Thioethers in photographic elements

This invention relates to a silver halide color photographic element comprising a support, a silver halide emulsion and poly(thioether)s wherein greater than 50 percent of the poly(thioether)s have acidic functional end groups with an aqueous pKa.ltoreq.10, or end groups which will react to form acidic functional end groups with an aqueous pKa.ltoreq.10 during development, on both termini and wherein the poly(thioether)s have a molecular weight greater than 800.

FIELD OF THE INVENTION 
This invention relates to the use of development accelerators in silver 
halide photographic elements. More specifically it relates to the use of 
poly(thioether)s as the accelerators. 
BACKGROUND OF THE INVENTION 
It is often desirable to obtain more rapid or accelerated photographic 
development during the processing of a silver halide photographic 
material. More rapid or accelerated photographic development is observed 
when the same exposure and process time provides increased photographic 
speed or higher Dmax for a photographic element. It is important that the 
increased photographic development not be accompanied by an undesirable 
increase in the amount of fog. 
In order to achieve more rapid photographic development, two approaches are 
possible. The first approach involves a change in the process such as an 
increase in the temperature of the process or a change in the composition 
of the developer. This approach is not often practical, especially when a 
photographic element has more than one light sensitive layer, and each 
layer responds differently to process changes. The second approach is to 
incorporate an additive which increases the rate of photographic 
development into a light-sensitive layer or an adjacent 
non-light-sensitive layer. 
A number of additives, sometimes called development accelerators, have been 
described which, when added to a photographic element, will increase the 
rate of photographic development. Some of these additives are 
poly(alkylene oxide)s as described in Y. Inaba and A. Kumai: Photo. Sci. 
Eng.,17, 499(1973); pyrazolidone/cyclodextran inclusion complexes as 
described in GB 2,261,740; and substituted diaminedithio-containing 
materials as described in U.S. Pat. No. 5,192,655. 
Various thioethers, particularly polymers, have been described as 
development accelerators in, for example, U.S. Pat. Nos. 3,046,132; 
3,813,247; 3,046,134; 3,046,129; 3,057,724; and 3,165,552. The manufacture 
of these materials for use as development accelerators has a problem in 
that some of the polymers synthesized have low photographic activity. The 
use of polymeric thioethers of variable and sometimes low photographic 
activity is unacceptable for the manufacture of photographic sensitized 
goods where uniform performance is desired. 
Other thioethers are described for use as development accelerators in U.S. 
Pat. No. 4,013,471 and 4,072,523. Polymers with pendant thioether groups 
are described for use in a developer solution in U.S. Pat. No. 4,038,075. 
However, none of these patents describe thioethers which consistently show 
the high activity and uniformity of those of the current invention. 
SUMMARY OF THE INVENTION 
This invention provides a silver halide color photographic element 
comprising a support, a silver halide emulsion and poly(thioether)s 
wherein greater than 50 percent of the poly(thioether)s have acidic 
functional end groups with an aqueous pKa.ltoreq.10, or end groups which 
will react to form acidic functional end groups with an aqueous 
pKa.ltoreq.10 during development, on both termini, and wherein the 
poly(thioether)s have a molecular weight greater than 800. This invention 
also provides a silver halide color photographic element comprising a 
support, a silver halide emulsion and poly(thioether)s wherein greater 
than 50 percent of the poly(thioether)s are represented by Formula I 
##STR1## 
wherein A and A' are independently acidic functional groups; 
L and L.sub.i are independently divalent organic linking groups; 
X.sub.i is independently a non-metallic heteroatom, with the proviso that 
at least one Xi must be a sulfur; and 
n is one to 300; and wherein the poly(thioether)s 
have a molecular weight greater than 800. 
The poly(thioether)s of this invention can provide a significant increase 
in development yield and speed, and a change in Dmax in a photographic 
element. Further, the poly(thioether)s of this invention provide more 
uniform development acceleration. 
DETAILED DESCRIPTION 
While thioethers and poly(thioether)s have been described as development 
accelerators, the inventors herein have discovered that the photographic 
activity of these materials can be dramatically and unexpectedly increased 
by forming derivatives of these materials such that the end groups are 
converted to acidic functional groups or groups which can react to form 
acidic functional groups under photographic development conditions. 
Examples of groups which may react are esters, amides and isocyanates all 
of which may hydrolyze during color development. Other groups may react 
via different mechanisms. The development step may be either with a color 
developer or, in the case of a color reversal process, it may take place 
with a black and white developer. 
The thioether polymers known in the art are often prepared by combining 
diols with dicarboxilic acids at high temperatures in condensation 
reactions, and removing the water which is formed under vacuum. Such 
polymers commonly have a statistical distribution of alcohol and 
carboxylic acid end groups. The total end group population of alcohol 
groups and population of carboxylic acid end groups will usually be equal 
to each other if the molar amounts of starting materials are also equal. 
In this invention, however, greater than 50 percent of the poly(thioether)s 
utilized in the photographic element have acidic functional end groups 
with an aqueous pKa.ltoreq.10, or end groups which will react to form 
acidic functional end groups with an aqueous pKa.ltoreq.10 during color 
development, on both termini. Preferably greater than 95 percent of the 
poly(thioether)s have such groups on both termini, more preferably greater 
than 98 percent have such groups on both termini and most preferably 
substantially all of the poly(thioether)s such groups on both termini. 
Acidic functional groups are preferred over groups which can react to form 
into acidic functional groups. 
Suitable poly(thioether)s have a molecular weight greater than 800. 
Preferably the poly(thioether)s have a molecular weight ranging between 
800 and 16000 AMU, more preferably between 800 and 10000 AMU and most 
preferably between 1000 and 7000 AMU. 
Polymers ending with carboxylic acid groups are particularly potent 
development accelerators. Polymers ending with other acidic functional 
groups are also possible. Such end groups could be (but are not restricted 
to) sulfonate groups or phosphoric acids groups. 
In one embodiment of this invention greater than 50 percent, more 
preferably greater than 95 percent, of the poly(thioether)s contained in 
the photographic element are represented by Formula I. 
##STR2## 
A and A' are independently acidic functional groups or a salts thereof with 
an aqueous pKa.ltoreq.10. Useful examples of A and A' include, but are not 
limited to, carboxylic acids, carboxylate salts, sulfonic acids, sulfinic 
acids, cyanamides, sulfonamides, hydroxamic acids, thiols, thiolates, and 
the like. 
L and Li are independently divalent organic linking groups, preferably of 
about 1-35 non-hydrogen atoms, and more preferably of about 1-20 
non-hydrogen atoms. The linking group may be substituted or unsubstituted. 
Preferred linking groups include alkylene, alkenyl, arylene, aralkylene or 
heteroarylene groups. Examples of suitable linking groups include 
##STR3## 
and the like. 
Xi is independently a non-metallic heteroatom, either substituted or 
unsubstituted. Useful examples include --O--, --S--, --SO--, --SO.sub.2 
--, --NR.sub.1 --wherein R.sub.1, is an organic substituent of about 1-20 
non-hydrogen atoms. R.sub.1 may be, for example, a substituted or 
unsubstituted alkyl, alkenyl, aryl, aralkyl or heteroaryl, acyl, sulfonyl, 
or ureido group. At least one of the Xi groups must be sulfur. 
Examples of (Li-Xi) which can be used in the present invention include the 
materials below. 
##STR4## 
The (Li-Xi) groups may be combined to form repetitive combinations of the 
same (Li-Xi) groups or may be combined to form linear combinations of 
different (Li-Xi) groups. As such, (Li-Xi) may be combined to form block 
copolymers. Useful examples include block copolymers of ethylene oxide and 
propylene oxide also known as PLURONIC and R PLURONIC block copolymers 
shown below. 
##STR5## 
(Li-Xi) may also include random copolymers of ethylene oxide and propylene, 
and the like. As noted above, at least one Xi must be a sulfur to form a 
thioether. The acidic functional group should be connected either directly 
or indirectly through a linking group to the thioether. It is preferred 
that the acidic functional group be separated from the thioether by a 
linking group. 
Suitable poly(thioether)s of Formula I have a molecular weight greater than 
800. Preferably the poly(thioether)s have a molecular weight ranging 
between 800 and 16000 AMU, more preferably between 800 and 10000 AMU and 
most preferably between 1000 and 7000 AMU. 
These materials can be prepared by modifying an existing polymer such as 
those described in U.S. Pat. Nos. 3,046,132; 3,813,247; 3,046,134; 
3,046,129; 3,057,724; and 3,165,552. This modification procedure, as 
demonstrated in the examples, is usually a separate process and results in 
a polymer where all the end groups are acidic functional groups or groups 
which can be converted into are acidic functional groups under 
photographic development conditions. One class of materials which are 
useful for this invention are polyesters whose end groups have been 
converted into acidic functional groups, as demonstrated in the examples. 
Typical polyesters can be made by methods well known in the art. They can 
be made from the reaction of dicarboxylic acids or anhydrides with 
glycols. Useful examples of dicarboxylic acids or anhydrides are: 
______________________________________ 
succinic suberic 
glutaric 4-thiapimelic 
adipic 3,6-dithiasuberic 
azelaic 3,7-dithiaazelaic 
sebacic 3,8-dithiasebacic 
pimelic 3-thiaadipic. 
______________________________________ 
Useful examples of glycols are: 
3,11-dithia-7-oxatridecane-1,13-diol 
3-thiapentane-1,5-diol 
3,6-dithiaoctane-1,8-diol 
4,10-dithiatridecane-1,13-diol 
4,15-dithiaoctadecane-1,18-diol 
7,13-dithianonadecane-1,19-diol 
7,13-dithiatetracosane-1,24-diol 
4,8-dithiaundecane-2,11-diol 
3-thiahexane-1,6-diol 
4-thiaheptane-1,7-diol 
3-thianonane-1,9-diol. 
These glycols may be combined with glycols containing aromatic groups. 
Examples of such glycols are: 
______________________________________ 
1,4-benzenedimethanol 
2,5-bis(3-hydroxypropyl)butoxybenzene 
1,4-benzenedipropanol 
2,5-(dihydroxymethyl)chlorobenzene 
2,5-toluenedimethanol 
2,2'-(4-methoxybenzylimino)diethanol 
2,5-phenetoledipropanol 
3,3'-(4-propylbenzylimino)dipropanol 
2,5-ethylbenzenedimethanol 
2,2'-(2-bromobenzylimino)diethanol 
2,2'-(benzylimino)diethanol 
4,4'-(3,5-dimethylbenzylimino)dibutanol. 
______________________________________ 
Another class of thioethers which is useful in our invention is indicated 
below. Values of n from 4 to 16 are preferred, and from 4 to 7 are most 
preferred. 
##STR6## 
It is understood that n in the above formula may be a single integer 
representing a single chemical entity or may also be a range of integers 
representing a blend of chemical entities. The pure compounds and the 
blends of components both have utility in this invention. When a blend of 
inventive compounds is used it is understood that the blend may be made by 
combining the pure compounds synthesized as described in the examples in 
any proportion or may also result from conventional condensation 
polymerization synthesis which is well known to those skilled in the art. 
It is understood throughout this specification and claims that any 
reference to a substituent by the identification of a group containing a 
substitutable hydrogen (e.g., alkyl, amine, aryl, alkoxy, heterocyclic, 
etc.), unless otherwise specifically described as unsubstituted or as 
substituted with only certain substituents, shall encompass not only the 
substituent's unsubstituted form but also its form substituted with any 
substituents which do not negate the advantages of this invention. 
Examples of suitable substituents include halogen, such as chlorine, 
bromine or fluorine; alkyl or aryl groups, including straight, branched or 
cyclic alkyl groups, such as those containing 1 to 30 carbon atoms, for 
example methyl, trifluoromethyl, ethyl, t-butyl, phenyl, tetradecylphenyl, 
4-t-butylphenyl, 2,4,6-trimethylphenyl and naphthyl; alkoxy groups, such 
as an alkoxy group containing 1 to 30 carbon atoms, for example methoxy, 
ethoxy, 2-ethylhexyloxy and tetradecyloxy; aryloxy groups, such as 
phenoxy, .alpha.- or .beta.- naphthyloxy, and 4-tolyloxy; acylamino 
groups, such as acetamido, benzamido, butyramido, tetradecanamido, 
.alpha.-(2,4-di-t-amylphenoxy)-acetamido, 
.alpha.-(2,4-di-t-amylphenoxy)butyramido, 
.alpha.-(3-pentadecylphenoxy)hexanamido, 
.alpha.-(4-hydroxy-3-t-butylphenoxy)tetradecanamido, 
2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolin-1-yl, 
N-methyltetradecanamido, and t-butylcarbonamido; sulfonamido groups, such 
as methanesulfonamido, benzenesulfonamido, p-toluenesulfonamido, 
p-dodecylbenzenesulfonamido, N-methyltetradecylsulfonamido, and 
hexadecanesulfonamido; sulfamoyl groups, such as N-methylsulfamoyl, 
N-hexadecylsulfamoyl, N,N-dimethylsulfamoyl; 
N-3-(dodecyloxy)propyl!sulfamoyl, 
N-4-(2,4-di-t-pentylphenoxy)butyl!-sulfamoyl, 
N-methyl-N-tetradecylsulfamoyl, and N-dodecylsulfamoyl; sufamido groups, 
such as N-methylsulfamido and N-octadecylsulfamido; carbamoyl groups, such 
as N-methylcarbamoyl, N-octadecylcarbamoyl, 
N-4-(2,4-di-t-pentyl-phenoxy)butyl!carbamoyl, 
N-methyl-N-tetradecylcarbamoyl, and N,N-dioctylcarbamoyl; diacylamino 
groups, such as N-succinimido, N-phthalimido, 2,5-dioxo-1-oxazolidinyl, 
3-dodecyl-2,5-dioxo-1-imidazolyl, and N-acetyl-N-dodecylamino; 
aryloxycarbonyl groups, such as phenoxycarbonyl and p-dodecyloxphenoxy 
carbonyl; alkoxycarbonyl groups, such as alkoxycarbonyl groups containing 
2 to 30 carbon atoms, for example methoxycarbonyl, tetradecyloxycarbonyl, 
ethoxycarbonyl, benzyloxcarbonyl, and dodecyloxycarbonyl; alkoxysulfonyl 
groups, such as alkoxysulfonyl groups containing 1 to 30 carbon atoms, for 
example methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl, and 
2-ethylhexyloxysulfonyl; aryloxysulfonyl groups, such as phenoxysulfonyl, 
2,4-di-t-amylphenoxysulfonyl; alkanesulfonyl groups, such as 
alkanesulfonyl groups containing 1 to 30 carbon atoms, for example 
methanesulfonyl, octanesulfonyl, 2-ethylhexanesulfonyl, and 
hexadecanesulfonyl; arenesulfonyl groups, such as benzenesulfonyl, 
4-nonylbenzenesulfonyl, and p-toluenesulfonyl; alkylthio groups, such as 
alkylthio groups containing 1 to 22 carbon atoms; for example ethylthio, 
octylthio, benzylthio, tetradecylthio, and 
2-(2,4-di-t-amylphenoxy)ethylthio; arylthio groups, such as phenylthio and 
p-tolylthio; alkoxycarbonylamino, such as ethoxycarbonylamino, 
benzyloxycarbonylamino, and hexadecyloxycarbonylamino; alkylureido groups, 
such as N-methylureido, N,N-dimethylureido, N-methyl-N-dodecylureido, 
N-hexadecylureido, N,N-dioctadecylureido, and N,N-dioctyl-N'-ethyl-ureido; 
acyloxy groups, such as acetyloxy, benzoyloxy, octadecanoyloxy, 
p-dodecanamidobenzoyloxy, and cyclohexanecarbonyloxy; nitro groups; cyano 
groups; carboxy groups or other acid groups and heterocyclic groups 
including 3- to 15-membered rings with at least one atom selected from 
nitrogen, oxygen, sulfur, selenium and tellurium such as pyrrolidine, 
piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, 
imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, 
benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, 
oxadiazole, or thiadiazole rings; where preferably the foregoing organic 
substituents contain not more than 10 and more preferably not more than 5 
carbon atoms. Furthermore, any reference to an alkyl group includes cyclic 
groups. 
The color silver halide photographic element of the invention can have any 
of the image forming or non-imaging forming layers known in the art. The 
photographic element is a multilayer, multicolor element and includes both 
negative and reversal elements. A multicolor element contains dye 
image-forming units sensitive to each of the three primary regions of the 
visible light spectrum. Each unit can be comprised of a single emulsion 
layer, or of multiple emulsion layers spectrally sensitive to the same or 
substantially the same region of the spectrum. The layers of the element, 
can be arranged in various orders as known in the art. 
In this invention the multicolor photographic element comprises a support 
having situated thereon, preferably in order from the support, a red 
light-sensitive, cyan dye-forming unit comprising a photosensitive silver 
halide emulsion layer and an image dye-forming coupler; a green 
light-sensitive, magenta dye-forming unit comprising a photosensitive 
silver halide emulsion layer and an image dye-forming coupler; and a blue 
light-sensitive, yellow dye-forming unit comprising a photosensitive 
silver halide emulsion layer and an image dye-forming coupler. 
Photographic emulsions are generally prepared by precipitating silver 
halide crystals in a colloidal matrix by methods conventional in the art. 
The colloid is typically a hydrophilic film forming agent such as gelatin, 
alginic acid, or derivatives thereof. 
The crystals formed in the precipitation step are washed and then 
chemically and spectrally sensitized by adding spectral sensitizing dyes 
and chemical sensitizers, and by providing a heating step during which the 
emulsion temperature is raised and maintained for a period of time. The 
precipitation and spectral and chemical sensitization methods utilized in 
preparing the emulsions employed in the invention can be those methods 
known in the art 
Chemical sensitization of the emulsion typically employs sensitizers such 
as: sulfur-containing compounds, e.g., allyl isothiocyanate, sodium 
thiosulfate and allyl thiourea; reducing agents, e.g., polyamines and 
stannous salts; noble metal compounds, e.g., gold, platinum; and polymeric 
agents, e.g., polyalkylene oxides. Preferably, the emulsion is sensitized 
both with gold and a chalcogenide, most preferably gold and sulfur. 
Examples of sulfur sensitizers include sodium thiosulfate, alkyl or aryl 
thiourea compounds, or thiourea compounds with nucleophilic substituents 
as described in U.S. Pat. No. 4,810,626. Examples of gold sensitizers 
include potassium tetrachloroaurate, potassium dithiocyanato gold (I), 
trisodium dithiosulfato gold(I), and the gold(I) compounds described in 
U.S. Pat. Nos. 5,049,484; 5,049,485; 5,252,455; 5,220,030; and 5,391,727. 
As described, heat treatment is employed to complete chemical 
sensitization. Spectral sensitization is effected with a combination of 
dyes, which are designed for the wavelength range of interest within the 
visible or infrared spectrum. It is known to add such dyes both before and 
after heat treatment. 
After spectral sensitization, the emulsion is coated on a support. Various 
coating techniques include dip coating, air knife coating, bead coating, 
curtain coating and extrusion coating. 
The compounds of this invention may be added to the silver halide emulsion 
at any time during the preparation of the emulsion, i.e., during 
precipitation, during or before chemical sensitization or during final 
melting and co-mixing of the emulsion and additives for coating. More 
preferably, these compounds are added during final melting and co-mixing 
of the emulsion and additives for coating. 
Useful levels of the poly(thioether)s range from 0.01 to 10.0 millimoles 
per silver mole. The preferred range is from 0.05 to 1.0 millimoles per 
silver mole with a more preferred range being from 0.1 to 0.4 millimoles 
per silver mole. 
The compounds may be added to the photographic emulsion using any technique 
suitable for this purpose. Preferably they are added as a direct 
dispersion prepared by the standard methods known to those skilled in the 
art. Combinations of more than one poly(thioether) may be utilized. 
The element may contain layers in addition to those described above. Such 
layers include filter layers, in particularly yellow and magenta filter 
dye layers, interlayers, overcoat layers, subbing layers, and the like. 
The photographic elements may also contain a transparent magnetic 
recording layer such as a layer containing magnetic particles on the 
underside of a transparent support, as described in Research Disclosure, 
November 1992, Item 34390 published by Kenneth Mason Publications, Ltd., 
Dudley Annex, 12a North Street, Emsworth, Hampshire PO10 7DQ, ENGLAND. 
Typically, the element will have a total thickness (excluding the support) 
of from about 5 to about 30 microns. Further, the photographic elements 
may have an annealed polyethylene naphthalate film base such as described 
in Hatsumei Kyoukai Koukai Gihou No. 94-6023, published Mar. 15, 
1994(Patent Office of Japan and Library of Congress of Japan) and may be 
utilized in a small format system, such as described in Research 
Disclosure, June 1994, Item 36230 published by Kenneth Mason Publications, 
Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire PO10 7DQ, 
ENGLAND, and such as the Advanced Photo System, particularly the Kodak 
ADVANTIX films or cameras. 
The silver halide emulsion employed in the dye-forming units of the 
invention can contain grains of any size and morphology. Thus, the grains 
may take the form of cubes, octahedrons, cubo-octahedrons, or any of the 
other naturally occurring morphologies of cubic lattice type silver halide 
grains. Further, the grains may be irregular such as spherical grains or 
tabular grains. 
The silver halide emulsion can be either monodisperse or polydisperse as 
precipitated. The grain size distribution of the emulsion can be 
controlled by silver halide grain separation techniques or by blending 
silver halide emulsions of differing grain sizes. 
The grains may be comprised of any halide combination, including silver 
chloride, silver bromide, silver bromochloride, silver chlorobromide, 
silver iodochloride, silver iodobromide, silver bromoiodochloride, silver 
chloroiodobromide, silver iodobromochloride, and silver iodochlorobromide 
emulsions. Preferred are iodobromide emulsions with an iodide content of 2 
to 12%. 
The grains can be contained in cap conventional dispersing medium capable 
of being used in photographic emulsions. Specifically, it is contemplated 
that the dispersing medium be an aqueous gelatino-peptizer dispersing 
medium, of which gelatin--e.g., alkali treated gelatin (cattle bone and 
hide gelatin)--or acid treated gelatin (pigskin gelatin) and gelatin 
derivatives--e.g., acetylated gelatin, phthalated gelatin--are 
specifically contemplated. When used, gelatin is preferably at levels of 
0.01 to 100 grams per total silver mole. Also contemplated are dispersing 
mediums comprised of synthetic colloids. 
Silver halide color reversal films are typically associated with an 
indication for processing by a color reversal process. Reference to a film 
being associated with an indication for processing by a color reversal 
process, most typically means the film, its container, or packaging (which 
includes printed inserts provided with the film), will have an indication 
on it that the film should be processed by a color reversal process. The 
indication may, for example, be simply a printed statement stating that 
the film is a "reversal film" or that it should be processed by a color 
reversal process, or simply a reference to a known color reversal process 
such as "Process E-6". A "color reversal" process in this context is one 
employing treatment with a non-chromogenic developer (that is, a developer 
which will not imagewise produce color by reaction with other compounds in 
the film; sometimes referenced as a "black and white developer"). This is 
followed by fogging unexposed silver halide, usually either chemically or 
by exposure to light. Then the element is treated with a color developer 
(that is, a developer which will produce color in an imagewise manner upon 
reaction with other compounds in the film). 
In a typical construction, a reversal film does not have any masking 
couplers. Furthermore, reversal films have a gamma generally between 1.5 
and 2.0, a gamma which is much higher than the gamma for typical negative 
materials. 
In the following Table, reference will be made to (1) Research Disclosure, 
December 1978, Item 17643, (2) Research Disclosure, December 1989, Item 
308119, (3) Research Disclosure, September 1994, Item 36544, and (4) 
Research Disclosure, September 1996, Item 38957, all published by Kenneth 
Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, 
Hampshire PO10 7DQ, ENGLAND, the disclosures of which are incorporated 
herein by reference. The Table and the references cited in the Table are 
to be read as describing particular components suitable for use in the 
elements of the invention. The Table and its cited references also 
describe suitable ways of preparing, exposing, processing and manipulating 
the elements, and the images contained therein. Photographic elements and 
methods of processing such elements particularly suitable for use with 
this invention are described in Research Disclosure, February 1995, Item 
37038, published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a 
North Street, Emsworth, Hampshire PO10 7DQ, ENGLAND, the disclosure of 
which is incorporated herein by reference. 
______________________________________ 
Reference Section Subject Matter 
______________________________________ 
1 I, II Grain composition, 
2 I, II, IX, X, 
morphology and 
XI, XII, preparation. Emulsion 
XIV, XV preparation including 
3&4 I, II, III, IX 
hardeners, coating aids, 
A&B addenda, etc. 
1 III, IV Chemical sensitization and 
2 III, IV spectral sensitization/ 
3&4 IV, V desensitization 
1 V UV dyes, optical 
2 V brighteners, luminescent 
3&4 VI dyes 
1 VI Antifoggants and stabilizers 
2 VI 
3&4 VII 
1 VIII Absorbing and scattering 
2 VIII, XIII, materials; Antistatic layers; 
XVI matting agents 
3&4 VIII, IX C 
&D 
1 VII Image-couplers and image- 
2 VII modifying couplers; Wash- 
3&4 X out couplers; Dye 
stabilizers and hue 
modifiers 
1 XVII Supports 
2 XVII 
3&4 XV 
3&4 XI Specific layer arrangements 
3&4 XII, XIII Negative working 
emulsions; Direct positive 
emulsions 
2 XVIII Exposure 
3&4 XVI 
1 XIX, XX Chemical processing; 
2 XIX, XX, Developing agents 
XXII 
3&4 XVIII, XIX, 
XX 
3&4 XIV Scanning and digital 
processing procedures 
______________________________________ 
Supports for photographic elements of the present invention include 
polymeric films such as cellulose esters (for example, cellulose 
triacetate and diacetate) and polyesters of dibasic aromatic carboxylic 
acids with divalent alcohols (for example, poly(ethylene-terephthalate), 
poly(ethylene-napthalates)), paper and polymer coated paper. Such supports 
are described in further detail in Research Disclosure 3, Section XV. 
The photographic elements may also contain additional materials that 
accelerate or otherwise modify the processing steps of bleaching or fixing 
to improve the quality of the image. Bleach accelerators described in 
European Patent Applications No. 193,389 and 301,477; U.S. Pat. Nos. 
4,163,669; 4,865,956; and 4,923,784 are particularly useful. Also 
contemplated is the use of nucleating agents, development accelerators or 
their precursors (UK Patent 2,097,140; U.K. Patent 2,131,188); electron 
transfer agents (U.S. Pat. Nos. 4,859,578 and 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 elements may also contain filter dye layers comprising colloidal silver 
sol and/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; European Patent Application 96,570; U.S. Pat. 
Nos. 4,420,556; and 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 photographic elements may further contain other image-modifying 
compounds such as "Developer Inhibitor-Releasing" compounds (DIR's). DIR 
compounds are disclosed, for example, 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. DIRs that have particular application in 
color reversal elements are disclosed in U.S. Pat. Nos. 5,399,465; 
5,380,633; 5,399,466; and 5,310,642. 
It is also contemplated that the concepts of the present invention may be 
employed to obtain reflection color prints. 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 
(European Patent Application 0 164 961); with additional stabilizers (as 
described, for example, in U.S. Pat. Nos. 4,346,165; 4,540,653 and 
4,906,559); 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. Nos. 
5,068,171 and 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; 90-072,633; 90-072,634; 
90-077,822; 90-078,229; 90-078,230; 90-079,336; 90-079,338; 90-079,690; 
90-079,691; 90-080,487; 90-080,489; 90-080,490; 90-080,491; 90-080,492; 
90-080,494; 90-085,928; 90-086,669; 90-086,670; 90-087,361; 90-087,362; 
90-087,363; 90-087,364; 90-088,096; 90-088,097; 90-093,662; 90-093,663; 
90-093,664; 90-093,665; 90-093,666; 90-093,668; 90-094,055; 90-094,056; 
90-101,937; 90-103,409; 90-151,577. 
The silver halide grains to be used in the invention may be prepared 
according to methods known in the art, such as those described in Research 
Disclosure 3 and James, The Theory of the Photographic Process. These 
include methods such as ammoniacal emulsion making, neutral or acidic 
emulsion making, and others known in the art. These methods generally 
involve mixing a water soluble silver salt with a water soluble halide 
salt in the presence of a protective colloid, and controlling the 
temperature, pAg, pH values, etc, at suitable values during formation of 
the silver halide by precipitation. 
The silver halide to be used in the invention may be advantageously 
subjected to chemical sensitization with noble metal (for example, gold) 
sensitizers, middle chalcogen (for example, sulfur) sensitizers, reduction 
sensitizers and others known in the art. Compounds and techniques useful 
for chemical sensitization of silver halide are known in the art and 
described in Research Disclosure 3 and the references cited therein. 
The emulsion can also include any of the addenda known to be useful in 
photographic emulsions. These include chemical sensitizers, such as active 
gelatin, sulfur, selenium, tellurium, gold, platinum, palladium, iridium, 
osmium, rhenium, phosphorous, or combinations thereof. Chemical 
sensitization is generally carried out at pAg levels of from 5 to 10, pH 
levels of from 5 to 8, and temperatures of from 30.degree. to 80.degree. 
C., as illustrated in Research Disclosure, June 1975, item 13452 and U.S. 
Pat. No. 3,772,031. 
The silver halide may be sensitized by sensitizing dyes by any method known 
in the art, such as described in Research Disclosure 3. Examples of dyes 
include dyes from a variety of classes, including the polymethine dye 
class, which includes the cyanines, merocyanines, complex cyanines and 
merocyanines (i.e., tri-, tetra-, and polynuclear cyanines and 
merocyanines), oxonols, hemioxonols, stryryls, merostyryls, and 
streptocyanines. The dye may be added to an emulsion of the silver halide 
grains and a hydrophilic colloid at any time prior to (e.g., during or 
after chemical sensitization) or simultaneous with the coating of the 
emulsion on a photographic element. The dye/silver halide emulsion may be 
mixed with a dispersion of color image-forming coupler immediately before 
coating or in advance of coating. 
Photographic elements of the present invention can be imagewise exposed 
using any of the known techniques, including those described in Research 
Disclosure 3. This typically involves exposure to light in the visible 
region of the spectrum, and typically such exposure is of a live image 
through a lens. However, the photographic elements of the present 
invention may be exposed in a film writer as described above. Exposure in 
a film writer is an exposure to a stored image (such as a computer stored 
image) by means of light emitting devices (such as light controlled by 
light valves, CRT and the like). 
Standard processing for negative or reversal elements may be utilized, 
including standard Kodak C-41 and Kodak E-6 processing. The color reversal 
process requires first treating the element with a black and white 
developer, followed by fogging non-exposed grains using chemical or light 
fogging, followed by treatment with a color developer. 
Preferred non-chromogenic developers (that is, black and white developers) 
are hydroquinones (such as hydroquinone sulphonate). 
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) ethylaniline 
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. 
Development is followed by bleach-fixing, to remove silver or silver 
halide, washing and drying. Bleaching and fixing can be performed with any 
of the materials known to be used for that purpose. Bleach baths generally 
comprise an aqueous solution of an oxidizing agent such as water soluble 
salts and complexes of iron (III) (e.g., potassium ferricyanide, ferric 
chloride, ammonium or potassium salts of ferric ethylenediaminetetraacetic 
acid), water-soluble persulfates (e.g., potassium, sodium, or ammonium 
persulfate), water-soluble dichromates (e.g., potassium, sodium, and 
lithium dichromate), and the like. Fixing baths generally comprise an 
aqueous solution of compounds that form soluble salts with silver ions, 
such as sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, 
sodium thiocyanate, thiourea, and the like. Further details of bleach and 
fixing baths can be found in Research Disclosure 3. 
The photographic elements can be incorporated into exposure structures 
intended for repeated use or exposure structures intended for limited use, 
variously referred to as single use cameras, lens with film, or 
photosensitive material package units. However, the color reversal 
elements of the present invention can also be used by exposing in an 
electronic film writer (such film writers typically expose the film by 
laser, laser diode, or some other controlled light source). 
The practice of the invention is described in detail below with reference 
to specific illustrative examples, but the invention is not to be 
construed as being limited thereto.

EXAMPLES 
Preparative Examples 
Compound 1 
To 3 L of tetrahydrofuran was added 223 g of bis(2-hydroxyethyl)sulfide, 
484 g glutaric anhydride (90% assay), and 700 mL triethylamine. The 
mixture was heated at reflux for 18 hr under nitrogen at which time the 
solvent was removed using the rotovap. The residue was diluted with 1 L of 
cold water which was immediately poured onto ice which contained 450 mL of 
concentrated HCl. The solid which formed was collected, and then purified 
by crystallization from methanol/water, obtaining 558 g of a white solid, 
mp 84.5.degree.-86.degree. C. 
Compound 2 
To a mixture of 105 g 1 and 900 mL dry methylene chloride was added 66 mL 
oxalyl chloride. The suspension was allowed to stir at room temperature 
for 4 hr during which time solution occurred. The solvent was removed on 
the rotary evaporator and the residue dissolved in 525 mL dry 
tetrahydrofuran. This solution was added dropwise at room temperature over 
a 4 hr period to a solution of 1833 g bis (2-hydroxyethyl)sulfide in 750 
mL dry tetrahydrofuran containing 113 mL triethylamine. Upon complete 
addition, the solution was allowed to stand at room temperature overnight. 
The solvent was then removed on the rotary evaporator and the residue 
taken up in 500 mL methylene chloride and 4 L water containing 40 mL 
concentrated HCl. After separating the layers, the aqueous layer was 
washed with two 500 mL portions of methylene chloride. The combined 
organic layers were washed with 2 L of distilled water and then dried over 
anhydrous magnesium sulfate. After removing the solvent, the residue was 
crystallized from ethanol at ice temperature, obtaining 160 g white solid, 
mp 50.degree.-55.degree. C. The product was analyzed by size exclusion 
chromatography, and found to be &gt;95% one component. The proton NMR was 
consistent with the desired material. 
Compounds 3 through 7 
The diacid 3 was prepared from 2 in a manner similar to the preparation of 
1. The dialcohol 4 was prepared from 3 in a manner similar to the 
preparation of 2.5 was then prepared likewise from 4,6 likewise from 5, 
and 7 was prepared likewise from 6. Each product was analyzed by size 
exclusion chromatography, and found to be &gt;95% one component of the proper 
molecular weight. An analogous series could be prepared using glutaryl 
dichloride and excess bis(2-hydroxyethyl)sulfide in the first step of the 
sequence. 
Compound 8 
A mixture of 115 g glutaric anhydride and 126 g bis(2-hydroxyethyl)sulfide 
was heated to 165.degree. C. and held at that temperature for 30 min. 
Vacuum of 30 mm Hg was applied for 5.5 hr, maintaining the temperature at 
165.degree. C., collecting the water condensate which was formed. The 
residue was cooled to 45.degree. C. and then suspended in 1 L methanol 
preheated to 55.degree. C . The suspension was cooled with rapid stirring 
to 5.degree. C., and the solid which formed was recovered by filtration, 
washing with cold methanol. End group analysis of the polymer by proton 
NMR and titration indicated about equal distribution of alcohol and acid 
ends: acid ends: 0.51 meq/g; alcohol ends: 0.50 meq/g. Size exclusion 
chromatography gave polystyrene equivalent number and weight average 
molecular weight of 2290 and 3520, respectively. The molecular weight of 8 
can be modified by changing either the reaction time or temperature or 
both. 
Compound 9 
To a solution of 3 g of the polyester Compound 8 in 10 mL of distilled 
tetrahydrofuran was bubbled a nitrogen gas stream containing 
freshly-generated diazomethane. The nitrogen/diazomethane gas stream was 
applied to the substrate solution until a distinct yellow color persisted 
in the solution indicating that an excess of diazomethane existed. The 
yellow solution was allowed to stand at room conditions in a 
loosely-capped vial for 72 hours to ensure completion of the 
esterification reaction. The solvent was removed under a vigorous nitrogen 
stream until a dark oil resulted. The oil was vacuum-dried at 50.degree. 
C. for 24 hours. The oil was then slurried in 20 mL methanol at room 
temperature for about 5 minutes and then cooled to 10.degree. C. with 
constant mechanical stirring resulting in crystallization of the product. 
The off-white solid was collected by vacuum filtration, washed with cold 
methanol and vacuum-dried at 25.degree. C. for 24 hours. The yield was 2.7 
g, 90% of expected. 
Analysis: &lt;0.005 meq/g total acid end groups by titration (typical examples 
of 8 contain from 0.1 to 1.0 meq/g acid ends). NMR (CDCl.sub.3) singlet at 
4 ppm from methyl ester end groups (this peak is absent in 8). 
Compound 10 
To a solution of 3 g of the polyester Compound 8 in 10 mL of distilled 
tetrahydrofuran was added with gentle stirring 0.22 g of glutaric 
anhydride and 0.20 g of triethylamine. The reaction mixture was stirred at 
70.degree. C. for 5 hours. After cooling, the solvent was stripped under a 
vigorous nitrogen stream to yield a thick, dark, oil. To this oil was 
added 10 mL of 10.degree. C. methanol containing 2 mL of aqueous 1N HCl 
with good mechanical stirring. The mixture was placed in an ice bath and 
stirred until crystallization took place. The off-white product was 
collected on a vacuum funnel, washed with cold methanol and vacuum-dried 
at 25.degree. C. for 24 hours. The yield was 2.9 g, 99.8% of theory. 
Analysis: 0.65 meq/g acid end groups by titration, 93% of the expected 
level based on the quantitative conversion of alcohol end groups in 8 to 
acid end groups. NMR (CDCl.sub.3) peak due to OH at 3.5 ppm is absent in 
product. 
Compound 12 
To a solution of 144 g of NaOH in 1.5 L of water at 55.degree. C., under a 
nitrogen atmosphere, was added 140 g 1,8-dimercapto-3,6-dioxaoctane 
followed by a solution of 299 g 6-bromohexanoic acid in 300 mL water. A 
slight exotherm to about 70.degree. C. occurs. The solution was then 
stirred at ambient temperature overnight, and then on the steampot for 3 
hr. Upon cooling to room temperature, the solution was added with rapid 
stirring to a mixture of 180 mL conc. HCL in ice/water. The solid which 
formed was collected, washed well with cold water, and air dried to yield 
316 g of white material. It was crystallized by dissolving in 2 L boiling 
acetonitrile, filtering hot through Celite to remove some sodium chloride, 
and cooling to ice temperature, collecting 270.5 g white solid, mp 
70.degree.-3.degree. C. The proton NMR spectrum was consistent for 
10,13-dioxa-7,16-dithiadocosane-1,22-dioic acid. To 100 mL dry methylene 
chloride (3 .ANG. molecular sieves) was added 12.31 g 
10,13-dioxa-7,16-dithiadocosane-1,22-dioic acid and 6.6 mL oxalyl 
chloride. The suspension was stirred at room temperature for 4 hr and then 
concentrated to an oil. The oil was dissolved in 450 mL dry 
tetrahydrofuran (3 .ANG. molecular sieves) and added dropwise to a 
solution of 1200 g of PEG 200 and 25.2 mL triethylamine in 900 mL dry 
tetrahydrofuran. The dropwise addition was carried out at room temperature 
and was complete in 100 min; the reaction mixture was allowed to remain at 
room temperature for 2.5 days. The solvent was removed and the residue was 
diluted with water containing 9 mL concentrated HCL. The suspension was 
extracted five times with 375 mL portions of methylene chloride. The 
combined methylene chloride fractions were washed twice with water to 
remove traces of PEG 200, dried over anhydrous magnesium sulfate, and 
concentrated to yield 34 g of a clear oil. An infrared spectrum of the oil 
indicated a broad OH peak at 3482 cm.sup.-1 and a carbonyl absorption at 
1735 cm.sup.-1. Size exclusion chromatography gave polystyrene equivalent 
number and weight average molecular weights of 1070 and 1130, 
respectively. 
To 100 mL dry tetrahydrofuran (3 .ANG. molecular sieves) was added 11.34 g 
of the oil from above, followed by 3.51 g glutaric anhydride and 4.6 mL 
triethylamine. The mixture was heated at reflux for 13 hr at which time 
the solvent was removed and the residue diluted with water containing 3 mL 
conc. HCL. The suspension was extracted four times with methylene chloride 
and the combined organic phases were dried over anhydrous magnesium 
sulfate, and then concentrated to yield 16.32 g of an oil. An infrared 
spectrum of the oil indicated a broad carboxylic acid OH peak and a 
carbonyl absorption at 1734 cm.sup.-1. Combustion analysis: Calculated for 
C.sub.46 H.sub.82 O.sub.21 S.sub.2 : C, 53.37; H, 7.98; S, 6.37. Found: C, 
53.68; H, 8.15; S, 6.37. Size exclusion chromatography gave polystyrene 
equivalent number and weight average molecular weights of 1330 and 1430, 
respectively. 
Compound 23 
To 200 mL dry pyridine (3 .ANG. molecular sieves) was added 75 g PEG 1500 
and the solution was cooled to 5.degree. C. To this solution was added all 
at once 20.97 g p-toluenesulfonyl chloride, and the flask was stored in 
the freezer for 4 days. The reaction mixture was poured into 375 mL cold, 
acidic water, and the bistosylate was isolated by extraction with 
methylene chloride. After drying over anhydrous magnesium sulfate, the 
methylene chloride was removed to give 57.64 g of a clear oil. The 
infrared spectrum showed the absence of a hydroxyl group. 
To 138 mL of 0.5M sodium methoxide in methanol containing 4.84 g of 
2-mercaptoethanol, all under nitrogen, was added a solution of 56.61 g of 
the bistosylate prepared above in 2250 mL methanol. The solution was 
heated at reflux for 40 hr, cooled to room temperature, and diluted with 
100 mL water. Most of the methanol was removed and 100 mL of a 5% salt 
solution and methylene chloride was added. After the layers were 
separated, the aqueous layer was extracted three more times with methylene 
chloride. The combined organic layers were washed with a saturated salt 
solution, dried over anhydrous magnesium sulfate, and concentrated to an 
oil. The oil was slurried in warm diethyl ether, and cooled to ice 
temperature where crystallization occurred; the dialcohol was collected, 
recovering 40.11 g of a white solid. The proton NMR spectrum (CDCl.sub.3) 
indicated a large singlet at 3.64 .delta., and a small triplet centered at 
2.75 .delta. with an area ratio of 18.7. There was a strong OH absorption 
in the infrared spectrum. 
Compound 24 
To 16.52 g of the dialcohol 23 was added 2.4 g of glutaric anhydride, and 
3.1 mL triethylamine in 70 mL of dry tetrahydrofuran. The solution was 
heated at reflux for 20 hr and then concentrated to an oil using the 
rotovap. The oil was diluted with water, and 2 mL concentrated HCL was 
added, and then extracted three times with methylene chloride. The 
combined organic layers were dried over anhydrous magnesium sulfate and 
concentrated to a clear oil. The oil was triturated in warm diethyl ether, 
cooled to ice temperature, collecting 14.70 g of a white solid. 
The preparations described above were modified as known to those skilled in 
the art in the preparation of the following compounds for which the 
preparation is not specifically described. Structures of the inventive and 
comparative compounds are provided in Table I. 
TABLE I 
__________________________________________________________________________ 
Cmpd. No. 
Compound 
__________________________________________________________________________ 
1.sup.c 
##STR7## 
2.sup.c 
##STR8## 
3.sup.c 
##STR9## 
4.sup.c 
##STR10## 
5.sup.i 
##STR11## 
6.sup.c 
##STR12## 
7.sup.i 
##STR13## 
8.sup.c 
##STR14## 
9.sup.c 
##STR15## 
10.sup.i 
##STR16## 
11.sup.c 
##STR17## 
12.sup.i 
##STR18## 
13.sup.i 
##STR19## 
14.sup.c 
##STR20## 
15.sup.c 
##STR21## 
16.sup.c 
##STR22## 
17.sup.c 
##STR23## 
18.sup.i 
##STR24## 
19.sup.c 
##STR25## 
20.sup.i 
##STR26## 
21.sup.c 
##STR27## 
22.sup.i 
##STR28## 
23.sup.c 
##STR29## 
24.sup.i 
##STR30## 
__________________________________________________________________________ 
.sup.i Inventive compounds used in Examples 
.sup.c Comparison compounds 
Example 1 
Each layer having the composition set forth below was coated on a cellulose 
triacetate film support containing a subbing layer to prepare a multilayer 
color photographic light-sensitive material which was designated sample 
101. The components utilized are shown as g/m.sup.2 except for sensitizing 
dyes and the comparison compounds which are shown in molar amounts/mole of 
silver halide present in the same layer. 
______________________________________ 
Photographic Element 101 
______________________________________ 
First Layer: Antihalation Layer 
Black Colloidal Silver 0.43 (as silver) 
Gelatin 2.44 
Second Layer: Intermediate Layer 
Gelatin 1.22 
Third Layer: Red Sensitive Layer 
Silver iodobromide emulsion 
1.08 (as silver) 
RSD-3/RSD-4 0.00075 
Cyan Coupler C-2 1.29 
Dibutyl phthalate 0.65 
Gelatin 1.62 
Forth Layer: Intermediate Layer 
Competitor CP-1 0.21 
Gelatin 0.43 
Fifth Layer: Green Sensitive Layer 
Silver iodobromide emulsion 
1.08 (as silver) 
Sensitizing dye GSD-3 0.00075 
Sensitizing dye GSD-4 0.00025 
Magenta coupler M1 0.68 
Tritoyl phosphate 0.34 
Gelatin 3.19 
Sixth Layer: Protective Layer 
Gelatin 3.19 
Bis(vinylsulfonylmethane) 
0.19 
______________________________________ 
Samples 102 and 114 were prepared in the same manner as described above for 
Sample 101 except for the addition of the poly(thioether)s listed in Table 
I to the green sensitive fifth layer. The poly(thioether)s were dispersed 
as direct dispersions in gelatin and added at 654 mg of addenda/silver 
mole. 
Each of the samples thus prepared was cut into a 35 mm width strip. The 
samples were exposed to a step exposure using white light. The samples 
were then processed in a color negative process using standard Kodak C-41 
processing solutions. Dmin, speed, contrast, and Dmax were determined for 
both the light sensitive layers. Table II shows the photographic response 
for the green sensitive fifth layer. In Table II Samples 102-106 are an 
analogous series increasing in molecular weight. Compound 1 was prepared 
from a thiodiethanol capped with two glutaric acid groups. Compound 2 is 
Compound 1 capped with two thiodiethanol groups, etc. What is observed in 
this series is decreasing activity of the alcohol ended Compounds as 
molecular weight increases. The acid solubilized Compounds show increasing 
development acceleration activity, higher Dmin, speed, contrast and Dmax 
with increasing molecular weight. Compound 5, an inventive Compound, is 
the most active development accelerator in this series while Compound 6, 
which is prepared from Compound 5 by capping with thiodiethanol, is the 
least active of the alcohol molecules. Compound 5 is also more active than 
the polymeric samples in Table II, including inventive Compound 10. 
Comparison Compound 8 is a polymer obtained by the co-polymerization of 
glutaric anhydride and thiodiethanol. Such polymers commonly have a 
statistical distribution of alcohol and carboxylic acid end groups. The 
total end group population of alcohol groups and the population of 
carboxylic acid end groups will usually be equal to each other if the 
molar amounts of starting materials are also equal. Sample 108 and 110 
both use Compound 8 at different molecular weight distribution. Compound 9 
was obtained by ester capping the free acid groups in Compound 8, two 
examples of which are shown in Samples 109 and 111. Compound 10 was 
obtained by acid capping the alcohol groups in Compound 8 to obtain an 
inventive example. The series Sample 108-109 and 110-111 both illustrate 
how the removal of acid solubilization leads to less development 
acceleration as demonstrated by speed, contrast and Dmax loss. This effect 
was seen using two different molecular weight polymers, but was most 
apparent for the higher activity polymer used in Sample 108. The inventive 
Compound 10 in Sample 112 shows significantly higher development 
acceleration activity than its parent comparison Compound 8 shown in 
Sample 110. Similar trends are seen when comparing sample 113 to its acid 
capped inventive analog in Sample 114. 
TABLE II 
__________________________________________________________________________ 
Example 1 Green Sensitive Layer Response 
Development Relative 
Sample 
Accelerator MW Dmin 
Speed.sup.c 
Contrast.sup.d 
Dmax 
__________________________________________________________________________ 
101 None (Check) 
check 
0.18 
2.88 0.68 1.53 
102 Cmpd 1 
(Comparison) 
160.sup.a 
0.17 
2.87 0.68 1.53 
103 Cmpd 2 
(Comparison) 
559.sup.a 
0.17 
2.88 0.86 1.85 
104 Cmpd 3 
(Comparison) 
787.sup.a 
0.18 
2.89 0.75 1.68 
105 Cmpd 4 
(Comparison) 
945.sup.a 
0.19 
2.91 0.79 1.78 
106 Cmpd 5 
(Invention) 
1223.sup.a 
0.27 
3.07 1.20 2.39 
107 Cmpd 6 
(Comparison) 
1432.sup.a 
0.19 
2.92 0.73 1.66 
108 Cmpd 8 
(Comparison) 
5160.sup.b 
0.22 
2.99 0.92 1.99 
109 Cmpd 9 
(Comparison) 
5290.sup.b 
0.19 
2.95 0.74 1.74 
110 Cmpd 8 
(Comparison) 
6290.sup.b 
0.18 
2.94 0.74 1.77 
111 Cmpd 9 
(Comparison) 
6230.sup.b 
0.18 
2.91 0.71 1.61 
112 Cmpd 10 
(Invention) 
6420.sup.b 
0.22 
2.99 0.85 1.97 
113 Cmpd 8 
(Comparison) 
6800.sup.b 
.21 
2.97 .77 1.82 
114 Cmpd 10 
(Invention) 
6970.sup.b 
.22 
3.00 .88 1.94 
__________________________________________________________________________ 
.sup.a Absolute molecular weight 
.sup.b Polystyrene equivalent weight average molecular weight, Pw, as 
determined by size exclusion chromatography 
.sup.c Photographic speed in log E units at a green density of 0.5 
.sup.d Photographic speed in log E units at a green density of 1.0 
Example 2 
Samples 201 to 214 were prepared in the same manner as described above. 
Each of the samples thus prepared was cut into a 35 mm width strip. The 
samples were exposed to a step exposure using white light. The samples 
were then processed using standard Kodak E-6 processing solutions and 
development conditions. Relative speed at two different speed points and 
Dmax was determined for the green sensitive fifth layer. Table III 
illustrates the photographic response of the green sensitive fifth layer. 
In a reversal format, development acceleration is seen by increases in 
speed and decreases in Dmax. In Table III Samples 202-206 are a molecular 
weight series of thioethers with alternating alcohol and acid end groups, 
as was discussed in Example 1. What is observed in this series is 
decreasing activity of the alcohol ended Compounds as molecular weight is 
increased. The acid solubilized Compounds show increasing development 
acceleration activity with increasing molecular weight. Compound 5, an 
inventive Compound, is the most active development accelerator in this 
series, while Compound 6, which is prepared from Compound 5 by capping 
with thiodiethanol, is the least active of the alcohol endgroup molecules. 
Compound 5 is also more active than the polymeric samples discussed later 
in the Table. 
Comparison Compound 8 was discussed in Example 1. Samples 208 and 210 both 
use Compound 8 at different molecular weight distributions. Compound 9 was 
obtained by ester capping the free acid groups in Compound 8, two examples 
of which are show in Samples 209 and 211. Compound 10 was obtained by acid 
capping the alcohol groups in Compound 8 to obtain an inventive example. 
The series Samples 208-209 and 210-211 both illustrate how the removal of 
acid solubilization leads to less development acceleration as demonstrated 
by speed loss. This effect was seen using two different molecular weight 
parent polymers. The inventive Compound 10 in Sample 212 shows 
significantly higher development acceleration activity than its parent, 
comparison Compound 8, shows in Sample 210. Similar trends are seen 
comparing sample 213 to its acid capped inventive analog in sample 214. 
TABLE III 
______________________________________ 
Example 2 Green Sensitive Layer Response 
Relative 
Relative 
Development Speed Speed 
Sample 
Accelerator MW 1.sup.c 
2.sup.d 
Dmax 
______________________________________ 
201 None (Check) check 
1.70 2.05 2.09 
202 Cmpd 1 (Comparison) 
160.sup.a 
1.70 2.05 2.08 
203 Cmpd 2 (Comparison) 
559.sup.a 
1.98 2.23 2.00 
204 Cmpd 3 (Comparison) 
787.sup.a 
1.86 2.17 1.99 
205 Cmpd 4 (Comparison) 
945.sup.a 
1.90 2.22 1.93 
206 Cmpd 5 (Invention) 
1223.sup.a 
2.29 2.50 1.76 
207 Cmpd 6 (Comparison) 
1432.sup.a 
1.78 2.10 2.05 
208 Cmpd 8 (Comparison) 
5160.sup.b 
1.97 2.29 1.89 
209 Cmpd 9 (Comparison) 
5290.sup.b 
1.90 2.24 1.88 
210 Cmpd 8 (Comparison) 
6290.sup.b 
1.87 2.20 2.05 
211 Cmpd 9 (Comparison) 
6230.sup.b 
1.77 2.11 2.01 
212 Cmpd 10 (Invention) 
6420.sup.b 
1.94 2.27 1.89 
213 Cmpd 8 (Comparison) 
6800.sup.b 
1.85 2.19 1.95 
214 Cmpd 10 (Invention) 
6970.sup.b 
1.94 2.28 1.87 
______________________________________ 
.sup.a Absolute molecular weight 
.sup.b Polystyrene equivalent weight average molecular weight, Pw, as 
determined by size exclusion chromatography 
.sup.c Photographic speed in log E units at a green density of 0.5 
.sup.d Photographic speed in log E units at a green density of 1.0 
Example 3 
Sample 301 was prepared like Sample 101 in Example 1. Samples 302 to 308 
were prepared in the same manner as described above for Sample 301 except 
for the addition of the poly(thioether)s listed in Table I to the green 
sensitive fifth layer. The poly(thioether)s were dispersed as direct 
dispersions in gelatin and added at the level indicated in mmol/silver 
mole. For polymeric materials the mmol level was parenthetically based on 
average molecular weight. 
Each of the samples thus prepared was cut into a 35 mm width strip. The 
samples were exposed to a step exposure using white light. The samples 
were then processed in a color negative process using standard Kodak C-41 
processing solutions. Dmin, speed, contrast, and Dmax were determined for 
both the green and red sensitive layers. Table IV provides the 
photographic response of the green sensitive fifth layer. Two molecular 
weight series are illustrated with different parent molecules. The first 
series, Samples 302-304, includes Compound 3 and Compound 5 discussed in 
Examples 1 and 2. This series had previously shown increased activity as 
molecular weight increased. Compound 7, having a further increase in 
molecular weight, is lower in development acceleration activity than 
Compound 5, illustrating a preferred molecular weight region for 
development acceleration activity, as indicated by fog, speed, contrast 
and Dmax increase. The second series, Samples 305-307, on a different 
parent molecule illustrate a similar trend. Activity increases as a 
function of molecular weight increase from Compound 11 to Compound 12, and 
then as molecular weight is further increased, activity decreases from 
Compound 12 to Compound 13. Compound 13, however, is still an active 
development accelerator particularly when compared to comparative Compound 
14. Compound 13 and Compound 14 have similar molecular weights, both 
contain solubilizing groups and both materials have two thioether groups. 
The inventive sample has separation between the solubilizing group and the 
thioether group, a previously unrecognized and important characteristic 
for activity. At 10.times. the molar laydown, Compound 14, approaches the 
activity of Compound 13, but fails to match the activity of Compound 12, 
which has the preferred molecular weight, and falls very short of Compound 
5, which has both preferred molecular weight and preferred structure. 
TABLE IV 
__________________________________________________________________________ 
Example 3 Green Sensitive Layer Response 
Development 
Sample 
Accelerator Level.sup.a 
MW Dmin 
Speed.sup.c 
Contrast.sup.d 
Dmax 
__________________________________________________________________________ 
301 None (Check) 
check 
check 
0.18 
2.72 
0.52 1.31 
302 Cmpd 3 
(Comparison) 
0.53 
786 
0.18 
2.76 
0.59 1.43 
303 Cmpd 5 
(Invention) 
0.53 
1223.sup. 
0.23 
2.92 
0.99 2.08 
304 Cmpd 7 
(Invention) 
0.53 
1660.sup. 
0.21 
2.88 
0.90 1.89 
305 Cmpd 11 
(Comparison) 
0.53 
727.sup.b 
0.19 
2.75 
0.56 1.39 
306 Cmpd 12 
(Invention) 
0.53 
1003.sup.b 
0.25 
2.86 
0.83 1.84 
307 Cmpd 13 
(Invention) 
0.53 
1803.sup.b 
0.21 
2.82 
0.72 1.62 
308 Cmpd 14 
(Comparison) 
0.53 
1892.sup.b 
0.18 
2.75 
0.54 1.40 
309 Cmpd 14 
(Comparison) 
5.30 
1892.sup.b 
0.19 
2.79 
0.73 1.70 
__________________________________________________________________________ 
.sup.a mmole compound/mole silver in the layer 
.sup.b parenthetically based on average molecular weight 
.sup.c Photographic speed in log E units at a green density of 0.2 above 
Dmin 
.sup.d Best Fit Contrast 
Example 4 
Sample 401 was prepared like Sample 101 in Example 1. Samples 402 to 413 
were prepared in the same manner as described above for Sample 301 except 
for the addition of the poly(thioether)s listed in Table I to the green 
sensitive fifth layer. The poly(thioether)s were dispersed as direct 
dispersions in gelatin and added at level of 0.53 mmol/silver mole. For 
polymeric materials the mmol level was parenthetically based on average 
molecular weight. 
Each of the samples thus prepared was cut into a 35 mm width strip. The 
samples were exposed to a step exposure using white light. The samples 
were then processed in a color negative process using standard Kodak C41 
processing solutions. Dmin, speed, contrast, Dmax and were determined for 
both the green and red sensitive layers. Table V shows the photographic 
response of the green sensitive fifth layer. Samples 402-409 compare a 
molecular weight series of alternating alcohol-capped poly(thioethers), 
(Compound 15, 17, 19, and 21) and carboxylic acid-capped derivatives 
(Compound 16, 18, 20, and 22). The alcohol-capped poly(thioethers) had a 
Dmin, speed, contrast and Dmax only slightly higher than control without 
developer accelerator, Sample 401. The carboxylic acid-capped compounds 
exhibited increased activity as molecular weight increased, this was most 
evident when comparing inventive Compound 20 and 22 to comparative 
Compound 19 and 21. 
In the second series, Samples 410 and 411, a poly(alkylene oxide) is capped 
with thiodiethanol to create comparison Compound 23. This alcohol ended 
poly(thioether) exhibits only slight evidence of development acceleration. 
Compound 23 was acid capped with glutaric acid to create inventive 
Compound 24. Addition of carboxylic acid solubilization to Compound 24 
leads to a boost in activity as can be seen by increased fog, speed, 
contrast and Dmax. The importance of spacing between the thioether and the 
acid functional group (solubilization group) is again illustrated by the 
branch comparison Compound 14, which is much less active as a development 
accelerator compared to the similar molecular weight inventive Compound 
24. Compound 5, shown in Sample 413, which contains the most preferred 
molecular weight and structure continues to offer the largest boost in 
development acceleration. 
TABLE V 
__________________________________________________________________________ 
Example 4 Green Sensitive Layer Response 
Development Relative 
Sample 
Accelerator MW.sup.a 
Dmin 
Speed.sup.b 
Contrast.sup.c 
Dmax 
__________________________________________________________________________ 
401 None (Check) 
check 
0.18 
2.72 0.46 1.25 
402 Cmpd 15 
(Comparison) 
559 
0.19 
2.78 0.50 1.34 
403 Cmpd 16 
(Comparison) 
787 
0.19 
2.78 0.47 1.27 
404 Cmpd 17 
(Comparison) 
750 
0.24 
2.76 0.50 1.39 
405 Cmpd 18 
(Invention) 
970 
0.20 
2.80 0.55 1.33 
406 Cmpd 19 
(Comparison) 
1150 
0.18 
2.77 0.49 1.30 
407 Cmpd 20 
(Invention) 
1370 
0.22 
2.86 0.64 1.61 
408 Cmpd 21 
(Comparison) 
1550 
0.19 
2.78 0.49 1.34 
409 Cmpd 22 
(Invention) 
1770 
0.23 
2.88 0.68 1.65 
410 Cmpd 23 
(Comparison) 
1652 
0.19 
2.75 0.46 1.28 
411 Cmpd 24 
(Invention) 
1880 
0.21 
2.84 0.63 1.54 
412 Cmpd 14 
(Comparison) 
1892 
0.18 
2.76 0.49 1.30 
413 Cmpd 5 
(Invention) 
1223 
0.23 
2.90 0.92 1.98 
__________________________________________________________________________ 
.sup.a Molecular weight parenthetically based on average molecular weight 
.sup.b Photographic speed in log E units at a green density of 0.2 above 
Dmin 
.sup.c Best Fit Contrast 
Structures used in Example 1-4: 
##STR31## 
Example 5 
In a prophetic example for a reversal format, the inventive thioether with 
acidic functional endgroups may be coated with an appropriately sensitized 
silver iodobromide emulsion in a multilayer reversal film that was 
prepared as follows. Each layer having the composition set forth below was 
coated on a cellulose triacetate support provided with a subbing layer to 
prepare a multilayer color photographic light-sensitive material. In the 
composition of the layers, the coating amounts are shown as grams per 
square meter except for sensitizing dyes, which are shown as the molar 
amount per mole of silver halide present in the same layer. Laydowns of 
silver halide are reported relative to silver. Emulsion sizes as 
determined by the disc centrifuge method are reported in 
diameter.times.thickness in microns. 
______________________________________ 
First layer: Antihalation Layer 
Black Colloidal Silver 0.43 
Gelatin 2.44 
Second layer: Intermediate Layer 
Gelatin 1.22 
Third Layer: Slow Red Sensitive Layer 
AgIBr tabular emulsion (4% I, 0.6 .times. 0.1) 
0.62 
RSD-1/RSD-2 0.00142 
C-1 0.20 
Dibutyl phthalate 0.10 
ST-1 0.06 
Gelatin 0.86 
Fourth Layer: Fast Red Sensitive Layer 
AgIBr tabular emulsion (4% I, 0.97 .times. 0.13) 
0.65 
RSD-1/RSD-2 0.00105 
C-1 1.00 
Dibutyl phthalate 0.50 
Gelatin 1.83 
Fifth Layer: Intermediate Layer 
DYE-1 0.07 
ST-1 0.12 
Gelatin 1.22 
Sixth Layer: Slow Green Sensitive Layer 
AgIBr emulsion (3.3% I, 0.15 cubic + 
0.70 
4%. I, 0.7 .times. 0.1 tabular) 
GSD-1/GSD-2 0.002 
M-1 0.07 
M-2 0.15 
Tritoyl phosphate 0.11 
Gelatin 0.83 
Seventh Layer: Fast Green Sensitive Layer 
AgIBr tabular emulsion (4% I, 0.97 .times. 0.13) 
0.50 
GSD-1/GSD-2 0.001 
M-1 0.32 
M-2 0.74 
Tritoyl phosphate 0.52 
Gelatin 1.67 
Eighth Layer: Interlayer Layer 
Gelatin 2.15 
Ninth Layer: Yellow Filter Layer 
Carey Lea Silver 0.002 
DYE-2 0.17 
ST-1 0.08 
Gelatin 0.61 
Tenth Layer: Slow Blue Sensitive Layer 
AgIBr tabular emulsion (3% I, 1.1 .times. 0.12) 
0.28 
BSD-1 0.00108 
Y-1 0.66 
Dibutyl phthalate 0.22 
Gelatin 1.00 
Eleventh Layer: Fast Blue Sensitive Layer 
AgIBr tabular emulsion (3% I, 1.7 .times. 0.1) 
0.78 
BSD-1 0.0016 
Y-1 1.68 
Dibutyl phthalate 0.56 
Gelatin 2.47 
Twelfth Layer: First Protective Layer 
UV-1 0.06 
UV-2 0.32 
UV-3 0.09 
ST-1 0.06 
Gelatin 1.40 
Thirteenth Layer: Second Protective Layer 
Fine grain AgBr emulsion 0.12 
Matte 0.02 
Bis(vinylsulfonylmethane) 0.26 
Gelatin 0.97 
______________________________________ 
Structures used in Example 5 
##STR32## 
Example 6 
In another prophetic example for a reversal format, the inventive thioether 
with acidic functional endgroups may be coated with appropriately 
sensitized silver iodobromide emulsions on a support 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-dime 
thyl-2-oxobutoxy)-,1-methylethyl 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 and mid 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-2-pr 
openamide; "Coupler 4": Benzamide, 
3-((2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-N-(2,4,6-tric 
hlorophenyl)-1H-pyrazol-3-yl; and "Coupler 5": Benzamide, 
3-(((2,4-bis(1,1-dimethylpropyl)phenoxy)-acetyl)amino)-N-(4,5-dihydro-5-ox 
o-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- 
hydroxyphenyl)-; 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)-; and a slow cyan layer containing 
Couplers 6, 7, and 8; 
(10) one or more interlayers possibly including fine-grained nonsensitized 
silver halide; and 
(11) an antihalation layer. 
Example 7 
In a prophetic example for a negative format, an inventive thioether with 
acidic functional endgroups may be coated with appropriately sensitized 
silver iodobromide emulsion in a multilayer photographic negative element 
produced by coating the following layers on a cellulose triacetate film 
support (coverages are in grams per meter squared, emulsion sizes as 
determined by the disc centrifuge method are reported in 
Diameter.times.Thickness in microns). 
Layer 1 (Antihalation layer): black colloidal silver sol at 0.151; gelatin 
at 2.44; UV-1 at 0.075; UV-2 at 0.075; DYE-3 at 0.042; DYE-4 at 0.088; 
DYE-5 at 0.020; DYE-6 at 0.008 and STAB-1 at 0.161. 
Layer 2 (Slow cyan layer): a blend of two silver iodobromide emulsions 
sensitized with a 1/9 mixture of RSD-3/RSD-4: (i) a small tabular emulsion 
(1.1.times.0.09, 4.1 mol % I) at 0.430 and (ii) a very small tabular grain 
emulsion (0.5.times.0.08, 1.3 mol % I) at 0.492; gelatin at 1.78; cyan 
dye-forming coupler C-2 at 0.538; bleach accelerator releasing coupler 
BARC-1 at 0.038; masking coupler MC-1 at 0.027. 
Layer 3 (Mid cyan layer): a red sensitized (same as above) silver 
iodobromide emulsion (1.3.times.0.12, 4.1 mol % I) at 0.699; gelatin at 
1.79; C-2 at 0.204; D-1 at 0.010; MC-1 at 0.022. 
Layer 4 (Fast cyan layer): a red-sensitized (same as above) tabular silver 
iodobromide emulsion (2.9.times.0.13, 4.1 mol % I) at 1.076; C-2 at 0.072; 
D-1 at 0.019; D-2 at 0.048; MC-1 at 0.032; gelatin at 1.42. 
Layer 5 (Interlayer): gelatin at 1.29. 
Layer 6 (Slow magenta layer): a blend of two silver iodobromide emulsions 
sensitized with a 6/1 mixture of GSD-3/GSD-4: (i) 1.0.times.0.09, 4.1 mol 
% iodide at 0.308 and (ii) 0.5.times.0.08, 1.3% mol % I at 0.584; magenta 
dye forming coupler M-3 at 0.269; masking coupler MC-2 at 0.064; 
stabilizer STAB-2 at 0.054; gelatin at 1.72. 
Layer 7 (Mid magenta layer): a green sensitized (as above) silver 
iodobromide emulsion: 1.3.times.0.12, 4.1 mol % iodide at 0.968; M-3 at 
0.071; MC-2 at 0.064; D-3 at 0.024; stabilizer STAB-2 at 0.014; gelatin at 
1.37. 
Layer 8 (Fast magenta layer): a green sensitized (as above) tabular silver 
iodobromide (2.3.times.0.13, 4.1 mol % I) emulsion at 0.968; gelatin at 
1.275; Coupler M-3 at 0.060; MC-2 at 0.054; D-4 at 0.0011; D-5 at 0.0011 
and stabilizer STAB-2 at 0.012. 
Layer 9 (Yellow filter layer): AD-1 at 0.108 and gelatin at 1.29. 
Layer 10 (Slow yellow layer): a blend of three tabular silver iodobromide 
emulsions sensitized with sensitizing dye BSD-2: (i) 0.5.times.0.08, 1.3 
mol % I at 0.295 (ii) 1.0.times.0.25, 6 mol % I at 0.50 and (iii) 
0.81.times.0.087, 4.5 mol % I at 0.215; gelatin at 2.51; yellow dye 
forming couplers Y-1 at 0.725 and Y-2 at 0.289; D-6 at 0.064; C-1 at 0.027 
and BARC-1 at 0.003. 
Layer 11 (Fast yellow layer): a blend of two blue sensitized (as above) 
silver iodobromide emulsions: (i) a large tabular emulsion, 
3.3.times.0.14, 4.1 mol % I at 0.227 and (ii) a 3-D emulsion, 
1.1.times.0.4,9 mol % I at 0.656; Y-1 at 0.725; Y-2 at 0.289; D-6 at 
0.029; C-1 at 0.048; BARC-1 at 0.007 and gelatin at 2.57. 
Layer 12 (UV filter layer): gelatin at 0.699; silver bromide Lippman 
emulsion at 0.215; UV-1 at 0.011 and UV-2 at 0.011. 
Layer 13 (Protective overcoat): gelatin at 0.882. 
Hardener (bis(vinylsulfonyl)methane hardener at 1.75% of total gelatin 
weight), antifoggants (including 
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene), surfactants, coating aids, 
emulsion addenda, sequestrants, lubricants, matte and tinting dyes were 
added to the appropriate layers as is common in the art. 
Structures Example 7 
##STR33## 
Example 8 
In a another example for a color negative element, an inventive thioether 
with acidic functional endgroups may be coated with appropriately 
sensitized silver iodobromide emulsions on 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-2yl!thio!-, methyl 
ester and "Coupler 3": 1-((dodecyloxy)carbonyl) 
ethyl(3-chloro-4-((3-(2-chloro-4-((1-tridecanoylethxy)carbonyl)anilino)-3- 
oxo-2((4)(5)(6)-(phenoxycarbonyl)-1H-benzotriazol-1-yl)propanoyl)amino))-be 
nzoate; 
(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'-dihydro-5'-oxo-1'-(2,4,6-trichlorophenyl)(1,4'-bi-1H-pyra 
zol)-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-methyl-propoxy)carbonyl)amino)-1-naphthalenyl)o 
xy)ethyl)thio)-, and "Coupler 8": Benzamide, 
3-((2-(2,4-bis(1,1-dimethylpropyl)-phenoxy)-1-oxobutyl)amino)-N-(4,5-dihyd 
ro-4-((4-methoxyphenyl)-azo)-5-oxo-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-y 
l)-; a mid-magenta layer and a slow magenta layer each containing "Coupler 
9": a ternary copolymer containing by weight in the ratio 1:1:2 
2-Propenoic acid butyl ester, styrene, and 
N-1-(2,4,6-trichlorophenyl)-4,5-dihydro-5-oxo-1H-pyrazol-3-yl!-2-methyl-2 
-propenamide; and "Coupler 10": Tetradecanamide, 
N-(4-chloro-3-((4-((4-((2,2-dimethyl-1-oxopropyl)amino)phenyl)azo)-4,5-dih 
ydro-5-oxo-1-(2,4,6-trichlorophenyl)-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)pro 
pyl)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. 
The invention has been described in detail with particular reference to 
certain preferred embodiments thereof, but it will be understood that 
variations and modifications can be effected within the spirit and scope 
of the invention.