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Description  |
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This invention relates to a new photographic coupler that is capable of
forming a wash-out dye in a photographic material upon photographic
processing to form an image having improved acutance, stability, and
interimage effects, and a photographic material and process using such a
coupler.
Various ways are recognized in the photographic art for release of a
photographically useful group (PUG), such as a color development
inhibitor, from a compound, such as a coupler, in a photographic material
and process. For example, U.S. Pat. Nos. 4,248,962, and 4,861,701
describes compounds that release photographically useful groups by means
of an intramolecular nucleophilic displacement reaction in photographic
materials. Other examples of means for release of photographically useful
groups are described in, for example, U.S. Pat. Nos. 4,409,323 and
4,861,701. These compounds, particularly couplers, capable of releasing a
photographically useful group provide a degree of control over timing and
rate of release as well as rate of diffusion and distance of diffusion of
the photographically useful group.
The part of the compound that remains in the photographic material after
release of the photographically useful group and dye that is formed in the
material from reaction with oxidized color developer often provides
undesired properties in the photographic material during or after
photographic processing. For example the dye formed from a coupler upon
release of a photographically useful group often adversely affects the
desired image. One answer to this has been to provide a coupler that has a
water solubilizing group on the parent coupler to enable the dye formed
from the coupler to be washed-out of the photographic element upon
photographic processing. Such couplers are described, for example, in U.S.
Pat. No. 4,482,629.
A need has existed to provide a coupler, in a photographic material and
process that enables formation of an image having improved acutance while
enabling removal by wash-out of the dye formed from the coupler during
photographic processing. Moreover, such needs have existed with the added
parameter that such a compound must not require significantly modifying
the development inhibitor group in a way that would adversely effect the
ultimate end use of the groups.
The present inventions solve these problems by means of a photographic
element comprising a support bearing at least one photographic silver
halide emulsion layer and at least one coupler (A) having a water
solubilizing group wherein coupler (A) is capable of forming a compound
that is washed out of the photographic element during photographic
processing and has a coupling-off group represented by the general
formula:
--X--REL--T--INH
wherein;
X is selected from oxygen, nitrogen or sulfur;
X--Rel is a releasing group for releasing T--INH from X--Rel by either
intramolecular displacement reaction or electron transfer reaction during
photographic processing without substantial delay of releasing;
T is a timing group that releases INH by either elimination electron
transfer reaction or intramolecular displacement reaction with timing
delay during photographic processing; and
INH is a development inhibitor group.
The X--Rel--T--INH is released from the coupler moiety upon oxidative
coupling of the coupler. During photographic processing, the reaction of
coupler (A) with oxidized color developing agent cleaves the bond between
the coupling-off group and the coupler moiety. Then the bond between
X--Rel (RELEASING GROUP) and the T (TIMING GROUP) is cleaved without
substantial delay of release. The bond between the T and the INH is then
cleaved with timing delay. The cleavage of the bond between the INH and
the T can be enabled by for example, an elimination such as the one
described in U.S. Pat. Nos. 4,409,323 and 4,959,299, or for example, by an
intramolecular displacement reaction, such as one described in, U.S. Pat.
No. 4,248,962. Choosing substituent parts of the X--Rel and T to
requirements of the given INH allows control over the timing and rate of
release of the INH.
The inventions are described in classes in more specific details as
follows:
Class 1
In the first invention a photographic element, as noted, is provided
comprising a support bearing at least one photographic silver halide
emulsion layer and at least one coupler (A) having a water solubilizing
group wherein coupler (A) is capable of forming a compound that is washed
out of the photographic element during photographic processing. Coupler
(A) has a coupling-off group represented by the formula:
--X--REL.sup.1 --T.sup.1 --INH
wherein;
X is selected from oxygen, nitrogen or sulfur
X--Rel.sup.1 is a releasing group for releasing T.sup.1 --INH from
X--Rel.sup.1 by intramolecular displacement reaction during photographic
processing without substantial delay of releasing;
T.sup.1 is a timing group that releases INH by elimination electron
transfer reaction with timing delay during photographic processing; and
INH is a development inhibitor group.
The X--Rel.sup.1 as described is any X--Rel.sup.1 releasing group which
releases T.sup.1 --INH from X--Rel.sup.1 by an intramolecular displacement
reaction during photographic processing without substantial delay of
releasing. The X--Rel.sup.1 as described is not a timing group that
substantially delays release of T.sup.1 --INH. The X--Rel.sup.1 can serve
as a carrier for a photographic ballast group for the coupler prior to
exposure and photographic processing.
A typical X--Rel.sup.1 group is represented by the formula:
##STR1##
wherein;
R.sup.1 and R.sup.2 is selected from hydrogen, substituted or unsubstituted
alkyl, and substituted or unsubstituted aryl;
R.sup.3 is unsubstituted or substituted alkyl or substituted or
unsubstituted aryl;
R.sup.4 is hydrogen or a substituent which does not substantially delay
release of T.sup.1 --INH;
Z.sup.1 represents the atoms necessary to complete a 5 or 6 member aryl or
heterocyclic group; and
n is 0, 1 or 2.
A substituent which does not substantially delay release of T.sup.1 --INH
and the substituted or unsubstituted alkyl and substituted or
unsubstituted aryl, may be selected from nitro, hydrogen, amino,
substituted amino, carboxylic acid, sulfonic acid, methoxy, chloro, bromo,
ester groups such as --CO.sub.2 CH.sub.3, keto groups such as
--COCH.sub.3, or --NHCOCH.sub.3, --CONHCH.sub.3, --NHSO.sub.2 CH.sub.3, or
--SO.sub.2 NHCH.sub.3.
At least one of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 can be a photographic
ballast group.
The T.sup.1 as described is any timing group that releases INH by an
elimination electron transfer reaction that enables a time delay between
the oxidative coupling of the coupler (A) and the release of INH. The
T.sup.1 differs from the X--Rel.sup.1 in that T.sup.1 enables time delay
whereas X--Rel.sup.1 does not enable substantial time delay.
A typical T.sup.1 is represented by the formula:
##STR2##
wherein;
Z.sup.2 represents the atoms necessary to complete a 5 or 6 member arylene
or heterocyclic group;
R.sup.5 and R.sup.6 is selected from hydrogen, substituted or unsubstituted
alkyl or substituted or unsubstituted aryl;
R.sup.7 is hydrogen or a substituent which does not substantially delay
release of T.sup.1 --INH from X--Rel.sup.1.
A substituent which does not substantially delay release of T.sup.1 --INH,
the substituted or unsubstituted alkyl and substituted or unsubstituted
aryl, may be selected from nitro, hydrogen, amino, substituted amino,
carboxylic acid, sulfonic acid, methoxy, chloro, bromo, ester groups such
as --CO.sub.2 CH.sub.3, keto groups such as --COCH.sub.3, or
--NHCOCH.sub.3, --CONHCH.sub.3, --NHSO.sub.2 CH.sub.3, or --SO.sub.2
NHCH.sub.3.
The X--Rel.sup.1 is preferably a group as described in U.S. Pat. No.
4,248,962 that enables release of T.sup.1 --INH from X--Rel.sup.1 by means
of intramolecular displacement and T.sup.1 is preferably a group as
described in U.S. Pat. Nos. 4,409,323 and 4,959,299 that enables release
of INH from T.sup.1 by means of an electron transfer, preferably by an
ethylenic conjugated chain.
A typical coupler (A) of Class 1 of the Invention is a naphtholic coupler
represented by the formula:
##STR3##
wherein;
R.sup.9 is selected from a photographic ballast and a substituent which
does not substantially delay release of T.sup.1 --INH;
R.sup.10 is selected from substituted and unsubstituted alkyl containing 1
to 3 carbon atoms and a photographic ballast; and
R.sup.11 is nitro. Other groups which may be considered in place of nitro
are hydrogen, amino, carboxylic acid, sulfonic acid, methoxy, chloro,
bromo, ester groups such as --CO.sub.2 CH.sub.3, keto groups such as
--COCH.sub.3, or --NHCOCH.sub.3, --CONHCH.sub.3 --NHSO.sub.2 CH.sub.3,
--SO.sub.2 NHCH.sub.3, or R.sup.11, in combination with the timing group
T.sup.1, can constitute a substituted or unsubstituted pyridyl moiety.
R.sup.12 is hydrogen, CH.sub.3, methoxyphenyl, hydroxyethoxyphenyl,
carboxyphenyl, --CH.sub.2 CO.sub.2 CH.sub.3, --CH.sub.2 CH.sub.2 COOH or
--CH.sub.2 OCH.sub.2 CH.sub.2 COOH; and
INH is a heterocyclic development inhibitor group.
An especially preferred naphtholic coupler is represented by the structures
I-1 through I-12, of table 1.
Class 2
In the second invention a photographic element as noted, is provided
comprising a support bearing at least one photographic silver halide
emulsion layer and at least one coupler (A) having a water solubilizing
group wherein coupler (A) is capable of forming a compound that is washed
out of the photographic element during photographic processing. Coupler
(A) has a coupling-off group represented by the formula:
--X--REL.sup.2 --T.sup.2 --INH
wherein;
X is selected from oxygen, nitrogen or sulfur
X--Rel.sup.2 contains a photographic ballast and is a releasing group for
releasing T.sup.2 --INH from X--Rel.sup.2 by elimination electron transfer
reaction during photographic processing without substantial delay of
releasing;
T.sup.2 is a timing group that releases INH by elimination electron
transfer reaction with timing delay during photographic processing;
INH is a development inhibitor group;
The X--Rel.sup.2 as described is any X--Rel.sup.2 releasing group which
releases T.sup.2 --INH from X--Rel.sup.2 by an elimination electron
transfer reaction during photographic processing without substantial delay
of releasing. The X--Rel.sup.2 as described is not a timing group that
delays release of T.sup.2 --INH. The X--Rel.sup.2 can serve as a carrier
for a photographic ballast group for the coupler prior to exposure and
photographic processing.
A typical X--Rel.sup.2 group is represented by the formula:
##STR4##
wherein
R.sup.13 is hydrogen or a substituent which does not substantially delay
release of T.sup.2 --INH;
R.sup.14 and R.sup.15 is selected from hydrogen, substituted or
unsubstituted alkyl, and substituted or unsubstituted aryl;
Z.sup.1 represents the atoms necessary to complete a 5 or 6 member aryl or
heterocyclic group. At least one of R.sup.13, R.sup.14 and R.sup.15 can be
a photographic ballast group.
A substituent which does not substantially delay release of T.sup.2 --INH
and the substituted or unsubstituted alkyl and substituted or
unsubstituted aryl, may be selected from nitro, hydrogen, amino,
substituted amino, carboxylic acid, sulfonic acid, methoxy, chloro, bromo,
ester groups such as --CO.sub.2 CH.sub.3, keto groups such as
--COCH.sub.3, or --NHCOCH.sub.3, CONHCH.sub.3, --NHSO.sub.2 CH.sub.3, or
--SO.sub.2 NHCH.sub.3.
The T.sup.2 as described is any timing group that releases INH by an
elimination electron transfer reaction that enables a time delay between
the oxidative coupling of the coupler (A) and the release of INH. The
T.sup.2 differs from the X--Rel.sup.2 in that T.sup.2 enables time delay
whereas X--Rel.sup.2 does not enable substantial time delay.
A typical T.sup.2 is represented by the formula:
##STR5##
wherein;
R.sup.16 is hydrogen or a substituent which does not substantially delay
release of T.sup.2 --INH from X--Rel.sup.2 ; R.sup.16, R.sup.17, and
R.sup.18 are choosen to provide a minimum time delay of at least 5
seconds.
R.sup.17 and R.sup.18 are selected from hydrogen, substituted or
unsubstituted alkyl or substituted or unsubstituted aryl and are chosen
not to substantially delay release of T.sup.2 --INH from X--Re.sup.12 ;
Z.sup.2 represents the atoms necessary to complete a 5 or 6 member arylene
or heterocyclic group.
A substituent which does not substantially delay release of T.sup.2 --INH,
and the substituted or unsubstituted alkyl and substituted or
unsubstituted aryl, may be selected from nitro, hydrogen, amino,
substituted amino, carboxylic acid, sulfonic acid, methoxy, chloro, bromo,
ester groups such as --CO.sub.2 CH.sub.3, keto groups such as
--COCH.sub.3, or --NHCOCH.sub.3, --CONHCH.sub.3, --NHSO.sub.2 CH.sub.3, or
SO.sub.2 NHCH.sub.3.
The X--Rel.sup.2 and T.sup.2 are preferably groups as described in U.S.
Pat. Nos. 4,409,323 and 4,959,299 that enables release of T.sup.2 --INH
from X--Rel.sup.2 and INH from T.sup.2 --INH by means of an electron
transfer, preferably by an ethylenic conjugated chain.
A typical coupler (A) of Class 2 of the Invention is a naphtholic coupler
represented by the formula:
##STR6##
wherein,
R.sup.19 is hydrogen, CH.sub.3, methoxyphenyl, hydroxyethoxyphenyl,
carboxyphenyl, --CH.sub.2 CO.sub.2 CH.sub.3, --CH.sub.2 CH.sub.2 COOH or
--CH.sub.2 OCH.sub.2 CH.sub.2 COOH;
R.sup.20 is a photographic ballast or a substituent which does not
substantially delay release of T.sup.2 --INH from X--Rel.sup.2 ;
R.sup.21 and R.sup.22 are selected from hydrogen, substituted or
unsubstituted alkyl or substituted or unsubstituted aryl or a photographic
ballast and are chosen not to substantially delay release of T.sup.2 --INH
from X--Rel.sup.2 ;
R.sup.23 is nitro. Other groups which may be considered in place of nitro
are hydrogen, amino, carboxylic acid, sulfonic acid, methoxy, chloro,
bromo, ester groups such as --CO.sub.2 CH.sub.3, keto groups such as
--COCH.sub.3 or --NHCOCH.sub.3, --CONHCH.sub.3, --NHSO.sub.2 CH.sub.3,
--SO.sub.2 NHCH.sub.3, or R.sup.23, in combination with the timing group
T.sup.2, can constitute a substituted or unsubstituted pyridyl moiety.
R.sup.24 and R.sup.25 are selected from hydrogen, substituted or
unsubstituted alkyl or substituted or unsubstituted aryl and are chosen
not to substantially delay release of T.sup.2 --INH from X--Rel.sup.2 ;
INH is a heterocyclic development inhibitor group.
An especially preferred naphtholic coupler is represented by the structures
I-13 through I-16, of table 2. While the invention has been described with
respect to naphtholic couplers, it has application to other couplers such
as yellow, or magenta dye forming couplers.
Class 3
In the third invention a photographic element as noted, is provided
comprising a support bearing at least one photographic silver halide
emulsion layer and at least one coupler (A) having a water solubilizing
group wherein coupler (A) is capable of forming a compound that is washed
out of the photographic element during photographic processing. Coupler
(A) has a coupling-off group represented by the formula:
--X--REL.sup.3 --T.sup.3 --INH
wherein;
X is selected from oxygen, nitrogen or sulfur
X--Rel.sup.3 contains a photographic ballast and is a releasing group for
releasing T.sup.3 --INH from X--Rel.sup.3 by intramolecular displacement
reaction during photographic processing without substantial delay of
releasing;
T.sup.3 is a timing group that releases INH by intramolecular displacement
reaction with timing delay during photographic processing;
INH is a development inhibitor group;
The X--Rel.sup.3 as described is any X--Rel.sup.3 releasing group which
releases T.sup.3 --INH from X--Rel.sup.3 by an intramolecular displacement
reaction during photographic processing without substantial delay of
releasing. The X--Rel.sup.3 as described, is not a timing group that
substantially delays release of T.sup.3 --INH. The X--Rel.sup.3 can serve
as a carrier for a photographic ballast group for the coupler prior to
exposure and photographic processing.
A typical X--Rel.sup.3 group is represented by the formula:
##STR7##
wherein;
Z.sup.1 represents the atoms necessary to complete a 5 or 6 member aryl or
heterocyclic group;
R.sup.26 is hydrogen or a substituent which does not substantially delay
release of T.sup.3 --INH;
R.sup.27 and R.sup.28 is selected from hydrogen, substituted or
unsubstituted alkyl, and substituted or unsubstituted aryl;
R.sup.29 is unsubstituted or substituted alkyl or substituted or
unsubstituted aryl;
R.sup.26, R.sup.27, R.sup.28 and R.sup.29 are chosen not to substantially
delay release of T.sup.3 --INH from X--Rel.sup.3 ;
At least one of R.sup.26, R.sup.27, R.sup.28 and R.sup.29 can be a
photographic ballast group;
n is 0, 1 or 2.
A substituent which does not substantially delay release of T.sup.3 --INH,
and the substituted or unsubstituted alkyl and substituted or
unsubstituted aryl, may be selected from nitro, hydrogen, amino,
substituted amino, carboxylic acid, sulfonic acid, methoxy, chloro, bromo,
ester groups such as --CO.sub.2 CH.sub.3, keto groups such as
--COCH.sub.3, or --NHCOCH.sub.3, --CONHCH.sub.3, --NHSO.sub.2 CH.sub.3, or
SO.sub.2 NHCH.sub.3.
The T.sup.3 as described is any timing group that releases INH by an
intramolecular displacement reaction that enables a time delay between the
oxidative coupling of the coupler (A) and the release of INH. The T.sup.3
differs from the X--Rel.sup.3 in that T.sup.3 enables time delay whereas
X--Rel.sup.3 does not enable substantial time delay.
A typical T.sup.3 is represented by the formula:
##STR8##
wherein;
R.sup.30 is hydrogen or a substituent which does not substantially delay
release of T.sup.3 --INH from X--Rel.sup.3, R.sup.30, R.sup.31, R.sup.32
and R.sup.33 are choosen to provide a minimum time delay of at least 5
seconds.
R.sup.31 and R.sup.32 is selected from hydrogen, substituted or
unsubstituted alkyl or substituted or unsubstituted aryl;
R.sup.33 is unsubstituted or substituted alkyl or substituted or
unsubstituted aryl;
R.sup.30, R.sup.31, R.sup.32 and R.sup.33 are chosen not to substantially
delay release of T.sup.3 --INH from X--Rel.sup.3 ;
Z.sup.2 represents the atoms necessary to complete a 5 or 6 member arylene
or heterocyclic group.
n is 0, 1 or 2.
A substituent which does not substantially delay release of T.sup.3 --INH,
and the substituted or unsubstituted alkyl and substituted or
unsubstituted aryl, may be selected from nitro, hydrogen, amino,
substituted amino, carboxylic acid, sulfonic acid, methoxy, chloro, bromo,
ester groups such as --CO.sub.2 CH.sub.3, keto groups such as
--COCH.sub.3, or --NHCOCH.sub.3, --CONHCH.sub.3, --NHSO.sub.2 CH.sub.3, or
--SO.sub.2 NHCH.sub.3.
The X--Rel.sup.3 and T.sup.3 are preferably groups as described in U.S.
Pat. No. 4,248,962 that enables release of T.sup.3 --INH from X--Rel.sup.3
and INH from T.sup.3 --INH by means of an intramolecular displacement.
A typical coupler (A) of Class 3 of the Invention is a naphtholic coupler
represented by the formula:
##STR9##
wherein;
R.sup.34 is hydrogen, CH.sup.3, methoxyphenyl, hydroxyethoxyphenyl,
carboxyphenyl, --CH.sub.2 CO.sub.2 CH.sub.3, --CH.sub.2 CH.sub.2 COOH or
--CH.sub.2 OCH.sub.2 CH.sub.2 COOH;
R.sup.35 is a photographic ballast, hydrogen, or a substituent which does
not substantially delay release of T.sup.3 --INH from X--Rel.sup.3 ;
R.sup.36 and R.sup.37 is selected from hydrogen, substituted and
unsubstituted alkyl containing 1 to 3 carbon atoms, or substituted or
unsubstituted aryl, and a photographic ballast;
R.sup.38 is selected from substituted and unsubstituted alkyl containing 1
to 3 carbon atoms, or substituted or unsubstituted aryl, and a
photographic ballast;
R.sup.39 is nitro. Other groups which may be considered in place of nitro
are hydrogen, amino, carboxylic acid, sulfonic acid, methoxy, chloro,
bromo, ester groups such as --CO.sub.2 CH.sub.3, keto groups such as
--COCH.sub.3, or NHCOCH.sub.3, CONHCH.sub.3, NHSO.sub.2 CH.sub.3, SO.sub.2
NHCH.sub.3, or R.sup.39, in combination with the timing group T.sup.3, can
constitute a substituted or unsubstituted pyridyl moiety;
R.sup.40 and R.sup.41 is selected from hydrogen, substituted and
unsubstituted alkyl containing 1 to 3 carbon atoms, or substituted or
unsubstituted aryl;
R.sup.42 is selected from substituted and unsubstituted alkyl containing 1
to 3 carbon atoms, or substituted or unsubstituted aryl;
n and m are individually 0, 1 or 2.
A substituent which does not substantially delay release of T.sup.3 --INH,
and the substituted or unsubstituted alkyl and substituted or
unsubstituted aryl, may be selected from nitro, hydrogen, amino,
substituted amino, carboxylic acid, sulfonic acid, methoxy, chloro, bromo,
ester groups such as --CO.sub.2 CH.sub.3, keto groups such as
--COCH.sub.3, or --NHCOCH.sub.3, --CONHCH.sub.3, --NHSO.sub.2 CH.sub.3, or
--SO.sub.2 NHCH.sup.3.
INH is a heterocyclic development inhibitor group.
An especially preferred naphtholic coupler is represented by the structures
I-17 through I-21, of table 3. While the invention has been described with
respect to naphtholic couplers, it has application to other couplers such
as yellow, or magenta dye forming couplers.
Class 4
In the fourth invention a photographic element as noted, is provided
comprising a support bearing at least one photographic silver halide
emulsion layer and at least one coupler (A) having a water solubilizing
group wherein coupler (A) is capable of forming a compound that is washed
out of the photographic element during photographic processing. Coupler
(A) has a coupling-off group represented by the formula:
--X--REL.sup.4 --T.sup.4 --INH
wherein;
X is selected from oxygen, nitrogen or sulfur
X--Rel.sup.4 is a releasing group for releasing T.sup.4 --INH from
X--Rel.sup.4 by elimination electron transfer reaction during photographic
processing without substantial delay of releasing;
T.sup.4 is a timing group that releases INH by intramolecular displacement
reaction with timing delay during photographic processing;
INH is a development inhibitor group.
The X--Rel.sup.4 as described is any X--Rel.sup.4 easing group which
releases T.sup.4 --INH from X--Rel.sup.4 by an elimination electron
transfer reaction during photographic processing without substantial delay
of releasing. The X--Rel.sup.4 as described is not serve as a carrier for
a photographic ballast group for the coupler prior to exposure and
photographic processing.
A typical X--Rel.sup.4 group is represented by the formula:
##STR10##
wherein;
R.sup.43 is hydrogen or a substituent which does not substantially delay
release of T.sup.4 --INH;
R.sup.44 and R.sup.45 is selected from hydrogen, substituted or
unsubstituted alkyl, and substituted or unsubstituted aryl and are
selected not to substantially delay release of T.sup.4 --INH;
R.sup.43, R.sup.44 and R.sup.45 can be a photographic ballast and are
selected not to substantially delay release of T.sup.4 --INH; and
Z.sup.1 represents the atoms necessary to complete a 5 or 6 member aryl or
heterocyclic group;
A substituent which does not substantially delay release of T.sup.4 --INH,
and the substituted or unsubstituted alkyl and substituted or
unsubstituted aryl, may be selected from nitro, hydrogen, amino,
substituted amino, carboxylic acid, sulfonic acid, methoxy, chloro, bromo,
ester groups such as --CO.sub.2 CH.sub.3, keto groups such as
--COCH.sub.3, or --NHCOCH.sub.3, --CONHCH.sub.3, --NHSO.sub.2 CH.sub.3, or
--SO.sub.2 NHCH.sub.3.
The T.sup.4 as described is any timing group that releases INH by an
intramolecular displacement reaction that enables a time delay between the
oxidative coupling of the coupler (A) and the release of INH. The T.sup.4
differs from the X--Rel.sup.4 in that T.sup.4 enables time delay whereas
X--Rel.sup.4 does not enable substantial time delay.
A typical T.sup.4 is represented by the formula:
##STR11##
wherein
Z.sup.2 represents the atoms necessary to complete a 5 or 6 member arylene
or heterocyclic group;
R.sup.46 is hydrogen or a substituent which does not substantially delay
release of T.sup.4 --INH from X--Rel.sup.4 ;
R.sup.47 and R.sup.48 are selected from hydrogen, substituted or
unsubstituted alkyl or substituted or unsubstituted aryl;
R.sup.49 is unsubstituted or substituted alkyl or substituted or
unsubstituted aryl;
R.sup.46, R.sup.47, R.sup.48 and R.sup.49 are choosen to provide a minimum
time delay of at least 5 seconds; and
A substituent which does not substantially delay release of T.sup.4 --INH,
and the substituted or unsubstituted alkyl and substituted or
unsubstituted aryl, may be selected from nitro, hydrogen, amino,
substituted amino, carboxylic acid, sulfonic acid, methoxy, chloro, bromo,
ester groups such as --CO.sub.2 CH.sub.3, keto groups such as
--COCH.sub.3, or --NHCOCH.sub.3, --CONHCH.sub.3 --NHSO.sub.2 CH.sub.3, or
--SO.sub.2 NHCH.sub.3.
The X--Rel.sup.4 is preferably a group as described in U.S. Pat. Nos.
4,409,323 and 4,959,299, that enables release of T.sup.4 --INH from
X--Rel.sup.4 by means of electron transfer and T.sup.4 is preferably a
group as described in U.S. Pat. No. 4,248,962 that enables release of INH
from T.sup.4 by means of intramolecular displacement.
A typical coupler (A) of Class 4 of the Invention is a naphtholic coupler
represented by the formula
##STR12##
wherein;
R.sup.50 is hydrogen, CH.sub.3, methoxyphenyl, hydroxyethoxyphenyl,
carboxyphenyl, CH.sub.2 CO.sub.2 CH.sub.3, --CH.sub.2 CH.sub.2 COOH or
--CH.sub.2 OCH.sub.2 CH.sub.2 COOH;
R.sup.51 is hydrogen, or a substituent which does not substantially delay
release of T.sup.4 --INH from X--Rel.sup.4 ;
R.sup.52 and R.sup.53 is selected from hydrogen, substituted and
unsubstituted alkyl, or substituted or unsubstituted aryl;
R.sup.54 is nitro. Other groups which may be considered in place of nitro
are hydrogen, amino, carboxylic acid, sulfonic acid, methoxy, chloro,
bromo, ester groups such as --CO.sub.2 CH.sub.3, keto groups such as
--COCH.sub.3, or --NHCOCH.sub.3, --CONHCH.sub.3, --NHSO.sub.2 CH.sub.3,
--SO.sub.2 NHCH.sub.3, or R.sub.54, in combination with the timing group
T.sup.4, can constitute a substituted or unsubstituted pyridyl moiety;
R.sup.55 and R.sup.56 is selected from hydrogen, substituted and
unsubstituted alkyl, or substituted or unsubstituted aryl;
R.sup.57 is selected from substituted and unsubstituted alkyl containing 1
to 3 carbon atoms or substituted or unsubstituted aryl;
R.sup.51, R.sup.52 or R.sup.53 contains a photographic ballast;
R.sup.51, R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.56 and R.sup.57 are
selected as not to substantially delay release of T.sup.4 --INH from
X--Rel.sup.4 ;
n and m are individually 0, 1, or 2; and
INH is a heterocyclic development inhibitor group.
An especially preferred naphtholic coupler is represented by the structures
I-22 through I-25, of table 4. While the invention has been described with
respect to naphtholic couplers, it has application to other couplers such
as yellow, or magenta dye forming couplers.
Delay of release as measured by half-life can extend to, but not beyond the
normal period of time required for developing the photographic element.
That is, in the present invention at least half of the INH that is coupled
off must be released at the end of the developing period. Delay of release
of INH is usually not less than about 5 seconds, preferably is in the
range of 5 to 600 seconds and typically in the range of 10 to 100 seconds.
This can be determined in most cases in an aqueous solution at pH 10 or pH
14.
In the present invention, release of the timing group in the development of
a photographic element is without substantial delay. Release of the timing
group (as measured by half-life), can occur in not normally greater than 5
seconds, preferably less than 2 to 3 seconds, and typically less than 1
second half-life. As noted, the half-life can be determined in most cases
in an aqueous solution at pH 10 or pH 14.
By "aqueous solution at pH 10" is meant an aqueous solution containing 3%
Triton X-100, (a non-ionic surfactant, available from the Aldrich Chemical
Co., Milwaukee, Wis.), at 23.degree. C. and pH adjusted to 10 using
phosphate buffer.
By aqueous solution at pH 14" is meant an solution containing 45%
acetonitrile and 55% aqueous 0.1N potassium hydroxide at 23.degree. C.
A coupler moiety to which the coupling-off group is attached is preferably
a cyan, magenta or yellow dye-forming coupler moiety. Acetanilide and
naphthol couplers are highly preferred.
As used herein the term "coupler" refers to the entire compound, including
the coupler moiety (COUP), and the coupling-off group including the INH.
The term "coupler moiety" refers to that portion of the compound other
than the coupling-off group.
A process of forming an image having the described advantages comprises
developing an exposed photographic element by means of a color developing
agent in the presence of described coupler (A).
The water solubilizing group (SOL) can be any water solubilizing group
known in the photographic art to enable wash-out of the dye formed in
photographic processing from the coupler (A). Typical water-solubilizing
groups include groups terminated with an acid group, such as carboxy,
sulfo or hydroxy which may also form a salt and other groups described in
U.S. Pat. No. 4,482,629 (col. 4, lines 1-3). The coupler (A) can have one
or more water-solubilizing groups. The number and type of water
solubilizing groups should not be sufficient to make the coupler (A)
mobile in the photographic element prior to exposure and processing.
A typical water-solubilizing group (SOL) is a carbonamido group
--CONHR.sub.a wherein R.sub.a is hydrogen, an alkyl group containing 1 to
3 carbon atoms, preferably --CONHCH.sub.3 or --CONHC.sub.2 H.sub.5 ; or a
group containing a water solubilizing group, such as carboxy, sulfo or
hydroxy groups, for instance, --CONH.sub.2 CH.sub.2 CH.sub.2 OH,
--CONH.sub.2 CH.sub.2 CO.sub.2 H, or --CONH.sub.2 CH.sub.2 CH.sub.2
CO.sub.2 H. Such a group can be, for example, in the 2-position of a
naphtholic coupler containing the coupling-off group in the coupling
position.
INH can be any releasable development inhibitor group. Typical INH groups
are described in, for example U.S. Pat. Nos. 4,477,563; 4,782,012;
4,886,736; 4,912,024; 4,959,299; and 5,026,628; the disclosures of which
are incorporated herein by reference. Preferred development inhibitor
groups are heterocyclic inhibitor groups which for example, include
mercaptotetrazoles, mercaptoxadiazoles, mercaptothiadiazoles and
benzotriazoles. Structures A-1 through A-8 as follows, represent typical
releasable development inhibitor groups.
##STR13##
wherein:
R.sub.b , R.sub.e, R.sub.h, and R.sub.i are individually hydrogen,
substituted or unsubstituted alkyl of 1 to 8 carbon atoms such as methyl,
ethyl, propyl, butyl, 1-ethylpentyl, 2-ethoxyethyl, substituted phenyl,
unsubstituted phenyl; substituted or unsubstituted phenyl of 6 to 10
carbon atoms; alkylthio, such as methyl, ethyl, propyl, butyl or
octylthio; or alkyl esters such as --CO.sub.2 CH.sub.3, --CO.sub.2 C.sub.2
H.sub.5, --CO.sub.2 C.sub.3 H.sub.7, --CO.sub.2 C.sub.4 H.sub.9,
--CH.sub.2 CO.sub.2 CH.sub.3, --CH.sub.2 CO.sub.2 C.sub.2 H.sub.5,
--CH.sub.2 CO.sub.2 C.sub.3 H.sub.7, --CH.sub.2 CO.sub.2 C.sub.4 H.sub.9,
--CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3, CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2
H.sub.5, --CH.sub.2 CH.sub.2 CO.sub.2 C.sub.3 H.sub.7, and --CH.sub.2
CH.sub.2 CO.sub.2 C.sub.4 H.sub.9 ; or aryl esters such as --CO.sub.2 Rj,
--CH.sub.2 CO.sub.2 Rj, --CH.sub.2 CH.sub.2 CO.sub.2 Rj, wherein Rj is
substituted or unsubstituted aryl; wherein:
R.sub.c, R.sub.d, R.sub.f, and R.sub.g are as described for R.sub.b,
R.sub.e, R.sub.h, and R.sub.i ; or, are individually one or more halogen
such as chloro, fluoro, or bromo; carboxyl, esters or other substituents
such as --NHCOCH.sub.3, --SO.sub.2 OCH.sub.3, --OCH.sub.2 CH.sub.2
SO.sub.2 CH.sub.3, --OCOCH.sub.2 CH.sub.3, --NHCOCH.sub.3 or nitro groups.
As used herein the term photographic ballast group (BALL) is a ballast
group that is known in the photographic art. The ballast group as
described is an organic group of such size and configuration as to confer
on the molecule sufficient bulk to render the molecule substantially
non-diffusible from the layer in which it is coated in a photographic
element. Representative ballast groups include substituted or
unsubstituted alkyl or aryl groups typically containing 8 to 40 carbon
atoms. The ballast group as described, is located on X--Rel.sup.1 and can
be either R.sup.9 or R.sup.10.
A process of forming an image having the described advantages comprises
developing an exposed photographic element by means of a color developing
agent in the presence of described coupler (A), as described.
A preferred coupler (A) is an acetanilide or naphtholic coupler.
The coupler moiety (COUP) can be any moiety having a water solubilizing
group, provided that the coupler moiety will react with oxidized color
developing agent to cleave the bond between the X--Rel (RELEASING GROUP)
portion of the coupling-off group and the coupler moiety. The coupler
moiety herein includes coupler moieties employed in conventional
color-forming couplers that yield colorless products on reaction with
oxidized color developing agents as well as coupler moieties that yield
colored products on reaction with oxidized color developing agents. Both
types of coupler moieties are known to those skilled in the photographic
art.
The coupler moiety can be ballasted or unballasted provided that the dye
formed upon oxidative coupling is capable of being washed out of the
photographic element. It can be monomeric, or it can be part of a dimeric,
oligomeric or polymeric coupler, in which case more that one group
containing PUG can be contained in the coupler, or it can form part of a
bis compound in which the INH forms part of a link between two coupler
moieties.
The INH can be any of the mentioned heterocyclic inhibitor groups that is
typically made available in a photographic element in an imagewise
fashion. Combinations of couplers, such as combinations of couplers (A),
are also useful. Combinations of at least one coupler (A) with ot | | |
