Note: Descriptions are shown in the official language in which they were submitted.
~8'77~
--1--
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
-2-
~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
--3--
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~
-4-
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
IR3
(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
-COOCH3
-COOC2Hs
-NHSO2CH3
-NHCOOCH3
-NHCOOC2Hs
-SO3H
-OH
~5
\ . _ . /
_ --
-COO~
-SO2NH2
-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:
-CH2 -
-CH2CH2
-CH2 CH2 CH2-
CH3
I
-CH2CH-CH2-
-CH2CH2CH2CH2-
8~7~
- CH~ CH-CH2 CH2 ~
t~2Hs
- CH2 C}12 - CH-CH2 ~
5 CH3
- CH -CH2 ~
CH3
10- CH2 CH2 OCH2 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
CH2CH
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
SCH2CH2COOH
lOH o
1i CNHcl2H25
/-
SCH2CH2COOH
OH o
1 I li 12 25
~./ ~j/
SCH2CH2COOH
0~1 o
3 i~ CNH(CH2)~O~~ CsHll-t
I Cs~ t
SCH 2 CH2COOH
~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
SCH2 CH2 COOH
77~
-12-
OH O
~ CNH~
¦ Ocl4H2s
S- ~ 11
N-N
CH2CH2COOH
IOH o
l; i i \ _ /
1 OCI4~2g
o
i-CH2NCH(CH3)2
\.~ C~O
SCH2CH2COOH
OH
il ~i/ ~i-CONH(CH2)4O--~ ~o-CsHll~t
~ C/Hl;-t
1~ /CH3
il i~N_COSCH2CH2N\
1 CH3
OH O CH3
_ CNH ( CH2 ) 4 _ 0 ~ - _ C _ C 2 H s
I CH3-C-CH3 CH3
SCH2CH2COOH C H
2 5
-13-
0}1 O CH3
CNH (OEl2) 4 - 0~ - C -C2HS
i CH3-C-CH3 CH3
SCH2 CH2 COOH C H
2 5
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:
R1 3 -N - N
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:
CH3 CH2 -N -- N
o~ -NH- (CH2 ) I oC~33
SCH2 CH2 COOH
\ ~ /O ~ NHC- (CH2 ) 1 2 CH3
SCH2 CH2 COOH
N -- N -- - (CH2 ) I oCH3
25 CH3CH2~\ 5~
H
SCH2 CH2 COOH
N -- N -- J--(CH2 ) 3 ~ NH--CCH~ ~ S02
H t~
SCH~ CH2 COOH
OH
76~
-15-
Cl\ ~ Cl
~-/ \N - N Cl\ ~,\
Cl~ NH_J~ U
NHCCI~H2~-n
SCH2CH2COOH
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
R22
O O
Il 11 .~.
~CH3)3C-C~CH-CNH~
.- - '~
~,2
R2
CHsCOCHCONH--~ ~
. -
R2 5
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
0 0 SO2NHCH3
(CH3 ) 3 C-CCHCNH~
t)CI ~H3 3
2 5 SCH2 CH2 COOH
o o C~ O
H3 3CI 60-~ CCHCNH-~
~
SO2N(CHI )2
SCH2 CH2 COOH
~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
CH2CH2COOH
O O C~,
Il ll ._. o CsHIl-t
(CH3) 3 CCCHCNH-~
~ NHC~CH2)~0-~ CsHIl-t
, ~ 11
i ~-CH2N-C-SCH2CH2COOH
~ C2Hs
NO2
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:
0
/ \
R ~~ H2)m
R ~~ H )
\./ \ O
il R.2 3
o
R2 9 _ ./ \ . _
R 3 O
o
wherein
R2 6 R27 R2~ R29 and R30 are ind~vi-
dually ballast groups) ~ is I o~ ~ ,
8 ~ 7 ~S
-19-
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
20SCH2CH2COOH
/ \. 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:
-CH2-COOH
- CH 2 CH 2 - C OOH
-CH2 CH2 CH2 -COOH
-CH2 CH2 CH2 CH2 -COOH
-CH2CH20H
-CH2CH2SO3H
-CH2 CH2 SO2NH2
-CHa CH2 CH2 SO2 NH2
-(:H2CH2-SO2-~ -OH
. .......... e.
: CH - COOH
CH2 CH2 COOH
-21-
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
HOOCCH2CH2S OM
~ ~3776
-23~
OH
./ ~. Cl,H
U\ ~
C~, 7
HOOCCH2 CH2 S
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
11
(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~
76
-24-
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
-25 -
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~
-26-
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
-27-
~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~
-28-
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
-30-
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
SCH2CH2COOH
3~7~;S
-31 -
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/
SCH2CH2COOH SO 2 -
765
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:
P-2
(CH ~ 3~ ~NO
CH3~
~ \N
¦ H
SCH2CH2COOH
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:
P-3
ClCOCHO~ SO2-~ OCOCH3
-~. O~
C~oH
~ 76~1
-33-
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
-34-
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
NO2
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
-36-
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
-37-
~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
OCH 3 OH
~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
-38-
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
OCH3 OH
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~
. ~
-39-
Cl
N~ \N-C~CONtl~ CHI
7 ~ COI)CHCOOC I 2 H2 s ) 2
~00~
and ~ gel~tln hsrdener
1 0
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
-40-
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 ~
0
K Il~ ,~ tJ
-42 -
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 .
CH2 CH2 COOH
~l~8~76~;
-43-
BARC-2 herein is:
OH ._.
NH(cH2)4o~-~ ~ -CsH" -t
C/HI;-t
O CH 3
N-COSCH2CH2-~
I; ~ CH 3 CH3
NO2
BARC-3 herein is:
/-~ /l~ /CONH(CH2)40~ CsHl~~t
C/HIl-t
SCH2CH2COOH
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
-44 -
_. .
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
-46-
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~
4H2 9
SCH2CH2COOH
~xa~le 4
BARC-6 herein is:
(CH2)~0 ~ C5HIl-t
CH O~ N ~ HI;-t
OCHI ¦ H
SCH2CH2COOH
7 ~65
-47-
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.
