8## 
##STR9## 
M-3 
##STR10## 
##STR11## 
M-4 
##STR12## 
##STR13## 
##STR14## 
M-5 
##STR15## 
##STR16## 
##STR17## 
M-6 
##STR18## 
##STR19## 
M-7 
##STR20## 
##STR21## 
M-8 
##STR22## 
##STR23## 
M-9 
##STR24## 
##STR25## 
M-10 
##STR26## 
##STR27## 
##STR28## 
M-11 
##STR29## 
##STR30## 
M-12 
##STR31## 
##STR32## 
##STR33## 
Couplers of the invention can be readily prepared by known general 
condensation reactions starting with appropriate known derivatives of the 
coupling moieties and bis linking group. One convenient general scheme is 
as follows, wherein --R--, --L--, D, E, Z, X--, and R.sup.1 -- are 
described above in regard to Structures (II) and (III): 
##STR34## 
A working example of a specific preparation of a specific coupler of the 
invention is as follows: 
##STR35## 
To a solution of 6.957 g (0.02 mol) of (1), 2.67 g (0.022 mol) of N, 
N-dimethyl aniline and 0.489 g (0.004 mol) of 4-dimethylaminopyridine in 
50 ml of dried tetrahydrofuran at room temperature was added 2.55 g (0.01 
mol) of 1,4-butane disulfonyl chloride (2). After being stirred at room 
temperature for 20 h, the reaction mixture was poured into ice-water 
containing 2 mL of concentrated hydrochloric acid. Filtration under 
suction afforded 8.2 g of crude product (M-1) as a solid. Flash 
chromotography (silica gel, gradient of 5-20% AcOet/Ligroin) yielded 6.58 
g (75%) of (M-1) as an off-white solid. Physical and spectroscopic data 
('HNMR and FDMS) were consistent with the assigned structure. 
Dyes in accordance with the invention are those formed by well-known 
coupling reaction of an oxidized photographic color developing agent with 
a coupler, in this case a coupler in accordance with the invention. 
The photographic elements of the invention each comprise a support having 
thereon a photographic silver halide emulsion layer and one or more of the 
new bis couplers of the invention. Such elements can contain any of the 
layers and components known in the photographic art, with at least one of 
the magenta-dye-forming couplers therein being a coupler of this 
invention. 
Couplers of the invention can be used in any of the ways and in any of the 
combinations in which couplers are used in the photographic art. Many such 
ways and combinations are well known to those in the photographic art. 
Typically, the coupler is incorporated in a silver halide emulsion and the 
emulsion is coated on a support to form a photographic element of the 
invention. Alternatively, the coupler can be incorporated in an element of 
the invention 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. 
The photographic elements of the invention 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 comprise a single emulsion layer or 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 an 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 of the invention comprises a 
support bearing a cyan-dye-image-forming unit comprising 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 magenta-dye-forming 
couplers in the element being a coupler of this invention. The element can 
contain additional layers, such as filter layers, interlayers, overcoat 
layers, subbing layers, and the like. 
If desired, the photographic element can be used in conjunction with an 
applied magnetic layer as described in Research Disclosure, November 1992, 
Item 34390 published by Kenneth Mason Publications, Ltd., Dudley Annex, 
12a North Street, Emsworth, Hampshire P010 7DQ, ENGLAND. 
In the following discussion of some suitable materials for use in the 
emulsions and elements of this invention, reference will be made to 
Research Disclosure, Issue Number 908, December 1989, Item 308119, pages 
993-1015, available as described above, 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. Some 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 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 supports are paper, cellulose acetate, and poly(ethylene 
terephthalate). 
Photographic elements can be exposed to actinic radiation, usually in the 
visible region of the spectrum, to form a latent image and then processed 
to form a visible dye image. Processing to form a visible dye image 
includes the step of contacting the element with a color developing agent 
to reduce developable silver halide and oxidize the color developing 
agent. Oxidized color developing agent in turn reacts with the coupler to 
yield a dye of the invention. 
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 this processing step leads to a 
negative image. To obtain a positive (or reversal) image, this step can be 
preceded by development with a non-chromogenic developing agent to develop 
exposed silver halide, but not form dye, and then uniformly fogging the 
element to render the unexposed silver halide developable. Alternatively, 
a direct positive emulsion can be employed to obtain a positive image. 
Development is followed by the conventional steps of bleaching, fixing, or 
bleach-fixing, to remove silver and silver halide, washing and drying. 
The following examples are presented to further illustrate some specific 
photographic elements of the invention containing couplers of the 
invention. 
Comparative examples are also provided containing couplers outside the 
scope of the present invention. Comparative couplers employed are as 
follows: 
##STR36## 
EXAMPLES 1-3 AND COMATIVE EXAMPLES A-D 
Preparation of Photographic Elements 
Dispersions of the couplers were prepared in the following manner: The 
quantities of each component are found in Table II. In one vessel the 
coupler, stablilizer 
(2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-5,5',6,6'-tetrapropoxy-1, 
1'-spirobi[1H-indene]), coupler solvent (diethyl dodecanamide), and ethyl 
acetate were combined and warmed to dissolve. In a second vessel, gelatin, 
Alkanol XC.TM. (surfactant and Trademark of E. I. DuPont Co., USA) and 
water were combined and warmed to about 40.degree. C. The two mixtures 
were mixed together 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. 
TABLE II 
__________________________________________________________________________ 
Grams 
Grams 
Grams 
Grams 
Dispersion 
Coupler 
Grams 
Grams 
Coupler 
Ethyl 
12.5% 
Alkanol 
Grams 
Number 
Number 
Coupler 
Stabilizer 
Solvent 
Acetate 
Gelatin 
XC (10%) 
Water 
__________________________________________________________________________ 
1 M-1 0.520 
0.260 
0.780 
1.559 
17.76 
2.22 13.90 
2 M-2 0.577 
0.288 
0.865 
1.730 
17.76 
2.22 13.56 
3 M-3 0.669 
0.335 
1.004 
2.007 
17.16 
2.22 13.01 
A C-1 0.469 
0.234 
0.703 
1.406 
17.16 
2.22 14.21 
B C-2 0.489 
0.244 
0.733 
1.467 
17.16 
2.22 14.09 
C C-3 0.616 
0.308 
0.924 
1.847 
17.16 
2.22 13.33 
__________________________________________________________________________ 
The photographic elements were prepared by coating the following layers in 
the order listed on a resincoated paper support: 
______________________________________ 
1st Layer 
Gelatin 3.23 g/m.sup.2 
2nd Layer 
Gelatin 1.61 g/m.sup.2 
Coupler Dispersion 
4.3 .times. 10-.sup.4 
mole coupling moieties/m.sup.2 
AgCl emulsion 0.17 g Ag/m.sup.2 and green-sensitized 
3rd Layer 
Gelatin 1.33 g/m.sup.2 
2-(2H-benzotriazol-2-yl)- 
0.73 g/m.sup.2 
4,6-bis-(1,1-dimethyl- 
propyl)phenol 
Tinuvin 326.TM. 
0.13 g/m.sup.2 
(Ciba-Geigy) 
4th Layer 
Gelatin 1.40 g/m.sup.2 
Bis(vinylsulfonylmethyl) 
0.14 g/m.sup.2 
ether 
______________________________________ 
Exposing and Processing of Photographic Elements 
The photographic elements were given stepwise exposures to green light and 
processed as follows at 35.degree. C. 
______________________________________ 
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- 5.00 g 
methylphenyl)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 g 
Water to make 1.00 L 
pH at 26.7.degree. C. adjusted to 6.7 
Bleach Fix 
Water 700.00 mL 
Solution of Ammonium thiosulfate 
127.40 g 
(56.4%) plus Ammonium sulfite (4%) 
Sodium metabisulfite 10.00 g 
Acetic acid (glacial) 10.20 g 
Solution of Ammonium ferric 
110.40 g 
ethylene diaminetetraacetate (44%) + 
ethylenediamine tetraacetic acid 
(3.5%) 
Water to make 1.00 L 
pH @ 26.7.degree. C. adjusted to 6.7 
______________________________________ 
The developer and bleach-fix were of the following compositions: 
______________________________________ 
Developer 45 seconds 
Bleach-Fix 45 seconds 
Wash (running water) 
90 seconds 
______________________________________ 
Photographic Tests 
Magenta dyes were formed upon processing. The following photographic 
characteristics were determined: D-max (the maximum density to green 
light). Speed (the relative reciprocal of log exposure required to yield a 
density to green light of 1.0); 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); 
Lambda-max (the wavelength of peak absorption at a density of 1.0); and 
Bandwidth (the width of the absorption spectrum in nanometers at half the 
peak density). These values for each example are tabulated in Table III. 
TABLE III 
__________________________________________________________________________ 
Example No. 
Dispersion 
Coupler 
D-max 
Contrast 
Speed 
Lambda-max 
Bandwidth 
__________________________________________________________________________ 
1 1 M-1 2.07 
2.21 121 549 100 
2 2 M-2 1.93 
2.06 121 550 102 
3 3 M-3 1.94 
1.96 119 549 98 
Comp. A 
A C-1 1.79 
1.94 119 548 100 
Comp. B 
B C-2 1.51 
1.41 149 551 108 
Comp. C 
C C-3 1.37 
1.14 99 549 101 
__________________________________________________________________________ 
Additional coatings prepared and processed as described above were 
illuminated by simulated daylight at 50 klux for periods of 2, 4 and 6 
weeks. The green densities were monitored and the time in weeks required 
for 30% density loss from an initial density of 1.0 (T30) was calculated. 
These data are found in Table IV. 
TABLE IV 
______________________________________ 
Example No. 
Dispersion Coupler T30 
______________________________________ 
1 1 M-1 2.65 
2 2 M-2 2.08 
3 3 M-3 1.95 
Comp. A A C-1 1.27 
Comp. B B C-2 0.85 
Comp. C C C-3 0.90 
______________________________________ 
The equivalent weight advantage of the couplers of the invention is 
illustrated in Table V. 
TABLE V 
______________________________________ 
Example 
No. Coupler No. 
Molecular Weight 
Equivalent Weight 
______________________________________ 
1 M-1 878 439 
2 M-2 974 487 
Comp. D 
C-4 728 728 
______________________________________ 
The data from Tables III and IV show that the bis-magenta couplers of this 
invention coated at levels proportional to their equivalent weights 
provide better coupling efficiency (Dmax and Contrast) and provide dyes 
with better light stability (T30) than those obtained from the comparison 
examples. 
The lower equivalent weights of the couplers of the present invention 
(shown in Table V) allow a reduction in coating load, resulting in thinner 
coating for improving transparency and optical sharpness of the layer. 
The invention has been described in detail with particular reference to 
certain preferred embodiments thereof, but it should be appreciated that 
variations and modifications can be effected within the spirit and scope 
of the invention.