CA1287765C - Dye-forming photographic material and process comprising bleach accelerator releasing compound - Google Patents

Abstract

DYE-FORMING PHOTOGRAPHIC MATERIAL AND PROCESS
COMPRISING BLEACH ACCELERATOR RELEASING COMPOUND

Abstract of the Disclosure Bleach accelerator releasing organic compounds which have a releasable bleach accelerator moiety represented by the moiety:

-(TIME)n-S-R1-R2 wherein TIME is a timing group;
n is 0 or 1;
R1 is a linking group; and R2 is a water solubilizing group, are useful in dye-forming photographic elements and processes. The bleach accelerator releasing compound enables improved images by means of release of the bleach accelerator moiety in the photographic element during processing.

Description

~8'77~

DYE-FORMING PHOTOGRAPHIC MATERIAL AND PROCESS
COMPRISING BLFACH ACCELERATOR RELEASING COMPOUND

BACKGROUND OF THE INVENTION
5This relates to photographic materials and processes which utilize a compound capable of releas ing a bleach accelerator moiety.
Photographic materials useful for forming dye images by means of a process which includes a bleaching step are known and used commerclally. Such materials and processes are described in, for exam-ple, _ Theory of the Photographic Process, 4th_ Edition, Edited by T.H. James, 1977, pages 462-463 and pages 335-361. The use in such pho~ographic materials of a bleach accelerator releasing coupler is described in Research Disclosure, 1973, Item No.
11449. The bleach arcelerator releasing coupler, also known as a BARC, has contained a heterocyclic group as the bleach accelerator moiety which is released during processing of the photographic element. These bleach accelerator releasing couplers cause an undesired degree of adverse development effects.
Couplers which have a thioether group at the coupling position have been known in the photographic art. Examples of such couplers are described in, for example, U.S. Patent 3,227,554 and U.S. Patent 4,293,691. These compounds have been useful as development inhibitor releasing (DIR) couplers.
Almost all of the couplers that are designed as development inhibitor releasing couplers have a thioether group and are oleophilic in order to help maintain the coupler in one location in the hydro-philic emulsion layers of the photographic material.
Typically such couplers have ballast groups for this purpose. These have not required a balance of a ~% ~7~765 ~trong affinity for ~ilver ~nd R balance of w~ter 601ubility as ls the case with bleach ~cceler~tor comp~unds.
SUMMARY 0~ TME INVENTION
_ It h~s been found that B bleach acceler~tor releasing compound, p~rticularly ~ coupler~ in a dye-formin~ ph~togr~phic 6ilver halide m~ter~al, whereln the compound has a relea~sble ble~ch ~cceler-ator moie~y repre~ented by the moiety:

- (TIME)n-S-R'-R2 wherein TIME is a timing group;
n i5 0 or 1;
R~ is a llnking group, prefer~bly slkylene comprising 1 to B carbon ~toms or ~ N
2 0 -c ~ 1l (L ' )--L' i6 ~lkylene conteining 1 to 8 carbon a~om~ or phenylene; and R2 is a water 601ubilizing group, prefer~bly a carboxy group;
en~bles de6ired ble~ching of 6ilver in 6uch photo-graphic m~teri~l6 upon exposure snd proce~6i~g.
It is important th~t the releasAble bleach accelerator moiety be ln a locstion on the compound c~rrying the moiety which enable~ rele~6e of the ~leach acceler~tor molety ~t ~ eime during proce~ing of the photogr~phic ele~ent which ensble6 acceler~-tion of the ble~ching 6tep. The ble~ch accelera~or releasing compound is preferably ~ coupler h~ving the 3'7~i5 bleAch accelerator moiety in the coupllng po~ition.
The coupler c~n be, but need n~t be, a dye-for~ing coupler.
One embodiment of the invention i~ a ~il~er hAlide photographlc element contsinlng ~ ble~ch acceler~eor rele~sing compound which has a reles~ble bleach ~ccPler~or moiety a~ de~rribed. Another embodiment of the invention compri6es/in ~ color development proce66 which include6 ~ 6ilver ble~ching ~tep, the improvement compri~ing c~rry$ng out the bleaching step ~n the pre~ence of ~ bleach ~cceler-ator moiety rele~sed from ~ ble~ch accelera~or releasing compound, prefer~bly ~ blesch accelerator releasing coupler, ~ de6cribed.
Herein the term "coupler" refers to the entire compound includin~ the coupler ~oiety ~nd the bleach accelerator moiety ~Tr~E~n-s-Rl-R2~ The term coupler moiety herein refer6 to tha~ portion of the compound other th~n the bleach acceler~tor noieey.
The particul~r Rl group l~nking ~he 6ulfur atom ~nd the water ~olub~lizing group R2 can be v~ried to control ~uch parameter6 ~6 water solubil-ity, diffusivity, 6ilver ~ffinity, ~ilver ion complex 601ubility, 6ilver development efect~ ~nd other sen~itome~ric effec~. Since the6e p~r~meter~ c~n be controlled by modif~cdtion of Rl~ they need not be empha~ized ~n 6electing ~ partlcular coupler moiety ~nd the particul~r w~er 601ubilizing ~roup, but provide freedom in 6electing 6uch moietie~ and 3roup~
for A p~rticulQr photogr~phic element ~nd proce6~-In proce6~ng, the ble~ch ~ccelera~or frag-~ent is rele~sed ~ an ~ppropriate time a8 a unit.
Th~t i6, -S-R'-R2 i6 released 88 a unit. The rate ~nd total time of diffu~ion of the bleach scceler~or fragment in the photographic element ~u~t be uch a6 to enable bleach acceler~tlon in ~he ~propriate lsyer~ of ~he pho~ograph~c element durin~

processing. The eiming group, when pre6en~, al60 releases _S~ R2 as a unit~ Selectio:rl O:e R' ~nd R2 ean also influence the raee ~nd ~otal t~m~ of rele~se of th~ bleach accelerator moiety Erom the remAlnder of the compound, preferably the remflinder of the coupler. It ~6 neces~ry ~hfit ehe bleach ~ccelerator moiety not adver6ely ~ffect the proces~ing ~eps and the photographlc element.
Selection of a ~ufficiently w~ter soluble bleach accelerstor moiety by Eelection of optimum Rl ~nd R2 groups minimize~ development inhibltion activity of the bleach acceler~eor molety while enhanclng bleach accelera~or activity. This helps separate those compounds which ~re u6eful ble~ch accelerAtor rele~s-ing compounds from tho~e compound6 which ~re u~efuldevelopment inhibitor reles~ing compound~.
Preferred photogr~phic couplers of the lnven~ion sre repe6ented by the formul~:

COUP - S- (C )m-COOH
R~

wherein COUP is a coupler moiety;
m i6 1 to 8;
R3 and R~ ~re lndividually hydrogen or slkyl containing 1 to 4 earbon stoms; and wherein the tot~l number of carbon atoms in (C)m i~ 1 to 8.
R~

35 Alkyl ~ncludes str~ight or br~nched chain ~lkyl, 6uch as methyl, ethyl, ~-propyl, l-propyl 3 n-butyl, ~nd t-butyl.

7~5 The coupler moiety can be any moiety that will react with oxidized color developing agent to enable release of the bleach accelerator moiety. The coupler molety includes coupler moieties which are useful in conventional dye-forming couplers which yield dyes on reaction with oxldized color developing agents as well as coupler moie~ies which yield colorless pro~ucts on reac~ion with oxidized color developing agents.
The coupler moiety can be unballasted or ballasted with an oil-soluble group. It can be monomeric, or it can form part of a dimeric, oligo-meric or polymeric coupler, in which case more ~han one bleach accelerator moiety can be contained in the coupler. Each coupling position can release a bleach accelerator moiety.
It will be appreciated that, depending upon the particular coupler moiety, the partlcular color developing agent and the type of processing, the reaction product of the coupler moiety and oxidized color developing agent can be: (1) colored and nondiffuslble, in which case it will remain in the location where it is formed; ~2) colored and diffu-sible, in which case it may be removed during processing from the location where it is formed or allowed to migrate to a different location; or (3) colorless and diffusible or nondiffusible, in which case it will not contribute to image density. In cases (2) and (3) the reaction product may be initially colored and/or nondiffusible but converted to colorless and/or diffusible products during the course of processing.
The bleach accelerator moiety is attached at the coupling position of the coupler moiety which enables the bleach accelerator moiety to be displaced upon reaction of the coupler with oxidized color developing agent.

~7~877~

In bleach accelerator releasing organic compounds as described, preferably bleach accelerator releasing couplers, the bleach accelerator moiety can be bonded to the remainder of the organic compound through a timing group (TIME). TIME in the described structures is a group which enables the timed release of -S-RI-R2 from COUPO The timing mechanism can be any timing mechanism which is useful for releasing photographically useful groups from coupler moie-ties. For example, the timing mechanism can be asdescribed in, for example, U.S. Patent 4,248,962 or U.S. Patent 4,409,323.
Release of the bleach accelerator moiety can involve a single reaction or i~ can involve sequen-tial reactions. For example, two or more sequentialreactions may be required within a TIME group to effect release of the bleach accelerator moiety. As another example, the TIME group can have ~wo bleach accelerator moieties bonded to different locations on the TIME group so that upon release of the TIME group from the coupler moiety two reactions can occur sequentially enabling sequential release of the two bleach accelerator moieties. Another example is a reaction in the TIME group which may release a second coupler moiety which contains another timing group to which a photographically useful group is attached and from which it is released after the second coupler moiety reacts with oxidized color developing agent.
The TIME group can contain moieties and substituents whlch will permit control of one or more of the rates of reaction of COUP with oxidized color developing agent, the rate of diffusion of -TIME-S-RI-R2 once it is released from COUP and the rate of release of -S-RI-R2. The TIME group can contain added substituents, such as added photo-graphically useful groups which can remain attached to the timing group and be rele~sed independently.
The TIME groups can contain a ballast group.

~ ~ ~ 7 ~S

R2 can optionally be a precursor to a water solubilizing group. For example, R2 can be an ester group which upon hydrolysis forms ~ water solubilizing carboxylic acid group.
The following R2 groups are examples of useful water solubilizing groups and thPir precursors:
-COOH

-COOC2Hs -NHCOOC2Hs -OH
~5 \ . _ . /

_ ---COO~

-NRsR 6 wherein Rs is H or alkyl of 1 to 4 carbons, R6 is alkyl of 1 to 4 carbons and wherein at least one of Rs and R6 is alkyl, and the total carbon atoms in Rs and R6 is no more than 8.
The following are examples of useful R
groups:

I

8~7~

- CH~ CH-CH2 CH2 ~
t~2Hs - CH2 C}12 - CH-CH2 ~

- CH -CH2 ~

~N--N
N--N
(L ) wherein L' is alkylene containing 1 to 8 carbon atoms such as \ 11 or ~N-N
N-N \N-N

The following is a listing of patents and publications which describe representative COUP
groups useful in the invention. In these structures the unsatisfied bonds in each of the COUP groups show 30 the point of attachment to TIME or, should no TIME
group be present, ~hen to the bleach accelerator moiety; the vertical unsatisfied bond in TIME shows the point of attachment of COUP and the horizontal unsatisfied bond in TXME shows the point of attach-5 ment of the bleach accelerator moiety.I. COUP's A. Useful couplers which form cyan dyes upon reac-tion with oxidized color developing agents ~re 377~;

g described in such representat~ve ps~ent~ ~nd public~
tions ~s: U.S. P~ent Nos. 2,772,162j 2,895,826;
3,002,B36; 3,034,892; 2,~74,293; 2,423,730;
2,367,531; 3,041,236; and 49666,9g9.
Preferably such coupler~ ~re phenol6 nnd naphthols which form cyan dyes on re~ction with oxidized color developing ~genes and h~ve ~he releae-able ble~ch ~ccelerator moiety ~t~ched ~t the coupling position, ~h~t is ~he carbon ~tom in the 4-position of the coupler moiety. Struc~ure6 of preferred cy~n-dye-forming coupler moietles ~re:

OH

~ \- NHCORB

R9-+ Ij-CNHRg OH
o~ \-NHCOR
R' coNH 1~ 11 OH

coNHR l 2 ~-/ \t~-7~5 - 1 o -wherein R~, R9, Rl, Rll ~nd Rl2 ind~vidually represent ball~se groups;
R7 ~nd R9 individu~lly repre~ent at leAst one halo~en ~tom, ~uch as chloro or fluoro; ~lkyl, ~uch ~s ~lkyl cont~ining 1 to 4 carbon ~tom~ r exQmple methyl, ethyl, propyl or butyl; or ~lkoxy, ~uch ~
alkoxy containing 1 to 4 ~arbon stom~, ~or exsmple methoxy, ethoxy, propoxy ~nd butoxy.
Examples of 6uch cysn dye forming coupler6 are:
OH

i~ \,i-NHCOC~ 2H2 s CH3--~ O

lOH o 1i CNHcl2H25 /-OH o 1 I li 12 25 ~./ ~j/

0~1 o 3 i~ CNH(CH2)~O~~ CsHll-t I Cs~ t ~lZ~3776~S

o~ o NHCNH~ CN
H;2 5 Cl 2 CONE~[ I
SCH2 C~12 CHz C:OOH

OH O
1 0 o ~NHCNH~ CN
n-c~Hs-cHcNH
Cs H~ I - t SC H2 CHz COOH
~./' CsHI l-t OH O
o T~ NHCNH~ --n-C4Hg-~HCNH __.~ '! \.. ' N--N
CsHI ~-t C:H2CH2COOH

OH o ~CNH~
OC I .. H2 9 77~

OH O
~ CNH~
¦ Ocl4H2s S- ~ 11 N-N

IOH o l; i i \ _ /
1 OCI4~2g o i-CH2NCH(CH3)2 \.~ C~O

OH

il ~i/ ~i-CONH(CH2)4O--~ ~o-CsHll~t ~ C/Hl;-t 1~ /CH3 il i~N_COSCH2CH2N\

_ CNH ( CH2 ) 4 _ 0 ~ - _ C _ C 2 H s 0}1 O CH3 CNH (OEl2) 4 - 0~ - C -C2HS
i CH3-C-CH3 CH3 B. Examples of couplers which form magenta dyes upon reaction with oxidized color developing agents are described in such representative patents and publica-tions as: U.S. Patent Nos. 2,600,788; 29369,489;
2,343,703; 2,311,082; 3,152~896; 3,519,429;
15 3,062,653; and 2,908,573.
Preferably such magenta dye-forming couplers are pyrazolones and pyrazolotriazoles which form magenta dyes upon reaction with oxidized color developing agents. Structures of preferred magenta 2 0 dye-forming couplers are:

O=!\ U-NH-R1 4 o Rl s-N -- N 11 o~ IC_R~ 6 R1 7 -N - N _ . -R18 ~ ! N

-` ~.2~ ;5 wherein R14, R16 and R17 are individually aryl, alkyl, such as alkyl containirlg 1 to 3 O ~arbon atoms; and Rl 3 ~ Rl S and Rl 8 ~re $ndiv~du~11y ball~6t groups, or are phenyl or sub~itueed phenyl, 6uch ~fi 2 ,4 ,6-trih~lophenyl, for ex~mple, 2 ~4 ,6-trichloro-phenyl .
Examples of ~uch magent~ dye-forming coup-l er s are:

o~ -NH- (CH2 ) I oC~33 \ ~ /O ~ NHC- (CH2 ) 1 2 CH3 N -- N -- - (CH2 ) I oCH3 25 CH3CH2~\ 5~
H

N -- N -- J--(CH2 ) 3 ~ NH--CCH~ ~ S02 H t~
SCH~ CH2 COOH
OH

76~

Cl\ ~ Cl ~-/ \N - N Cl\ ~,\
Cl~ NH_J~ U
NHCCI~H2~-n C. Coupler~ which form yellow dye~ upon reaction with oxidized color developin~ agent6 are de~cribed ~n ~uch representative p~tent6 ~s: U.S. P~tent No~.
2,875,057; 2,407,210; 3,265,506; 2,2~8,443;
3,048,194; and 3,447~928.
Prefer~bly ~uch yellow dye-forming couplers are ~cylamides, for example,benzoylacetanilides and pivalyl~cetanilides.
Examples of ~uch yellow dye-forming coupler~
are:

R2 o O O
~ C-CH-CNH--~ ~
R~ 3 R 2 1 O O
Il 11 .~.
~CH3)3C-C~CH-CNH~
.- - '~
~,2 CHsCOCHCONH--~ ~
. -Xl where in R2 ~ ~ R2 ' and R2 5 ~re individually b~lla~tgroups; ~nd Rl 9 R2 o ~,2 2 and R24 are lnd~vldually 5 hydrogen or one or more halogen, 6uch ~ chlorlne and fluoride; ~lkyl, such a6 ~lkyl contalning l ~o 4 cArbon atoms, for example methyl, ethyl, propyl and butyl; ~lkoxy, 6uch 8~ ~lkoxy contAinlng 1 ~o 20 carbon stoms; or ~ b~ t group.
ExAmple~ of ~uch yello~ dye-forming cc>upler~
are :
O O Cl CH 3 0 ~ C - CH - CNH ~
SCH2 CH2 COOH CNHC I 2~ ~ 5 o (CH3 ) 3 C-CCHCNH~
t)CI ~H3 3 o o C~ O
H3 3CI 60-~ CCHCNH-~
~
SO2N(CHI )2 ~2 ~7 ~17-O O Cl (CH3~3C-C-CH-CNH~ O
. C~3 NHC ~CH2 ~ 3 -O- D ~ C-C2H5 SCH2CH2COOH CH3- ~CH3 CH
C2Hs o C
Il ,_.
I \.~./ CH3 ScH2cH2cooH Co2cHco~CI2H 3 5 ) 2 o Cl CH~CNH~
S ~N-N \-~-/ CH3 \N-N CO2CHCOzCI2H2s)2 O O C~, Il ll ._. o CsHIl-t (CH3) 3 CCCHCNH-~
~ NHC~CH2)~0-~ CsHIl-t , ~ 11 i ~-CH2N-C-SCH2CH2COOH
~ C2Hs D. Coupler6 which form colorle~ product6 or form products which do not 6ignific~ntly ~b60rb electro-magnetic radiation wi~hin ehe visible r~nge of the ~ ~37765 -lB-~pectrum are descrlbed in ~uch represent~tlve p~tent6 a6: U.K. pfltent No. 861,138; U.S. Patent Nos.
3,632,345; 3,928,041; 3,958,993; and 3,961,959.
Preferably such couplers are cyclic ~arbonyl contain-5 ing compounds which form colorle~6 product~ on reaction with oxidized color developlng ~gent~.
Structures of repre~entative couplers which form colorless products ~re:

/ \
R ~~ H2)m R ~~ H ) \./ \ O

il R.2 3 o R2 9 _ ./ \ . _ o wherein R2 6 R27 R2~ R29 and R30 are ind~vi-dually ballast groups) ~ is I o~ ~ , 8 ~ 7 ~S

Examples of such couplers cflp~ble oE forming a colorless or ne~rly colorless produc~ are:
o 5i \~-SCH2CH2COOH
CH3(CH2)l0-- !

10i \--SCH2CH2COOH
CH3(CH2) D l!
CH3(CH2)9-il/ ~i/ \~-SCH2CH2COOH

/ \. o (CH2)9CH3 o o CH3(CH2) 9 - i/ \i -SCH2CH2COOH
/-\ /-~(CH2)sCH3 30HOOCCH2CH2S 1i 1~ 8~7 ~ 20 -Other colorle6s couplers are ~lso u~eful, 6uch a~
oxazolinones, for example, o ll N~ \0 CH,2CH2COOH
Cl o H 2 I-CHCN~
~ ~ \./ \ ~N -- N
o i~ , U S ~

li, ~i S02~ OH
~.

O

CHs-CH-CNH-i~ O

li 1 S~
/ \ ~ \
CsHIl-t CsHIl~t wherein R is:

-CHa CH2 CH2 SO2 NH2 -(:H2CH2-SO2-~ -OH
. .......... e.
: CH - COOH

COOH

a = ~
COOH
E. Couplers which form black dyes upon reaction with oxidized color developing agents are described in such representative pa~ents as: U.S. Patent Nos.
1,939,231; 2,181,944; 2,333,106; 4,429,035;
4,439,518; 4,254,213; 4,387,158; 4,126,461; and 4,200,466.
Preferably such couplers are resorcinols or m-aminophenols which form black products on reaction with oxidized color developing agents. Structures of preferred couplers capable of forming a black dye are:
OH
NHCoR3 / \OH

OH
. _ . /
/-= \
OH

OH
R ~1\ R3 3 N\
t R34 ~ ~8776~

-~2-wherein R3l and R3 2 are individually alkyl, such as alkyl containlng 3 to 20 carbon atoms, phenyl or phenyl substi~uted with hydroxy, halo, such as chloro or bromo, amino, alkyl, such as alkyl containing 1 to 20 carbon atoms, or alkoxy, such as alkoxy containing l to 20 carbon atoms; and R3 3 and R3 4 are individually hydrogen, alkyl, such as alkyl containing 1 to 20 carbon atoms, alkenyl, such as alkenyl containing 1 to 20 carbon atoms, or aryl, such as aryl containing 6 ~o 20 carbon atoms; and~
R3s is one or more halogen, such as chlorine or bromine, alkyl, such as alkyl containing l to 20 carbon atoms, alkoxy, such as alkoxy containing l to 20 carbon a~oms, or other monovalent organic groups that do not adversely affect the dye formation or release of the bleach accelerator moiety.
Examples of such couplers capable of forming a black dye are:
OH
~ NHCOCI 2 M2s HOOCCH2CHzS OH

OH
O ~ COOCl2H2s ~ ~3776 -23~

OH

./ ~. Cl,H
U\ ~
C~, 7 II. TIME's TIME æroups which are useful en~ble relea6e of ~he ble~ch Qccelerator moiety ~t the ~ppropriate time during processing, that 1~ ~t the time which en~bles sccelera~ed bleaching of ~he photogr~phic element. Ex~mples o$ ~uch TIME groups ~re:
15 A. Acyclic TIME groups:

Z' O

(CH2)n N C
Rt 6 wherein n is 1 to 4;
o Z' is 0; C~0 or S;

R3 6 ~ S hydrogen, alkyl, ~uch ~6 alkyl cont~in-ing 1 to 20 carbon atomsj or aryl, ~uch ~6 ~ryl containing 6 ~o 2Q carbon ~tom~, prefersbly un6ub6tl-tuted phenyl or 6ub~tituted phenyl.
B. Aromstic TIME groups~

;~ ~U-(CH2) -N-C-~ R3~

wherein n is 0 or l, Z2 iS O; O; O; S; NH or NH

CH2 C=0 S02 C-O;

R37 is hydrogen, alkyl, such as alkyl contain-ing 1 to 20 carbon atoms; or aryl, such as aryl containing 6 to 20 carbon atoms, for example, phenyl;
X is hydrogen; cyano; ~luoro; chloro; bromo;
iodo; nitro; alkyl, such as alkyl containing 1 to 20 carbon atoms; preferably methyl, ethyl, propyl or butyl; or aryl, such as aryl containing 6 to 20 carbon atoms, preferably unsubstituted phenyl or substituted phenyl.
The bleach accelerator releasing coupler can be used in combination with a colorless coupler or a colored coupler and added to a silver halide emulsion together with an image dye-forming coupler, or alternatively in the form of an independent emulsion in an auxiliary layer, such as an intermediate layer and/or an undercoat layer. The bleach accelerator releasing compounds are useful alone or in combina-tions of two or more bleach accelerator releasing compounds.
The bleach accelerator releasing couplers can be incorporated in photographic elements so that upon development of an exposed photographic element they will be in reactive association with oxidized color developing agent. Coupler compounds incorpor-ated in photographic processing solutions should beof such molecular size and configuration that they will diffuse through photographic layers with the processing solution. When incorporated in a photo-graphic element, as a general rule, the couplercompounds should be nondiffusible; that is, they 77~5 should be of such molecular size and confi~uratlon that they will not significantly dif~use or wander ~rom the layer in which they are coated.
Photographic elements in which the photo-graphic couplers of this invention are incorporated can be a simple element comprising a support and a single silver halide emulsion layer or they can be multilayer, multicolor elements. The coupler compounds of this invention can be incorporated in the silver halide emulsion layer or in another layer, such as an adJacent layer, where they will come into reactive association with oxidized color developing agent which has developed silver halide in the emulsion layer. The silver halide emulsion layer can contain, or have associated with it, other photo-graphic coupler compounds, such as development inhibitor releasing ~DIR) couplers, color forming couplers and colored masking couplers. These other photographic coupler compounds can form dyes of the same or different color and hue as the bleach accel-erator releasing compounds. Addi~ionally, the silver halide emulsion layer can contain addenda convention-ally contained in such layers.
A typical multilayer, multicolor pho~o-graphic element according to this invention can comprise a support having thereon a red-sensitive silver halide emulsion unit having associated there-with a cyan dye image providing material, a green-sensitive silver halide emulsion unit having associated therewith a magenta dye image providing material and a blue-sensitive silver halide emulsion unit having associated therewith a yellow dye image providing material, at least one of the silver halide emulsion units having associated therewith a bleach accelerator releaslng compound of the invention.
Each silver halide emulsion uni~ can be composed of one or more layers and the various units and layers ~l2~

can be arran~ed in dif~erent locations with respect to one another. Typica:l arrangements are described in U.S. Patent Nos. 3,227,554; 3,620,747; 3,~43,369;
and ~.K. Patent No. 923~045. The co-lpler compounds of this invention can be incorporated in or associ-ated with one or more layers or units of the element. The layer(s) and unit(s) af~ected by the bleach accelerator moiety can be controlled by incorporating in appropriate locations in the element scavenger layer(s) which will confine the action o~
the bleach accelerator moiety to the desired layer~s) or unit(s).
The light sensitive silver halide emulsions can include coarse, regular or fine grain silver halide crystals or mixtures thereof and can be comprised of such silver halides as silver chloride, silver bromide 3 silver bromoiodide, silver chloro-bromide, silver chloroiodide, silver chlorobromo-iodide and mixtures thereof. The emulsion can be 20 negative-working or a direct-positive emulsion. They can form latent images predominantly on the surface of the silver halide grains or predominantly in the interior of the silver halide grains. They can be chemically and spectrally sensitized. The emulsions typically will be gelatin emulsions although other hydrophillic colloids can be used in accordance with usual practice. Tabular grain photographic silver halide emulsions, described in, for example, Research Disclosure, January 1983, Item No. 22534 and U.S.
30 Patent 4,434,226 are particularly useful.
The support can be any support used with photographic elements. Typical supports include cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polyethylene terephthalate film, polycarbonate film and related films or resi-nous materials as well as glass, paper, metal and the like. Typically, flexible support is employed, such ~2 ~s a polymeric film or psper ~upport. P~per 6upport6 c~n be ~ceeylated or coa~ed with bsryt~ ~ndtor ~n -olefin polymer, particularly ~ polymer of ~n ~-olefin containing 2 to 10 cArbon atoms 6uch a8 S polyethylene, polypropylene, ethylene-bu~ene copoly~
mers and the like.
If the coupler moiety i6 ~ dye-forming coupler, it can reac~ wl~h oxidized developing ~gent in the same or an ad~acent l~yer to form ~ dye ~ ~he same or different color or hue as thQt obt~ined from the primary coupler. If the coupler mo$ety i~ ~
competing coupler, it can react with oxidized color developing agent in the ~ame or an ad~acent layer to reduce dye density.
The optimum concentration range of ble~ch accelerator rele~sing compound will depend upon 6uch factors as the desired image, the location of ehe bleach accelerator releasing compound, process~ng conditions, the particulsr ble~ch compo~ition, the particulsr layers of the photographic element, processing steps and the p~rticular bleach scceler-ator moie~y. A typical concen~r~ion of bleach ~ccelerator releasing compound in a photogr2phic element is wlthin the range of a~out 50 to about SOO
mg/6q meter.
A p~rticularly u6eful photographic elemen~
~ccording to the invention i~ ~ dye-forming pho~o~
graphic element having ~ layer formQt known to be useful in forming ~ multicolor image by a 6ubtr~ctlve color process. Any or ~11 of the respective color records can be in the orm of ~ double or triple layer 6tructure.
The process of forming a dye image ln a photogrQphic element ~6 described compri6e6 conven-~onal color processing ~nvolving a bleaching 6~ep.The bleaching ~tep i~ preferably conduc~ed ~eparately from fixing. The bleaching compo~it~on compri~e~

known bleaching agents. Examples of ~ypical processes are described in Research Dis~losure, December 1978, Item No. 17643 and in "Modern Photographic Processing", by Grant Haist, Vol. 2, pages 569-587, John Wiley and Sons, N.Y., 1979.
Processing of a dye-orming photographic element according to the invention ~ypically comprisPs a color development step, a bleaching step and a fixing step. The bleaching step and fixing step can be combined into one step if desired. Other processing steps which are also useful in this process include a pre-hardening step, a neutralization step, a first development step (black-and-white development), a stabilizing step, and water washing step. Processing steps are typically carried out at a temperature within the range of 18C to 60C.
The bleach accelerator releasing compounds are prepared by organic synthesls procedures known in the organic compound synthesis art. For example 9 the coupler moiety can be reacted with the bleach accel-erator moiety in an appropriate solvent. The follow-ing are representative preparations of bleach accelerator releasing couplers:
Synthesis Example A:
This relates to the synthesis of the follow-ing bleach accelerator releasing coupler:
~H O
~ CNH(CH2).,0 ~ ~--CsHll~t ~./ \.~ /
I CsHll~t S
~ \N-CH2CH2COOH
N=~=N

~7~6S

~29 -A solution of 20 g (33 m~ol) of the follow-ing compound (coupler mo~ety~:
OH O
i ~ CNH(CH2)~0--~ ~D-CsHll-t ~ CsH" -t 5.8 g (33 ~mol) of 1-~2-carboxyeehyl) tetr~zol~ne-5-thione (bleach ~cceler~tor mo~ety)~ and 14 g of pot~ssium carbonate (K2CO3~ ln 500 mL of dimethylforma~ide (601vent) ~re heated 2 hour6 ~t 80C. The re6ulting compos~on i6 then cooled ~nd drowned in ice cold dilute hydrochloric ~c$d. The 5 resulting product i~ i~ol~ted and purlfied. Thi8 c~n be done by extr~ction ~nd then purific~ion by 6il$ca gel chromatography ~nd recry~t~llizatlon from aceto-nitrile to yield ~ n~arly colorle6s product which ~6 iden~ified by element~l anAly~16 a~ ~he de~ired ble~ch acceler~tor rele~ing coupler.
Synthesis Example B:
Thi6 rel~tes to the synthesis of th~ following ble~ch scceler~tor relea6~ng coupler:
OH
CONH(CH2)~0~ -C5HI~-t C/H,I_t li/ ~;-N-COSCH2CH2 ~

~;287~65 To a solution of 5.6 g (8 mmol) of the coupler moiety:
OH
S Ij/ ~ -CONH(CH2)40-~ CsHl l-t \.~ \.~ /
O C5HIl-t COCl ~ CH3 (prepared by procedures described in U.S. Petent 4,248,962) is added 1.1 g (8 mmol) of 2 dimethyl-aminoethanethiol hydrochloride represented by theformula:

HSCH3CH2 ~
I\CH3 HCl in 25 mL of dry pyridine. The mixture is stirred overnight and then drowned in water. The resulting product is then extracted and purified. The desired product can be isolated by ethyl ece~ete extraction, triturated with ligroin and dried to obtain the desired bleach accelerator releasing coupler having a melting point of 130-131C, and which is identlfed by spectral and elemental analysis.
Synthesis Example C:
This relates to the synthesis of the bleach accelerator releasing coupler:
OH
coNH (cH2 ) 4 o~ C s H, l - t C s Hl l - t 3~7~;S

To a solutloD of 5g (9.9 mmol) of the coupler moie~y:
OH
~ CONH(CH2)~0~ C5HIl-t S i 1! i 1 sH~l-t SH

in 75 mL of tetrahydrofuran, stirred under nitrogen, is added 1.4 g (9.9 mmol) of tetrame~hylguan~dine ~nd ~hen 1.1 mL (9.9 mmol~ of ethyl acryl~te. After 30 minutes 50 mL of methanol and 10 mL of 1.25 N sodium hydroxide solution ~re added and the resulting composition ~tirred for 15 minutes. The mixture ls then drowned in ice-cold dilute hydrochloric scid.
The desired produc~ ls extr~cted ~nd purified. For example, the desired product i6 extracted with diethyl ether to obtain, ~f~er cryst~lliz~tion, ehe desired bleach scceler~tor releAslng coupler which i6 a colorless solid h~ving a melting poin~ of 139C ~o 141C. The product is ~lso identlfied by elemental and spectral an~lysis.
Synthesis Example D: .
This relates to the ~ynthesis of the bleach sccelerator releasing coupler:

(CH2)3~ MHCOCHCloH

~-~ \N/

To a ~irred 601ution of 20 g (70 mmol~ of the compound ~CH3)~ NO2 CH3-. ~ ~ ~

~nd 7.4 g (70 mmol) 3-mercapeopropionic acid (HSCH2CH2COOH) ~n 75 mL of dimethylformamide is added, dropwi6e, 3.85 mL of bromlne in ~5 mL of dimethylform~mide. Afeer 6eirring o~ernight ~he mixture is drowned in water. A single 3produr:t, designated as P-2:

(CH ~ 3~ ~NO

CH3~
~ \N
¦ H

is isolated by filtration. Next, 11 g of zinc is added to a 601ution of 5.6 g (13.7 mmol) of P~2 in 200 mL of gl8ci~1 acetic acid ~nd 6tirred 30 minuee6 before filtration. Then 6.9 g (13.7 mmol) of the compound, design~ted as P-3:

ClCOCHO~ SO2-~ OCOCH3 -~. O~
C~oH

~ 76~1 is added ~o the fll~r~te, 6tirred for 1 hour ~nd the m~xture poured ineo wster. The re6ulting produc~
i~olated by extraction, i6 then di~601ved ln methanol/tetrahydrouran (equal parts by volume~
S then hydrolyzed with 50% sodium hydroxlde 601ution, And ~cidified with cold exce~ dilute hydrochloric ~cid. The desired bleach ~ccelerator relea~ng coupler is then extr~cted and purl~ied by 6ilic~ gel ch~omatography. This blesch scceler~tor relea61ng 10 coupler has ~ melting point of 120-122C and i6 identlied by element21 ~naly6is indic~ting one water of hydration is pre6ent.

~7 ~6 The Eollowing examples further illustrate the invention:
Examp~e 1 This illustrates a multilayer color photo-graphic element comprising a bleach acceleratorreleasing coupler according to the invention.
A multilayer color photographic element, designated herein as Sample a, was prepared by coating the following layers on a cellulose triace-tate film support in the designated order (levelscoated are given in mg/m2 with silver halide stated as silver level):
.
Layer 1: Slow Cyan Layer-(bottom Slow, red-sensitized silver bromoiodide layer)tabular grain gelatino emulsion ~1615 mg/m2), gelatin ~2153 mg/m2). This layer also comprises a cyan image dye-forming coupler, designated as C-l (603 mg/m2):
OH
/1~ /NHCONH~ CN
i! !
C4Hg CHCONH/ \-~

o 1~ /CsHl,-t i!,t ~ i CsHl,-t ~35~
~ nd a colored coupler (65 m~/m2), de~ignated ns C-3 and de6crlbed below, ~5 well 8S ~ development iDhibit~r rele~ing coupler, de~ignated a~ D-l (43 ~g/m2) OH
CONH~

U\ ~i C3H7-i 7 . .____ _ _ Layer 2: Fsst Cyan L~yer-Fast red-~en~itized 6ilver bromo~odide t~bul~rgr~in gelat~no emulsion, prep~red a6 de~crlbed ln U.S. PAten~ 49434~226 of Wilgu6. Thi~ layer 8160 compr~6e6 gel~tin (1615 mg/m2) ~nd ~ cy~n lmage dye-forming coupler, de6ign~ted ~6 C-2 ~194 mg/m2):
OH ._.
~1 ~NHCONH-~ ~n-CN

C~Hs-HCCNH/ ~i/ .
\ ~--OCH3 11 _ ./
CsHIl-t 7~5 and a colored coupler, designat.ed as C-3 (16 mg/m2) OH O .
~ /CONH(CH2) 4 ~ CsHl~-t CsHll-t o i~ i1 OH NHCOCH3 S~3H`-/ \ ~ \SO3H

Layer 3: . Interlayer-Gelatin (1292 mg/m2) .
Layer 4: Slow Magenta Layer-Green sensitized silver bromoiodide 20tabular-graîn gelatino emulslon, prepared as described in U.S. Patent 4,434,226 of Wilgus. This layer also comprises a magenta image dye-forming coupler, designated as coupler M-l:

(CH2) 3 ~ ~--NHCOlcHcl oH2 1 CH3\ ~N ~ 1~ =- O

c~ !~ ,!1 S02~ OH

~nd ~ colored coupler 3 de6igns~ed a6 M-3:

N~ C~

5Cl 0~ ~ ~ COCHC12H2s ll l N O
.~ \. .~ \O
1! ! 1!
~l/ \OCH3 ~o/ \C~H~-t ~s well ~ ~ development inhib~tor rele~ing coupler, design~ted a6 DIR coupler D-2:

CH3CHjCHCONH~ N
O 0~

I~ X,C~ H5 CsHI l-t Layer 5~t Magent~ L~yer-F~st green-~en~itized ~ilver bromoiodide tabulsr-grAin gel~tlno emul6~0n prepared ~s de6cribed ln U.S. Patent 4,434~226 of Wilgus. Thl6 lsyer ~180 compri6e6 a magenta lmage dye-for~ing coupler, design~ted aB coupler M-2:

~1 ~7 i~ ll ~ /N~ NH- 7 O \NHCOCHCloH
O
I

i~ /li SO2~ -OH
and a colored coupler, designated as M-3:

C~ ~-\ /Cl 1 \ N/ ~ -NH~

O N NHCOCHCl2H2 5 Il I
N O
i~ \n ~i/ \OCH3 ~i/ \C4Hs-t 25 Layer 6: Interlayer-Gelatin Layer 7:Slow Yellow Layer-Blue-sensitized silver bromoiodide tabular-grain gelatino emulsion (3 to 6 mol % iodide) prepared as described in U.S. Patent 4,434,226 of Wilgus. This layer also comprises yellow image dye-forming coupler Y-l and a development inhibitor releasing coupler ~DIR coupler):

.

~8776~
. ~

Cl N~ \N-C~CONtl~ CHI
7 ~ COI)CHCOOC I 2 H2 s ) 2 ~00~

and ~ gel~tln hsrdener Layer 8: F~6~ Yellow Layer-F~se, blue-~en6itized ~ilver bromoiodide gelut~no emul~ n ~6 de6cribed ln U.S. P~tent 153,320,069 of Illlng6worth, ~nd op~ ally senYitized with sulfur ~nd ~old. Thi6 l~yer also contain~ a yellow ilDage-dye-forming coupler de~ignated B6 coupl~s Y-l:
o Cl Il 11 0_-(CH3 ) 3 CC-CH-CNH~
I
NHSO2C, 6H~,, ,/ ~,.

\.~
SO2-~ -OH
.~.

_ 30 Layer 9: Proteceive overcoBt-Blend of U.V. ~b60rber~ ~nd gel~tin _ Ssmples b, d, f, llnd h were prep~red in the 35 s~me manner as f~r Sample ~ except that collpler C-2 ln Layer 2 WBS replaced by the ~moune~ ind~c~l:ed in ,. :.

~ 7~5 Table 1 of comp~rison coupler C-4, ~nd bleach ~ccel-erator releasing couplers designaeed ~ BARC-ll -X, or -3, respeceively. Further, S~ple~ c D e, g, ~nd 1 were similArly prep~red by replacing half of coupler C-l in Layer 1 of Sample n by the ind~c~ted smount~
of comparison coupler C-4 and BAR couplers 1, 2~ or 3, r~spectively. These ~amples were s~ch given 8 white llght exposure through ~ gr~du~ted den6ity ~tep t~blet and processed for 3.25 minute~ in ~ color developer of the type de6cribed in ~he Brl~i~h Journal of Photography Annusl, 1979~ pp. 204-206.
From plots of density eo red ligh~ vs. log exposure the D-min, D-max, and relative photogrsphic speed ~S (in log E units ~e D ~ fog + 0.1) were de~er-mined as reported in Tsble A. The re61dual ~llverrem~ining af~er the ble~ch 6~ep w~s determined by x-ray fluorescence me~surement ~nd the aver~ge for the two highest exposure 6teps i6 glven ln T~ble A.

~r~

~ ~7~6~
_al-r~ o ~ o o ~4 o ~ ~ ~ ~ oc~ o ~, o ~: e ~,~0~ ~
C~4 1 ~ ~ C~ ~ ~ o o o ~ e o r~o ~ ~ ~
U~ ~ N~ O O O
O + OI C~
~` O
l . . .,, ~ . . . .
a _, _, ~ ,_ ~ ,. ~ ,, c~

Ei ~ ~) ~ N ~rl ~ N ~1 C~
E~ ~

. ~
v E ~ I~ ~ ~D ~ O
~3 -- I ~ O r_ ~ O ~, U~

a~
~ ~ I ~ ~ I
¢ ~ ¢ ~ ¢ C

S~
u~
~ ,~
O O
,_ co co o r _~ . O o O ~ --' --I --' '' '' ~ cJ ~

K Il~ ,~ tJ

The d~ta :Ln T~ble A ~how th~t ~ddit~on of BARC-l, -2, or -3 to cyan l~yer~ of the an~lt~ l~yer element improves the removsl of ~ilver which other-wi~e would be retsined cau6irlg color reprod-lct~on problems. When added ~o ~che f~6'c l~yer ~t relatively hlgh levels BARC 1 ~nd -2 g~ve 6ub~tsnti~1 speed lo~ses while for BARC-3 6uch 106s 115 minimal. All except BARC-2 when ~dded to ehe 610w layer incre~6e the min:lmum den6ity.
comparison c-~a herein is:
OH ._.
ONH(CH2)~ HI 1 _ t 5OCH 2C~2SCE~2COOH
BARC- 1 herein i6:
OH
/CONH ( CH 2 ) ~ 0~ s H I l - t !~ ! C/HI ~ -t S .

~l~8~76~;

BARC-2 herein is:
OH ._.
NH(cH2)4o~-~ ~ -CsH" -t C/HI;-t N-COSCH2CH2-~
I; ~ CH 3 CH3 BARC-3 herein is:

/-~ /l~ /CONH(CH2)40~ CsHl~~t C/HIl-t Example 2 Multilayer ncorporated coupler photographic elements were prepared in the same manner as for Sample a of Example 1, with coated amounts given in 25 mg/m2. Control Sample j was coated as follows on the film support:

~77~i5 _. .
Layer 1:Slow Cyan Layer-(bottomComprising a red-sensitiæed silver layer)bromoiodide tabular-grain emulsion blend (1615), gelatin (2153), cyan image coupler C-l (603), colored coupler C-3 (32), and DIR coupler D-l (32).
.
Layer 2:Fast Cyan Layer-Comprising a fast red-sensitized silver bromoiodide tabular-grain emulsion (1076), gelatin ~1615), cyen image coupler C-2 (151), and colored coupler C 3 (48).
-15 Layer 3:Interlayer-Comprising gelatin ~1292).

Layer 4:Slow Magenta Layer-Comprising a green-sensitized silver 20bromoiodide tabular-grain emulsion blend (1292), gelatin (1615), magenta image coupler M-l (646), colored coupler M-3 (43), and DIR coupler D-2 (13).

25 Layer 5:Fast Magenta Layer-Comprising a fast green-sensitized silver bromoiodide tabular-grain emulsion (969), gelatin (1292), magenta image coupler M-2 (108), and colored coupler M-3 (46).
Layers 6 through 9 were the same as for Sample a, Example 1.
-~ ~ ~7 ~6~

S~mple k was prep~red ~8 for S~mple J butwith the following changes in the m~gent~ l~yerB:

Layer 4: Coupler M-l ~484)c coupler D-2 (32), and ~dded ble~ch ~ccelerator rele~6ing coupler de6ign~ted ~ BARC-4 (108).

Lsyer 5: Coupler M-2 t54) ~nd added B~RC~4 (54).

Sample 1 wa~ prepflred a6 for Sample ~ but with the following changes in the cyan l~yers:

Layer 1: Coupler C-l (517) ~nd added BARC-3 (86).

Layer 2: Couple~ C-2 (75) and ~dded BARC-3 (60).

Sample m wa~ prepared a6 for S~mple ~ but adding bleach accelerator relea~ing c~upler~ to both cyan ~nd ~agenta l~yer~ 1, 2, 4~ ~nd 5 ~ccording t~
the changes ind~cated $n prep~ring Samples k and 1.
Photographic re6ults ~fter expo6ure ~nd proce~sing as in Example ~ arR ~hown in T~ble B, where R, G, and W ind~cate ~amples were given red, green, or white light expo6ure~, re6pectively.
TABLE B
Residual Ag in mg/m2 (and % ~llver Removed) Sample BAR Compd. G R W
~ -- (control) 34(0)77(0) 85(0) k magenta layers 7(80~60(22) 21(75) 1 cyan lsyer6 3(91)St94) 8(91) m magen~ ~nd cyan layer6 B(76)7(91) 6(93) ~7~ 6 BARC-4 h~rein is:

(CH23 3~~NHCOCHCIoH

CH3~ N J
j H
SCH2CH2COOH ~ ~9_-~
SO2~ OH

The following examples can be carried out ac~ording to Example 1 w~th ~he exception that the bleach acceler~tor relessing coupler is repl~ced by ehe bleach ~cceler~or releasing coupler designated in the following examples:
Ex~mple 3 BARC-5 herein is:
OH ._.
. !~ ,~ONH~

~xa~le 4 BARC-6 herein is:

(CH2)~0 ~ C5HIl-t CH O~ N ~ HI;-t OCHI ¦ H

7 ~65 Exam~le 5 BARC-7 herein ls:
o CH3CH2O ~ N-N
S~
i! ! , t GH2CH2COOH
oCI2H2s The invention has been de6cribed ln det~l with pRrticul~r reference to preferred embodiment6 thereof, but it will be under~tood th~t v~ri~lon~
~nd modification6 csn be effected wlthin the splrit ~nd scope of the invention.

Claims (11)

1. In a photographic element comprising a support bearing a photographic silver halide emulsion layer and a bleach accelerator releasing coupler, the improvement wherein said bleach accelerator releasing coupler comprises a coupler moiety having a releasable bleach accelerator moiety represented by the formula:
-(TIME)n-S-R1-R2 wherein TIME is a timing group;
n is 0 or 1;
R1 is a linking group selected from the group consisting of alkylene comprising 1 to 8 carbon atoms and ;

L' is alkylene containing 1 to 8 carbon atoms or phenylene; and R2 is a water solubilizing group that enables said bleach accelerator moiety to be water soluble while minimizing development inhibition activity.

2. A photographic element as in claim 1 wherein said water solubilizing group is a carboxy group.

3. A photographic element comprising a support bearing a photographic silver halide emulsion layer and a bleach accelerator releasing coupler represented by the formula:

wherein COUP is a coupler moiety;
m is 1 to 8;
R3 and R4 are individually hydrogen or alkyl containing 1 to 4 carbon atoms;
and, wherein the total number of carbon atoms in is 1 to 8.

4. A photographic element as in claim 1 wherein said -S-R1-R2 is and n is 0.

5. A photographic element as in claim 3 wherein said bleach accelerator releasing coupler is a compound of the formula:

6. A photographic element as in claim 3 wherein said bleach accelerator releasing coupler is

7. A process of developing a photographic element as defined in claim 1 comprising developing a dye image in said photographic element in a color developer and bleaching the resulting photographic element in a bleach composition.

8. A process as in claim 7 also comprising fixing said photographic element.

9. A process of developing an image in an exposed photographic element comprising a support bearing a photographic silver halide emulsion layer and a bleach accelerator releasing coupler repre-sented by the formula:

wherein COUP is a coupler moiety;
m is 1 to 8;
R3 and R4 are individually hydrogen or alkyl containing 1 to 4 carbon atoms;
and, wherein the total number of carbon atoms in is 1 to 8;

said process comprising developing a dye image in said photographic element in a color developer and bleaching the resulting photographic element in a bleach composition.

10. A process of forming a color image in an exposed photographic silver halide element comprising a support bearing at least one cyan dye-forming silver halide photographic emulsion layer, at least one magenta dye-forming silver halide photographic emulsion layer, and at least one yellow dye-forming silver halide photographic emulsion layer, and a bleach accelerator releasing coupler of the formula said process comprising developing said photographic element in a black-and-white developer; developing the photographic element in a color developer;
bleaching the photographic element in a bleach composition and fixing the resulting photographic element.

11. A process of forming a color image in an exposed photographic silver halide element comprising a support bearing at least one cyan dye-forming silver halide photographic emulsion layer, at least one magenta dye-forming silver halide emulsion layer, and at least one yellow dye-forming silver halide photographic emulsion layers and a bleach accelerator releasing coupler of the formula:

said process comprising developing said photographic element in a black-and-white developer; developing the photographic element in a color developer;
bleaching the photographic element in a bleach composition and fixing the resulting photographic element.