Note: Descriptions are shown in the official language in which they were submitted.
1069369
mis invention relates to new 2-equivalent yellow couplers
and their use for the production of yellow dye images in color
photographic silver halide materials~
In the production of color photographic images, it is
usual to develop the exposed silver halide in a light-sensi-
tive silver halide emulsion layer with an aromatic developer
containing primary amine groups. The color couplers react with
the oxidized color developer to form an image dye corresponding
to the silver image.
In subtractive three-color photography a light-sensitive
multi-layer material is generally used containing red-sensi-
tized, a green-sensitized and a blue-sensitized silver halide
emulsion layer. When these are developed, using suitable
couplers, they give a blue-green, a purple and ~ellow image
respectively.
The couplers used to ~orm blue dyes are generally
phenols or naphthols, those producing magenta are usually
pyrazolones and those producing yellow are generally
compounds containing a methylene group with two carbonyl
groups attached theretoO m e dyes formed by coupling are
azomethines, indamines or indophenols, according to the
coupler and the developer usedO
! The conventional yellow couplers contain an active
methylene group which reacts during development with the
oxidized color developer four equi~alents of developable
silver halide being required for the reaction. mese co~plers
are therefore called ~-equivalent coupl~rs. Other known
couplers contain a methylene group in which ~ne hydrogen
A-G 1206 - 2 - ~
~)69369
`:
atom is replaced by a group which splits off during the
coupling reaction. In the latter case only two equivalents
of developable silver halide are required to form the dye.
., ~.
For this reason these couplers are called 2-equivalent
couplers. For yellow couplers the following splittable groups
;' have already been suggested:
~`~ 10 Halogen, as described, for example, in French Patent
,~ ~
5pecification Nos. 991 453 and 869 169; US Patent
Specification Nos. 2 728 658 and 3 277 155 and British
; 10 Patent Specification NoO 1 351 395;
,.,,t 20 the group OR, where R = alkyl, aryl or a heterocyclic
or an acyl radical, as described, for example, in
British Patent Specification NoO 1 092 506, in French
Patent Specifications Nos. 1 411 385 and 1 385 696 and
in US Patent Specification Nos. 3 447 928 and 3 408 194;
3. a group SR, as described, for example, in British Patent
Specification NoO 953 454 and US Patent Specification
No. 3 265 506;
4~ a group: R1
~ ~ R2
-N
\ ~ ~ \ R
R4 3
as described in US Patent Specification No. 3 617 291;
the radicals S03H and SCN, as described in British Patent
Specification NoO 638 039 and US Patent Specification
No. 3 253 924;
A-G 1206 - 3 -
~L0693~9
6. a group:
/co-~ /so2-.~
-N Z or -N Z
\CO-' \CO_ ~
as described in German Offenlegungsschriften NosO
2 213 461 and 2 057 541 and British Patent Specification
; 5 No. 1 3~1 179;
7. certain pyridones and pyridazones, as described in
German Offenlegungsschrift No. 2 318 8070
The advantage of 2-equivalent couplers compared with
4-equivalent couplers is well known in principle:
The amount of silver halide required to form a specific
amount of dye is about half as much as is required using
4-equivalent couplers, so that less silver halide is requir~d
to produce the light-sensitive photographic material. As a
result~ the layer of emulsion can be thinner, which in turn
has an advantageous e~fect on the resolution and sharpness
of the photographic materialO
Among the ~-equivalent yellow couplers known in the art
which have the above mentioned splittable groups, those
having a halogen as splittable group have proved to be
particularly suitable in practice, because when color
development is carried out9 a sufficiently large reactivity
of the 2-equivalent yellow couplers is necessary to guarantee
sufficient color densities even with short developing
processes.
In practice, however, 2-equi~alent yellow couplers with
flourine as the splittable radical have, for preparative
reasons, not been successful. 2-equivalent yellow couplers
A-G 1206 ! ¦ - 4 -
.
~0693~9
i,~
with chlorine as the splittable radical, on the other hand,
frequently have an adverse effect on the photographic proper-
ties of the silver halide emulsionO As described in British
Patent Specification NoO 1 351 395, only certain yellow
couplers of the benzoyl acetanilide type with chlorine as the
separable radical are relatively inert and influence the
formation of colored fog during development only slightlyO
Nevertheless, even the said couplers do not satisfy photo-
graphic requirements in every respect, since an increase in
fog formation during development cannot be completely excluded
where unprocessed photographic material containing these
couplers is stored in moist and warm conditions.
- There has been no lack of practical attempts to find new
2-equiY.alent yellow couplers which should be easily accessible
for preparative purpose and whose reactivity in the develop-
ment of color photographs should be sufficient or at least
comparable with that of the 2-equivalent couplers known at
present which have fluorine or chlorine as the splittable
group. In this respect, however, the 2-equivalent yellow
couplers known in the art with splittable groups, described
in the above paragraphs 2 to 5 and 7~ are inferior to the
2-equivalent yellow couplers having fluorine or chlorine as
splittable groupO
One further problem, not yet sati~factorily solved in
practice, is the fact, that the 2-equivalent couælers must
be permanently absorbed into the hydrophilic colloidal layers
of the photographic mater~al in finely distributed form,
A-G 1206 - 5 ~ ~
~L0693~9
`:
without either recryqtallizing out in the layer or otherwise
influencing the photographic or mechanical properties of the
layers in any adverse wayO
Furthermore, if photographic material is stored for some
length of time, particularly in moist and warm conditions, the
2-equivalent couplers should be sufficiently stable to avoid
separation of the splittable group before color development
takes place. On the other hand, the splittable group should be
easily and completely separated during the process, in order
to attain a high concentration of color in the images as well
as adequate sensitivity. m ese properties must, of course, be
independent of the method of the addition of the couplers to
the hydrophilous colloidal layersO Non-diffusing hydrophobic
couplers are usually firstly solved either by the use of
solubilizing groups in alkaline solution or by the use of an
organic solvent, and are th~ emulsified with the gelatin
- solution in the usual manner, possibly with the addition of
an oily coupler solvent. m e reactivity of the couplers
depends in a known way on how the emulsion is produced. To
obtain a su~ficient reactivity of 2-equivalent couplers, which
is independent of how they are added to the layer, the hydro-
philic colloidal layer and/or the hydrophobic drop of oil
must be able to influence favourably the separation of the
splittable group during color development by means of
solvationO
The splittable group, of course, should be photographi-
cally inert and should not have any influence on the colors
formed or on the stability of the remaining color coupler in
the layerO
A-G 1206 - 6 -
iO1~93~9
The compounds described in British Pstent Specification No.
; 1,331,179 and United States Patent Specification No. 3,671,291 are not
satisfactory in practice, since their stability in unprocessed photographic
materials is inadequate when exposed to moist warm air. On this point men-
tion should also be made of the Canadian Patent Application Serial No.
201,911.
The Canadian Patent Application ~uoted above suggests the use
of 2 equivalent yellow couplers, which are easily prepared and which have
as splittable group a 5-membered unsaturated heterocyclic group containing
nitrogen which heterocyclic group has a C=C double bond (which is part of the
unsaturated or aromatic heterocyclic ring) adjoining the nitrogen atom, across
which linking with the active methylene group of the yellow coupler takes
place. lmidazoles are the preferred splittable group, preferably containing
electro-negative substituents.
The yellow couplers named above are, admi~tedly, superior as
regards both production and stability during storage to those described in
the United States Patent Specification No. 3,671,291, however, the preparation
o~ the heterocyclic group containing elect-ronegative substituents required -
for substituting the chlorine atom of the corresponding 2-equivalent couplers
with chlorine as splittable group, is not without problems. For instance,
four reaction steps are required for the production of an imidazole carboxylic
ester.
Moreover, nitro-imidazole compounds for instance are easily ac-
`~ cessible and extremely suitable as a separable group,
: ~0~9369
but ~hey are yellow in color and can therefore give rise to color distor-
tions.
It was, therefore, necessary in practice to produce new 2-
equivalent ycllow couplers, which can easily be prepared and which are
excellently suitable for use in light-sensitive color photographic materials
to produce the yellow partical images and whose photographic properties are
superior to those couplers known at present.
It now has been found that certain nitrogen containing 6-
membered heteroaromatic compounds are particularly suitable for the produc-
tion of splittable groups for 2-equivalent yellow coupler compounds. The
heteroaromatic compound contains a carbonyl carbon atom or its tautomeric
hydroxyl-substituted carbon atom at the 2-position adjacent to the nitrogen
atom and is either hydroxy-substituted at the 4-position or contains at
least one other ring-nitrogen atom at the 3-, 4-, 5- or 6-position of the
heterocyclic ~ing and in the case where two nitrogen atoms are contained
which are adjoining to each other the heterocyclic ring is hydroxy-substi-
tuted at the 5-position.
The heterocyclic compound can easily link to the coupling posi-
tion of a 2-equivalent yellow coupler by known means by the said nitrogen
atom, whereby the corresponding 2-equivalent yellow coupler with chlorine
as splittable group are reacted with the salts of the said heterocyclic
compound. The protuction of the salt of the said heterocyclic compound is
as easy as with compounds of the above mentioned Canadian Patent Application
Serial No. 201,911.
~ ~0693~;9
:
Thus, according to the present invention the splittable
groups are derived especially from 3-hydroxy-pyridazinons-6,
pyrimidinone-2 or pyrimidinone-6, pyrazinone-2, 4-hydroxy-
pyridinone-2, 1,2,4- or 1,2,3-triazinones, which may be substi-
tuted. Suitable benzo-condensed derivatives of the above
heterocyclic compounds are, for example, ~uinazolinones,
benzotriazinones or quinoxalinones.
In the heterocyclic splittable groups of this invention
; the nitrogen atom adjoining the carbonyl group is therefore
sufficiently electron-deficient to form the corresponding
B salts with thoir bases, and sufficiently nucleophilic to
ef~ect a smooth substitution with the halogen atom of the
~ active methylene group of the yellow coupler usedO Of course,
the polarity of the splittable group also has a marked e~fect
on the reaction speed of the corresponding couplers with the
oxidized color developerO Polar substituents, such as
hydroxyl or acid groups or groups such as carbonyl or nitrogen
in the splittable group promote the reaction speed of the
coupler with the oxidized color developer but can, conversely,
cause instability of the coupler during storageO The yellow
couplers of this invention with new heterocyclic splittable
groups are not only very easy to produce, but are also
particularly stable during storage, even in extreme storage
conditions; in addition they ar~ extremely reactive so that
during chromogenouæ development the heterocyclic radical is
easily split offO Their sensitivity and color yteld are out-
standing. Moreover, the splittable groups of the yellow
couplers in this! invention in comparison with the correspon-
ding 4-equlvalent yellow couplers bring about no adverse
A-~ 1206 - 9 -
10693~;9
changes in the absorptive power of the colors produced from
them nor that of the remaining coupler radical when they are
used for color photography and are chromogeneously developed.
According to one embodiment o~ the present invention
5 there is provided a light-sensitive color photographic material
with at least one silver halide emulsion layer and 2-equivalent
yellow coupler of the ~ollowing formula:
~ N ~
E 3 4 5 B
where0 K - represents a yellow coupler radical substituted in the
methylene group, e~g. an open-chain keto-methylene coupler
radical, such as ~or example an acyl acetonitrile coupler
radical or an acyl acetyl coupler radical;
A and B together represent:
X Y X OH
1) -C-C- 2) -C=N-or 3) -N=C-
and D and E together represent:
~' X' X
1) -C=C- 2) -C=N-or 3) -N=C-
or A and B together, or D and E together represent:
4) -N=N-
A-G 1206 - 10 -
~0~;93f~9
in which ormulae X and Y can be either the same or preferably different and
represent hydrogen, alkoxy such as methoxy, halogen, acyl, acyloxy, acylamino,
carbamyl, sulfamyl, alkyl, preferably with 1 - 4 C atoms, especially methyl,
aryl, such as phenyl or X and Y together represent the atoms required for a
condensed aromatic or heteroaromatic ring; X' and Y' represent the same as X
and Y or hydroxy; provided that D and E together represent OH H
- C = C -
unless at least one of the groups A and B together as well as D and E
together represents one of ~2) and (3) above or D and E together complete a
condensed aromatic or heteroaromatic ring and provided that D and E together
do not complete a condensed benzene ring unless A and B together represent
one of (2) and (3) above.
If X and Y or X' and Y' represent phenyl or together form the
ring members necessary for an aromatic or heteroaromatic ring, preferably a
benzene ring, then the phenyl radical or condensed ring may be further
substituted, e.g. with alkyl in particular trifluoralkyl, alkoxy, alkylthio, ~'
; aryl, acyl, acyloxy, acylamino, carbamyl, sulfamyl, carboxy~ nitro, cyano,
halogen.
The 2-equivalent coupler radical K which forms a yellow color in
accordance with this invention is derived from the usual known 4-equivalent
couplers. Preferred couplers for this invention are those of the general
formula above, where K represents an open-chain ketomethylene yellow coupler
radical, e.g. acylacetonitrile or acylacetyl coupler in particular of the
following formula (I):
Bl
1069369
(I) B - C - CH - B'
where
B represents an alkyl radical with 1 - 32 C-atoms,
: preferably 1 - 18 C-atoms, branched or unbranched;
in the case of a secondary or tertiary alkyl radical
the secondary or tertiary carbon atom should
preferably be linked directly with the carbonyl radical;
/oa, 1 1<~ 1
or an alkoxyalkyl radical, a ~b~ }~cef} radical,
a heterocyclic radical or an aryl radical, especially
: 10 a phenyl radical which may, i~ necessary, be substi-
tuted on e or several time~ by alkyl with 1 - 18
C-atoms, aryl, aralkyl9 alkoxy with 1 - 18 C-atoms,
aroxy, halogen (eOg. fluorine or bromine), acyl,
acyloxy, acylamino, amino-, carbamyl- or sulfamyl
groups which m~y be substituted by identical or
dif~erent arylaralkyl? alkyl or heterocyclic radicals,
sulfo or carboxy; ~
B' represents cyano or the group
.,
/R1
-C-N
~ represents hydrogen or a short-chain alkyl radical
with 1 ~ 5 C-atoms, for example a methyl or ethyl
radical and
A-G 1206 - 12 -
~0693f~9
R2 represents an alkyl radical with 1 - 18 C-atoms or
preferably an aryl radical, for example a phenyl
radical which may be substituted by identical or
different groups such as alkyl with 1 - 18 C-atoms,
alkoxy with 1 - 18 C-atoms, aryl, aralkyl, aroxy,
halogen (eOgO fluorine or bromine), acyl, acyloxy,
acylamino, amino, carbamyl or sulfamyl groups which
may be substituted by identical or different aryl,
aralkyl, alkyl or heterocyclic radicals, sul~o or
carboxy.
Preferred coupler radicals are naturally those which are
derived from 4-equivalent yellow couplers having extremely
suited properties with respect to absorption of the dyes and
of the stability of the azomethine dyes produced on chromogenic
development. Benzoylacetanilides in particular o-alkoxybenzoyl-
acetanilides and pivaloylacetanilides which may be substituted
in the anilid group of the coupler molecule by one or several
_ ,~
optionally one to three substituents preferably in the ~ , 4-
and 5-position o~ the anilid group are found to be of pre-
ferred practical importance.
The new yellow couplers of this invention are easily
produced unexpectealy stable during storage when they ar~ used
C c>~ llng
in light-sensitive materials and they possess a high bonding
capacity, iOeO they give color images with a high color
de~sJ7~y
o~tr-~tion and high sensitivity and they are extremely
suitable ~or use in light-sensitive sllver halide emulsion
layers of single or multi-layered color photographic materialgO
However, it is not absoIutely necessary for the yellow
couplers to be incorporated into the light-sensitive layers;
A-G 1206 - 13 -
lC~69369
it is also possible to accomodate them in a layer of binder
adjacent to the light-sensitive silver halide emulsion layer.
The yellow couplers of this invention can be used as
diffusionfast or non-diffusionfast couplers for the formation
of yellow dye images in color photography according to a
further embodiment of the invention by a suitable choice of
substituents R1, R2, B or B' as defined abo~eO To o~tain a
sufficient degree of diffusionfastness, the substituents R1,
R2, B or B', preferably B or B', are provided with radicals
which prevent diffusion, eOgO straight-chain or branched alkyl
radicals with 10 - 18 C-atoms, or they can be substituted by
; alkyl-substituted phenoxy radicals which are bonded either
directly or indirectly via -0-, -S- 9 -CONH- ~ -NHCO- ~ -S02NH-
-NHS02 or other intermediate members to the radicals B, B' 9
. 15 R1 or R2 (which may be aromatic)0
If solubility in alkalis is desired, at least one of
the radicals B, B', R1 or R2 may carry groups which favour
this property, especially sulfo groupsO
P~ P/~Us/~k e~pler5
DiffuEion-promotin~ g~Y~ff~ are particularly suitable for
use in developer solutions, in order to develop the yellow
color in exposed color films which contains no yellow coupler.
Examples of suitable yellow couplers which are to be
used according to the invention are as follows:
A-G 1206 - 14 -
.. . ~ , . . ~ .. . - . .
1069369
Table 1
--- 0~ N
B-C0-CH-C0-NH~/~ 9 x = ~--
x ~. ~ "
R"
. . . . . . . .
No. B R' R" mOp C
.
1 ~ ll H ~ 1
2 t-butylC1 6H33 -S02NEICH3 130-131
_~ 6H33 S02N ( CH3 )
4 t-butylCl -NH-C 0~ ( CH2 ) 3 180
~ o
_ .
L~ ~'1 -NHCOC~5H31
172-173
7 t-butyl ~ lla -S02NHCH3
1 Z0
A-G 1206 - 15 -
. .
110~93~9
No. B . R" mOp. C
8 t-butyl Cl C14H29 47-50
_ .
9 t-butyl C1 C14H29 60-63
.
~ 10 t-butyl Cl CH3
'1 _ . _
:~ 11 t-butyl C16H33 H 98-99
12 C16 33 -O,H3 -S0z-Yu
)C1BH37 -S2-NH ~ ~ 8
H3 ~ -N(cH3)c18H37 -S02NHCH3 110-111
.- ,..... - - ..
~3
A-G 1206 - 16 -
,
.. . . . .
.,
10~93~;9
No. B R' R" m-p- C ¦
=~ ¦ ( ~ C1 aH37 -502NHC4H9
LL~:~ w
A-G 1206 - 17 -
110693fà9
~ ., ~ ~
j
_ ~ -
3,-X ~ ~D a
. ~ ~ ~
o a: ~ ~ ~
~1 z o ~=
A-G 1206 - 18 -
.. . ~ , .. ~ ,. ... . .. .
~10693~9
Table 1 (cont.)
q' ~
B-CO-CH_CONH ~ X = ~ N
R"
No. B R' . - m.p.C
.. .. .
22 t-butyl C16H33 -S02NHCH3 78
-NHCOC1 5H31
Z4 t-butyl Cl -NHCO(CH2/ 0 ~ 200
. 5
25 t-butyl C16H33 S02N(CH3)2 65-67
_ . ... _
,C~C1 4H29
26 t ~utyl Cl -COO-CH 55
C1 4H29 . . ~. -
27 ~ OCH3 H 84
28 t-b~tll 0~14HZ9 105
A-G 1206 - 19 -
~LO~9;~t;i9
Table 1 (cont. )
IR ' 0~ N l
B-CO-CH-CONH~ X =¢~ N
R~ I
Cl
, . . . .
NQ . B R' R" mp C
_ ,
~t~ 3 -S02NHCH3
30 t-butyl C1 4H29-S02NHCH3 . 96-99
.
31 t_bUtYI C 16~ . 67 6B
-W11
. ' "' L ~I~ s
L ~ ,, . ~ ICH2 ~t C4Hg .
A-G 1206 - 20 -
l~t~
o, 1
~t
~ ~ o~
A-G 1206 - 21 -
'
~0~;93~9
. ..
~ tC - ~ ~tC C'~
. . ..... __
I 1~ PC C X ~ tC
i~ ~ ~ ~ ~
:,
~; '
m ~
:~ ,_~. ~ ' .~_
A-G 1206 - 22 -
;93~;9
~ ~ +~
~c I ~ I
L~ . ,~
---r
A-a 12()6 - 2~ ~
10693~9
~ ~ ~ `
X z ~ o ~ ~ ~
1l~ I ~ Z-~
~ ~ ¢~ ~
.
I¢ 1~ 1 o I 50 1 ~o
--~ .
a~ ~3
~= I ~ I ~
A-G 1206 - 24 _
~L0~9;~;9
o~ ~ ~ o
;~
~ ~`
~ i L ~
A-G 1206 - 25 -
10693~9
. '_-~ ~
A-G 1206 - 26 -
~069369
_ .
- ~Z; ~- ~;
:~ ~~ -~ ' ~m~ ~
11 II I 1
.
_ oNm oN N
~~ U2 U~ U~ U~
i~ r I~1~
~ ~ ~. ~ ~
:
; A-G 1206 - 27 - -
10~93f~9
L~
~ Q~
~, ~ ~ ~ ~o ~ ~
o ~, ~ ~ U~
.
A-G 1206 - 28 -
~0693~;9
. oC~ :~ ~ o
~ ,~ o ~ ~ ~
.
L~L I ~
A-G 1206 - 29 -
10693~9
,~.~, o
o ~r: ~: , ~ ~1 .
V~ ~ ~ V
~ ~'
A-G 1206 - 30 -
~()693~9
r
A-G 1206 - 31 -
- . .
-: ` , ;,: . -
10~;93~;9
~:~
,=:z " ~ ~ ~ ~
h~ ~i
~ I ~
~1 ~
. . . .
L~L~ I OD ¦ GD ¦ D
A-G 1206 - 32 -
10~93~:;9
lo~ I
~ ~ . ~
~C _
I I
: ~_- ~ ~ A ~ :~
D-~ ~ _ ~ o O ~ c ~
~)~ O ' ~' ~
A-G 1206 1 - 33 -
1.0~93f~9
~r ~ ~ .
- ~ 3
... . .
V'
~ a~ ~c~ :r~
L~ ~ ~ z~, I N
~ V ~ O
A-G1206 - 34 -
iO693~9
As already mentioned, the yellow couplers in this in-
vention may be produced in a conventional manner by reaction
o~ the corresponding 2-equivalent couplers having chlorine as
their splittable group with the corresponding heterocyclic
compound in the presence of a base, as is described, for
;; example, in German Offenlegungsschrift 2 213 4610
m e reaction can take place in an aprotic solvent, pre-
ferably a polar solvent, such as, for example, acetonitrile
or dimethyl formamide, and with the use of suitable bases,
such as aliphatic amines, e.gO triethylamine; basic hetero-
cyclic compounds, e.gO pyridine; or alkali s~lt~ of alcoholates,
e.g. sodium alcoh~late. me reaction is also particularly
successful in the presence of hexamethyl phosphoric acid tri-
A~ C~a~'~n
; ~ amide as solvent as described in ~ritih patent application
20~
Serial No. ~5 3~1J740
The heterocyclic compounds required ~or the said reaction
; can be prepared by known methods. For example, 3-hydroxy-
pyridazinone-6 can be obtained from suitable substituted
maleic acid derivatives by reaction with hydrazine. By re-
action o~ suitably substituted B-dicarbonyl compounds with
urea, good yields of p~rimidinones are possible. Pyrazinones
are formed from suitable substituted ~-amino-aldehydes or
oC-~mino ketones by oxidation in air. Quinoxalinones are
- produced fr,om o-phenylene diamines with ~ -keto carboxylic
acid, such as, ~or example, pyroracemic acid; a~d 1,2t4-tri-
azinones are produced by reaction of semicarbazide with
oC-di~eto qompounds (e.g. benzil)O 1,2,3-benzotriazinone is
produced by dehydration of o-diazobenzo amides, The reaction
of u~ea with ~-amino benzoyl compounds gives 2-quinazolinone.
A-G 1206 _ 35 _
.. . .
10693~9
Pyrazinones-4 can be produced by reaction of ~-keto carboxylic esters with
thiourea followed by reduction with nickel; similarly, the corresponding
,` benzo-condensed compound of quinazolinone can be produced by reaction of o-
amino benzoic acid with formamide. In each case the reaction conditions of
these reactions are well known in principle and need not therefore be des-
cribed here.
The preparation of several couplers used in this invention is
described in detail below:
Preparation of coupler No. 5
4.4 g benzo triazinone are dissolved in 200 ml acetonitrile
whilst stirring, ant then 20 g 2,4-dimethoxybenzoyl- ~-chloro-(2'-cetyloxy-
5~-N-methylsulfamoyl-acetanilide and 5.25 ml of a 30 % sodium methylate
solution are adted. The reaction mixture is boiled for one hour using a
reflux condenser. &bsequently it is filtered and the solution is stirred
into iced water. After the precipitate has been sucked off, the reaction
product is dissolved in hot isopropanol, clarified with ac~ive charcoal,
cooled and the supernatant solution decanted off. The residue is then puri-
fied with petroleum ether.
Yield: 14 g of coupler No. 5.
Preparation of coupler No. 29
3.6 g 7-chloro-4-quinazolinone, 12 g ~-pivaloyl- ~ chloro-(2-
cetyloxy-5-N-methylsulfamoyl~acetanilide and 3.4 ml of a 30 % sodium methy-
late solution are dissolved in 100 ml acetonitrile and 50 ml dimethyl forma-
mide and boiled for 2 hours in a reflux condenser. After evaporating the
solvents, the residue is stirred with methanol and the resulting product is
recrystallized from methanol. Yield: 8 g of coupler No. 29~
10~;93~9
Preparation o coupler No. 6
4.6 g 3-phenylureidopyrazinone-2, 12 g ~piv810yl- C~-chloro-~2-
cetyloxy-5-N-methylsulfamoyl)-acetanilide and 3.4 ml of a 30 % methylate
solution are dissolved in 200 ml dimethylsulfoxide and warmed for 2 hours to
60 - 70C. After cooling, the reaction solution is added to 800 ml water and
the precipitated reaction product is recrystallized from isopropanol.
Yield: 8 g of coupler No. 6.
Preparation of coupler No. 42
2.7 g 2-phenyl-4,5-dichloro-pyrimidinone-6 and 5.9 ~ ~-pivaloyl-
c~-chloro-(2-cetyloxy-5-N-methylsulfamoyl acetanilide are mixed with 100 ml
acetonitrile and 1.85 ml of a 30 % methylate solution and boiled for 2 hours
in a reflux condenser. Subsequently, the reaction product is added to iced
water and the precipitated reaction product is recrystallized from methanol.
Yield: 4.5 g of coupler No. 42
Preparation of coupler No. 60
To a solution of 15 g O~pivaloyl-ci-chloro-(2-cetyloxy-5-N-
methylsulfamoyl~acetanilide in 150 ml hexamethyl phosphoric acid triamide
are added 2.9 g maleic acid hydrazide at a temperature of 50C and then 3.5
g potassium-t-butylate, portion by portion. After a reaction time of 2
hours at 50C, the reaction mixture is added to ice/HCl, and the precipitated
product is filtered off and washed with water, After the usual purification
process, the product is recrystallized from ether.
Yield: 6 g of coupler No. 60.
10~;93~;9
Preparation of cou~ler No. 19
The preparation is as described for coupler NoO 60,
except that 4 g uracil are used instead of maleic acid hydra-
zide, and 4 g potassium-t-butylate instead of ~.5 gO
Yield: 2.7 g of cou~ler NoO 190
The preparation of the other couplers used in this in-
vention can be carried out by analogous methods.
As regards those yellow couplers in this invention which
are diffusionsfast, they are extremely emulsifiable, very
resistant to digestion in the coating solution and in the
photographic material and do not impair the photographic
; proparties of the emulsion, even under extreme conditions of
storage.
By the preparation of the light-sensitive color materials
according to the present invention diffusionfast yellow
couplers of the above general ~ormula can be incorporated into
the casting composition o~ a silver halide emulsion ~ other
colloidal layers which are in water-permeable relation thereto
by any known means. For example, the water-soluble color
couplers, iOe. those containing one or several water-soluble
groups such as a sul~o or carboxyl group (as an acid or salt)
can be incorporated into the casting composition of the
specific layer from an aqueous solutionO Similarly, color
couplers which are not or which are insu~ficien~ly water-
soluble are incorporated from a solution into, respectively,suitable water-miscible or non-water-miscible, h~gh-boiling
or low-boiling~organic solvents or mixtures thereofO m ere-
upon, the solution obtained is dispersed in a hydrophilic
colloidal composition (using, if necessary, a wetting or a
A-G 1206 - 38 -
:
... .. .:. .- - .
1069369
dispersing agent) wnich forms either the whole or simply a
part of the binding agent of the colloidal layer. Moreover,
the hydrophilic colloidal composition may contain any other
type of ingredient besides the colloidO The non-water-soluble
color couplers which contain fluoro-~ul~onyl groups or carb-
oxylic acid ester groups such as ethoxy carbonyl groups may
also be converted by alkaline hydrolysis into the corresponding
sulfonic acids or carboxylic acids respectively, which in turn
can be incorporated into hydrophilic colloidal compositions
in the form o~ their alkali metal salts from aqueous solutions.
me solution of the color couplers does not need to be
directly dispersed or dissolved in the casting composition
of silver halide emulsion or some other water-permeable layer.
The ~olution may advantageously first be dispersed or dissolved
~o~ ,
in an aqueous~,llight-sensitive solution of a hydrophilic
colloid; subsequently, the mixture obtained is thoroughly
mixed with .the ca~ting composition o~ the light-sensitive
silver halide emulsion or other water-permeable layer just
before casting (after removal of the organic solvent used).
E urther details about particularly suitable techniques for
the incorporation of color couplers into the hydrophilic
colloidal layers of photographic materials may be found in
the Dutch Patent Application NosO 6 516 423, 6 516 424,
6 600 098, 6 600 099 and 6 600 628, in the Belgian Patent
Specification NoO 750 889, in the UOSo Patent Specification
No. 2 304 940 and in the British Patent Specification No.
791 2190
A-G 1206 _ 39 _
106i93~9
To produce photographic color images, an exposed layer
of silver halide emulsion is developed with an aromatic
primary amino-developer in the presence of a color coupler
according to the invention. me developer substances used
may be any color developer which are able to yield azomethine
dyes by chromogenic development. Suitable substances are
aromatic compounds, such as ~-phenylene diamine and i*s
derivatives, for example N,N-dialkyl-~-phenylenediamine,
N,N-die~hyl-~-phenylenediamine, N,N-dialkyl-N'-sulfomethyl-
~-phenylenediamine and N,N-dialkyl-N'-carboxymethyl-~-
phenylenediamineO
Suitable light-sensitive emulsions are emulsions of
silver halides, such as silver chloride, silver bromide or
mixtures thereof which may have a small content of silver
iodide up to 10 Mols-%, in one of the hydrophilic binding
agents normally used. Gelatin is the preferred binding agent
for the photographic layers. m is can, howeverJ be replaced
wholly or in part by other natural or synthetic binding
agents. Suitable natural binding agents are eOgO alginic
acid and its derivatives such as salts 9 esters or amides;
- cellulose derivatives such as carboxymethylcellulose;
alkylcellulose such as hydroxyethylcellulose; starch or its
derivatives such as ethers or esters; or caragenates.
Among the synthetic binding agents, polyvinylalcohol,
partially saponified polyvinylacetate, polyvinylpyrrolidone
and ~ e like should be mentionedO
me emulsions may also be chemically sensitized, eOg.
by the addition of suliur-containing compounds during
chemical ripening, ~cr example, allylisothiocyanate, allyl-
A-G 1206 _ 40 _
10693~9
thiourea and sodiumthio~ulfateO Furthermore, reducing agents
such as, for example, the tin compounds described in Belgian
Patent Specification Nos. 493 464 or 568 687, as well as
polyamines such as diethyltriamine or aminomethane sulfinic
acid derivatives (as in Belgian Patent Specification 547 323)
may also be used as chemical sensitizers. In addition, the
rare metals such as gold, platinum, palladium, iridium,
ruthenium or rhodium are suitable as chemical sensitizersO
m is method of chemical sensitization has been described in
the article by R. KOSLOWSKY, ZoWisS.Phot., Vol. 46, 65 - 72,
(1951).
It is also possible to sensitize the emulsions with
polyalkyleneoxide derivatives, e.g. with polyethylene oxide
having a molecular weight o~ from 1.000 to 20.000, and
further with the condensation products of alkylene oxides
and aliphatic alcohols, glyccls, cyclic dehydration products
of hexitoles; with alkyl-substituted phenols, aliphatic
carboxylic acids, aliphatic amines, aliphatic diamines and
amides.
The condensation products have a molecular weight of
at least 700, preferably of more than 1000. To obtain special
ef~ects, the sensitizers can, of course, be combined, in the
manner described in Belgian Patent Specification No. 537 278
and in British Patent Speci~ication NoO 727 982.
me emulsions must exhibit suf~icient sensitivity in
the blue region of the æpectrumO For this 9 unsensitized
emulsions are generally used, their sensitivity depending on
that of the specific silver halide used.
A-G 1206 - 41 -
. . ~
.
10693~9
It is, however, also possible to sensitize the silver halide
emulsions in the blue region of the spectrum, e.g. by sensi-
tizers such as are described in the Briti~h P~tent Speci-
fication No. 1 285 078.
m e emulsions can cont~in conventional stabilizers, e.gO
homopolar or salt-like compounds of mercury with aromatic or
heterocyclic rings, such as mercaptotriazoles, simple mercuric
salts, sulfonium mercuric double salts and other mercury
compoundsO Other suitable stabilizers are azaindenes, pre-
ferably tetra- and pentazaindenes, especially those which
are substituted with hydroxyl or amino groupsO Such compounds
have been described in the article by BIRR, Z.Wiss.PhotO,
Vol. 47~ 2 ~ 58 ~1952)o Other æuitable stabilizers are hetero-
cyclic mercapto compounds, e.g. phenylmercaptotetrazole,
quaternary benzothiazole derivatives and benzotriazole.
m e emulsions can be hardened in the U5Ual manner~ for
example with formaldehyde or with haIo~en-substitut~d alde-
hydes containing a carboxyl group such ac mucobromic acid~
d$ketones, methane sulfonic acid ester and dialdehydes~
me following examples illustrate the advantages of the
couplers of this invention:
Exam~a~_~
2 m~ol of the couplers (~ormula given below) are each
dissolved in ~ ml ethyl acetate and, after adding 0.5 g di-
butylphthalate, emulsified with 20 ml of a 5 % gelatin
~olution at 60C in the usual way. The emulsion contains
0.16 g sodium dodecylbenzosulfonateO
Sub~equently the emulsion is mixed with 85 g of a 7.5 %
gelatin solution, containing 1.93 g dispersed silver bromide,
A-G 1206 ` - 42 -
10693~;9
and then diluted with water until the casting viscosity is
reachedO
After casting the emulsion on to a transparent support
of cellulose triacetate, the material thus produced is ex-
posed behind a grey step wedge and cut into several test
samplesO
One test sample is stored for 7 days at 57C and 34 %
relative humidity in a heating cupboard before being photo-
graphically processed.
The untreated test samples are developed ~or 2 minutes
or 8 mi~utes in a conventional color developer, containing
diethyl-~-phenylene-diamine as developer, and are then bleached
and fixed as usual. me stored test samples are developed
in the same way for 8 minutes.
The couplers used are of the ~ollowing formula, the
following Table showing the meanings of X:
CH3 0 o C16H33
CH~ - C - C - CH - C - NH -
CH X
3 S02NHCH3
The sensitometric evaluation o~ the individual test
samples is shown in the following Table which gives a compari-
son between test samples using 2- and 4-equivalent couplers
in relative val~es. C~umn 1 showæ the fog values ~S) obtained
with those test samples developed for 8 minutes; column 4
compares the increa~e in basic fog values (~ S) between the
test samples stored in the heating cupboard before being
de~eloped for 8 minutes and the unstored test samples in
relative values.
A-G 1206 _ 43 _
10693f~9
o. ' o. .. ~o
o o o ~,
.~ O O~ E` a~
~, ~ CU,
X~3 0 o ~_ a~
o . ~ .
o
~a o u~ ~i _~
~o. ~o. ~ C~
tQ O O , O O
1~1
:' _
~, bO O 00 0
,~ ~ .~ U~ ~D
o ~ o ~ I O
~ ~ h 0 m o o~c~ h ~;0 ~ h
: . ~ . o .~om ~omoo . oom
. _ 1~ ~ ~ ~ ~a ~ N , _ _
A-G 1206 ~ - 44 -
10693~9
1~ L+ I~
~ .~ c~ 0. a~ o~
~ 0 ~ C~l ~ C~l
. . .
~ ~ ~ . . ~
.~ ~ ~ o ~
~1
L
A-G 1206 - 44 a -
10~93~9
As can be seen from the Table, the rates of reaction of
the couplers of this invention (Nos. 2, 22, 60 and 44) are
comparable to that of the reference coupler D, taken from the
British Patent Specification No. 1,331,179, since the density
values obtained for the variou~ development times are
approximately equal.
However, the reference coupler D is adversely affected
in stability during warm and damp storage so that a considerable
increase in the fog value ~ S can be ob~ervedO
Compared with coupler C (described in the German Offen-
legungsschrift DT-OS 2,318,807) the yellow couplers of this
invention are remarkable on account of their greater sensi-
tivity as well as their higher rate of reaction.
ExamPles 2
A photographic material was prepared with coupler No~ 5,
as described in Example 1 above. A test sample of this material
was stored in a heating cupboard (as described in Example 1)
and a second test sample was developed immediately for
8 minutesO
The sensitometric evaluation of the test samples was
carried out as in Example 1, the following results being
obtained:
Coupler X S Sensi- Dmax ~ S
- - ; ,, ~
o ~ N~ 0.07 + 6.3 2~9 + 0.05
~ N
A-G 1206 _ 45 _
10693f~9
A comparison o~ these values with the corre~ponding
values o~ the yellow couplers of this invention in the
above Table shows that benzoylacetanilide yellow couplers
also exhibit extremely good properties as regards
reactivity, sensitivity and stability during storageO
A-G 1206 . - 46 -
