Note: Descriptions are shown in the official language in which they were submitted.
--1--
PHQTOG~ Ic MAT~RIAL A~ PROCESS
COMPRISING WAS~-OU~ NAP~THOLIC COUPLER
Thi3 invention relate~ to a new photographic
naphtholic coupler capable upon oxidative coupling of
5 forming a dye that is capable of being washed out of
the photographic material containing the coupler upon
proce~sing and to photographic materials and
proces~es compri3ing the naphtholic coupler.
Various coupler3 are known in photographic
10 material3 and proce~e~. One of the clas~es o~
photographic coupler~ includes naphtholic coupler3
that typically form cyan dyes upon oxidative co~pling
in photographic materials and processe3. The~e
naphtholic couplerq typically for~ cyan dyes upon
15 oxidative coupling with color developing agents.
Such naphtholic couplers are also known which are
capable of forming dye3 upon o~idative coupling that
can be wa~hed out of ~he photographic ma~erial upon
proce~sing. The~e naphtholic couplers are described
20 in, for example, U.S. Patent 4,482,629.
The naphtholic couplers that are capa~le of
forming dye3 that can be wa~hed out of the
photographic material upon photographic processing
contain a water ~olubilizing group, ~uch a~ a carboxy
25 group or ~ulfonic acid group, ~ub~tituted on a group
in the 2- po~ition of the naphtholic coupler. It has
been desirable to provide a naphtholic coupler that
i~ not a~ e~pensive ~o manufacture a~ the de~cribed
naphtholic couplers and Qtill provides a useful dye
30 that can be washed out of the photographic material
with the added advantage that the coupler enable~ a
lower concentration o~ coupler to be used in a
photographic element without 3igni~icantly changing
imaging results.
It has al~o been de3irable to provide ~uch a
naphtholic coupler that contain~ a coupling-o~f group
that enable~ desired acutanee and desired interimage
effect3 in a color photographic ~ilver halide
material and proce~s ~t lower concentrations of
coupler.
The present invention ~olve~ the~e problem~
by providing a photographic element comprising a
support bearing at lea~t one photographic ~ilver
halide emulsion layer and an immobile naphtholic
coupler capable upon oxidative coupling of forming a
dye that i`Q capable of being wa~hed out of the
photcgraphic element upon photographic proce~3ing,
wherein the immobile naphtholic coupler compri~e~ a
balla~t free naphtholic coupler moiety compri3ing a
-CONH2 group in the 2- po~ltion and a balla3ted
coupling-off group in the 4- position The balla3ted
coupling-off group preferably compri~es a relea~able
photographically u3eful group ~PUG).
The immobile naphtholic coupler is typically
represented by the formula:
~
(~l)Z~ -CN~2
wherein Z i~ a ballasted coupling-of~ group, Rl i~
a balla~t-fzee sub~tituent that does not ad~ersely
affect thc desired properties of the coupler and dye,
and z i8 0, 1, ~ or 3. Rl doe~ not compri~e a
balla~t group becau~e such a group adversely a~fect~
wa~h-out properties of the d~e formed from the
naphtholic coupler.
The balla~ted coupling-off group (Z) enables
the naphtholic coupler to be immobile in the
photographic element prior to expo3ure and
procea~ing. Upo~ exposure and proce~ing of the
described element the naphtholic coupler react~ with
J ~
oxidized color developing agent to form a dyc that i~
washed out of the element during proce~ing. Al~o,
the coupling~off group i~ released during
proce3~ing. The portion of the coupling-off group
containing the ballast group remain~ in the location
in which it wa~ coated. The coupling-off group
preferably comprises a releasable photographically
useful group (PUG) which is released upon
photographic processing. The PUG either i~
immobilized to remain in the location of the element
in which it wa~ coated or the PUG is mobile to allow
it, after release, to move to a location in the
element at which it can serve its in~ended function.
A preferred naphtholic coupler as de~cribed
comprises a coupling-off group represented by the
formula:
--(LIN}~)n (TIME)m--PUG
wherein
TI~E i3 a relea~able timing group capa~le of
being relea~ed ~rom the LIN~ moiety during
photographic proces3ing:
LINK i~ a relea~able li~king group capable of
being relea~ed from the naphtholic coupler moiety
upon oxidative coupling of the naphtholic coupler;
n and m individually are 0, 1 or 2;
PUG is a relea~able photographically u~eful
group, preferably a releagable developme~t inhibitor
group; and, preferably,
at lea~t one o~ n and m is 1 or ~.
A proces~ of forming an image having the
de3cribed advantage3 compri~e~ developing an exposed
photographic element as described by means of a color
dev~lsping agent in the pre~ence of the de cribed
naphtholic coupler and washing-out the dye formed
from the naphtholic coupler.
,
,
~ J IJ
A~y naphtholie coupler moiety i~ u~eful that
can contain the -CONH~ group in the 2- position and
a balla~ted coupling-o~f group in the 4- po3ition and
can form a compound, especially a dye, that can be
wa~hed out of the element upon oxidative coupling of
the coupler. It will be appreciated that depending
upon the particular developing agent and the
particular type of proce~sing, the reaction product
of the coupler moiety and the oxidized developing
agent can be colored or colorlesY. Examples of
useful naphtholic coupler moietie~ can be
unsubstituted except for the required ~ub~tituent~ in
the 2- and 4- po~itions a~ de~cribed. Optionally the
naphtholic coupler moietie~ in addition to the
sub~tituent3 in the 2- and 4- po~ition~ can contain
other substituent~ that do not adverQely affect the
de~ired properties of the element and coupler.
~xample~ of ~uch ~ubstituent~ include 5~N~S02CE3,
5-NHCOCH3 or 6-NHS02CH3. ~geful naphtholic
coupler moietie~ include those de~cribed in, for
example, the following patents in which the group
described in the 2- po~ition iq replaced with
-CONH2, e~pecially thoge having a ballasted
coupling-off group: U.S. Patents 4,840,884;
4,861,701; 2,474,293; 3,227,554; 4,482,629 and
4,857,447.
Any coupling o~f group containing a ballast
group known in ~he photographic art i9 u~eful in the
4- position of the de~cribed naphtholic coupler
30 moiety. Example~ o~ useful coupling-off group3 are
de3cribed in, for example, U.S. Patent 4,861,701.
Preferred coupling-of~ groups are tho~e that enable
relea~e of a PU~ upon photographic proceq~ing,
e~pecially tho~e that have a relea~able ti~ing group
be~ween the bond to the coupling position of the
coupler and the releasable PUG. Preferred timing
group3 are described in, for example, U.S. Patents
~ ~ i s ~
4,861,701; 4,248,962; 4,409,323; 4,482,629 and
4,857,447.
A preferred naphtholic coupler i3
repre~ented by formula:
0
(Rl)z~\O/ I-C~2
lû O
1 ' .
X ~ ALL ~2
Q or p-~f-(T2) -PU~)
R3
wherein
X repre~ent~ the atom~ completing a 5-, 6- or
7-member ring, such a3 an aryl or heterocyclic group;
Rl i~ a ballast-free substltuent;
Z i8 Q, 1, 2 o~ 3;
BALL i~ a ballas~ group known in the photographic
~ art;
: T2 i~ a releasable timing group;
R2 and R3 individually are hydroge~,
25 un~ub~tituted or ~ubqtituted alkyl or aryl, such a~
alkyl con'aining 1 to 40 carbon atoms or aryl
containing 6 to 40 carbon atom~, 3uch as a phenyl or
naphthyl group; and,
q i8 0, 1 or 2.
T2 i~, ~or example, a group that enables
release of PUG by means of intramolecular
nucleophilic di3placement, ~uch as described in
U.S. 4,248,962 and U.S. 4,861,701.
.-
--6--
In the ca~e o~ such coupler3 that relea~e a
PUG by means of a timing group, reaction of th~
coupler with oxidized color developing agent cleave3
the bond between the coupler and the coupling-off
group. Then the bond between the PUG and the
remainder of the coupling-off group i~ cleaved. Bond
cleavage between the PUG and the remainder of the
coupling-off group preferably doe~ not involve the
action of oxidized color developing agent. The
cleavage of the bond between the PUG and the
remainder of the coùpling-of group can involve any
reaction known in the photographic art ~or cleavage
of such groups, for example an intramolecular
nucleophilic displacement reaction or other
elimination reaction.
Any balla~t group known in the photographic
art can be u~e~ul on the coupling-off group. The
ballast group (~ALL) herein mean3 an organic group o~
~uch size and configuration as to confer on the
coupler molecule sufficient bulk to render the
coupler sub3tantially non-diffu~ible ~rom the layer
in which it is coated in a photographic element prior
to exposure and proces~ing. Representa~ive ballast
groups include ~ubstituted or un~ub tituted alkyl or
25 aryl group~ con~aining, for egample, 8 to 40 carbon
atoms. Other use~ul balla~t group~ include
sulfonamido group3 containing 8 to 40 carbon atoms,
carbonamido, carbamoyl, sul~amoyl, e~ter, sulfone,
ether, thioether and amino groups.
A typical timing group T~ i9 a group that
enable~ release o~ a PUG by means o~ intramolecular
nucleophilic displacement, such a~ de3cribed in U.S.
Patents 4,861~701; 4,857,440; 4,847,185 and 4,248,962.
fJ ~ ~ J ~
Illustrative timing group~ T2 are as
follow~:
1 l4 l6 0 Rll
O -- C -- C -- CH2--NCOPUG ~ ~ ,N 1I PVG
1 11 --I\N~ I N_C--PUG
COPUG R15 R16
1 l6a 1 R~7/R18
O - C - N - N-COPUG R2 ~ 1 / C
o R7 ¦ Rlg O
O -- C --\C/ ,N\ ,, ~0
ll \N-COPUG ~ I
¦ . C 22
~\
R24 COPUG
and other illu3trative group~ described in U.S.
Patent 4,857,447.
In the above ~tructure~, R4, R5, R6, R6a, R7, R8
Rg, Rlot Rll~ R12, R13, ~14~ Rls' ~16' R17' 18' 19
R20, R21, R22, R23 and R24 individually are hydrogen
or ~ubstituent~ that do not adver~ely a~fect ~he
desired properties of the naphtholic coupler or dye
~;~J . ~ /-3 J ,f s
formed, ~uch a un3ub~tituted or qub~tituted alkyl,
for example, methyl, ethyl, propyl, n-butyl, t-butyl
and eicosyl, or un~ubqtituted or ~ub~tituted aryl,
such a3 phenyl, or ~ub~tituted phenyl, and PUG i3 a
releasable photographically useful group. At lea~t
one of the de3cribed group~ on the coupling-off group
i9 a balla~t group.
A~ used herein the term "naphtholic coupler"
refers to the entire compound including the coupler
10 moiety and the coupling~off group. The term
~naphtholic coupler moiety" herein refer~ to that
portion of the coupler other than the coupling-off
group.
The PUG can be any group that i~ typically
15 made available in a photographic element in an
imagewi~e fa~hion. The PUG can be a photographic
reagent or a photographic dye. A photographic
reagent herein i~ a moiety that upon relea3e further
react~ with component~ in the phstographic element,
such a~ a development inhibi~or, a development
accelerator, a bleach inhibitor, a bleach
accelerator, a coupler (for example, a competing
coupler, a dye-forming coupler, or a development
inhibitor releasing coupler (DIR coupler)), a dye
precur~or, a dye, a developing age~t (for egample, a
competing developing agent, a dye-forming developing
agent, or a ~ilver halide de~eloping agent), a ~ilver
complexing agent, a fixing agent, an image toner, a
stabilizer, a hardener, a tanning agent, a fogging
30 agcnt, an ultraviolet radiation ab~orber, an
antifoggant, a nucleator, a chemical or spectral
~en~itizer or a de~ensitizer.
The PUG can be pre~ent in the coupling-off
group as ~ preformsd pecie~ or it can be pre~ent in
a blocked ~orm or a~ a precur~or. The PUG can be for
example a preformed development inhibitor or the
development inhibiting function can be blocked by
~; ~ ,?~J ~
- 9 -
being the point of attachment to the carbonyl group
bonded to PUG in the coupling-off group. Other
examples are a preformed dye, a dye that i~ blocked
to Qhift it3 absorption, and a leuco dye.
A preferred naphtholic coupler a~ described
i~ a photographic coupler containing a naphtholic
coupler moiety and a PU~ containing a hetero atom
from VIb or Vb of the Periodic Table having a
negative valence of 2 or 3 bonded to a carbonyl group
10 of the coupling-of~ group.
Any coupler~ known to be u~eful in the
photographic art can be used with the de~cribed
naphtholic coupler~ and in various location~ known in
the art in a photographic element. There follow~ a
15 li~ting of patents and publicationq that describe
representative couplerQ that can be useful in
combination with the described naphtholic coupler~:
I. COUP~s
A. Couplers which form cyan dyes upon
reaction with oxidized color developing agent~ are
described in 3uch representative patent~ and
publication~ a~: U.S. Pat. Nos. 2,772,162;
2,895,826; 3,002,836; 3,034,892; 2,474,293;
2,423,730; 2,367,531; 3,041,236; 4,333,999 and
"Farbkuppler-eine LiteraturUbersicht,~ published in
Agfa Mitteilungen, Band III, pp. 156-175 ~1961).
Pre~erably ~uch couplers are phenols and
naphthols that form cyan dyeæ on reaction with
o~idized color developing agentQ.
B. Couplers which form magenta dyes upon
reaction with o~idized color developing agent are
described in such repre~entative patents and
publications aQ u. 5 . Pat. No~. 2,600,788;
2,369,48g; 2,343,703; 2,311,082; 3,152,896;
3,519,429; 3,062~653; 2,998,573 and "Farbkuppler-eine
Literatur~bersicht," publi~hed in Agfa
Mi~teilungen,Band III, pp. 126-156 (1961).
"
t ~ ~ ~ L
--10--
Preferably ~uch couplerQ are pyrazolones and
pyrazolotriazole~ that form magenta dyes upon
reaction with oxidized color developing agent3.
C. Couplers which form yellow dyes upon
reaction with oxidized and color developing agent are
described in ~uch representative patent3 and publica-
tiOnQ as: U.S. Pat. Nos. 2,875,057; 2,407,210;
3,265,506; 2,298,443; 3,048,194; 3,447>928 and
~Farbkuppler eine Literatur~ber3icht," publi~hed in
10 Agfa Mitteilungen, Band III, pp. 112-126 (1961).
Preferably such couplers are acylacetamides,
such a~ benzoylacetanilide3 and pivaloylacetanilide~
that form yellow dye3 upon reaction with oxidized
color developing agent~. -
D. Coupler~ which form colorle~Q product~
upon reaction with oxidized color developing agent
are de~cribed in ~uch repre~entative patent~ as:
U.K. Patent No. 861,138; U.S. Pat. No3. 3,632,345;
3,928,041; 3,95a,993 and 3,961,959. Preferably ~uch
couplers are cyclic carbonyl containing compound~
which form colorles~ product~ on reaction with
oxidized color developing agent.
Any relea~able PUG known in the photographic
art i~ useful in the coupling-o~f group a~
described. Example~ of u~eful PUG' 3 are as follo~:
PUG'~
A. PUG'~ whic~ ~orm development inhibitor~
upon relea~e are described in such repre~entative
patents as U. 5 . Pat. Nos. 3,227,554; 3,3~4,657;
3,615,506; 3,617,291; 3,733,201; 4,861,701 and U.K.
Pat . No . 1, 450, 47g . Preferred development inhibitors
are iodide and heterocyclic compound~ such a~
mercap~otetrazoles, 3elenotetrazole3,
msrcap~obenzothiazoles, ~elenobenzothiazole~,
35 mercaptobenzoxazoles, selenobenzoxazoles,
mercaptobenzimidazoles, selenobenzimidazoles,
~ ~?~ ~J ~,
oxadiazole~, benzotriazole~ and benzodiazole3.
Structures of preferred development inhibitor
moietie~ are:
N-N
-S ~ 1l IIIA-l
lo - S .~ O ~I IIIA-2
/o\ /.~
s ~ I IIIA-3
S, ,0~ ~I IIIA-4
R26
R27 IIIA-5
N
- ~ ~ IIIA-6
/ ~
0.~ + ~-
R28
0 29 IIIA-7
where R2g i~ unsub~tituted or subst;tuted alkyl,
~uch as butyl, l-ethylpentyl, and 2-ethoxyethyl, or
alkylthio, ~uch a~ butylthio and octylthio;
~ ~'J~ J
-12-
R25 and R26 individually are hydrogen, alkyl of 1 to
8 carbon atomQ such a~ methyl, ethyl, or butyl,
phenyl or sub3tituted phenyl; and R27 and R28
individually are hydrogen or one or more halogen such
a~ chloro, fluoro or bromo; alkyl of 1 to 4 carbon
atom~, carboxyl, esters, such as -COOC~3, or other
~ubstituent~ such a~ -NHCOOCH3~ S020CH3,
-OC~2CH2S02CH3~ -OCoc~2cE3~ -N~CCOCH3 or nitro group~-
O 00
B. PUG~s which are, or form, dye~ upon
relea~e:
Suitable dye~ and dye precur~or3 include
azo, azomethine, azopyrazolone, indoaniline, indo-
phenol, anthraquinone, triarylmethane, alizarin,nitro, quinoline, indigoi~ and phthalocyanine dyes or
precur~or~ of ~uch dyeg such a~ leuco dyes, tetra-
zolium alts or shifted dye~. These dye~ can be
metal complexed or metal complexable. Representatlve
patent3 de~cribing ~uch dyes are U.S. Pat. No~.
3,880,658; 3,931,144; 3,932,380; 3,932,381 and
3,942,987. Preferred dye~ and dye precur~or~ are
azo, azomethine and indoaniline dye3 and dye
precur~or~. Structure~ of ~ome preferred dye~ and
dye precur~or~ are:
S02C~3
-O o~ N=N-.~ ~^-N02 IIIB-l
~ ~'-NHl2
I~ ,LSO2N~2
3~
JS
--13
1 02CH3
--0~ --N=N~ N02 IIIB-- 2
._ 0=.
.~ ~--NHS02 1C5~ -t
~./ S92NE3(C~2)40--o~ ,~--C5Hll--t
~---
Cl NHC0-~ ~- OC E -n
--O--~ --N=~ --0 C2cH2c6}~5 IIIB--3
15 Cl N~ECO(C~2~4-I ~
OCO2CH2C6~I5
l_ .
0 \ z /---N--N--R31 IIIB--4
R30 ~1
25 -1~
S2 1 (C~2)2 1 S2C16~33
3 CH3
-Cl ~ s02N~
Cl4~2s~a
S~2N~IC6~l3-n
--Cl--~ ~---S02NH--~ ~
~ 0--. .=~
- S02~C6~13-~
~.~ s 3 J , j ~ ~
C. PUG~s which are coupler~:
Coupler~ relea3ed can be nondiffusible
color-forming couplers, non-color forming couplers or
diffusible competing couplers. Repre~entative
patent~ and publications describing competing
couplers are: "On the Chemistry of White Couplers,"
by ~. Puschel, Agfa-Gevaert AG Mitteilungen and der
Forschungs-Laboratorium der Agfa-Gevaert AG, Springer
Verlag, 1954, pp. 352-367; U.S. Pat. No3. 2,998,314;
2,808,329; 2,68g,793; 2,742,832; German Pat. No.
1,168,769 and British Pat. No. 907,274. Structures
of pre~erred competing coupler~ are:
-0--~ ~ R33 IIIC-l
~,_~
R32HN R34
20 where R32 is hydrogen or alkylcarbonyl, such a~
ac~tyl, and R33 and R34 are individually hydrogen
or a ~olubilizing group, such as sul~o, aminosul-
fonyl, and carboxy
l36 ~o\
IIIC-2
~./
where R35, which i~ the same a~ R34 a~ defined
above, and R36 i8 halogen, aryloxy, aryl~hio, or a
development inhibitor, such as a mercaptotetraæole,
such as phenylmercaptotetrazole or ethylmercapto-
tetrazole.
D. PUG's which ~orm developing agents:
Developing agent~ relea~ed can be color
developing agent8, black-and-white developing agents
~g
-15-
or cross-oxidi2ing developing agents. They include
aminophenols, phenylene diamine3, hydroquinone~ and
pyrazolidone~. Representative patents are: U.S.
Pat. Nos. 2,193,015; 2,108,243; 2,592,364; 3,656,950;
3,658,52~; 2,751,297; 2,289,367; 2,772,282;
2,743,279; 2,753,256 and 2,304,953.
Structures of preferred developing agents are:
R38
~ _ ~ 37 IIID-l
where R37 is hydrogen or alkyl of 1 to 4 carbon
atom~ and R38 i8 hydrogen or one or more halogen
such as chloro or bromo; or al~yl of 1 to 4 carbon
atom~ such a~ methyl, ethyl or butyl groups.
-0--~ + ~--OH IIID-2
R38
where R38 i3 as defined above.
Z5 R40
O C~2 t ~ IIID~3
N
~1~
~ ~ R39
~.
R40
41 t~ IIID-4
~ N
~l~
I~
39
~' 3)~ .A,
-16-
43 IIID-5
s
HO-~ \ O IIID-6
lo t
C~IC~120H
OH
where R39 i3 hydrogen or alkyl of 1 to 4 carbon
atoms and R40, R41~ R42, R43 an 44
individually hydrogen, alkyl of 1 to 4 carbon atom3
such a~ methyl or ethyl; hydroxyalkyl of 1 to 4
carbon atoms ~uch a~ hydroxymethyl or hydroxyethyl or
sulfoalkyl containing 1 to 4 carbon atom~.
E. PUG's which are bleach inhibitor~:
Repre~entative patent~ are U.S. Pat. No~.
3,705,801; 3,715,208; and German OLS No. 2,405,279.
Structure~ of preferred bleach inhibitor3 are:
S- \ ll IIIE-l
N-N
NHC-~45
.
3~
N-N O
-S~ IIIE-2
S-C-N~C-R45
:
~17--
S O~ O ~e R45IIIE--3
~N---
--S--~ IIIE--4
where R45 i~ an alkyl group of 6 to 20 carbon atom~.
F. PUG'~ which are bleach accelerator~:
-S ~s/~-R46 IIIF-l
-S~ -R46 IIIF-2
R47
--StC~I2~ ~R4gIIIF--3
49
~N--N
--S~ I I IF--4
\N--N
--SC~2C~21:~00~F--5
~:
wherein R46 i8 hydrogen, alkyl9 such a~ ethyl and
butyl, alkoxy, such as etho2y and butoxy, or
alkylthio, such as ethylthio and butylthio, for
exampl~ containing 1 to 6 carbon atom~, and which may
be unsub~tituted or sub~tituted; R47 is hydrogen,
-18-
alkyl or aryl, such as phenyl; R4~ and R49 are
individually alkyl, such a~ alkyl containing 1 to 6
carbon atoms, for example ethyl and butyl; z i~ 1 to
6.
The image dye-forming couplers can be
incorporated in photographic element3 and/or in
photographic processing solution~, ~uch a~ developer
~olution3, so that upon development of an exposed
photographic element they will be in reactive
association with oxidized color developing agent.
Coupler compounds incorporated in photographic
proce3~ing ~olution~ ~hould be of such molecular ~ize
and configuration that they will diffuse through
photographic layer~ with the processing Qolution.
15 When incorporated in a photographic element, aq a
general rule, the coupler compound3 should be
nondiffu~ible, that i~ they should be of Quch
molecular size and configuration that they will not
significantly dif~use or wander from the layer in
20 w~ich they are coated.
Photographic element~ of thi3 invention can
be proce~ed by conventional technique~ in w~ich
color ~ormin~ coupler3 and color developing agents
are incorporated in ~eparate proce~sing solution~ or
compo~itions or in the element.
Photographic elements in which the compounds
of thi~ invention are incorporated can be a ~imple
element comprising a ~upport and a ~ingle silver
halide emul~ion layer or they can be multilayer,
30 multicolor element3. The compound3 of thi3 invention
can be incorporated in at least one of the ~ilver
halide emulsion layers and/or in at least one other
layer, such a~ an adjacent layer, where they will
come into reactive as~ociation with oxidized color
developing agent which ha3 developed silver halide in
the emulsion layer. The silver halide emul~ion layer
can contain or have as30ciated with it, other
r
--19--
photographic coupler compound3, ~uch a3 dye-~orming
couplers, colored masking couplers, and/or competing
coupler3. These other photographic coupler~ can form
dyes of the same or different color and hue as the
photographic couplers of thi3 invention. Addition-
ally, the 3ilver halide emulsion layer3 and other
layer3 of the photographic element can contain
addenda conventionally contained in such layers.
A typical multilayer, multicolor
photographic element can compri e a upport having
thereon a red-~ensitive silver halide emulqion unit
having associated therewith a cyan dye image-
providing material, a gree~-sengitive ~ilver halide
emulsion unit having a~ociated therewith a magenta
dye image-proYiding material and a blue-3ensitive
silver halide emulsion unit having a~qociated
therewith a yellow dye image-providing material 9 at
least one of the silver halide emulsion unit3 having
aæsociated therewith a photographic coupler o~ the
invention. Each 3ilver halide emul~ion unit can be
composed o~ one or more layer~ and the variou~ unit~
and layers can be arranged in different locations
wi~h re~pect ~o one another.
The couplers o~ thi~ invention can be
incorporated in or a~ociated with one or more layer~
or unit~ of the photographic element. For e~ample, a
layer or unit af~eeted by PUG can be controlled by
incorporating in appropriate locations in the element
a scavenger layer which will confine the action of
PUG to the desired layer or unit. At lea~t one of
the layer3 o~ the photographic elemen~ can be, for
example, a mordant layer or a barrier layer.
The light ~ensitive silver halide emul~ion3
can include coar~e, regular or ~ine grain silver
halide cry~tals or mixturea thereof and can be
comprised of such ilver halide~ a3 silver chloride,
3ilver bromide, ~ilver bromoiodide, 3ilver
-2~-
chlorobromide, silver chloroiodide, ~ilver
chlorobromoiodide and mixture3 thereof. The
emul3ionq can be negative-working or direct-positive
emulsions. They can form latent image~ predominantly
on the surface of the silver halide grain3 or
predominantly on the interior of the 3ilver halide
grains. They can be chemically and spectrally
sensitized. The emulsion~ typically will be gelatin
emulsions although other hydrophilic colloid~ are
10 u~eful. Tabular grain light sensitive 3ilver halide~
are particularly useful such ax de~cri~ed in Re~earch
Di3clo~ure, January 1983, Item No. 22534 and U.S.
Patent 4,434,226.
The ~upport can be any support used with
15 photographic element~. Typical support~ include
cellulo~e nitrate film, cellulose acetate film,
polyvinylacetal film, polyethylene ~erephthalate
film, polycarbonate film and related film~ or
re3inous materials a~ well as gla~, paper, metal and
20 ~he like. Typically, a flexible support is employed,
such a~ a polymeric film or paper ~upport. Paper
support3 can be acetylated or coated with baryta
and/or an a-olefin polymer, particularly a polymer
of an a-olefin eontaining 2 to 10 carbon atoms such
25 a~ polyethylene, polypropylene, e~hylene-butene
copolymer3 and the like.
It is preferred that the coupling-off group
contain a releasable PUG. Depending upon the nature
of the particular PUG, the couplers can be
30 incorporated in a photographic elemen~ for different
purpo~e3 and in differe~t locations.
In the following discu~sion of 3uitable
materials ~or use in the emulsions and elements of
~hi~ in~vention, reference will be made to Res~arch
35 ~ lo~ure. December 1978, Item 17643, published by
Industrial Opportunities Ltd., ~omewell Havant,
~amp~hir2, P09 lEF, U.K., the disclo3ure3 of which
,~' ?
-21-
are incorporated herein by reference. Thi3
publication will be identified hereafter by the ~erm
~Re~earch DiQclosure".
The photographic elementg can be coated on a
variety of ~upports a~ de~cribed in Re~earch
Disclosure Section XVII and the references de~cribed
therein.
Photographic element~ can be exposed to
actinic radiation, typically in the vi~ible region of
the ~pectrum, to form a latent image ag described in
Research Di~clo~ure Section XVIII and then proces~ed
to form a vi~ible dye image a deQcr;bed in Re~earch
Disclo~ure Section XIX. Proces~ing to form a visible
dye image include~ the step of contacting the element
15 with a color developing agent to reduce developable
silver halide and oxidize the color developing
agent. Oxidized color developing agent in turn
react~ with the coupler to yield a dye.
Preferred color developing agent~ uYeful in
20 the invention are p-phenylene diamineq. E~pecially
preferred are 4-amino-N,N~diethylaniline hydro-
chloride; 4-amino-3-methyl-N,N-diethylaniline
hydrochloride; 4-amino-3-methyl-N-ethyl-N-~-
(methane3ulfonamido)ethylaniline sulfate hydrate;
4-amino-3-methyl-N-ethyl-N-~-hydroxyethylaniline
sulfate; 4-a~i~o~3-~-(methanesulfonamido)-
ethyl-N,N-diethylaniline hydrochloride; and
4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine
di-p-toluene~ulfonic acid.
With negative working 3ilver halide. th~
processing step de~cribed above give~ a negative
image. To obtain a positive (or reversal) image,
thia step can be preceded by development wit~ a
non-chromogenic developing agent to develop expo ed
silver halide, but not form a dye, and then uniformly
fogging the element to render unexposed silver halide
developable. Alternatively, a direct po~itive
emul~ion can be employed to obtain a po~itive image.
Development i9 followed by the conventional
step~ of bleaching, fixing, or bleach-fixing, to
remove ~ilver and ~ilver halide, washing and drying.
~Japhtholic coupler3 as de~cribed can be
prepared by reaction~ and methods known in the
organic compound synthe~i~ art. Similar reaction~
and methods are de~cribed in U.S. Patent 4,482,629.
Typically, the naphtholic coupler i~ prepared by the
following method:
10 Synthe~i~ A:
~ OH
~ t-CO2Ph N~40~ I ~ç~ coN~
15 o~ O~
(Al) (A2)
o
2~ o/ ~
ClC02C2H5 ~ O KOd
pyridine I~ /0\ ~t Cl
o~ N2
(A3) t~
CEO
O O
O/~ 0/ ~
30 ~ NaB~4 ~ aqu. KOH
t~ I ---- -~
o o
~ O ~\t~
CHO CH20
(A4) (A5)
.
, ~
23--
OH ~ ~
~ ~~I Ra/Ni I 11 ~-CONH2 3 2
o~ No 0~ ssI
CH2H CH20H
(A6 ) (A7 )
~ OH
~0~~1~ (ClCH2C0320
~CN~2 ~ \R/ ~7-CO~
pyridine ~ 2
O O
0 I ~ES2Cl6H33 n ~ ~t~NHS2C16H33-n
C~2H C~I20CI:)C~2C
(A8) (A9)
0~
PhN~2 ,KI ~. 1 COCl
~ ' I O ~I-CN~ 2
DME, 60 C
t
O I-N~so2cl6H33-n
C~120COCH2NHph
(A10 )
--24--
0~ 0
CONH2 PUG~ -co
o o
I-NHS2C16H33_n O I~NHS2C16H33_n
c~2occH2N~P CH20COC~I2
(All ) (A12 )
OH
15(A8) 3 ~e\ ~1~
O ~t N~S02C16H33 n
t
C~2B r
(A13 )
2~ 0
PUG t~\~ CON~
~ ' `t~
~, ¦ NHS~Cl 6H3 3--
t
CR2PUG
: 35 (A14)
Ph herein means phenyl.
-25~ J ~ 3
Svnthesis Example A: -
Co~2ound (A2):
Phenyl-1,4-dihydroxy-2-naphthoate (100.0 g,
356.78 mmol) wa~ dis~olved in deoxygenated
tetrahydrofuran (500 mL) and deoxygenated methanol
(500 mL) added. To thi~ solution, stirred at room
temperature under the nitrogen atmo~phere, wa~ added
ammonium acetate (50.0 g, 648.63 mmol) followed by
concen~rated ammonium hydrogide ~1.0 L). After
~tirring for 3 hours the reaction was then poured
into ice cold 2N-HCl (4.0 L) and enough concentrated
~Cl added to bring the pH to 1. The resulting
product, compound (A2~ wa3 filtered off, wa~hed well
with water and air dried. The crude product was
wa3hed with dichloromethane and air dried. Yield
62.0 g ~72%).
Com~ound (A3):
Compound (A2) (50.0 g, 0.246 mol) wa3
di~solved in dry pyridine (150 mL) and acetonitrile
(75 mL) added. The solution wa~ ~tirred and cooled
to -5 to 0C. ~thyl chloroformate (50 mL, 0.523 mol)
was then added dropwise with stirring while main-
taining the temperature at 0C. After the addition,
ths cooling bath was removed and the te~perature
allowed to reach roo~ temperature. The reaction
mixture wa~ then gradually heated to reflux and the
solvent allowed to diQtill off. Thi~ procedure was
continued until the temperature had ri~en to
approximately 120C and 150 mL of 301vent ~ad been
30 collec~ed. ~eating under reflux wa~ continued for an
additional 1 hour period. The reaction mixture waq
then cosled to approximately 50C and poured into
2r1-HCl, (3.0 L) held at room temperature. This
~uspen3ion wa then stirred for approximately 15
35 minute~, filtered and the residue wa~hed well with
water> acetonitrile and finally ether. Thi~ gave the
product, compound (A3) 3uf~iciently pure for the next
step. Yield 43.5 g (77%).
Compound (A4):
Compound (A3) (23.0 g, 100.35 mmol) wa~
taken up in deoxygenated dimethylqulphoxide (250 mL)
and deoxygenated water (25 mL) added. To this
S solution, ~tirred at room temperature under nitrogen,
was added 8570-potas~ium hydroxide (9.9 g, 150.53
mmol) and stirring continued until di~solution,
approximately 15 minute~. 4-Chloro-3-nitrobenzal-
dehyde (18.62 mmol) was then added all at once and
10 the regulting solution stirred at 60C for 1 hour.
The reaction mixturè wa~ ~hen poured into ice cold
2N-HCl (2.0 L) and flltered off. The product,
compound (A4), wa~ wa~hed ~ith water and, while ~
wet, Qlurried in methanol, filtered and washed with
ether. Thi~ product wa~ pure enough to be u~ed in
the next ætep. Yield 28.0 g (74
Com~ound (A5~:
Compound (A4) (28.0 g, 74.01 mmol), in a
powdered form, was ~uspended in tetra~ydrofuran (150
20 mL) and methanol ~100 mL). Water (100 mL) wa~ added
followed by ~odium borohydride (2.8 g, 74.01 mmol) in
small portions. More tetrahydrofuran (50 mL) was
added to aid stirring. At the end of the sodium
borohydride addition complete disQolution had been
25 achieved. The reaction wa~ allowed to proceed for a
further 15 minutes, then poured into ice cold 2N-HCl
(2.0 L) and the product ~iltered o~f. The product-
compound (A5) wa~ wa~hed with methanol and while
Qtill wet wi~h 801vent, u~pended in ethanol and
30 heated to reflux. The ~olution wa~ cooled, filtered,
washed with methanol, ether and finally air dried. A
~eçond crop of material wa~ obtained on concentrating
the mother liquor. Total yield 19.5 g (67%).
Compound (A5) ~19.0 g, 50 mmol) was
guspended in water (200 mL) containing 857~-potas~ium
hydro~ide (~6.34 g, 400 mmol~. To this mixture was
'9 ~ ~ 9 ''5 ~j
-27-
added methanol (50 mL) and then heated to 800C for 1
hour. The re~ulting dark yellow-brown ~olution was
cooled and poured into ice cold 2N-HCl (2.0 L). The
yellow product wae filtered off, wa~hed well with
water and air dried. Yield 17.7 g (100%).
Compound (A7~:
Compound (A6) (17.7 g, 70 mmol) was
dissolved in tetrahydrofuran (80 mL) and methanol
(300 mL) added. Raney-Nickel which had been wa3hed
several times with water and then methanol ~as added
and the solution hydrogenated at 55pYi for 2 ~our3
after which hydrogen up-take had cea~ed. Ths
cataly~t wa~ filtered off, washed with methanol and
the filtrate concentrated under reduced pres~ure to
15 give the product, compound (A7). This product wa~ -
deemed sufficiently pure to be carried on to the next
~tep. Yield 100%.
Compound (48):
Compound (A7) (50.0 mmol) was di~301ved in
dry pyridine (150 mL) and hexadecyl~ulfonyl chloride
(16.2 g, 50.0 mmol) added. The ~olution wa~ ~tirred
at room temperature under a-nitrogen atmosphere for
30 minutes. The pyridine ~as concentrated under
reduced pre~ ure and the re~idue taken up in ethyl
acetate. This ethyl acetate solution ~a~ then wa~hed
with 2N-~Cl (X3), dried (MgS04), filtered and
concentrated. The solvent wag r~moved under reduced
pres~ure and the re~idual oil crys~allized from
acetonitrile. After filtering, wa~hing with
acetonitrile and drying, thc yield of produc~
compound (A8) amounted to 16.3 g (53% calculated from
compound (A5)).
Compound (A92:
Compound (A8) ~16.3 g, 26.6 mmol) wa~
dissolved in tet~ahydro~uran (150 mL) to which was
added pyridine (3.~ mL, 39.90 mmol) followed by
chloroacetic anhydride (6.82 g, 3~.89 mmol) in
~i~ f ,~ ' ~ 5, ~ ~
-28-
tetrahydrofuran (30 mL) at a reasonably rapid rat2.
After 3tirring at room temperature for 30 minute~ the
solvent wa~ removed under reduced pres~ure and the
re~idue diY~olved in ethyl acetate. The ethyl
acetate ~olution wa3 then washed with 2N-HCl ~X2),
dried ~MgS04) and concentrated under reduced
pressure. The re3idue cry~tallized from acetonitrile
to give compound (A9) 12.2 g (66%).
CompQund (A10):
Compound (A9) (12.2 g~ 17.7 mmol) wa3
dissolved in dimethylformamide (150 mL) To which waQ
added potas ium iodide (4.4 g, 25.55 mmol) and
aniline ~8.2 mL, 88.5 mmol) and the reaction mixture
heated to 60C for 1.5 hour~. The reaction was
poured into 2N-~Cl and extracted with ethyl acetate
(X2). The combined ethyl acetate extracts were
wa~hed with 2N-~Cl (X3), dried (MgS04), ~iltered
and then concen~rated. This re~idue was used a~ ~uch
in the next step of the reaction sequence but it
could be cryQtallized from acetonitrile. Yield
assumed to be 100%.
Compoun~
Compound (A10~ (83.0 g, 111.26 mmol~ was
di~olved i~ tetrahydrofuran (800 mL) and the
~olution stirred at room temperature.
N,N-4-diethylanili~e (17.7 mL, 111.26 mmol) was adde
followed by a ~olution of 12% pho~gene in toluene
(275 mL, 33~.78 mmol). The reaction mixture wa3
~tirred at room temperature for 15 minute~,
concentrated under reduced preQ~ure and the residue
u~ed as ~uch in the next ~tep. The yield of the
product, compound (All~, wa~ assumed to be lOOZ.
Com~Q~ ~ (A12):
Compound ~All) as de~cribed above (111.26
35 mmol) was dis~olved in dry pyridine ~800 mL) and PMT
(19.83 g, 111.26 mmol) added to the reaction
301ution. The mixture wa~ ~tirred at room
temperature ~or 1 hour. It was then concentrated
under reduced pre3sure and the re~idue taken up in
? ~5 J ~
-2g-
ethyl acetate. The ethyl acetate wa3 washed with
2N-HCl (X3), dried (MgS043, filtered and
concentrated to an oil. The oil wa~ taken up in a
mixture of ethyl acetate, dichloromethane, heptane
5 and acetonitrile in the ratio o~ 20:20:56.4,
re~pectively and subjected to fla~h chromatography
eluting with the same solvent sy~tem to elute
impuritie~ from the column and then changed to a
ratio of 27:50:20.4 to elute the product, compound
(A12). The product could be recry3tallized from
acetonitrile. Yield 61.0 g (58%).
Calculated for C50~59N78S2
%C=63.20, %H=6.26, %N=10.32, %S=6.75
Found: %C=63.14, %H=6.2g~ %N=10.23, %S=6.62
CompQun~_~A13):
Compound (A8) (4.0 g, 6.53 mmol) wa~
su~pended in dry ether (30 mL) and phosphorou~
tribromide (0.68 mL, 7.18 mmol) in ether (20 mL)
20 added dropwise over a 15 minute period. After the
addition the reaction wa3 diluted with ether and the
ether solution washed wlth 2N-HCl (Xl)~ dried
~MgS04), filtered and concentrated to give compound
(A13). The yield was 100%.
25 Com~Qund (A14):
Compound (A13) (6.53 mmol) wa~ dis~olved in
dimethylformamide (40 mL) to which wa~ added PMT
(1.51 g, 7.54 mmol) and the re~ulting 301ution
tirred at room temperature for 1 hour. The compound
30 (A14) was i~olated by pouring the reaction mixture
into 2N HCl and extracted with ethyl acetate (X2).
The combined ethyl acetate extracts wer~ then wa~hed
with 2N HCl (X3), dried (MgS04), filtered and
concentrated. The residue wa~ taken up in a mixture
35 of ethyl acetat~ heptane and dichloromethane in the
ratio of 15:30:5, respectively and subjected to flash
chromatography eluting with the ~ame solvent
ç~., 2.3
-30-
mixture. The fir t major band wa~ collected to give
the product. Yield 4.0 g (79%).
Calculated for C41H52N605S2:
70C=63~70~ %H=6.78, %N=10.87, %S=8.30
5 Found: %C=63. 40~ ~/oH=6. 80, %N=10. 76~ %S=8.14
O Cl
0/ NH / ~ - NO
10 ~ o/~ o + ~ KO~
CO DMSO, 60
OH / ~
O~ ~I
15(A3) t
C15~31 n
~B15)
0 9
0/ ~ 0
1,~ ,0~ ~ ,0~ ~I
0 0
O~ ~I--NO `t~
c=o c~o~
~`til 1
C15~31 ~ ~15~31
35 (B16~ (B17~
.
-31-
OH OH
5 I~,O~~~t 2 ~ t-CO~2
o l I-N ~ -No
10 C~OE . CHBr
,1~ ' ,1
0~ ~I 0~ ~I
15C15~31-~ C15~31-~
(B18) (B19)
OEr
PMT
~ CON~
D I-N2
~
C~PMT
,1~
C15~31-~
(B20~
PMT herein mean~ phenylmereaptote~razole.
~ nt~e~ m~
compGund (~163:
Compound (A3) (3.4 g, 14.83 mmol) waa
di~solved in deoxygenated dimethyl~ulpho~ida (100 mL)
;~ ~ s~ ~ ~} ~
-32-
and stirred at room temperature under a nitrogen
atmo3phere. To thi~ ~olution wa~ added 857O-pota~sium
hydroxide ~1.71 g, 25.95 mmol) followed by
deoxygenated water (10 mL). The reaction mixture wa~
stirred at room temperature for 15 minute~ and then
the benzophenone (B15) (7.0 g, 14.83 mmol) was added
as a ~olid in a qingle batch. The dark colored
solution wa~ then heated to 60OC and qtirring
continued for 2.5 hour3. While still at 60C the
10 warm ~olution wa3 poured into ice cold 2N-HCl
(600 mL). The yellow product waA filtered off,
washed with water, methanol and air dried. Yield of
compound (B16) 8.8 g (89%).
Com~Q~nd (Bl7~:
Compound (B16) (8.8 g, 13.24 mmol) wa~
dis~olved in ~etrahydrofuran (40 mL) to which waa
added methanol (20 mL) and water (20 mL). Sodium
borohydride (0.5 g, 13.24 mmol) waY added to the
su3pen~ion portionwise with stirring. At the end of
20 the additio~ dis~olution wa3 complete and the
~olution stirred continually for a further 15
minutes. The reaction solution wa~ then poured into
ice cold 2N-HC1 ~600 mL) and the product compound
(B17) filtered of~, washed with water, methanol and
25 air dried. Yield 7.9 g (89%~.
5Om~ound (~18~:
Compound (B17) (10.0 g, 15.0 mmol) wa~
suspended in water (70 mL) and 85Z-potas~ium
hydroxide ~7.90 g, 120.0 mmol) added together with
30 methanol (20 mL). This mixture wa~ ~tirred at 80OC
for 1 hour, cooled and poured into ice cold 2N-HCl
and the mixture extracted with ethyl acetate (X2).
The combined ethyl acetate e~tracts were then dried,
(MgS04), filtered and concentrated. Ths re~idue
35 compound (B18) was u~ed as such in the next step o~
the reaction ~equence. Yield (100%~.
Compound (B19):
Compound (B18) (15 mmol) wa3 dissolved in
ether (70 mL) and phosphorous tribromide (1.6 mL,
16.5 ~mol) in ether (15 mL) added dropwi3e over a
period of 15 minutes. At the end of the addition the
reaction ~olution waa ~tirred at room temperature for
a further 15 minutes. The solution was then diluted
with ether, wa~hed with 2N-~Cl (X3), dried (MgSO4),
filtered and concentrated under reduced pre~sure.
10 Thi~ gave compound (B19), ~ufficiently pure to be
used in the next ~tep. Yield 100%.
CompQ~nd (B20):
Compound (B19) (15.Q mmol) was dis~olved in
dimethylformamide (50 mL) and treated with ~odium PMT
(3.55 g, 17.73 mmol) while stirring at room
temperature for a l hour period. The reaction
~olution wa~ then diluted with ethyl acetate and
wa~hed with 2N-~Cl (X4). The organic layer wa~ then
dried (MgS04), filtered and concentrated under
reduced pre~ure. The oil was dis~olved in 25% ethyl
acetate in heptane and subjec~ed to fla~h
chromatography eluting ~ith the same solvent
mixture. The fir~t major band wa~ colleoted to give
the product compound (B20). Yield 5.0 g [42% from
compound (B17)].
Calculated for C46~52N60sS:
%C-68.98, %H-6.54, %N=10.49, %S=4.00
Found: %C=69 ~ 07 ~ %~-6 ~ 44 t %N=10.31, %S=4.1Z
Coupler3 that can be prepared by these
method3 of ~ynthesis include, for example:
~ COM~2
S, 3 ,~
--34--
Compound
Numb e ~_ Z
1.
NHS02C16~33-~
~ O C6H
C~2--O_e_C~2 N--CO--S--C~ 11
N--N
û~ ~t
15 2.
I-N~so2cl6H33-n
N--N
C1~2--S--C~ 11
2 3
25 3.
O ~I
CH2--N--C ~ S--C,N ¦¦
t
N~SO2Cl6~33-n
~.~ 'J ~,~ 1J ,, .
--35--
Compound
Number z2
4.
1 C12H25--n
~t~I 11 o~\t/~ _,
N02 C~3
5.
H33C16 ~ CH2S~
c2~s
6. ll6H33 n
f t ~N--N
C--C~CH2--N~ S~C~N 11
0 C~3 .
0~ ~I
7 . l 16H33
l O~I
t ,o~
C --CH2--N--C--S--il il C4~9 t
0 0 N -- N
~J ~
--36--
Compound
Number z2
8 . Cl 1 6H3 3 a
0~ ~I
t s~N--N
C --C~I2--N--C--S~ C ¦¦
tH2
O~ ~I
t
OCH3
9.
o--CH2CH2--S--ICH--Cl2H25 n
coo~
i
20 10.
C3H7--1
--CH2--N--C--O
NO 2I~
t t
N=N N~S2C16H33 ~
3Q T
N02
11.
C3H7--i
NE~C16H33 ~ C4H9--
.
~J ~ -~J ) J ~ ,s_
--37--
Compound
Numb e r z2
12.
C3 7 i W N
CH
C16H3~--n ,1.
0~ ~I
OCH3
13.
S
N~ ~N--Cl 6H3 3--
N = N
14.
Cll I ,N--W
NHCO I HO~ C5
C2HS C5
30 15. O ~O_~
=-
C 6~5
3~ N~S
--38--
Compound
Numbe r z2
16 .
lC6H5
N--N
--CX2--N--CO--S--/ 11
T o I
o No2 `t~
N~502C16X33 n
~ C~:z--W-CO-S~ 4 9
NHCOC~I3 `t~
52NHC12~25 n
18. OCH3
0/ ~I
~I ,7~
T ~ ~ o
N2 \ ~
N~52C1 6H3 3--~L
--39-- -
Compound
Numbe r z2
19.
~ I co s C~N N
T CH2
S2NHcl2~2s~a
~T~I
oc~3
15 2Q.
12~25-~
~ ~T N ICl-s-(c~2)
N02
21.
Z5
iT~ ¦¦ o~ ~ CR3
N02
22.
0~ ~I co S ( C~2 ) 2C2H
T
S2C16~33 ~
~d ~ s ~
- 4
Compound 2
Numb e r Z
23.
o/ ~ ICO--I H--0--~ --C5Hll ~;-
2 5 CS}Ill-t
CH~
¦ N~C6H5
~CO-S-o~ 11
N N
C~2~ --OC~13
15 24.
o
~ 2512E25--n
O I Cl
- t ,1
1 ~ I
~5C6--Cl~--OCOCH2--N/~.~ N--N
CO~S~
N--N
C6~5
25. 1 1C8H17--~
O--C--N--N-- C--S--,
C8~17-~L C
26.
S02C16~}33-a 0 1 6~5
~ I 2 S~ND
~J 'i~ ;~J ~
--41-- -
Compound
Num~ z2
27.
C3H7--1 1 6 5
1 6H3 3 n l H2
lo O\ ~I
oc~3
15 28.
~0~ \CH2--IN_C_S ( C~2 ) 2C2
C12E25 n
2 9 .
~ 0 3~ ~I
~-~ ~Cl~ N C ¢N--
~1 6H3 3--n
I (C~ ) _¢C12~25 n
, , ,
,
~ J -~ J ~
-42-
The following examples further illu3t~ate
the invention.
Exam~le 1 -- 3:
Photographic element~ were prepared by coating the
following layers on a cellulose e~ter film ~upport
(amounts of each component are indicated in mg/m2):
Emulsion layer l: Gelatin -2420; red ~ensitized
silver bromoiodide (as Ag~ - 1615;
yellow image coupler dispersed in
dibutyl p~thalate (REGEIVER LAYER)
Interlayer: Gelatin - 860;
didodecylhydroquinone - 113
Emulsion layer 2: Gelatin - 2690; green sen~itized
silver bromoiodide (a~ Ag) - 1615;
magenta image coupler di~per~ed in
tritolyl pho~phate; DIR compound
of Table 1 dispersed in
N,N-diethyl-dodecanamide and
coated at a level sufficient to
provide a contrast of 0.5 (half)
of the original contrast after
stepwise green light expo~ure and
proces Q ing.(CAUSER LA~ER)
Protective Gelatin - 5380;
30 Overcoat bi~vinyl~ulfonylmethyl ether at 2%
total gelatin.
Structures of th~ image coupler~ are as follows:
5,~ ~ V '~' ~
-43-
Magenta Image Çoupler:
S ~ Os~Y\ /~
t COCEtO-~ so2-~ -o~
Clo~I21 n
10 Y~llow Image CQ~P1er: -
0 o Cl
~CH3)3cCc~eNH~
/l~ NXS2C16~33-n
0~ ~I
S02-~ OCH2-~ ~O
S~rip~ of each element were e~posed to green
light through a graduated density step table~ 7 or
through a 35% modulation fringe chart for sharpne~
mea~urements, and then developed 3.25 minute~ at 38~C
in the following color developer, ~topped, wa~hed,
bleached, fixed, washed and dried.
Colo~ Devel.~p~:
Di~tilled water 800 mL
3~ Sodium Metabi3ulite 2.78 g
Sodium Sulfite, anhydrou~. 0.38 g
CD-4 4.52 g
Pota~ium Carbonate, anhyd. 34.3 g
Potas~ium Bicarbonate 2.32 g
Sodium Bromide 1.31 g
Pota3~ium Iodide 1.20 mg
Hydroxylamine Sul~ate (HAS) 2.41 g
-4~-
Diethylenetriaminepentacetic 8.43 g
acid, penta~odium alt (4079
Soln.)
Di3tilled water to 1 L
Adjust p~ to 10Ø
CD-4 i9 4-amino-3-methyl-N-ethyl-N-beta-hydroxy-
ethylaniline sulfate.
Proce~sed image~ were read with green light
to determine the contrast and AMT acuta~ce. From
plot~ of AMT acutance v~. the logarithm of the
contra^~t for variation~ in the coated level of each
development inhibitor releasing (DIR) compound, the
acutance was determined at a contra~t or 0.5 compared
to its original contra~t without the pre~ence of the
lS DIR compound. The acu~ance ~or thc control DIR
coupler was 3ubtracted ~rom each AMT value to provide
the relative ~harpne~3 value reported a~ change i~
AMT in Table I. AMT calculation~ employed the
following formula in which ~he cascaded area under
the ~ystem mvdulation curve is shown i~ equation
(21.104) on page 6Z9 o~ the "Theory o~ the
Photographic Proce~", 4th Edition, 1977, edited by
T.H. Jame~: AMT = 100~66Logtca~caded area/2.6696M]
wherein th magnification factor M i~ 3.8 for the 35mm
gy9tem AMT. The u~e of CMT acuta~ce i9 described by
R.G. Gendron in "An Improved Objective Method of
Rating Picture Sharpness: CMT acutance" in the
Journal o~ SMPTE, Vol. 82, pages 1009-12, (1973).
AMT i~ a further modification of CMT u~eful for
evaluating system~ which include th~ viewing o~ a
po~itive print made from a negative.
f r~
--45--
TABLE X
Gamma
Causer
Example No./ Change Gamma
Coupler No. in AMT Receiver
. .
Cntrl Cplr 0 1.0
1 1.2 2.1
2 O 1.7
3 2.6 2.5
1 Control Coupler:
o
Is~ C2~s o~ `t' ~ -i
~o ~C
N N--C 6H5
N = N
, " ,~
,~, J 5~
Coupler l -46-
OH
./ \ ,~
i~ ~I NHso2cH2tc~2tl4c~3
~N--N
CH2--S~
C~I2CH3
Cou~
OH
O
~o ,1.~ .
0~ I NHso2~cH2tlscH3
t ~N--N
CH2--S 11
\N--N
C6~5
~ple~ 3
OX
30 I~ ~o' ~-coN~z
~o/ ~ ~
,1~
0~ ~I S2tCE2tl5C~3 ,N--N
C~2 Il_C~2_ IN_cO_s C
C6~5
rj ~ ~ ?' ~
-47-
Compared to the control coupler the coupler~
of Example~ 1 - 3 provide improved acutance and
interimage effect~.
Example 4:
A photographic film was prepared, expo3ed
and processed like the film in Example3 1 - 3. The
processed image~ were read with green light to
determine the contrast. From plot~ of the logarithm
of the contra~t compared to the coated level o~ each
DIR coupler, the reactivity wa~ determined a3 the
amount of DI~ coupler in micromole~ per square meter
to reduce the contrast (gamma~ to half (0.5) compared
to its orginal contra~t without the pre~ence of the
DIR coupler. The smaller the amoun~ of the DIR
compound required, the higher wa~ the reactivity of
the DIR coupler. Coupler 3 wa~ a~ de3cribed in
Example 3. The re~ult3 are given in following Table
II:
TABL~ II
Amount of DIR
Coupler to Reduce
Gamma in Half
(Micromoles Per
Exam~Lç_No. Cou~ler_NQ. Squ~e Meter~
4 3 lOB
C (Compari~on) C 157
D (Comparison) D 151
f ~ ? ~ ~ ',j,
-
-4~-
Coupler C
OH
I `~ coN~cH3
NHSO2-Cl6~33-n
10 \ ~
t N--N
CH2--0--C--CH2 N--CO--S--C~
Q /~ i
3~.~I o~ ~I
Coupler
OH
t o I-CON~C2~5
SO2-Cl6~33-~
25CE2-0-C-C~2-N-CO-~-
O /~ 1
~' ~t
The invention ha~ been described in detail
with partacular re~erence to pre~erred embodimentæ
th~reo~, but it will be understood that variation~
and modification3 c~n be e~ected within the ~pirit
and scope o~ the invention.
: 35
