CA2036041A1 - Photographic material and process comprising wash-out naphtholic coupler - Google Patents

Abstract

- O -PHOTOGRAPHIC MATERIAL AND PROCESS
COMPRISING WASH-OUT NAPHTHOLIC COUPLER
Abstract of the Disclosure A photographic naphtholic coupler comprising a ballast free naphtholic coupler moiety containing a -CONH2 group in the 2- position and a ballasted coupling-off group in the 4- position enables good wash out of dye formed upon oxidative coupling from a photographic material during processing of such a photographic material. Such a naphtholic coupler is useful in photographic silver halide materials and processes.

Description

PHQTOG~ Ic MAT~RIAL A~ PROCESS
COMPRISING WAS~-OU~ NAP~THOLIC COUPLER
Thi3 invention relate~ to a new photographic naphtholic coupler capable upon oxidative coupling of 5 forming a dye that is capable of being washed out of the photographic material containing the coupler upon proce~sing and to photographic materials and proces~es compri3ing the naphtholic coupler.
Various coupler3 are known in photographic 10 material3 and proce~e~. One of the clas~es o~
photographic coupler~ includes naphtholic coupler3 that typically form cyan dyes upon oxidative co~pling in photographic materials and processe3. The~e naphtholic couplerq typically for~ cyan dyes upon 15 oxidative coupling with color developing agents.
Such naphtholic couplers are also known which are capable of forming dye3 upon o~idative coupling that can be wa~hed out of ~he photographic ma~erial upon proce~sing. The~e naphtholic couplers are described 20 in, for example, U.S. Patent 4,482,629.
The naphtholic couplers that are capa~le of forming dye3 that can be wa~hed out of the photographic material upon photographic processing contain a water ~olubilizing group, ~uch a~ a carboxy 25 group or ~ulfonic acid group, ~ub~tituted on a group in the 2- po~ition of the naphtholic coupler. It has been desirable to provide a naphtholic coupler that i~ not a~ e~pensive ~o manufacture a~ the de~cribed naphtholic couplers and Qtill provides a useful dye 30 that can be washed out of the photographic material with the added advantage that the coupler enable~ a lower concentration o~ coupler to be used in a photographic element without 3igni~icantly changing imaging results.
It has al~o been de3irable to provide ~uch a naphtholic coupler that contain~ a coupling-o~f group that enable~ desired acutanee and desired interimage effect3 in a color photographic ~ilver halide material and proce~s ~t lower concentrations of coupler.
The present invention ~olve~ the~e problem~
by providing a photographic element comprising a support bearing at lea~t one photographic ~ilver halide emulsion layer and an immobile naphtholic coupler capable upon oxidative coupling of forming a dye that i`Q capable of being wa~hed out of the photcgraphic element upon photographic proce~3ing, wherein the immobile naphtholic coupler compri~e~ a balla~t free naphtholic coupler moiety compri3ing a -CONH2 group in the 2- po~ltion and a balla3ted coupling-off group in the 4- position The balla3ted coupling-off group preferably compri~es a relea~able photographically u3eful group ~PUG).
The immobile naphtholic coupler is typically represented by the formula:

~
(~l)Z~ -CN~2 wherein Z i~ a ballasted coupling-of~ group, Rl i~
a balla~t-fzee sub~tituent that does not ad~ersely affect thc desired properties of the coupler and dye, and z i8 0, 1, ~ or 3. Rl doe~ not compri~e a balla~t group becau~e such a group adversely a~fect~
wa~h-out properties of the d~e formed from the naphtholic coupler.
The balla~ted coupling-off group (Z) enables the naphtholic coupler to be immobile in the photographic element prior to expo3ure and procea~ing. Upo~ exposure and proce~ing of the described element the naphtholic coupler react~ with J ~

oxidized color developing agent to form a dyc that i~
washed out of the element during proce~ing. Al~o, the coupling~off group i~ released during proce3~ing. The portion of the coupling-off group containing the ballast group remain~ in the location in which it wa~ coated. The coupling-off group preferably comprises a releasable photographically useful group (PUG) which is released upon photographic processing. The PUG either i~
immobilized to remain in the location of the element in which it wa~ coated or the PUG is mobile to allow it, after release, to move to a location in the element at which it can serve its in~ended function.
A preferred naphtholic coupler as de~cribed comprises a coupling-off group represented by the formula:

--(LIN}~)n (TIME)m--PUG

wherein TI~E i3 a relea~able timing group capa~le of being relea~ed ~rom the LIN~ moiety during photographic proces3ing:
LINK i~ a relea~able li~king group capable of being relea~ed from the naphtholic coupler moiety upon oxidative coupling of the naphtholic coupler;
n and m individually are 0, 1 or 2;
PUG is a relea~able photographically u~eful group, preferably a releagable developme~t inhibitor group; and, preferably, at lea~t one o~ n and m is 1 or ~.
A proces~ of forming an image having the de3cribed advantage3 compri~e~ developing an exposed photographic element as described by means of a color dev~lsping agent in the pre~ence of the de cribed naphtholic coupler and washing-out the dye formed from the naphtholic coupler.

, , ~ J IJ

A~y naphtholie coupler moiety i~ u~eful that can contain the -CONH~ group in the 2- position and a balla~ted coupling-o~f group in the 4- po3ition and can form a compound, especially a dye, that can be wa~hed out of the element upon oxidative coupling of the coupler. It will be appreciated that depending upon the particular developing agent and the particular type of proce~sing, the reaction product of the coupler moiety and the oxidized developing agent can be colored or colorlesY. Examples of useful naphtholic coupler moietie~ can be unsubstituted except for the required ~ub~tituent~ in the 2- and 4- po~itions a~ de~cribed. Optionally the naphtholic coupler moietie~ in addition to the sub~tituent3 in the 2- and 4- po~ition~ can contain other substituent~ that do not adverQely affect the de~ired properties of the element and coupler.
~xample~ of ~uch ~ubstituent~ include 5~N~S02CE3, 5-NHCOCH3 or 6-NHS02CH3. ~geful naphtholic coupler moietie~ include those de~cribed in, for example, the following patents in which the group described in the 2- po~ition iq replaced with -CONH2, e~pecially thoge having a ballasted coupling-off group: U.S. Patents 4,840,884;
4,861,701; 2,474,293; 3,227,554; 4,482,629 and 4,857,447.
Any coupling o~f group containing a ballast group known in ~he photographic art i9 u~eful in the 4- position of the de~cribed naphtholic coupler 30 moiety. Example~ o~ useful coupling-off group3 are de3cribed in, for example, U.S. Patent 4,861,701.
Preferred coupling-of~ groups are tho~e that enable relea~e of a PU~ upon photographic proceq~ing, e~pecially tho~e that have a relea~able ti~ing group be~ween the bond to the coupling position of the coupler and the releasable PUG. Preferred timing group3 are described in, for example, U.S. Patents ~ ~ i s ~

4,861,701; 4,248,962; 4,409,323; 4,482,629 and 4,857,447.
A preferred naphtholic coupler i3 repre~ented by formula:

(Rl)z~\O/ I-C~2 lû O
1 ' .
X ~ ALL ~2 Q or p-~f-(T2) -PU~) wherein X repre~ent~ the atom~ completing a 5-, 6- or 7-member ring, such a3 an aryl or heterocyclic group;
Rl i~ a ballast-free substltuent;
Z i8 Q, 1, 2 o~ 3;
BALL i~ a ballas~ group known in the photographic ~ art;
: T2 i~ a releasable timing group;
R2 and R3 individually are hydroge~, 25 un~ub~tituted or ~ubqtituted alkyl or aryl, such a~
alkyl con'aining 1 to 40 carbon atoms or aryl containing 6 to 40 carbon atom~, 3uch as a phenyl or naphthyl group; and, q i8 0, 1 or 2.
T2 i~, ~or example, a group that enables release of PUG by means of intramolecular nucleophilic di3placement, ~uch as described in U.S. 4,248,962 and U.S. 4,861,701.

.-In the ca~e o~ such coupler3 that relea~e a PUG by means of a timing group, reaction of th~
coupler with oxidized color developing agent cleave3 the bond between the coupler and the coupling-off group. Then the bond between the PUG and the remainder of the coupling-off group i~ cleaved. Bond cleavage between the PUG and the remainder of the coupling-off group preferably doe~ not involve the action of oxidized color developing agent. The cleavage of the bond between the PUG and the remainder of the coùpling-of group can involve any reaction known in the photographic art ~or cleavage of such groups, for example an intramolecular nucleophilic displacement reaction or other elimination reaction.
Any balla~t group known in the photographic art can be u~e~ul on the coupling-off group. The ballast group (~ALL) herein mean3 an organic group o~
~uch size and configuration as to confer on the coupler molecule sufficient bulk to render the coupler sub3tantially non-diffu~ible ~rom the layer in which it is coated in a photographic element prior to exposure and proces~ing. Representa~ive ballast groups include ~ubstituted or un~ub tituted alkyl or 25 aryl group~ con~aining, for egample, 8 to 40 carbon atoms. Other use~ul balla~t group~ include sulfonamido group3 containing 8 to 40 carbon atoms, carbonamido, carbamoyl, sul~amoyl, e~ter, sulfone, ether, thioether and amino groups.
A typical timing group T~ i9 a group that enable~ release o~ a PUG by means o~ intramolecular nucleophilic displacement, such a~ de3cribed in U.S.
Patents 4,861~701; 4,857,440; 4,847,185 and 4,248,962.

fJ ~ ~ J ~

Illustrative timing group~ T2 are as follow~:
1 l4 l6 0 Rll O -- C -- C -- CH2--NCOPUG ~ ~ ,N 1I PVG

1 11 --I\N~ I N_C--PUG

1 l6a 1 R~7/R18 O - C - N - N-COPUG R2 ~ 1 / C

o R7 ¦ Rlg O

O -- C --\C/ ,N\ ,, ~0 ll \N-COPUG ~ I
¦ . C 22 ~\

and other illu3trative group~ described in U.S.
Patent 4,857,447.
In the above ~tructure~, R4, R5, R6, R6a, R7, R8 Rg, Rlot Rll~ R12, R13, ~14~ Rls' ~16' R17' 18' 19 R20, R21, R22, R23 and R24 individually are hydrogen or ~ubstituent~ that do not adver~ely a~fect ~he desired properties of the naphtholic coupler or dye ~;~J . ~ /-3 J ,f s formed, ~uch a un3ub~tituted or qub~tituted alkyl, for example, methyl, ethyl, propyl, n-butyl, t-butyl and eicosyl, or un~ubqtituted or ~ub~tituted aryl, such a3 phenyl, or ~ub~tituted phenyl, and PUG i3 a releasable photographically useful group. At lea~t one of the de3cribed group~ on the coupling-off group i9 a balla~t group.
A~ used herein the term "naphtholic coupler"
refers to the entire compound including the coupler 10 moiety and the coupling~off group. The term ~naphtholic coupler moiety" herein refer~ to that portion of the coupler other than the coupling-off group.
The PUG can be any group that i~ typically 15 made available in a photographic element in an imagewi~e fa~hion. The PUG can be a photographic reagent or a photographic dye. A photographic reagent herein i~ a moiety that upon relea3e further react~ with component~ in the phstographic element, such a~ a development inhibi~or, a development accelerator, a bleach inhibitor, a bleach accelerator, a coupler (for example, a competing coupler, a dye-forming coupler, or a development inhibitor releasing coupler (DIR coupler)), a dye precur~or, a dye, a developing age~t (for egample, a competing developing agent, a dye-forming developing agent, or a ~ilver halide de~eloping agent), a ~ilver complexing agent, a fixing agent, an image toner, a stabilizer, a hardener, a tanning agent, a fogging 30 agcnt, an ultraviolet radiation ab~orber, an antifoggant, a nucleator, a chemical or spectral ~en~itizer or a de~ensitizer.
The PUG can be pre~ent in the coupling-off group as ~ preformsd pecie~ or it can be pre~ent in a blocked ~orm or a~ a precur~or. The PUG can be for example a preformed development inhibitor or the development inhibiting function can be blocked by ~; ~ ,?~J ~

being the point of attachment to the carbonyl group bonded to PUG in the coupling-off group. Other examples are a preformed dye, a dye that i~ blocked to Qhift it3 absorption, and a leuco dye.
A preferred naphtholic coupler a~ described i~ a photographic coupler containing a naphtholic coupler moiety and a PU~ containing a hetero atom from VIb or Vb of the Periodic Table having a negative valence of 2 or 3 bonded to a carbonyl group 10 of the coupling-of~ group.
Any coupler~ known to be u~eful in the photographic art can be used with the de~cribed naphtholic coupler~ and in various location~ known in the art in a photographic element. There follow~ a 15 li~ting of patents and publicationq that describe representative couplerQ that can be useful in combination with the described naphtholic coupler~:
I. COUP~s A. Couplers which form cyan dyes upon reaction with oxidized color developing agent~ are described in 3uch representative patent~ and publication~ a~: U.S. Pat. Nos. 2,772,162;

2,895,826; 3,002,836; 3,034,892; 2,474,293;
2,423,730; 2,367,531; 3,041,236; 4,333,999 and "Farbkuppler-eine LiteraturUbersicht,~ published in Agfa Mitteilungen, Band III, pp. 156-175 ~1961).
Pre~erably ~uch couplers are phenols and naphthols that form cyan dyeæ on reaction with o~idized color developing agentQ.
B. Couplers which form magenta dyes upon reaction with o~idized color developing agent are described in such repre~entative patents and publications aQ u. 5 . Pat. No~. 2,600,788;
2,369,48g; 2,343,703; 2,311,082; 3,152,896;

3,519,429; 3,062~653; 2,998,573 and "Farbkuppler-eine Literatur~bersicht," publi~hed in Agfa Mi~teilungen,Band III, pp. 126-156 (1961).

"

t ~ ~ ~ L

Preferably ~uch couplerQ are pyrazolones and pyrazolotriazole~ that form magenta dyes upon reaction with oxidized color developing agent3.
C. Couplers which form yellow dyes upon reaction with oxidized and color developing agent are described in ~uch representative patent3 and publica-tiOnQ as: U.S. Pat. Nos. 2,875,057; 2,407,210;
3,265,506; 2,298,443; 3,048,194; 3,447>928 and ~Farbkuppler eine Literatur~ber3icht," publi~hed in 10 Agfa Mitteilungen, Band III, pp. 112-126 (1961).
Preferably such couplers are acylacetamides, such a~ benzoylacetanilide3 and pivaloylacetanilide~
that form yellow dye3 upon reaction with oxidized color developing agent~. -D. Coupler~ which form colorle~Q product~
upon reaction with oxidized color developing agent are de~cribed in ~uch repre~entative patent~ as:
U.K. Patent No. 861,138; U.S. Pat. No3. 3,632,345;
3,928,041; 3,95a,993 and 3,961,959. Preferably ~uch couplers are cyclic carbonyl containing compound~
which form colorles~ product~ on reaction with oxidized color developing agent.
Any relea~able PUG known in the photographic art i~ useful in the coupling-o~f group a~
described. Example~ of u~eful PUG' 3 are as follo~:
PUG'~
A. PUG'~ whic~ ~orm development inhibitor~
upon relea~e are described in such repre~entative patents as U. 5 . Pat. Nos. 3,227,554; 3,3~4,657;
3,615,506; 3,617,291; 3,733,201; 4,861,701 and U.K.
Pat . No . 1, 450, 47g . Preferred development inhibitors are iodide and heterocyclic compound~ such a~
mercap~otetrazoles, 3elenotetrazole3, msrcap~obenzothiazoles, ~elenobenzothiazole~, 35 mercaptobenzoxazoles, selenobenzoxazoles, mercaptobenzimidazoles, selenobenzimidazoles, ~ ~?~ ~J ~, oxadiazole~, benzotriazole~ and benzodiazole3.
Structures of preferred development inhibitor moietie~ are:
N-N

-S ~ 1l IIIA-l lo - S .~ O ~I IIIA-2 /o\ /.~
s ~ I IIIA-3 S, ,0~ ~I IIIA-4 N
- ~ ~ IIIA-6 / ~
0.~ + ~-where R2g i~ unsub~tituted or subst;tuted alkyl, ~uch as butyl, l-ethylpentyl, and 2-ethoxyethyl, or alkylthio, ~uch a~ butylthio and octylthio;

~ ~'J~ J

R25 and R26 individually are hydrogen, alkyl of 1 to 8 carbon atomQ such a~ methyl, ethyl, or butyl, phenyl or sub3tituted phenyl; and R27 and R28 individually are hydrogen or one or more halogen such a~ chloro, fluoro or bromo; alkyl of 1 to 4 carbon atom~, carboxyl, esters, such as -COOC~3, or other ~ubstituent~ such a~ -NHCOOCH3~ S020CH3, -OC~2CH2S02CH3~ -OCoc~2cE3~ -N~CCOCH3 or nitro group~-B. PUG~s which are, or form, dye~ upon relea~e:
Suitable dye~ and dye precur~or3 include azo, azomethine, azopyrazolone, indoaniline, indo-phenol, anthraquinone, triarylmethane, alizarin,nitro, quinoline, indigoi~ and phthalocyanine dyes or precur~or~ of ~uch dyeg such a~ leuco dyes, tetra-zolium alts or shifted dye~. These dye~ can be metal complexed or metal complexable. Representatlve patent3 de~cribing ~uch dyes are U.S. Pat. No~.
3,880,658; 3,931,144; 3,932,380; 3,932,381 and 3,942,987. Preferred dye~ and dye precur~or~ are azo, azomethine and indoaniline dye3 and dye precur~or~. Structure~ of ~ome preferred dye~ and dye precur~or~ are:

S02C~3 -O o~ N=N-.~ ~^-N02 IIIB-l ~ ~'-NHl2 I~ ,LSO2N~2 3~

JS

--0~ --N=N~ N02 IIIB-- 2 ._ 0=.
.~ ~--NHS02 1C5~ -t ~./ S92NE3(C~2)40--o~ ,~--C5Hll--t ~---Cl NHC0-~ ~- OC E -n --O--~ --N=~ --0 C2cH2c6}~5 IIIB--3 15 Cl N~ECO(C~2~4-I ~

OCO2CH2C6~I5 l_ .
0 \ z /---N--N--R31 IIIB--4 R30 ~1 25 -1~

S2 1 (C~2)2 1 S2C16~33 -Cl ~ s02N~

Cl4~2s~a S~2N~IC6~l3-n --Cl--~ ~---S02NH--~ ~
~ 0--. .=~

- S02~C6~13-~

~.~ s 3 J , j ~ ~

C. PUG~s which are coupler~:
Coupler~ relea3ed can be nondiffusible color-forming couplers, non-color forming couplers or diffusible competing couplers. Repre~entative patent~ and publications describing competing couplers are: "On the Chemistry of White Couplers,"
by ~. Puschel, Agfa-Gevaert AG Mitteilungen and der Forschungs-Laboratorium der Agfa-Gevaert AG, Springer Verlag, 1954, pp. 352-367; U.S. Pat. No3. 2,998,314;
2,808,329; 2,68g,793; 2,742,832; German Pat. No.
1,168,769 and British Pat. No. 907,274. Structures of pre~erred competing coupler~ are:

-0--~ ~ R33 IIIC-l ~,_~

20 where R32 is hydrogen or alkylcarbonyl, such a~
ac~tyl, and R33 and R34 are individually hydrogen or a ~olubilizing group, such as sul~o, aminosul-fonyl, and carboxy l36 ~o\

~./

where R35, which i~ the same a~ R34 a~ defined above, and R36 i8 halogen, aryloxy, aryl~hio, or a development inhibitor, such as a mercaptotetraæole, such as phenylmercaptotetrazole or ethylmercapto-tetrazole.
D. PUG's which ~orm developing agents:
Developing agent~ relea~ed can be color developing agent8, black-and-white developing agents ~g or cross-oxidi2ing developing agents. They include aminophenols, phenylene diamine3, hydroquinone~ and pyrazolidone~. Representative patents are: U.S.
Pat. Nos. 2,193,015; 2,108,243; 2,592,364; 3,656,950;
3,658,52~; 2,751,297; 2,289,367; 2,772,282;
2,743,279; 2,753,256 and 2,304,953.
Structures of preferred developing agents are:

~ _ ~ 37 IIID-l where R37 is hydrogen or alkyl of 1 to 4 carbon atom~ and R38 i8 hydrogen or one or more halogen such as chloro or bromo; or al~yl of 1 to 4 carbon atom~ such a~ methyl, ethyl or butyl groups.

-0--~ + ~--OH IIID-2 where R38 i3 as defined above.

O C~2 t ~ IIID~3 N

~1~
~ ~ R39 ~.

41 t~ IIID-4 ~ N
~l~
I~

~' 3)~ .A, s HO-~ \ O IIID-6 lo t C~IC~120H
OH
where R39 i3 hydrogen or alkyl of 1 to 4 carbon atoms and R40, R41~ R42, R43 an 44 individually hydrogen, alkyl of 1 to 4 carbon atom3 such a~ methyl or ethyl; hydroxyalkyl of 1 to 4 carbon atoms ~uch a~ hydroxymethyl or hydroxyethyl or sulfoalkyl containing 1 to 4 carbon atom~.
E. PUG's which are bleach inhibitor~:
Repre~entative patent~ are U.S. Pat. No~.
3,705,801; 3,715,208; and German OLS No. 2,405,279.
Structure~ of preferred bleach inhibitor3 are:

S- \ ll IIIE-l N-N

NHC-~45 .

3~
N-N O
-S~ IIIE-2 S-C-N~C-R45 :

~17--S O~ O ~e R45IIIE--3 ~N-----S--~ IIIE--4 where R45 i~ an alkyl group of 6 to 20 carbon atom~.

F. PUG'~ which are bleach accelerator~:

-S ~s/~-R46 IIIF-l -S~ -R46 IIIF-2 --StC~I2~ ~R4gIIIF--3 ~N--N
--S~ I I IF--4 \N--N

--SC~2C~21:~00~F--5 ~:
wherein R46 i8 hydrogen, alkyl9 such a~ ethyl and butyl, alkoxy, such as etho2y and butoxy, or alkylthio, such as ethylthio and butylthio, for exampl~ containing 1 to 6 carbon atom~, and which may be unsub~tituted or sub~tituted; R47 is hydrogen, alkyl or aryl, such as phenyl; R4~ and R49 are individually alkyl, such a~ alkyl containing 1 to 6 carbon atoms, for example ethyl and butyl; z i~ 1 to 6.
The image dye-forming couplers can be incorporated in photographic element3 and/or in photographic processing solution~, ~uch a~ developer ~olution3, so that upon development of an exposed photographic element they will be in reactive association with oxidized color developing agent.
Coupler compounds incorporated in photographic proce3~ing ~olution~ ~hould be of such molecular ~ize and configuration that they will diffuse through photographic layer~ with the processing Qolution.
15 When incorporated in a photographic element, aq a general rule, the coupler compound3 should be nondiffu~ible, that i~ they should be of Quch molecular size and configuration that they will not significantly dif~use or wander from the layer in 20 w~ich they are coated.
Photographic element~ of thi3 invention can be proce~ed by conventional technique~ in w~ich color ~ormin~ coupler3 and color developing agents are incorporated in ~eparate proce~sing solution~ or compo~itions or in the element.
Photographic elements in which the compounds of thi~ invention are incorporated can be a ~imple element comprising a ~upport and a ~ingle silver halide emul~ion layer or they can be multilayer, 30 multicolor element3. The compound3 of thi3 invention can be incorporated in at least one of the ~ilver halide emulsion layers and/or in at least one other layer, such a~ an adjacent layer, where they will come into reactive as~ociation with oxidized color developing agent which ha3 developed silver halide in the emulsion layer. The silver halide emul~ion layer can contain or have as30ciated with it, other r photographic coupler compound3, ~uch a3 dye-~orming couplers, colored masking couplers, and/or competing coupler3. These other photographic coupler~ can form dyes of the same or different color and hue as the photographic couplers of thi3 invention. Addition-ally, the 3ilver halide emulsion layer3 and other layer3 of the photographic element can contain addenda conventionally contained in such layers.
A typical multilayer, multicolor photographic element can compri e a upport having thereon a red-~ensitive silver halide emulqion unit having associated therewith a cyan dye image-providing material, a gree~-sengitive ~ilver halide emulsion unit having a~ociated therewith a magenta dye image-proYiding material and a blue-3ensitive silver halide emulsion unit having a~qociated therewith a yellow dye image-providing material 9 at least one of the silver halide emulsion unit3 having aæsociated therewith a photographic coupler o~ the invention. Each 3ilver halide emul~ion unit can be composed o~ one or more layer~ and the variou~ unit~
and layers can be arranged in different locations wi~h re~pect ~o one another.
The couplers o~ thi~ invention can be incorporated in or a~ociated with one or more layer~
or unit~ of the photographic element. For e~ample, a layer or unit af~eeted by PUG can be controlled by incorporating in appropriate locations in the element a scavenger layer which will confine the action of PUG to the desired layer or unit. At lea~t one of the layer3 o~ the photographic elemen~ can be, for example, a mordant layer or a barrier layer.
The light ~ensitive silver halide emul~ion3 can include coar~e, regular or ~ine grain silver halide cry~tals or mixturea thereof and can be comprised of such ilver halide~ a3 silver chloride, 3ilver bromide, ~ilver bromoiodide, 3ilver -2~-chlorobromide, silver chloroiodide, ~ilver chlorobromoiodide and mixture3 thereof. The emul3ionq can be negative-working or direct-positive emulsions. They can form latent image~ predominantly on the surface of the silver halide grain3 or predominantly on the interior of the 3ilver halide grains. They can be chemically and spectrally sensitized. The emulsion~ typically will be gelatin emulsions although other hydrophilic colloid~ are 10 u~eful. Tabular grain light sensitive 3ilver halide~
are particularly useful such ax de~cri~ed in Re~earch Di3clo~ure, January 1983, Item No. 22534 and U.S.
Patent 4,434,226.
The ~upport can be any support used with 15 photographic element~. Typical support~ include cellulo~e nitrate film, cellulose acetate film, polyvinylacetal film, polyethylene ~erephthalate film, polycarbonate film and related film~ or re3inous materials a~ well as gla~, paper, metal and 20 ~he like. Typically, a flexible support is employed, such a~ a polymeric film or paper ~upport. Paper support3 can be acetylated or coated with baryta and/or an a-olefin polymer, particularly a polymer of an a-olefin eontaining 2 to 10 carbon atoms such 25 a~ polyethylene, polypropylene, e~hylene-butene copolymer3 and the like.
It is preferred that the coupling-off group contain a releasable PUG. Depending upon the nature of the particular PUG, the couplers can be 30 incorporated in a photographic elemen~ for different purpo~e3 and in differe~t locations.
In the following discu~sion of 3uitable materials ~or use in the emulsions and elements of ~hi~ in~vention, reference will be made to Res~arch 35 ~ lo~ure. December 1978, Item 17643, published by Industrial Opportunities Ltd., ~omewell Havant, ~amp~hir2, P09 lEF, U.K., the disclo3ure3 of which ,~' ?

are incorporated herein by reference. Thi3 publication will be identified hereafter by the ~erm ~Re~earch DiQclosure".
The photographic elementg can be coated on a variety of ~upports a~ de~cribed in Re~earch Disclosure Section XVII and the references de~cribed therein.
Photographic element~ can be exposed to actinic radiation, typically in the vi~ible region of the ~pectrum, to form a latent image ag described in Research Di~clo~ure Section XVIII and then proces~ed to form a vi~ible dye image a deQcr;bed in Re~earch Disclo~ure Section XIX. Proces~ing to form a visible dye image include~ the step of contacting the element 15 with a color developing agent to reduce developable silver halide and oxidize the color developing agent. Oxidized color developing agent in turn react~ with the coupler to yield a dye.
Preferred color developing agent~ uYeful in 20 the invention are p-phenylene diamineq. E~pecially preferred are 4-amino-N,N~diethylaniline hydro-chloride; 4-amino-3-methyl-N,N-diethylaniline hydrochloride; 4-amino-3-methyl-N-ethyl-N-~-(methane3ulfonamido)ethylaniline sulfate hydrate;

4-amino-3-methyl-N-ethyl-N-~-hydroxyethylaniline sulfate; 4-a~i~o~3-~-(methanesulfonamido)-ethyl-N,N-diethylaniline hydrochloride; and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene~ulfonic acid.
With negative working 3ilver halide. th~
processing step de~cribed above give~ a negative image. To obtain a positive (or reversal) image, thia step can be preceded by development wit~ a non-chromogenic developing agent to develop expo ed silver halide, but not form a dye, and then uniformly fogging the element to render unexposed silver halide developable. Alternatively, a direct po~itive emul~ion can be employed to obtain a po~itive image.

Development i9 followed by the conventional step~ of bleaching, fixing, or bleach-fixing, to remove ~ilver and ~ilver halide, washing and drying.
~Japhtholic coupler3 as de~cribed can be prepared by reaction~ and methods known in the organic compound synthe~i~ art. Similar reaction~
and methods are de~cribed in U.S. Patent 4,482,629.
Typically, the naphtholic coupler i~ prepared by the following method:
10 Synthe~i~ A:
~ OH
~ t-CO2Ph N~40~ I ~ç~ coN~

15 o~ O~
(Al) (A2) o 2~ o/ ~
ClC02C2H5 ~ O KOd pyridine I~ /0\ ~t Cl o~ N2 (A3) t~
CEO
O O
O/~ 0/ ~
30 ~ NaB~4 ~ aqu. KOH

t~ I ---- -~
o o ~ O ~\t~

(A4) (A5) .
, ~

OH ~ ~

~ ~~I Ra/Ni I 11 ~-CONH2 3 2 o~ No 0~ ssI

(A6 ) (A7 ) ~ OH
~0~~1~ (ClCH2C0320 ~CN~2 ~ \R/ ~7-CO~
pyridine ~ 2 O O

0 I ~ES2Cl6H33 n ~ ~t~NHS2C16H33-n C~2H C~I20CI:)C~2C
(A8) (A9) 0~
PhN~2 ,KI ~. 1 COCl ~ ' I O ~I-CN~ 2 DME, 60 C
t O I-N~so2cl6H33-n C~120COCH2NHph (A10 ) 0~ 0 CONH2 PUG~ -co o o I-NHS2C16H33_n O I~NHS2C16H33_n c~2occH2N~P CH20COC~I2 (All ) (A12 ) OH
15(A8) 3 ~e\ ~1~

O ~t N~S02C16H33 n t C~2B r (A13 ) 2~ 0 PUG t~\~ CON~

~ ' `t~

~, ¦ NHS~Cl 6H3 3--t : 35 (A14) Ph herein means phenyl.

-25~ J ~ 3 Svnthesis Example A: -Co~2ound (A2):
Phenyl-1,4-dihydroxy-2-naphthoate (100.0 g, 356.78 mmol) wa~ dis~olved in deoxygenated tetrahydrofuran (500 mL) and deoxygenated methanol (500 mL) added. To thi~ solution, stirred at room temperature under the nitrogen atmo~phere, wa~ added ammonium acetate (50.0 g, 648.63 mmol) followed by concen~rated ammonium hydrogide ~1.0 L). After ~tirring for 3 hours the reaction was then poured into ice cold 2N-HCl (4.0 L) and enough concentrated ~Cl added to bring the pH to 1. The resulting product, compound (A2~ wa3 filtered off, wa~hed well with water and air dried. The crude product was wa3hed with dichloromethane and air dried. Yield 62.0 g ~72%).
Com~ound (A3):
Compound (A2) (50.0 g, 0.246 mol) wa3 di~solved in dry pyridine (150 mL) and acetonitrile (75 mL) added. The solution wa~ ~tirred and cooled to -5 to 0C. ~thyl chloroformate (50 mL, 0.523 mol) was then added dropwise with stirring while main-taining the temperature at 0C. After the addition, ths cooling bath was removed and the te~perature allowed to reach roo~ temperature. The reaction mixture wa~ then gradually heated to reflux and the solvent allowed to diQtill off. Thi~ procedure was continued until the temperature had ri~en to approximately 120C and 150 mL of 301vent ~ad been 30 collec~ed. ~eating under reflux wa~ continued for an additional 1 hour period. The reaction mixture waq then cosled to approximately 50C and poured into 2r1-HCl, (3.0 L) held at room temperature. This ~uspen3ion wa then stirred for approximately 15 35 minute~, filtered and the residue wa~hed well with water> acetonitrile and finally ether. Thi~ gave the product, compound (A3) 3uf~iciently pure for the next step. Yield 43.5 g (77%).

Compound (A4):
Compound (A3) (23.0 g, 100.35 mmol) wa~
taken up in deoxygenated dimethylqulphoxide (250 mL) and deoxygenated water (25 mL) added. To this S solution, ~tirred at room temperature under nitrogen, was added 8570-potas~ium hydroxide (9.9 g, 150.53 mmol) and stirring continued until di~solution, approximately 15 minute~. 4-Chloro-3-nitrobenzal-dehyde (18.62 mmol) was then added all at once and 10 the regulting solution stirred at 60C for 1 hour.
The reaction mixturè wa~ ~hen poured into ice cold 2N-HCl (2.0 L) and flltered off. The product, compound (A4), wa~ wa~hed ~ith water and, while ~
wet, Qlurried in methanol, filtered and washed with ether. Thi~ product wa~ pure enough to be u~ed in the next ætep. Yield 28.0 g (74 Com~ound (A5~:
Compound (A4) (28.0 g, 74.01 mmol), in a powdered form, was ~uspended in tetra~ydrofuran (150 20 mL) and methanol ~100 mL). Water (100 mL) wa~ added followed by ~odium borohydride (2.8 g, 74.01 mmol) in small portions. More tetrahydrofuran (50 mL) was added to aid stirring. At the end of the sodium borohydride addition complete disQolution had been 25 achieved. The reaction wa~ allowed to proceed for a further 15 minutes, then poured into ice cold 2N-HCl (2.0 L) and the product ~iltered o~f. The product-compound (A5) wa~ wa~hed with methanol and while Qtill wet wi~h 801vent, u~pended in ethanol and 30 heated to reflux. The ~olution wa~ cooled, filtered, washed with methanol, ether and finally air dried. A
~eçond crop of material wa~ obtained on concentrating the mother liquor. Total yield 19.5 g (67%).

Compound (A5) ~19.0 g, 50 mmol) was guspended in water (200 mL) containing 857~-potas~ium hydro~ide (~6.34 g, 400 mmol~. To this mixture was '9 ~ ~ 9 ''5 ~j added methanol (50 mL) and then heated to 800C for 1 hour. The re~ulting dark yellow-brown ~olution was cooled and poured into ice cold 2N-HCl (2.0 L). The yellow product wae filtered off, wa~hed well with water and air dried. Yield 17.7 g (100%).
Compound (A7~:
Compound (A6) (17.7 g, 70 mmol) was dissolved in tetrahydrofuran (80 mL) and methanol (300 mL) added. Raney-Nickel which had been wa3hed several times with water and then methanol ~as added and the solution hydrogenated at 55pYi for 2 ~our3 after which hydrogen up-take had cea~ed. Ths cataly~t wa~ filtered off, washed with methanol and the filtrate concentrated under reduced pres~ure to 15 give the product, compound (A7). This product wa~ -deemed sufficiently pure to be carried on to the next ~tep. Yield 100%.
Compound (48):
Compound (A7) (50.0 mmol) was di~301ved in dry pyridine (150 mL) and hexadecyl~ulfonyl chloride (16.2 g, 50.0 mmol) added. The ~olution wa~ ~tirred at room temperature under a-nitrogen atmosphere for 30 minutes. The pyridine ~as concentrated under reduced pre~ ure and the re~idue taken up in ethyl acetate. This ethyl acetate solution ~a~ then wa~hed with 2N-~Cl (X3), dried (MgS04), filtered and concentrated. The solvent wag r~moved under reduced pres~ure and the re~idual oil crys~allized from acetonitrile. After filtering, wa~hing with acetonitrile and drying, thc yield of produc~
compound (A8) amounted to 16.3 g (53% calculated from compound (A5)).
Compound (A92:
Compound (A8) ~16.3 g, 26.6 mmol) wa~
dissolved in tet~ahydro~uran (150 mL) to which was added pyridine (3.~ mL, 39.90 mmol) followed by chloroacetic anhydride (6.82 g, 3~.89 mmol) in ~i~ f ,~ ' ~ 5, ~ ~

tetrahydrofuran (30 mL) at a reasonably rapid rat2.
After 3tirring at room temperature for 30 minute~ the solvent wa~ removed under reduced pres~ure and the re~idue diY~olved in ethyl acetate. The ethyl acetate ~olution wa3 then washed with 2N-HCl ~X2), dried ~MgS04) and concentrated under reduced pressure. The re3idue cry~tallized from acetonitrile to give compound (A9) 12.2 g (66%).
CompQund (A10):
Compound (A9) (12.2 g~ 17.7 mmol) wa3 dissolved in dimethylformamide (150 mL) To which waQ
added potas ium iodide (4.4 g, 25.55 mmol) and aniline ~8.2 mL, 88.5 mmol) and the reaction mixture heated to 60C for 1.5 hour~. The reaction was poured into 2N-~Cl and extracted with ethyl acetate (X2). The combined ethyl acetate extracts were wa~hed with 2N-~Cl (X3), dried (MgS04), ~iltered and then concen~rated. This re~idue was used a~ ~uch in the next step of the reaction sequence but it could be cryQtallized from acetonitrile. Yield assumed to be 100%.
Compoun~
Compound (A10~ (83.0 g, 111.26 mmol~ was di~olved i~ tetrahydrofuran (800 mL) and the ~olution stirred at room temperature.
N,N-4-diethylanili~e (17.7 mL, 111.26 mmol) was adde followed by a ~olution of 12% pho~gene in toluene (275 mL, 33~.78 mmol). The reaction mixture wa3 ~tirred at room temperature for 15 minute~, concentrated under reduced preQ~ure and the residue u~ed as ~uch in the next ~tep. The yield of the product, compound (All~, wa~ assumed to be lOOZ.
Com~Q~ ~ (A12):
Compound ~All) as de~cribed above (111.26 35 mmol) was dis~olved in dry pyridine ~800 mL) and PMT
(19.83 g, 111.26 mmol) added to the reaction 301ution. The mixture wa~ ~tirred at room temperature ~or 1 hour. It was then concentrated under reduced pre3sure and the re~idue taken up in ? ~5 J ~
-2g-ethyl acetate. The ethyl acetate wa3 washed with 2N-HCl (X3), dried (MgS043, filtered and concentrated to an oil. The oil wa~ taken up in a mixture of ethyl acetate, dichloromethane, heptane 5 and acetonitrile in the ratio o~ 20:20:56.4, re~pectively and subjected to fla~h chromatography eluting with the same solvent sy~tem to elute impuritie~ from the column and then changed to a ratio of 27:50:20.4 to elute the product, compound (A12). The product could be recry3tallized from acetonitrile. Yield 61.0 g (58%).
Calculated for C50~59N78S2 %C=63.20, %H=6.26, %N=10.32, %S=6.75 Found: %C=63.14, %H=6.2g~ %N=10.23, %S=6.62 CompQun~_~A13):
Compound (A8) (4.0 g, 6.53 mmol) wa~
su~pended in dry ether (30 mL) and phosphorou~
tribromide (0.68 mL, 7.18 mmol) in ether (20 mL) 20 added dropwise over a 15 minute period. After the addition the reaction wa3 diluted with ether and the ether solution washed wlth 2N-HCl (Xl)~ dried ~MgS04), filtered and concentrated to give compound (A13). The yield was 100%.
25 Com~Qund (A14):
Compound (A13) (6.53 mmol) wa~ dis~olved in dimethylformamide (40 mL) to which wa~ added PMT
(1.51 g, 7.54 mmol) and the re~ulting 301ution tirred at room temperature for 1 hour. The compound 30 (A14) was i~olated by pouring the reaction mixture into 2N HCl and extracted with ethyl acetate (X2).
The combined ethyl acetate extracts wer~ then wa~hed with 2N HCl (X3), dried (MgS04), filtered and concentrated. The residue wa~ taken up in a mixture 35 of ethyl acetat~ heptane and dichloromethane in the ratio of 15:30:5, respectively and subjected to flash chromatography eluting with the ~ame solvent ç~., 2.3 mixture. The fir t major band wa~ collected to give the product. Yield 4.0 g (79%).
Calculated for C41H52N605S2:
70C=63~70~ %H=6.78, %N=10.87, %S=8.30 5 Found: %C=63. 40~ ~/oH=6. 80, %N=10. 76~ %S=8.14 O Cl 0/ NH / ~ - NO
10 ~ o/~ o + ~ KO~
CO DMSO, 60 OH / ~
O~ ~I
15(A3) t C15~31 n ~B15) 0/ ~ 0 1,~ ,0~ ~ ,0~ ~I

O~ ~I--NO `t~
c=o c~o~

~`til 1 C15~31 ~ ~15~31 35 (B16~ (B17~
.

OH OH
5 I~,O~~~t 2 ~ t-CO~2 o l I-N ~ -No 10 C~OE . CHBr ,1~ ' ,1 0~ ~I 0~ ~I

15C15~31-~ C15~31-~
(B18) (B19) OEr PMT
~ CON~

~
C~PMT
,1~

C15~31-~

(B20~
PMT herein mean~ phenylmereaptote~razole.

~ nt~e~ m~
compGund (~163:
Compound (A3) (3.4 g, 14.83 mmol) waa di~solved in deoxygenated dimethyl~ulpho~ida (100 mL) ;~ ~ s~ ~ ~} ~

and stirred at room temperature under a nitrogen atmo3phere. To thi~ ~olution wa~ added 857O-pota~sium hydroxide ~1.71 g, 25.95 mmol) followed by deoxygenated water (10 mL). The reaction mixture wa~
stirred at room temperature for 15 minute~ and then the benzophenone (B15) (7.0 g, 14.83 mmol) was added as a ~olid in a qingle batch. The dark colored solution wa~ then heated to 60OC and qtirring continued for 2.5 hour3. While still at 60C the 10 warm ~olution wa3 poured into ice cold 2N-HCl (600 mL). The yellow product waA filtered off, washed with water, methanol and air dried. Yield of compound (B16) 8.8 g (89%).
Com~Q~nd (Bl7~:
Compound (B16) (8.8 g, 13.24 mmol) wa~
dis~olved in ~etrahydrofuran (40 mL) to which waa added methanol (20 mL) and water (20 mL). Sodium borohydride (0.5 g, 13.24 mmol) waY added to the su3pen~ion portionwise with stirring. At the end of 20 the additio~ dis~olution wa3 complete and the ~olution stirred continually for a further 15 minutes. The reaction solution wa~ then poured into ice cold 2N-HC1 ~600 mL) and the product compound (B17) filtered of~, washed with water, methanol and 25 air dried. Yield 7.9 g (89%~.
5Om~ound (~18~:
Compound (B17) (10.0 g, 15.0 mmol) wa~
suspended in water (70 mL) and 85Z-potas~ium hydroxide ~7.90 g, 120.0 mmol) added together with 30 methanol (20 mL). This mixture wa~ ~tirred at 80OC
for 1 hour, cooled and poured into ice cold 2N-HCl and the mixture extracted with ethyl acetate (X2).
The combined ethyl acetate e~tracts were then dried, (MgS04), filtered and concentrated. Ths re~idue 35 compound (B18) was u~ed as such in the next step o~
the reaction ~equence. Yield (100%~.

Compound (B19):
Compound (B18) (15 mmol) wa3 dissolved in ether (70 mL) and phosphorous tribromide (1.6 mL, 16.5 ~mol) in ether (15 mL) added dropwi3e over a period of 15 minutes. At the end of the addition the reaction ~olution waa ~tirred at room temperature for a further 15 minutes. The solution was then diluted with ether, wa~hed with 2N-~Cl (X3), dried (MgSO4), filtered and concentrated under reduced pre~sure.
10 Thi~ gave compound (B19), ~ufficiently pure to be used in the next ~tep. Yield 100%.
CompQ~nd (B20):
Compound (B19) (15.Q mmol) was dis~olved in dimethylformamide (50 mL) and treated with ~odium PMT
(3.55 g, 17.73 mmol) while stirring at room temperature for a l hour period. The reaction ~olution wa~ then diluted with ethyl acetate and wa~hed with 2N-~Cl (X4). The organic layer wa~ then dried (MgS04), filtered and concentrated under reduced pre~ure. The oil was dis~olved in 25% ethyl acetate in heptane and subjec~ed to fla~h chromatography eluting ~ith the same solvent mixture. The fir~t major band wa~ colleoted to give the product compound (B20). Yield 5.0 g [42% from compound (B17)].
Calculated for C46~52N60sS:
%C-68.98, %H-6.54, %N=10.49, %S=4.00 Found: %C=69 ~ 07 ~ %~-6 ~ 44 t %N=10.31, %S=4.1Z

Coupler3 that can be prepared by these method3 of ~ynthesis include, for example:

~ COM~2 S, 3 ,~

Compound Numb e ~_ Z
1.
NHS02C16~33-~
~ O C6H
C~2--O_e_C~2 N--CO--S--C~ 11 N--N
û~ ~t 15 2.

I-N~so2cl6H33-n N--N
C1~2--S--C~ 11 25 3.
O ~I

CH2--N--C ~ S--C,N ¦¦
t N~SO2Cl6~33-n ~.~ 'J ~,~ 1J ,, .

Compound Number z2 4.
1 C12H25--n ~t~I 11 o~\t/~ _, N02 C~3 5.

H33C16 ~ CH2S~

c2~s 6. ll6H33 n f t ~N--N
C--C~CH2--N~ S~C~N 11 0 C~3 .
0~ ~I

7 . l 16H33 l O~I
t ,o~
C --CH2--N--C--S--il il C4~9 t ~J ~

Compound Number z2 8 . Cl 1 6H3 3 a 0~ ~I
t s~N--N
C --C~I2--N--C--S~ C ¦¦

tH2 O~ ~I
t 9.
o--CH2CH2--S--ICH--Cl2H25 n coo~
i 20 10.

NO 2I~
t t N=N N~S2C16H33 ~

11.
C3H7--i NE~C16H33 ~ C4H9--.

~J ~ -~J ) J ~ ,s_ Compound Numb e r z2 12.
C3 7 i W N

CH
C16H3~--n ,1.
0~ ~I

13.
S
N~ ~N--Cl 6H3 3--N = N

14.

Cll I ,N--W

NHCO I HO~ C5 30 15. O ~O_~
=-C 6~5 3~ N~S

Compound Numbe r z2 16 .
lC6H5 N--N

T o I
o No2 `t~
N~502C16X33 n ~ C~:z--W-CO-S~ 4 9 NHCOC~I3 `t~
52NHC12~25 n 18. OCH3 0/ ~I
~I ,7~
T ~ ~ o N2 \ ~
N~52C1 6H3 3--~L

Compound Numbe r z2 19.

~ I co s C~N N

S2NHcl2~2s~a ~T~I
oc~3 15 2Q.
12~25-~
~ ~T N ICl-s-(c~2) 21.

iT~ ¦¦ o~ ~ CR3 22.

0~ ~I co S ( C~2 ) 2C2H
T
S2C16~33 ~

~d ~ s ~

Compound 2 Numb e r Z
23.

o/ ~ ICO--I H--0--~ --C5Hll ~;-2 5 CS}Ill-t CH~
¦ N~C6H5 ~CO-S-o~ 11 N N
C~2~ --OC~13 15 24.
o ~ 2512E25--n O I Cl - t ,1 1 ~ I
~5C6--Cl~--OCOCH2--N/~.~ N--N
CO~S~
N--N

C6~5 25. 1 1C8H17--~
O--C--N--N-- C--S--, C8~17-~L C
26.
S02C16~}33-a 0 1 6~5 ~ I 2 S~ND

~J 'i~ ;~J ~

Compound Num~ z2 27.

1 6H3 3 n l H2 lo O\ ~I
oc~3 15 28.

~0~ \CH2--IN_C_S ( C~2 ) 2C2 C12E25 n 2 9 .

~ 0 3~ ~I
~-~ ~Cl~ N C ¢N--~1 6H3 3--n I (C~ ) _¢C12~25 n , , , , ~ J -~ J ~

The following examples further illu3t~ate the invention.
Exam~le 1 -- 3:

Photographic element~ were prepared by coating the following layers on a cellulose e~ter film ~upport (amounts of each component are indicated in mg/m2):

Emulsion layer l: Gelatin -2420; red ~ensitized silver bromoiodide (as Ag~ - 1615;
yellow image coupler dispersed in dibutyl p~thalate (REGEIVER LAYER) Interlayer: Gelatin - 860;
didodecylhydroquinone - 113 Emulsion layer 2: Gelatin - 2690; green sen~itized silver bromoiodide (a~ Ag) - 1615;
magenta image coupler di~per~ed in tritolyl pho~phate; DIR compound of Table 1 dispersed in N,N-diethyl-dodecanamide and coated at a level sufficient to provide a contrast of 0.5 (half) of the original contrast after stepwise green light expo~ure and proces Q ing.(CAUSER LA~ER) Protective Gelatin - 5380;
30 Overcoat bi~vinyl~ulfonylmethyl ether at 2%
total gelatin.

Structures of th~ image coupler~ are as follows:

5,~ ~ V '~' ~

Magenta Image Çoupler:

S ~ Os~Y\ /~
t COCEtO-~ so2-~ -o~
Clo~I21 n 10 Y~llow Image CQ~P1er: -0 o Cl ~CH3)3cCc~eNH~
/l~ NXS2C16~33-n 0~ ~I

S02-~ OCH2-~ ~O
S~rip~ of each element were e~posed to green light through a graduated density step table~ 7 or through a 35% modulation fringe chart for sharpne~
mea~urements, and then developed 3.25 minute~ at 38~C
in the following color developer, ~topped, wa~hed, bleached, fixed, washed and dried.

Colo~ Devel.~p~:
Di~tilled water 800 mL
3~ Sodium Metabi3ulite 2.78 g Sodium Sulfite, anhydrou~. 0.38 g CD-4 4.52 g Pota~ium Carbonate, anhyd. 34.3 g Potas~ium Bicarbonate 2.32 g Sodium Bromide 1.31 g Pota3~ium Iodide 1.20 mg Hydroxylamine Sul~ate (HAS) 2.41 g -4~-Diethylenetriaminepentacetic 8.43 g acid, penta~odium alt (4079 Soln.) Di3tilled water to 1 L
Adjust p~ to 10Ø
CD-4 i9 4-amino-3-methyl-N-ethyl-N-beta-hydroxy-ethylaniline sulfate.
Proce~sed image~ were read with green light to determine the contrast and AMT acuta~ce. From plot~ of AMT acutance v~. the logarithm of the contra^~t for variation~ in the coated level of each development inhibitor releasing (DIR) compound, the acutance was determined at a contra~t or 0.5 compared to its original contra~t without the pre~ence of the lS DIR compound. The acu~ance ~or thc control DIR
coupler was 3ubtracted ~rom each AMT value to provide the relative ~harpne~3 value reported a~ change i~
AMT in Table I. AMT calculation~ employed the following formula in which ~he cascaded area under the ~ystem mvdulation curve is shown i~ equation (21.104) on page 6Z9 o~ the "Theory o~ the Photographic Proce~", 4th Edition, 1977, edited by T.H. Jame~: AMT = 100~66Logtca~caded area/2.6696M]
wherein th magnification factor M i~ 3.8 for the 35mm gy9tem AMT. The u~e of CMT acuta~ce i9 described by R.G. Gendron in "An Improved Objective Method of Rating Picture Sharpness: CMT acutance" in the Journal o~ SMPTE, Vol. 82, pages 1009-12, (1973).
AMT i~ a further modification of CMT u~eful for evaluating system~ which include th~ viewing o~ a po~itive print made from a negative.

f r~

TABLE X

Gamma Causer Example No./ Change Gamma Coupler No. in AMT Receiver . .
Cntrl Cplr 0 1.0 1 1.2 2.1 2 O 1.7 3 2.6 2.5 1 Control Coupler:
o Is~ C2~s o~ `t' ~ -i ~o ~C

N = N

, " ,~
,~, J 5~

Coupler l -46-OH

./ \ ,~

i~ ~I NHso2cH2tc~2tl4c~3 ~N--N
CH2--S~

C~I2CH3 Cou~
OH

O
~o ,1.~ .
0~ I NHso2~cH2tlscH3 t ~N--N

\N--N
C6~5 ~ple~ 3 OX
30 I~ ~o' ~-coN~z ~o/ ~ ~

,1~
0~ ~I S2tCE2tl5C~3 ,N--N

C~2 Il_C~2_ IN_cO_s C
C6~5 rj ~ ~ ?' ~

Compared to the control coupler the coupler~
of Example~ 1 - 3 provide improved acutance and interimage effect~.

Example 4:
A photographic film was prepared, expo3ed and processed like the film in Example3 1 - 3. The processed image~ were read with green light to determine the contrast. From plot~ of the logarithm of the contra~t compared to the coated level o~ each DIR coupler, the reactivity wa~ determined a3 the amount of DI~ coupler in micromole~ per square meter to reduce the contrast (gamma~ to half (0.5) compared to its orginal contra~t without the pre~ence of the DIR coupler. The smaller the amoun~ of the DIR
compound required, the higher wa~ the reactivity of the DIR coupler. Coupler 3 wa~ a~ de3cribed in Example 3. The re~ult3 are given in following Table II:
TABL~ II

Amount of DIR
Coupler to Reduce Gamma in Half (Micromoles Per Exam~Lç_No. Cou~ler_NQ. Squ~e Meter~
4 3 lOB
C (Compari~on) C 157 D (Comparison) D 151 f ~ ? ~ ~ ',j, --4~-Coupler C
OH
I `~ coN~cH3 NHSO2-Cl6~33-n 10 \ ~
t N--N
CH2--0--C--CH2 N--CO--S--C~
Q /~ i 3~.~I o~ ~I

Coupler OH
t o I-CON~C2~5 SO2-Cl6~33-~
25CE2-0-C-C~2-N-CO-~-O /~ 1 ~' ~t The invention ha~ been described in detail with partacular re~erence to pre~erred embodimentæ
th~reo~, but it will be understood that variation~
and modification3 c~n be e~ected within the ~pirit and scope o~ the invention.
: 35

Claims (13)

1. A photographic element comprising a support bearing at least one photographic silver halide emulsion layer and an immobile naphtholic coupler capable upon oxidative coupling of forming a dye that is capable of being washed out of the photographic element upon photographic processing, wherein the immobile naphtholic coupler comprises a ballast-free naphtholic coupler moiety comprising a -CONH2 group in the 2- position and a ballasted coupling-off group in the 4- position.

2. A photographic element as in claim 1 wherein the immobile naphtholic coupler is represented by the formula:

wherein Z is a ballasted coupling-off group; R1 is a ballast-free substituent; and z is 0, 1, 2 or 3.

3. A photographic element as in claim 1 wherein the coupling-off group is represented by the formula:

wherein TIME is a releasable timing group capable of being released from the LINK moiety during photographic processing of the element;
LINK is a linking group capable of being released from the naphtholic coupler moiety upon oxidative coupling of the naphtholic coupler;
n and m individually are 0, 1, or 2;

PUG is a releasable photographically useful group; and at least one of n and m is 1 or 2.

4. A photographic element as in claim 1 wherein the naphtholic coupler is represented by the formula:

wherein X represents the atoms completing a 5-, 6- or 7-member ring, such as an aryl or heterocyclic group;
BALL is a ballast group;
T2 is a releasable timing group;
R2 and R3 individually are hydrogen, unsubstituted or substituted alkyl or aryl;
q is 0, 1 or 2; and PUG is a releasable photographically useful group.

5. A photographic element as in claim 1 wherein the naphtholic coupler is:

or

6. A photographic element as in claim 1 wherein the ballasted coupling-off group comprises a releasable photographically useful group that is a releasable development inhibitor, developing agent, development accelerator, bleacher inhibitor, bleach accelerator, dye, dye precursor, stabilizer, coupler, nucleator, fixing agent, image toner, hardener, antifoggant, or ultraviolet radiation absorber, directly or indirectly bonded to the coupling position of the naphtholic coupler moiety.

7. A process of forming a photographic image which comprises developing an exposed photographic silver halide emulsion layer with a color developing agent in the presence of a naphtholic coupler as defined in claim 1.

8. A process of forming a photographic image as in claim 7 wherein the naphtholic coupler is as defined in in claim 4.

9, A photographic process as in claim 7 wherein the naphtholic coupler is as defined in claim 5.

10. A photographic naphtholic coupler comprising a ballast-free naphtholic coupler moiety containing a -CONH2 group in the 2- position and a ballasting coupling-off group in the 4- position.

11. A photographic naphtholic coupler as in claim 10 represented by the formula:

wherein Z is a coupling-off group; R1 is a ballast-free substituent; and z is 0, 1, 2 or 3.

12. A photographic naphtholic coupler as in claim 10 represented by the formula:

wherein R1 is a ballast-free substituent;
Z is 0, 1, 2 or 3;
TIME is a timing group capable of being released from the LINK moiety upon photographic processing of a photographic element containing the coupler;
n and m individually are 0, 1, or 2;
LINK is a linking group capable of being released from the naphtholic coupler upon oxidative coupling of the naphtholic coupler;
PUG is a releasable photographically useful group; and at least one of n and m is 1 or 2.

13. A photographic coupler that is or