Color photographic recording material containing a color coupler of the pyrazoloazole series

Color photographic images having advantageous sensitometric properties, in particular high maximum magenta color density, can be obtained by use of a color photographic recording material containing a pyrazoloazole type magenta coupler of formula I EQU Q--L--COOH I In the formula PA0 Q denotes the bicyclic group capable of color coupling in a pyrazolo[3,2-c]-1,2,4-triazole magenta coupler and PA0 L denotes a linking member which is not split off in the color coupling reaction and which cointains a ballast residue unless a ballast residue which cannot be split off is attached to the non-coupling ring of the bicyclic group Q.

This invention relates to a colour photographic recording material 
containing at least one silver halide emulsion layer and a colour coupler 
of the pyrazoloazole series which enables magenta colour images with high 
colour density to be produced by virtue of the presence of a particular 
group in the ballast residue. 
It is known that coloured photographic images may be produced by 
chromogenic development, i.e. by developing silver halide emulsion layers 
which have been exposed imagewise by means of suitable colour producing 
developer substances, so-called colour developers, in the presence of 
suitable colour couplers which react with the oxidation product of 
developer substances formed in areas corresponding to the silver image to 
produce a dye image. The colour developers used are normally aromatic 
compounds containing primary amino groups, in particular compounds of the 
p-phenylenediamine series. 
Pyrazolone couplers are normally used for producing magenta dye images. The 
absorption of the image dyes obtained from these pyrazolone couplers is in 
many cases not ideal, one particular problem being the yellow side colour 
density which necessitates the use of masking couplers or other masking 
techniques if brilliant colours are to be obtained in the photographic 
image. Other disadvantages commonly found when pyrazolone couplers are 
used include the inadequate resistance to the action of formaldehyde or 
the action of light, heat and moisture during storage. 
Magenta couplers of the pyrazoloazole series have been found to be 
preferable in this respect. They generally give rise to magenta dye images 
with a purer colour but it is difficult to obtain a sufficient colour 
density with these couplers when the usual methods of processing are 
employed. Magenta couplers of the pyrazoloazole series are described, for 
example in DE-A No. 1 810 462, DE-A No. 3 516 996, EP-A No. 0 143 570 and 
EP-A No. 0 176 804. 
It is an object of the present invention to provide a colour photographic 
recording material containing at least one silver halide emulsion layer 
and at least one magenta coupler from which magenta dyes with the desired 
purity of colour and high colour density can be obtained by chromogenic 
development. 
The invention relates to a colour photographic recording material 
containing at least one silver halide emulsion layer and at least one 
non-diffusible colour coupler of the pyrazoloazole series, characterised 
in that the coupler corresponds to the following general formula I 
EQU Q--L--COOH (I) 
wherein 
Q denotes the bicyclic group capable of colour coupling in a 
pyrazolo[3,2-c]-1,2,4-triazole magenta coupler and 
L denotes a linking member which is not split off in the colour coupling 
reaction and which contains a ballast residue unless a ballast residue 
which cannot be split off is attached to the non-coupling ring of the 
bicyclic group Q. 
The magenta couplers according to the present invention also correspond to 
the general formula I-1 
##STR1## 
wherein the substituents S and T may be hydrogen, alkyl, aralkyl, aryl, 
alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, 
alkoxycarbonyl, carbamoyl or sulphamoyl and these groups may in turn be 
substituted but at least one of the groups S or T is a group denoted by 
--L--COOH as defined in formula I. Couplers in which one of the groups S 
or T is a group L--COOH in which the connecting member L contains a 
ballast residue are preferred. In formula I-1, X stands for hydrogen or a 
residue which may be split off in the colour coupling reaction, such as a 
halogen atom or a group, preferably a cyclic group, which is linked to the 
coupling position by an oxygen atom, a sulphur atom or a nitrogen atom. 
If the releasable group is a cyclic group, it may be attached to the 
coupling position of the coupler molecule either directly through an atom 
which forms part of a ring, e.g. a nitrogen atom, or indirectly through a 
linking member. Many releasable groups of this kind are known, e.g. the 
fugitive groups of 2-equivalent magenta couplers. 
Examples of releasable groups attached to oxygen correspond to the formula 
EQU --O --R 
wherein R denotes an acyclic or cyclic organic group, e.g. alkyl, aryl, a 
heterocyclic group or acyl, which may be derived, for example, from an 
organic carboxylic or sulphonic acid. In particularly preferred releasable 
groups of this kind, R stands for a substituted or unsubstituted phenyl 
group. 
Examples of releasable groups attached through nitrogen are described in 
the following German Offenlegungsschriften (DE-A-): Nos. 2 536 191, 2 703 
589, 2 813 522, 3 339 201. 
Many of these groups are 5-membered heterocyclic rings connected to the 
coupling position of the magenta coupler by a ring nitrogen atom. The 
heterocyclic rings frequently contain activating groups such as carbonyl 
or sulphonyl groups or double bonds in positions adjacent to the nitrogen 
atom through which the rings are attached to the coupling position of the 
coupler. 
If the releasable group is attached to the coupling position of the coupler 
by a sulphur atom, the group may be a residue of a diffusible carbocyclic 
or heterocyclic mercapto compound which is capable of inhibiting the 
development of silver halide. Many such inhibitor groups have been 
described as releasable groups attached to the coupling position of 
couplers, including magenta couplers, e.g. in U.S. Pat. No. 3,227,554. 
The non-releasable connecting member L attached to a non-coupling position 
may have a composite structure, for example as represented by the formula: 
EQU --(L.sup.0).sub.k --L.sup.1 --(L.sup.2).sub.l --(L.sup.3).sub.m 
--(L.sup.4).sub.n --(L.sup.5).sub.o --(L.sup.6 
wherein L.sup.0 denotes the part of the connecting member closest to the 
group Q, and L.sup.7 denotes the part of the connecting member closest to 
the carboxyl group, and 
L.sup.0, L.sup.2, L.sup.4 and L.sup.6, which may be identical or different, 
denote O, NH, NHCO, CONH, NHSO.sub.2 or SO.sub.2 NH, 
L.sup.1, L.sup.3, L.sup.5 and L.sup.7, which may be identical or different, 
denote alkylene, aralkylene or arylene, and 
k, l, m, n, o, p and q each represent 0 or 1 such that l-m+n-o+p-q=0, and l 
and m preferably both have the value 1. 
An alkylene group denoted by L.sup.1, L.sup.3, L.sup.5 or L.sup.7 may be 
straight chained or branched and may have up to 20 carbon atoms. 
An aralkylene group denoted by L.sup.1, L.sup.3, L.sup.5 or L.sup.7 may be, 
for example, one of the following groups: 
##STR2## 
An arylene group denoted by L.sup.1, L.sup.3, L.sup.5 or L.sup.7 is 
preferably a phenylene group which may be substituted, e.g. with alkyl, 
alkoxy, halogen or acylamino. 
The non-releasable connecting member L preferably contains a ballast 
residue, especially when the noncoupling ring of the 
pyrazolo[3,2-c]-1,2,4-triazole ring system is not substituted with a 
ballast residue (different from --L--COOH). If, as is preferred, the 
non-releasable connecting member L contains a ballast residue, then this 
residue may consist of the totality of connecting member components 
L.sup.1 to L.sup.7 or it may be formed, for example, by one of the 
connecting member components L.sup.1, L.sup.3, L.sup.5 or L.sup.7 
containing a ballast residue in the form of a substituent. An alkylene 
group, for example, may be a 1,2-alkylene group or an alkylidene group 
with up to 20 carbon atoms; or an arylene group my be substituted, e.g. 
with an alkoxy group or an acyl-amino group, the said alkoxy group or 
acylamino group containing up to 20 carbon atoms and/or optionally also 
containing substituents. 
Groups may be regarded as ballast residues if they enable the magenta 
couplers according to the invention to be incorporated in a diffusion-fast 
form in the hydrophilic colloids conventionally used in photographic 
recording materials. These groups are preferably organic groups, generally 
containing straight chained or branched aliphatic groups with generally 8 
to 20 carbon atoms and optionally also containing carbocyclic or 
heterocyclic, optionally aromatic groups. These ballast residues are 
attached to the remaining part of the molecule either directly or 
indirectly, e.g. through one of the following groups: NHCO, NHSO.sub.2, NR 
(wherein R denotes hydrogen or alkyl), O or S. Such a ballast residue may 
in addition contain groups which confer solubility in water, e.g. hydroxyl 
groups or carboxyl groups, which may be present in an anionic form. Since 
the resistance to diffusion depends on the molecular size of the whole 
compound, it is in some cases sufficient to use ballast residues 
consisting of several relatively short chained groups. The ballast 
residues used according to the invention preferably have a molecular 
weight of less than 1000. 
The magenta couplers according to the invention may contain a ballast 
residue which is not identical to the group --L--COOH. A coupler contains 
such a ballast residue especially if the group --L--COOH does not itself 
contain a ballast residue. Such an additional ballast residue may have the 
structure --L--H in which L has the same meanings as defined for L in 
L--COOH but always contains a ballast residue. 
Examples of pyrazoloazo couplers according to the invention are shown below 
(Formula I-1): 
3 
coupler (M-) S X T 
1 CH.sub.3 Cl 
##STR3## 
2 C.sub.4 
H.sub.9t H 
##STR4## 
3 CH.sub.3 Cl 
##STR5## 
4 CH.sub.3 F 
##STR6## 
5 C.sub.4 
H.sub.9t Cl 
##STR7## 
6 C.sub.4 
H.sub.9t Cl 
##STR8## 
7 CH.sub.3 
##STR9## 
##STR10## 
8 CH.sub.3 
##STR11## 
##STR12## 
9 CH.sub.3 
##STR13## 
##STR14## 
10 (CH.sub. 2).sub.3COOH Br 
##STR15## 
11 CH.sub.3 Cl 
##STR16## 
12 
##STR17## 
Cl C.sub.3 H.sub.7 
13 
##STR18## 
H C.sub.4 H.sub.9 
14 CH.sub.3 H 
##STR19## 
The couplers according to the invention may be synthesized by various 
methods, e.g. as described in Research Disclosure 12 443 (August 1974): 
##STR20## 
In the above scheme of formulae, B denotes a group --L--COOH or --L--CO--Z 
wherein Z may be a protective group for the free carboxyl group (e.g. 
--OC.sub.2 H.sub.5). 
Another method of synthesis used, for example, for the coupler M-14 
consists of the reaction of 
2-[3-(4-aminophenyl)-propyl]-6-methyl-pyrazolo[3,2-c]-1,2,4-triazole with 
octadecenyl-succinic acid anhydride. 
In many cases of synthesizing the couplers according to the invention, it 
is advantageous for practical reasons of preparation to release the 
required carboxyl group only in the last stage of the synthesis. 
EXAMPLE OF SYNTHESIS 1 
Preparation of Coupler M-3 
p-Nitrophenoxy-butyric acid chloride was prepared in accordance with the 
method of synthesis of Coupler 3 given as an example in U.S. Pat. No. 
2,865,751. This compound was used instead of p-nitrophenyl-butyric acid 
chloride to prepare, by the method described in Example 2 of DE-A-No. 3 
610 702, under otherwise identical conditions, the compound 
3-methyl-4-chloropyrazolone-(5)-N'-.omega.-4-nitrophenoxy-butyryl-hydrazon 
e from which 
7-chloro-6-methyl-3-(p-nitrophenoxypropyl)-1z-H-pyrazolo[3,2-c]-s-triazole 
was obtained by the method described in Example 4 of DE-A-No. 3 610 702. 
1st Stage 
300 g of 3-methyl-4-chloropyrazolone-5-hydrazone (75%) were dissolved in 
2.3 l of water at 0.degree..degree.C., and 
280 g of sodium acetate followed by 
500 ml of methylene chloride were added to the solution. A solution of 
500 ml of methylene chloride was added dropwise at 0.degree. C. with rapid 
stirring within 2 hours. 
Stirring was continued for 30 minutes and the reaction mixture was then 
suction filtered and washed with a large quantity of water, and the 
product was dried at 50.degree. C. 
Yield: 286 g=84% of theoretical. 
M.pt. 155.degree.-158.degree. C. 
The proportion of product present was determined by titration with 
tetrabutyl ammonium hydroxide and found to be 99%. 
2nd Stage 
143 g of the acylhydrazone obtained as described above were heated to 
50.degree.-60.degree. C. in 
540 ml of Sulpholan, and 
145 ml of phosphorus oxychloride were added within 1-2 minutes while the 
acylhydrazone was heated. Complete solution occurred at 90.degree. C. and 
stirring was then continued for 30 minutes at 115.degree.-120.degree. C. 
After cooling, 
2500 ml of water were stirred in and stirring was continued for 1 hour. The 
product was then suction filtered, suspended in ethanol and stirred for 15 
minutes. 
Yield: 198 g=72% of theoretical 
M.pt. 188.degree.-189.degree. C. 
3rd Stage 
256 g of 
7-chloro-6-methyl-3-(p-nitrophenoxypropyl)-1-H-pyrazolo[3,2-c]-s-triazole 
obtained as product in Stage 2 were heated to boiling with 
256 g of Fe powder in 
2560 ml of methanol. 
256 ml of concentrated hydrochloric acid were then added dropwise within 20 
minutes. The starting product then completely dissolved. 
100 ml of concentrated hydrochloric acid were subsequently added and when 
the reaction was completed the iron was removed by suction filtration. The 
filtrate was precipitated into ice/water, suction filtered, washed and 
dried. 
Yield: 165 g=93% of theoretical 
M.pt.: 172.degree.-175.degree. C. with decomposition. 
4th Stage 
120 g of 
7-Chloro-6-methyl-3-(p-aminophenoxypropyl)-1-H-pyrazolo[3,2-c]-s-triazole 
were dissolved or suspended in 
900 ml of dioxane, and 
200 ml of pyridine were then added. 
215 g of .alpha.-(4-chlorosulphonylphenoxy)-myristic acid ethyl ester were 
added dropwise at room temperature. 
After completion of the reaction, the product was stirred into ice/HCl, 
taken up in ethyl acetate and separated. The solution in ethyl acetate was 
treated with Fuller's earth and freed from solvent under vacuum. The 
coupler M-3 crystallised towards the end. Recrystallisation from 
acetonitrile. 
Yield: 199 g=70% of theoretical. 
M.pt. 75.degree. C. 
The product was again dissolved in ethanol and hydrolysed with half 
concentrated sodium hydroxide solution. The product obtained after 
reprecipitation in ice/hydrochloric acid was recrystallised twice from 
methanol with active charcoal. 
Yield: 175 g 
M.pt.: 50.degree.-55.degree. C. 
Apart from the advantageous spectral properties of the image dyes produced 
from them and the excellent stability of the emulsions, the couplers 
according to the invention are particularly distinguished by the fact that 
the dyes obtained from them by the conventional process of colour 
development are produced with a high colour yield so that high maximum 
colour densities are obtained. Furthermore, the coupling activity of these 
couplers is comparatively unaffected by fluctuations in the pH of the 
developer solution, in particular by the sometimes unavoidable lowering of 
the pH. This is particularly advantageous for the sensitometric properties 
of the colour photographic recording material. 
For the preparation of light-sensitive colour photographic recording 
materials, the diffusion-resistant couplers according to the present 
invention may be incorporated in a known manner in the casting solution 
for the silver halide emulsion layers or for other colloid layers. Oil 
soluble or hydrophobic couplers, for example, may advantageously be added 
to a hydrophilic colloid solution from a solution in a suitable coupler 
solvent (oil former), optionally in the presence of a wetting or 
dispersing agent. The hydrophilic casting solution may, of course, contain 
the usual additives in addition to the binder. The solution of coupler 
need not be directly dispersed in the casting solution for the silver 
halide emulsion layer or other water-permeable layer but may 
advantageously first be dispersed in an aqueous, light-insensitive 
solution of a hydrophilic colloid and the resulting mixture may then be 
added to the casting solution for the light-sensitive silver halide 
emulsion layer or other water-permeable layer, the low boiling organic 
solvent used being first removed if necessary, and the resulting mixture 
may then be cast. 
The light-sensitive silver halide emulsions used may be emulsions of silver 
chloride, silver bromide or mixtures thereof, optionally with a small 
silver iodide content of up to 10 mol-%, in one of the conventionally used 
hydrophilic binders. The binder used for the photographic layers is 
preferably gelatine although this may be partly or completely replaced by 
other natural or synthetic binders. 
The emulsions may be chemically or spectrally sensitized in the usual 
manner and the layers of emulsion as well as other, light-insensitive 
layers may be hardened in the usual manner with known hardeners, in 
particular with hardeners containing compounds which activate carboxyl 
groups, such as carbamoyl pyridinium salts (e.g. according to DE-A No. 22 
25 230, DE-A No. 23 17 677, DE-A No. 24 39 551). 
Colour photographic recording materials normally contain at least one 
silver halide emulsion layer for recording light from each of the three 
spectral regions, red, green and blue. The light-sensitive layers are 
spectrally sensitized for this purpose by means of suitable sensitizing 
dyes in a known manner. Blue-sensitive silver halide emulsion layers need 
not necessarily contain a spectral sensitizer since the intrinsic 
sensitivity of the silver halide is in many cases sufficient for recording 
blue light. 
Each of the above-mentioned light-sensitive layers may consist of a single 
layer or it may be composed of two or more silver halide emulsion partial 
layers in a known manner, for example as in the so-called double layer 
arrangement (DE-C-1 121 470). Red-sensitive silver halide emulsion layers 
are normally arranged closer to the layer support than green-sensitive 
silver halide emulsion layers, which in turn are arranged closer to the 
layer support than blue-sensitive layers, and the blue-sensitive and 
green-sensitive layers are generally separated by a light-insensitive 
yellow filter layer, although other arrangements could be used. A 
light-insensitive interlayer is generally provided between layers which 
differ in their spectral sensitivity. This interlayer may contain means 
for preventing accidental diffusion of developer oxidation products. If 
several silver halide emulsion layers of the same spectral sensitivity are 
provided, these may be arranged directly adjacent to one another or they 
may be separated by a light-sensitive layer having a different spectral 
sensitivity (DE-A No. 1 958 709, DE-A No. 2 530 645, DE-A No. 2 622 922. 
Colour photographic recording materials for the production of multicolour 
images by chromogenic development normally contain non-diffusible colour 
couplers arranged in spatial and spectral association with the silver 
halide emulsion layers of the various spectral sensitivities to produce 
partial colour images in cyan, magenta and yellow. 
The term "spatial association" is used to denote that the colour coupler is 
situated in such a spatial relationship to the silver halide emulsion 
layer that the coupler and the layer are capable of interacting to give 
rise to an imagewise correspondence between the silver image formed on 
development and the colour image produced from the colour coupler. This is 
generally achieved by arranging the colour coupler in the silver halide 
emulsion layer or in an adjacent layer of binder which may be insensitive 
to light. 
The term "spectral association" is used to denote that the spectral 
sensitivity of each of the lightsensitive silver halide emulsion layers 
and the colour of the partial colour image produced from the spatially 
associated colour coupler are in a certain relationship to one another, 
each of the spectral sensitivities (red, green, blue) being associated 
with a partial colour image of a different colour (generally, for example, 
the colours cyan, magenta and yellow, in this sequence). 
Each of the silver halide emulsion layers sensitized to different regions 
of the spectrum may be associated with one or more colour couplers. If the 
photographic material contains several silver halide emulsion layers 
having the same spectral sensitivity, each of these layers may contain a 
colour coupler and the colour couplers need not necessarily be identical, 
provided only that on colour development they give rise to at least 
approximately the same colour, normally a colour which is complementary to 
the colour of the light to which the particular silver halide emulsion 
layers are predominantly sensitive. 
In the preferred embodiments, therefore, red-sensitive silver halide 
emulsions are associated with at least one non-diffusible colour coupler 
for producing the cyan partial colour image, generally a coupler of the 
phenol or .alpha.-naphthol series; green-sensitive silver halide emulsion 
layers are associated with at least one non-diffusible colour coupler for 
the production of the magenta partial colour image, in the present case a 
colour coupler corresponding to formula I; lastly, blue-sensitive silver 
halide emulsion layers are associated with at least one non-diffusible 
colour coupler for production of the yellow partial colour image, 
generally a colour coupler containing an open chain keto methylene group. 
Many colour couplers of this kind are known and have been described in 
numerous Patent Specifications and other documents; see, for example, the 
publication entitled "Farbkuppler" by W. Pelz in "Mitteilungen aus den 
Forschungslaboratorien der Agfa, Leverkusen/Me,uml/u/ unchen", Volume III, 
page 111 (1961) and the publication by K. Venkataraman in "The Chemistry 
of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press (1971). 
The colour couplers may be 4-equivalent couplers or they may be 
2-equivalent couplers. The latter are derived, as is known from 
4-equivalent couplers in that they contain, in the coupling position, a 
substituent which is released in the coupling reaction. The 2-equivalent 
couplers include both those which are virtually colourless and those which 
have an intense colour of their own which disappears in the process of 
colour coupling and may be replaced by the colour of the image dye 
produced (masking couplers). The known white couplers are in principle 
also 2-equivalent couplers although they give rise to substantially 
colourless products in their reaction with colour developer oxidation 
products. Also to be included among the 2-equivalent couplers are those 
couplers which carry in the coupling position a group which is released in 
the reaction with colour developer oxidation products to develop a certain 
photographic activity, e.g. as development inhibitor or accelerator, 
either directly or after removal of one or more further groups from the 
group originally released (e.g. DE-A No. 2 703 145, DE-A No. 2 855 697, 
DE-A No. 3 105 026 and DE-A No. 3 319 428). Examples of such 2-equivalent 
couplers include the known DIR couplers as well as DAR and FAR couplers. 
Suitable DIR couplers are described, for example, in GB-A No. 953 454, DE-A 
No. 1 800 420, DE-A No. 2 015 867, DE-A No. 2 414 006, DE-A No. 2 842 063 
and DE-A No. 3 427 235. 
Suitable DAR couplers and FAR couplers are described, for example, in GB-A 
No. 1 591 641, DE-A No. 3 209 110, EP-A No. 0 089 834, EP-A No. 0 117 511 
and EP-A No. 0 118 087. 
Since the DIR, DAR and FAR couplers are used mainly because of the activity 
of the group released in the coupling reaction and the colour producing 
properties of these couplers is less important, those DIR, DAR and FAR 
couplers which give rise to substantially colourless products in the 
coupling reaction are also suitable, for example those described in DE-A 
No. 1 547 640. 
The releasable group may be a ballast residue so that the reaction with 
colour developer oxidation products may give rise to coupling products, 
e.g. dyes which are diffusible or at least have a certain, limited 
mobility, for example as described in U.S. Pat. No. 4,420,556. 
High molecular weight colour couplers are described, for example, in DE-C 
No. 1 297 417, DE-A No. 2 407 569, DE-A No. 3 148 125, DE-A No. 3 217 200, 
DE-A No. 3 320 079, DE-A No. 3 324 932, DE-A No. 3 331 743, DE-A No. 3 340 
376, EP-A No. 27 284 and U.S. Pat. No. 4,080,211. The high molecular 
weight colour couplers are generally prepared by the polymerisation of 
ethylenically unsaturated, monomeric colour couplers although they may be 
obtained by polyaddition or polycondensation reactions. 
According to the present invention, the colour photographic recording 
material contains at least one coupler having the structure corresponding 
to formula I. The advantages achieved with such a coupler may be seen from 
the examples described below. Although the exact relationships are not 
known in detail, it is assumed that the advantages obtained with the 
couplers according to the invention are due to the structure of the 
couplers illustrated in formula I, in particular the special structure of 
the --L--COOH group. 
The characteristic group of the couplers of formula I has no major 
influence on the spectral properties of the image dyes produced but the 
carboxyl group has an advantageous effect on the maximum colour density 
obtainable and the stability to fluctuations in the pH of the colour 
developer solution. 
In addition to the components already mentioned, the photographic recording 
material according to the present invention may contain additives such as, 
for example, anti-oxidants, dye stabilizers and substances influencing the 
mechanical and electrostatic properties. It is advantageous, for example, 
to use UV absorbent compounds in one or more of the layers of the 
recording material, preferably one of the upper layers, for the purpose of 
preventing or reducing the adverse effect of UV light on the colour images 
produced with the colour photographic recording material according to the 
invention. Suitable UV absorbents are described, for example, in U.S. Pat. 
No. 3,253,921, DE-C No. 2 036 719 and EP-A No. 0 057 160. 
For the production of colour photographic images, the colour photographic 
recording material according to the invention, which contains at least one 
silver halide emulsion layer and at least one coupler of formula I 
associated with this layer, is developed with a colour developer compound. 
The colour developer compound used may be any developer compound whose 
oxidation product is capable of reacting with colour couplers to form 
azomethine dyes. Suitable colour developer compounds include aromatic 
compounds of the p-phenylenediamine series containing at least one primary 
amino group; for example, N,N-dialkyl-p-phenylenediamines such as 
N,N-diethyl-p-phenylenediamine, 
1-(N-ethyl-N-methyl-sulphonamidoethyl)-3-methyl-p-phenylenediamine, 
1-(N-ethyl-N-hydroxyethyl)-3-methyl-p-phenylenediamine and 
1-(N-ethyl-N-methoxyethyl)-3-methyl-p-phenylenediamine. 
Other suitable colour developers are described, for example, in 
J.Amer.Chem.Soc. 73, 3100 (1951) and in Modern Photographic Processing by 
G. Haist, 1979, John Wiley and Sons, New York, pages 545 et seq. 
After colour development, the material is bleached and fixed in the usual 
manner. Bleaching and fixing may be carried out separately or together. 
The usual bleaching compounds may be used, e.g. Fe.sup.3+ salts and 
Fe.sup.3+ complex salts such as ferricyanides, dichromates, water-soluble 
cobalt complexes, etc. Iron-III complexes of amino-polycarboxylic acids 
are especially preferred, e.g. the complexes of ethylene diaminotetracetic 
acid, of N-hydroxyethyl-ethylene-diaminotriacetic acid, of 
alkyliminodicarboxylic acids and of the corresponding phosphonic acids. 
Persulphates are also suitable bleaching agents.

EXAMPLE 1 
8 mmol of each magenta coupler were dissolved in ethyl acetate (EA) at 
about 50.degree. C. in proportions of 1:3 and dibutylphthalate (DBP) and a 
wetting agent (di-n-octyl sulfosuccinate) were added so that the 
components were present in the following proportions: 
EQU Coupler : DBP : EA : wetting agent=1:1:3:=O.1. 
The mixture was then emulsified in 7.5% gelatine solution and the emulsion 
was stirred at 1000 revs/min for 6 minutes, during which it heated up to 
about 50.degree. C. EA was removed by suction filtration in a water jet 
vacuum (200-300 mbar). The emulsions prepared as described above were 
mixed with a silver iodobromide emulsion (0.7 mol-% iodide) in proportions 
of 1 mol of coupler to 5.2 mol of AgNO.sub.3, and each mixture was applied 
to a layer support of cellulose acetate and covered wtih a protective 
layer of a 3% gelatine solution containing carbamoyl pyridinium betaine 
(CAS Reg. No. 65411-60-1) as hardener. The samples were dried and cut up 
and then exposed behind a step wedge and processed by the negative-AP 70 
process (38.degree. C.). 
______________________________________ 
Bath min 
______________________________________ 
Colour developer (CD 70) 
3.25 
Bleaching bath 6.5 
Washing 3.0 
Fixing bath 6.5 
Washing 6.0. 
______________________________________ 
The following baths were used: 
Colour developer 
8000 ml water 
17 g sodium hydroxyethane diphosphonate 
12 g ethylene diaminotetracetic acid (EDTA acid) 
47 g 1-(N-ethyl-N-hydroxyethyl)-3-methyl-p-phenylene diamine 
25 g hydroxylammonium sulphate 
39 g sodium sulphite 
15.5 g sodium bicarbonate 
335 g potassium carbonate 
13.5 g potassium bromide made up with water to 10 l; pH 10.0 
Bleaching bath 
8000 ml water 
1390 g ammonium bromide 
865 g EDTA NH.sub.4 -Fe 
163 g EDTA acid 
100 g ammonia made up with water to 10 l and adjusted to pH 6.0 .+-.0.1 
with about 15 ml glacial acetic acid 
Fixing bath 
8000 ml water 
1500 g ammonium thiosulphate 
100 g sodium sulphite 
20 g sodium hexametaphosphate made up with water to 10 l; pH 7.5 
Further developments were carried out with the only difference that the 
colour developer bath was adjusted to a pH value of 9.6, 9.8, 10.2 and 
10.4, respectively. The maximum magenta colour densities obtained are 
shown in Table 1. 
TABLE 1 
__________________________________________________________________________ 
D.sub.max at the following pH 
of colour developer: 
Coupler pH: 9.6 9.8 10.0 10.2 10.4 
__________________________________________________________________________ 
COUP 1 0.31 0.5 1.02 1.58 1.64 
COUP 2 0.54 0.62 1.52 1.70 1.84 
COUP 3 Comparison 
0.32 0.71 1.38 1.84 1.84 
COUP 4 0.40 0.48 1.22 1.68 1.70 
M-3 0.80 1.85 2.00 2.64 2.66 
M-4 according to 
0.68 1.96 2.22 2.84 2.90 
M-11 the invention 
0.95 2.10 2.58 2.80 2.82 
M-14 1.20 2.20 2.60 2.94 2.92 
__________________________________________________________________________ 
The following couplers were used for comparison: 
##STR21## Coup 1 
##STR22## Coup 2 
##STR23## Coup 3 
##STR24## Coup 4 
Further samples of colour photographic recording materials were prepared 
and processed as described in Example 1, using the couplers mentioned in 
Table 2 (Coupler according to the invention and Comparison Couplers). 
The following Comparison couplers were used: 
##STR25## 
The results of photographic sensitivity E, gradation .gamma., colour yield 
FA and fog S are shown in Table 2. 
TABLE 2 
______________________________________ 
Coupler E .gamma. FA S 
______________________________________ 
COUP 5 standard 0.6 1.40 0.13 
COUP 6 -0.6 0.42 1.60 0.12 
COUP 7 -2.5 0.68 1.82 0.10 
COUP 8 +0.6 0.48 2.0 0.18 
M-6 +3.0 1.04 2.82 0.12 
______________________________________ 
EXAMPLE 3 
A colour photographic recording material for negative colour development 
was prepared by applying the following layers in the given sequence to a 
transparent layer support of cellulose triacetate. The quantities are 
based in each case on 1 m.sup.2. The quantities of silver halide applied 
are given in the corresponding quantities of AgNO.sub.3. All the silver 
halide emulsions were stabilized with 0.5 g of 
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene per 100 g. 
Layer 1 (Antihalation layer) 
Black colloidal silver sol containing 
0.18 g Ag 
0.30 g UV absorbent UV-1 and 
1.5 g gelatine 
Layer 2 (Interlayer) 
Silver iodobromide emulsion (0.8 mol-% 
iodide) obtained from 0.15 g AgNO.sub.3 with 
0.15 g 2,5-dioctylhydroquinone 
0.11 g coupler C-1 and 
0.3 g gelatine 
Layer 3 (1st red-sensitized layer) 
Red-sensitized silver iodobromide emulsion 
(5 mol-% iodide) obtained from 0.7 g 
AgNO.sub.3 with 
0.1 g Coupler C-2, 
0.3 g Coupler C-3, 
0.01 g Coupler C-4 and 
1.2 g gelatine 
Layer 4 (2nd red-sensitized layer) 
Red-sensitized silver iodobromide emulsion 
(10 mol-% iodide) obtained from 1.2 g 
AgNO.sub.3 with 
0.1 g Coupler C-2, 
0.05 g Coupler C-3, 
0.05 g Coupler C-5 and 
0.9 g gelatine 
Layer 5 (3rd red-sensitized layer) 
Red-sensitized silver iodobromide emulsion 
(10 mol-% iodide) obtained from 2.0 g 
AgNO.sub.3 with 
0.05 g Coupler C-3, 
0.15 g Coupler C-5, 
0.003 g Coupler C-6 and 
0.8 g gelatine 
Layer 6 (Interlayer) 
0.5 g gelatine 
Layer 7 (1st green-sensitized layer) 
Green sensitized silver iodobromide emulsion 
(5 mol-% iodide) obtained from 0.5 g AgNO.sub.3 
with 
0.3 g Coupler C-7, 
0.4 g Coupler C-8, 
0.5 g Coupler C-9, 
0.5 g Coupler C-10 and 
1.2 g gelatine 
Layer 8 (2nd green-sensitized layer) 
Green-sensitized silver iodobromide emulsion 
(6 mol-% iodide) obtained from 1.0 g AgNO.sub.3 
with 
0.25 g Coupler C-7, 
0.01 g Coupler C-8, 
0.01 g Coupler C-9, 
0.01 g Coupler C-10 and 
1.7 g gelatine 
Layer 9 (3rd green-sensitive layer) 
Green-sensitized silver iodobromide emulsion 
(10 mol-% iodide) obtained from 1.5 g 
AgNO.sub.3 with 
0.015 g Coupler C-8, 
0.07 g Coupler C-11, 
0.002 g Coupler C-12 and 
1.0 g gelatine 
Layer 10 (Yellow filter layer) 
Yellow colloidal silver sol obtained from 
0.05 g Ag with 
0.03 g 3,5-ditert.-octylhydroquinone and 
0.6 g gelatine 
Layer 11 (1st Blue-sensitive layer) 
Silver iodobromide emulsion (5 mol-% iodide) 
obtained from 0.3 g AgNO.sub.3 with 
0.7 g Coupler C-13, 
0.03 g Coupler C-14 and 
1.4 g gelatine 
Layer 12 (2nd blue-sensitive layer) 
Silver iodobromide emulsion (5 mol-% iodide) 
obtained from 0.3 g AgNO.sub.3 with 
0.25 g Coupler C-13 and 
0.6 g gelatine 
Layer 13 (Micrate layer) 
Silver iodobromide emulsion (2 mol-% iodide) 
obtained from 0.4 g AgNO.sub.3 with 
0.1 g gelatine 
Layer 14 (3rd blue-sensitive layer) 
Silver iodobromide emulsion (10 mol-% 
iodide) obtained from 0.8 g AgNO.sub.3 with 
0.2 g Coupler C-13 and 
0.5 g gelatine 
Layer 15 (1st protective layer) 
0.14 g UV absorbent UV-1, 
0.20 g UV absorbent UV-2 and 
0.4 g gelatine 
Layer 16 (2nd protective layer) 
0.95 g of hardener CAS Reg. No. 65411-60-1 and 
0.23 g gelatine. 
The recording material prepared as described above will be referred to as 
Material A (not according to the invention). A material B conforming to 
the present invention was prepared by the same method. This Material B 
differed from Material A only in that layers 7, 8 and 9 contained the 
couplers M-3 and M-11 instead of couplers C-7 and C-11. 
The following sensitometric data (Table 3) were obtained after exposure and 
processing as described in Example 1: 
TABLE 3 
______________________________________ 
Material 
Coupler E D.sub.max 
.gamma. 
.lambda..sub.max 
S 
______________________________________ 
A C-7/C-11 .+-.0 2.2 0.8 555 0.12 
(standard) 
B M-3/M-11 +1.8 3.3 1.42 553 0.12 
______________________________________ 
The following D.sub.max values (Table 4) are obtained after exposure and 
processing if the materials A and B are exposed to a formalin 
concentration of 10 ppm at 70% relative humidity for 0, 3, 7, 14 or 21 
days prior to exposure: 
TABLE 4 
______________________________________ 
D.sub.max 
Days: 
Material Coupler 0 3 7 14 21 
______________________________________ 
A C-7/C-11 2.2 2.2 1.9 1.5 1.0 
B M-3/M-11 3.3 3.2 3.08 3.08 3.0 
______________________________________ 
The following compounds were used: 
##STR26##