Colour print material with variable gradation

A color photographic print material with the usual three different sensitized silver halide emulsion layers and at least one silver halide emulsion layer containing no color coupler (control layer) with a spectral sensitization range outside the sensitization range of the image-producing layers, wherein the control layer contains a substance A, which, on negative development of the silver halide emulsion used in the control layer (control emulsion), releases a compound B which alters the gradation of the image-producing layers, is usable as a print material with variable gradation.

The present invention relates to a colour photographic print material with 
which, after exposure through a negative and negative processing, images 
of variable gradation may be obtained. 
Manufacturers of colour photographic print materials currently offer them 
for sale in varying gradations, for example with flat gradation for 
portraits and similar images, with medium gradation for the majority of 
amateur photographs and with steep gradation for professional promotional 
photographs. 
This situation is disadvantageous not only in that three materials of 
different composition must be produced, but also in that the grade of 
paper must frequently be changed in the printer or the printer must be 
arranged such that several cassettes with different materials may be 
accommodated. 
A final disadvantage is that no more levels of gradation may be achieved 
than there are available grades of paper with differing gradation, 
continuous adjustment of gradation is thus not possible. 
There is thus a requirement for a colour negative print material with 
variable gradation, in particular a colour negative paper with variable 
gradation. 
Black-&-white papers with variable gradation have long been known 
(Ullmann's Encyclopedia of Industrial Chemistry, vol. A20, Photography, pp 
138-139, VCH Verlagsgesellschaft mbH, D-6940 Weinheim, 1992). 
The photosensitive layer of such black-&-white papers customarily contains, 
for example, a silver halide emulsion sensitive to blue light and a silver 
halide emulsion sensitive to blue and green light, which emulsions differ 
in gradation. 
By systematically altering the copy light, the gradation of the image may 
be varied over a broad range. This process, known as the filter process, 
is restricted to black-&-white materials and cannot be transferred to 
colour materials as it would lead to extreme colour distortion in a colour 
material. 
It is only for colour reversal materials that a method is known for the 
production of lower contrast prints (lower gradation) from very high 
contrast slides (steep gradation) by performing a generally subliminal 
pre-exposure without the image using white light and thereafter performing 
the customary exposure with the image and then subjecting the material to 
reversal development. The scope for changing gradation using this process 
is slight. The process is restricted to reversal materials and is usable 
only to reduce gradation (U.S. Pat. No. 4,021,831, EP 408 882). 
The object of the present invention was to provide a colour print material 
with variable gradation and preferably a colour negative paper with 
variable gradation. 
The object is achieved with a colour photographic print material which 
contains on a support at least one blue-sensitive silver halide emulsion 
layer containing at least one yellow coupler, at least one green-sensitive 
silver halide emulsion layer containing at least one magenta coupler and 
at least one red-sensitive silver halide emulsion layer containing at 
least, one cyan coupler, and which contains in at least one layer 
containing no colour coupler (control layer) a silver halide emulsion 
(control emulsion) sensitized differently to the blue-, green- or 
red-sensitized silver halide emulsions and a substance A, which, on colour 
negative development of the control emulsion, releases a compound B which 
alters the gradation of at least one layer containing colour coupler. 
Print material is taken to be a material which, after exposure through a 
colour negative and negative processing, displays a positive image. 
Its support may be transparent (display material) or reflective (colour 
negative paper). 
The control emulsion and substance A may be arranged in a layer above all 
the layers containing colour coupler or in a layer below all the layers 
containing colour coupler (in each case starting from the support 
material) or in any desired interlayer. 
The control emulsions and substance A may also be arranged in two or more 
layers containing no colour coupler. 
The control emulsion and substance A are preferably arranged in the layers 
containing no colour coupler such that the gradation of all the layers 
containing colour coupler is altered in the same direction and to 
approximately the same extent. 
Component B may act either to increase gradation or to decrease gradation. 
Development accelerators, for example, act to increase gradation, 
development inhibitors to decrease gradation. Accordingly, in one case 
substance A is, for example, a DIR compound and in the other case a DAR 
compound (DIR compound: development inhibitor releasing compound; DAR 
compound: development accelerator releasing compound). 
DIR compounds will preferably be used in a material with high gradation and 
DAR compounds in a material with low gradation. 
The substances A preferably have a reaction rate constant with the 
developer oxidation product of K.sub.DOP .gtoreq.30,000 
[l/mol.multidot.s]. This reaction rate constant is determined according to 
EP-A-0 537 545, pages 8 and 9. 
The substances B preferably have diffusibility of .gtoreq.0.4. The method 
for determining this parameter is also contained in EP-A-0 537 545, pages 
19 to 21. 
Suitable compounds A are compounds of the formulae I and II: 
##STR1## 
in which INH means the residue of an inhibitor bonded via an N atom or via 
an S atom, preferably from the series of mono- or bicyclic triazoles or of 
mercapto-1,2,4-thia-diazoles, which residue is attached to the coupling 
site directly or via a time control member, 
R.sub.1 means a residue R.sub.3 --CO--, R.sub.3 --NR.sub.2 --CO--, R.sub.6 
CO--NR.sub.2 --NR.sub.2 --CO--, 
##STR2## 
R.sub.2 means hydrogen, alkyl, aralkyl, or alkylene attached to an 
adjacent aromatic residue, 
R.sub.3 means an optionally substituted aromatic carbocyclic or 
heterocyclic residue, 
R.sub.4 means the atoms necessary to complete an aromatic or heterocyclic 
residue, 
R.sub.5 means a substituent with a Hammett constant .sigma..sub.meta of at 
least 0.1, preferably a carbonamido or carbamoyl group, 
R.sub.6 means alkyl, aryl, aralkyl, alkoxy, alkylamino, arylamino or 
aralkylamino, 
R.sub.7 means alkyl, aryl or aralkyl, 
R.sub.8 means --NR.sub.2 -- or --S--, 
R.sub.9 and R.sub.10 mean hydrogen, alkyl, aryl, alkoxy, alkylcarbonyl, 
arylcarbonyl, alkylsulphonyl, arylsulphonyl or together C.sub.3 -C.sub.5 
alkylene or the remaining members of an aromatic carbocyclic or 
heterocyclic ring. 
Preferred compounds A are of the formula III 
##STR3## 
in which R.sub.11 means --CO-- or --SO.sub.2 -- 
R.sub.12 means hydrogen, halogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 
-C.sub.4 alkoxy, 
R.sub.13, R.sub.14, R.sub.15 mean hydrogen, halogen, alkyl, aryl, alkoxy, 
aryloxy, alkylthio, arylthio, sulphonamido, sulphamoyl, carbamoyl, 
acylamino, ureido, alkoxycarbonyl, acyloxy, aminocarbonyloxy or sulphonyl, 
wherein sulphonamido, sulphamoyl, carbamoyl, ureido, aminocarbonyloxy and 
sulphonyl are further substituted and at least one of the substituents 
R.sub.13, R.sub.14, R.sub.15 is a ballast residue. 
Examples of suitable compounds are: 
##STR4## 
The control emulsion is preferably used in a quantity of 0.001 to 2.0 
mmol/m.sup.2 per control layer; compound A in a quantity of 0.0005 to 1.0 
mmol/m.sup.2 per control layer. 
In particular, the control emulsion is used in a quantity of 0.05 to 1.0 
mmol/m.sup.2 per control layer; compound A in a quantity of 0.005 to 0.1 
mmol/m.sup.2 per control layer. 
The material may in particular contain up to 4 control layers. The material 
preferably contains 3 control layers. 
The control emulsion is preferably sensitized to the spectral range between 
green and red, i.e. for example to a range from 570 to 690 nm, preferably 
580 to 680 nm, or to the infra-red range, i.e. for example to a range 
above 730 nm, preferably 740 to 800 nm. Appropriate sensitizers are known 
from the literature or may be produced using processes known from the 
literature. 
Suitable spectral sensitizers for the range 570 to 690 nm belong, for 
example, to the following classes: benzothiazoletrimethinecyanines of the 
formula 
##STR5## 
in which R.sub.1 means CH.sub.3, C.sub.2 H.sub.5 
R.sub.2, R.sub.3 mean C.sub.2 H.sub.5, (CH.sub.2).sub.n SO.sub.3 
n means 2, 3, 4 
R.sub.4, R.sub.5, R.sub.6, R.sub.7 mean Cl, CN or CH.sub.3 
for example 
EQU R.sub.1 =CH.sub.3, R.sub.2 =(CH.sub.2).sub.3 SO.sub.3, R.sub.3 
=(CH.sub.2).sub.3 SO.sub.3 H, R.sub.4, R.sub.6 =Cl, R.sub.5, R.sub.7 =H, 
.lambda..sub.max =655 nm; S-1 
EQU R.sub.1 =C.sub.2 H.sub.5, R.sub.2 =(CH.sub.2).sub.4 SO.sub.3, R.sub.3 
=(CH.sub.2).sub.4 --SO.sub.3 H, R.sub.4, R.sub.6 =Cl, R.sub.5, R.sub.7 =H, 
.lambda..sub.max =650 nm; S-2 
Naphthoxazolebenzothiazoletrimethinecyanines of the formula 
##STR6## 
in which R.sub.1, R.sub.2, R.sub.3, R.sub.6, R.sub.7 and n have the 
meaning stated above, 
for example 
EQU R.sub.1 =CH.sub.3, R.sub.2 =(CH.sub.2).sub.3 SO.sub.3, R.sub.3 
=(CH.sub.2).sub.3 SO.sub.3 H, R.sub.6 =Cl, R.sub.7 =H, .lambda..sub.max 
=610 nm; S-3 
EQU R.sub.1, R.sub.2 .ltoreq.C.sub.2 H.sub.5, R.sub.3 =(CH.sub.2).sub.4 
SO.sub.3, R.sub.6 =Cl, R.sub.7 =H, .lambda..sub.max =605 nm; S-4 
Naphthothiazolebenzimidazoletrimethinecyanines of the formula 
##STR7## 
in which R.sub.1, R.sub.2, R.sub.3, R.sub.6, R.sub.7 and n have the 
meaning stated above, 
for example 
EQU R.sub.1 =CH.sub.3, R.sub.2 =(CH.sub.2).sub.3 SO.sub.3, R.sub.3 
=(CH.sub.2).sub.3 SO.sub.3 H, R.sub.6, R.sub.7 =Cl, .lambda..sub.max =610 
nm; S-5 
EQU R.sub.1 =C.sub.2 H.sub.5, R.sub.2 =(CH.sub.2).sub.4 SO.sub.3, R.sub.3 
=C.sub.2 H.sub.5, R.sub.6, R.sub.7 =Cl, .lambda..sub.max =605 nm; S-6 
Naphthoxazolebenzoselenazoletrimethinecyanines of the formula 
##STR8## 
in which R.sub.1, R.sub.2, R.sub.3, R.sub.6, R.sub.7 and n have the 
meaning stated above, 
for example 
EQU R.sub.1 =CH.sub.3, R.sub.2 =(CH.sub.2).sub.3 SO.sub.3, R.sub.3 
=(CH.sub.2).sub.3 SO.sub.3 H, R.sub.6 =OCH.sub.3, R.sub.7 =CH.sub.3, 
.lambda..sub.max =620 nm; S-7 
EQU R.sub.1, R.sub.2 =C.sub.2 H.sub.5, R.sub.3 =(CH.sub.2).sub.3 SO.sub.3, 
R.sub.6 =OCH.sub.3, R.sub.7 =CH.sub.3, .lambda..sub.max =610 nm. S-8 
Suitable spectral sensitisers for the infra-red range belong, for example, 
to the following classes: 
Benzothiazolepentamethinecyanines of the formula 
##STR9## 
in which R.sub.2, R.sub.3, R.sub.5, R.sub.6 and n have the meaning stated 
above, 
for example 
EQU R.sub.2, R.sub.3 =C.sub.2 H.sub.5, R.sub.5, R.sub.6 =Cl, .lambda..sub.max 
=750 nm; S-9 
Naphthothiazolepentamethinecyanines of the formula 
##STR10## 
in which R.sub.2, R.sub.3 and n have the meaning stated above, 
for example 
EQU R.sub.2 =(CH.sub.2).sub.3 SO.sub.3, R.sub.3 =(CH.sub.2).sub.3 SO.sub.3 H, 
.lambda..sub.max =760 nm; S-10 
Naphthoselenazolepentamethinecyanines of the formula 
##STR11## 
in which R.sub.2, R.sub.3 and n have the meaning stated above, 
for example 
EQU R.sub.2, R.sub.3 =C.sub.2 H.sub.5, .lambda..sub.max =765 nm. S-11 
The absorption maxima were determined on spectrally sensitized 
AgCl.sub.0.995 Br.sub.0.005 emulsions from example 2, 3rd, 5th or 7th 
layer. 
Further suitable spectral sensitizers for the infra-red range belong to the 
following classes: 
benzothiazoleheptamethinecyanines, 
benzoxazolebenzothia-zoleheptamethinecyanines, 
benzoxazolehephthiazolehepta-methinecyanines, 
naphthiazoleheptamethinecyanines and benzoselenazoleheptamethinecyanines. 
The control emulsion used is preferably a silver halide emulsion which may 
be developed very rapidly and which releases compound B from substance A 
by development and reaction with the developer oxidation product more 
rapidly than the silver halide emulsions of the layers containing colour 
coupler develop. 
The control emulsion is preferably fine-grained (average grain size 0.05 to 
1.0, preferably 0.1 to 0.4 .mu.m) and preferably has a high chloride 
content (.gtoreq.70 mol. % AgCl, in particular .gtoreq.95 mol. % AgCl). 
Colour photographic silver halide materials are known containing a silver 
halide emulsion layer which contains no colour coupler. The silver halide 
emulsion of said silver halide emulsion layer is sensitive for a region of 
the visible light for which the image-producing layers are insensitive and 
said silver halide emulsion layer contains a DIR compound (DE 29 02 681, 
EP 167 173, DE 37 00 419). No print materials are disclosed but only 
colour films with camera sensitivity, wherein these means yield 
improvements with respect to sharpness, high colour density and pure 
colours. An influence of these means on gradation is not known from these 
references. According to the invention an influence on gradation is only 
obtained under specific conditions which are described below. 
Commercially known print materials do not contain silver halide emulsion 
layers containing DIR compounds and being free from colour couplers. 
Alteration of gradation is achieved with the material according to the 
invention by the material being exposed non-imagewise, before or after the 
imagewise exposure, with light of a wavelength within the spectral range 
to which the control emulsion is sensitive, and the imagewise exposure 
being performed with light which contains no fractions to which the 
control emulsion is sensitive. The different exposures may be performed by 
using appropriately filtered white light. 
Exposure of the control emulsion may also be performed with a laser 
emitting light in the desired spectral range or other suitable light 
sources. 
By varying the quantity of light in the spectral range to which the control 
emulsion is sensitive, the gradation of the three chromophoric layers may 
be continuously varied in the desired direction. The quantity of light is, 
for example, varied by altering the exposure time to the same light 
source. By varying the type and quantity of the DIR or DAR coupler in the 
control layer, gradation of the chromophoric layers may be further 
altered. 
Suitable supports for production of the colour photographic materials are, 
for example, films and sheets of semi-synthetic and synthetic polymers 
such as cellulose nitrate, cellulose acetate, cellulose butyrate, 
polystyrene, polyvinyl chloride, polyethylene terephthalate and 
polycarbonate and paper laminated with a barytes layer or an 
.alpha.-olefin polymer layer (for example polyethylene). The surface of 
the support is generally subjected to a treatment in order to improve the 
adhesion of the photographic emulsion layer, for example to a corona 
discharge with subsequent application of a substrate layer. 
The photographic emulsion layers (apart from the control layer) 
substantially comprise binders, silver halide grains and colour couplers. 
Gelatine is preferably used as the binder. Gelatine may, however, be 
entirely or partially replaced with other synthetic, semi-synthetic or 
also naturally occurring polymers. Synthetic gelatine substitutes are, for 
example, polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyacrylamides, 
polyacrylic acid and the derivatives thereof, in particular the copolymers 
thereof. Naturally occurring gelatine substitutes are, for example, other 
proteins such as albumin, chitosan, chitin or casein, cellulose, sugar, 
starch or alginates. Semi-synthetic gelatine substitutes are usually 
modified natural products. Cellulose derivatives such as hydroxyalkyl 
cellulose, carboxymethyl cellulose and phthalyl cellulose together with 
gelatine derivatives obtained by reaction with alkylating or acylating 
agents or by grafting polymerisable monomers, are examples of such 
products. The binders should have a sufficient quantity of functional 
groups available so that satisfactorily resistant layers may be produced 
by reaction with suitable hardeners. Such functional groups are in 
particular amino groups, but also carboxyl groups, hydroxyl groups and 
active methylene groups. 
The preferably used gelatine may be obtained by acid or alkaline digestion. 
Oxidised gelatine may also be used. The production of such gelatines is 
described, for example, in The Science and Technology of Gelatine, edited 
by A. G. Ward and A. Courts, Academic Press 1977, pages 295 et seq. The 
gelatine used in each case should have a content of photographically 
active impurities which is as low as possible (inert gelatine). Gelatines 
with high viscosity and low swelling are particularly advantageous. 
The silver halide present in the photographic material as the 
photosensitive constituent may contain chloride, bromide or iodide or 
mixtures thereof as the halide. 
For example, the halide content of at least one layer may consist of 0 to 
15 mol % iodide, 0 to 100 mol % chloride and 0 to 100 mol % bromide. The 
emulsions are preferably silver chloride-bromide emulsions with a chloride 
content of .gtoreq.95 mo. % up to pure silver chloride emulsions. The 
crystals may be predominantly compact, for example regularly cubic or 
octahedral or they may have transitional shapes. Lamellar crystals may, 
however, also be present, the average ratio of diameter to thickness of 
which is preferably at least 5:1, wherein the diameter of a grain is 
defined as the diameter of a circle the contents of which correspond to 
the projected surface area of the grain. The layers may, however, also 
have tabular silver halide crystals, in which the ratio of diameter to 
thickness is substantially greater than 5:1, for example 12:1 to 30:1. 
The silver halide grains may also have a multi-layered grain structure, in 
the simplest case with one internal zone and one external zone of the 
grain (core/shell), wherein the halide composition and/or other 
modifications, such as for example doping, of the individual grain zones 
are different. The average grain size of the emulsions is preferably 
between 0.2 .mu.m and 2.0 .mu.m, in particular between 0.45 and 1.20 
.mu.m, the grain size distribution may be both homodisperse and 
heterodisperse. A homodisperse grain size distribution means that 95% of 
the grains do not deviate by more than .+-.30% from the average grain 
size. The emulsions may, in addition to the silver halide, also contain 
organic silver salts, for example silver benzotriazolate or silver 
behenate. 
Two or more types of silver halide emulsions which are produced separately 
may be used as a mixture. 
The material according to the invention preferably contains a total 
quantity of silver halide, stated as the equivalent quantity of 
AgNO.sub.3, of at most 1 g/m.sup.2, in particular 0.6 to 0.8 g/m.sup.2. 
The photographic emulsions may be produced by various methods (for example 
P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris 
(1967), G. F. Duffin, Photographic Emulsion Chemistry, The Focal Press, 
London (1966), V. L. Zelikman et al., Making and Coating Photographic 
Emulsion, The Focal Press, London (1966)) from soluble silver salts and 
soluble halides. 
The silver halide emulsions are generally subjected to chemical 
sensitization under defined conditions--pH, pAg, temperature, gelatine 
concentration, silver halide concentration and sensitizer 
concentration--until the optimum sensitivity and fog are achieved. The 
procedure is described in, for example, H. Frieser, Die Grundlagen der 
Photographischen Prozesse mit Silberhalogeniden, pages 675-734, 
Akademische Verlagsgesellschaft (1968). 
Chemical sensitization may here proceed with the addition of compounds of 
sulphur, selenium, tellurium and/or compounds of metals of subgroup VIII 
of the periodic table (for example gold, platinum, palladium, iridium), 
furthermore there may be added thiocyanate compounds, surface-active 
compounds, such as thioethers, heterocyclic nitrogen compounds (for 
example imidazoles, azaindenes) or also spectral sensitizers (described, 
for example, in F. Hamer, The Cyanine Dyes and Related Compounds, 1964, or 
Ullmanns Encyclopadie der technischen Chemie, 4th edition, volume 18, 
pages 431 et seq, and Research Disclosure 17643 (December 1978), section 
III). Alternatively or additionally, reduction sensitization may be 
performed by adding reducing agents (tin(II) salts, amines, hydrazine 
derivatives, aminoboranes, silanes, formamidinesulphinic acid), by 
hydrogen, by low pAg (for example, less than 5) and/or high pH (for 
example, greater than 8). 
The photographic emulsions may contain compounds to prevent fogging or to 
stabilize photographic function during production, storage or photographic 
processing. 
Particularly suitable are azaindenes, preferably tetra- and 
pentaazaindenes, particularly those substituted with hydroxyl or amino 
groups. Such compounds have been described, for example, by Birr, Z. Wiss. 
Phot., 47, (1952), pages 2-58. Furthermore, salts of metals such as 
mercury or cadmium, aromatic sulphonic or sulphinic acids such as 
benzenesulphinic acid, or heterocyclics containing nitrogen such as 
nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles 
or benzothiazolium salts may also be used as anti-fogging agents. 
Particularly suitable are heterocyclics containing mercapto groups, for 
example mercaptobenzothiazoles, mercaptobenzimidazoles, 
mercaptotetrazoles, mercaptothiadiazoles, mercapto-pyrimidines, wherein 
these mercaptoazoles may also contain a water solubilising group, for 
example a carboxyl group or sulpho group. Further suitable compounds are 
published in Research Disclosure 17643 (December 1978), section VI. 
The stabilizers may be added to the silver halide emulsions before, during 
or after ripening thereof. Naturally, the compounds may also be added to 
other photographic layers which are associated with a silver halide layer. 
Mixtures of two or more of the stated compounds may also be used. 
The photographic emulsions of the layers containing colour coupler may be 
spectrally sensitized by using methine dyes or other dyes. Particularly 
suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine 
dyes. 
A review of the polymethine dyes suitable as spectral sensitizers, suitable 
combinations thereof and combinations with supersensitizing effects is 
contained in Research Disclosure 17643 (December 1978), section IV. 
In particular, the following dyes--classified by spectral range--are 
suitable: 
1. As Red Sensitizers 
9-ethylcarbocyanines with benzothiazole, benzoselenazole or naphthothiazole 
as basic terminal groups, which may be substituted in 5th or 6th position 
by halogen, methyl, methoxy, carbalkoxy, aryl, together with 
9-ethyl-naphthoxathia- or -selenocarbocyanines and 9-ethyl-naphthothiaoxa- 
or -benzoimidazocarbocyanines, provided that the dyes bear at least one 
sulphoalkyl group on the heterocyclic nitrogen. 
2. As Green Sensitizers 
9-ethylcarbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a 
benzothiazole as basic terminal groups, together with 
benzimidazolecarbocyanines, which may also be further substituted and must 
also contain at least one sulphoalkyl group on the heterocyclic nitrogen. 
3. As Blue Sensitizers 
symmetrical or asymmetrical benzimidazo-, oxa-, thia- or selenocyanines 
with at least one sulphoalkyl group on the heterocyclic nitrogen and 
optionally further substituents on the aromatic ring, together with 
apomerocyanines with a rhodanine group. 
Sensitizers may be dispensed with if the intrinsic sensitivity of the 
silver halide is adequate for a specific range of the spectrum, for 
example the blue sensitivity of silver bromides. 
The differently sensitized emulsion layers are, as explained at the 
beginning, associated with non-diffusing monomeric or polymeric colour 
couplers. 
Colour couplers to produce the cyan partial colour image are generally 
couplers of the phenol or .alpha.-naphthol type. 
Colour couplers to produce the magenta partial colour image are generally 
couplers of the 5-pyrazolone, indazolone or pyrazoloazole type. 
Colour couplers to produce the yellow partial colour image are generally 
couplers with an open-chain ketomethylene grouping, in particular couplers 
of the .alpha.-acylacetamide type; suitable examples of these couplers are 
.alpha.-benzoylacetanilide couplers and .alpha.-pivaloylacetanilide 
couplers. 
The colour couplers may be 4-equivalent couplers, but also 2-equivalent 
couplers. The latter are differentiated from 4-equivalent couplers by 
containing a substituent at the coupling site which is eliminated on 
coupling. 
High molecular weight colour couplers are, for example, described in DE-C-1 
297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, 
DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, U.S. Pat. No. 
4,080,211. The high molecular weight colour couplers are generally 
produced by polymerization of ethylenically unsaturated monomeric colour 
couplers. They may, however, also be produced by polyaddition or 
polycondensation. 
The incorporation of couplers or other compounds into silver halide 
emulsion layers may proceed by initially producing a solution, dispersion 
or emulsion of the compound concerned and then adding it to the coating 
solution for the layer concerned. Selection of the appropriate solvent or 
dispersant depends on the particular solubility of the compound. 
Methods for the introduction of compounds which are essentially insoluble 
in water by a grinding process are described, for example, in DE-A-26 09 
741 and DE-A-26 09 742. 
Hydrophobic compounds may also be introduced into the coating solution by 
using high-boiling solvents, so-called oil formers. 
Corresponding methods are described, for example, in U.S. Pat. No. 
2,322,027, U.S. Pat. No. 2,801,170, U.S. Pat. No. 2,801,171 and EP-A-0 043 
037. 
Oligomers or polymers, so-called polymeric oil formers, may be used instead 
of high-boiling solvents. 
The compounds may also be introduced into the coating solution in the form 
of loaded latices. Reference is, for example, made to DE-A-25 41 230, 
DE-A-25 41 274, DE-A-28 35 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-0 130 
115, U.S. Pat. No. 4,291,113. 
The non-diffusible inclusion of anionic water-soluble compounds (for 
example dyes) may also proceed with the assistance of cationic polymers, 
so-called mordanting polymers. 
Suitable oil formers are, for example, phthalic acid alkyl esters, 
phosphonic acid esters, phosphoric acid esters, citric acid esters, 
benzoic acid esters, amides, fatty acid esters, trimesic acid esters, 
alcohols, phenols, aniline derivatives and hydrocarbons. 
Examples of suitable oil formers are dibutyl phthalate, dicyclohexyl 
phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl 
phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, 
tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, 
tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl 
phosphate, 2-ethylhexyl benzoate, dodecyl benzoate, 
2-ethylhexyl-p-hydroxybenzoate, diethyldodecanamide, 
N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, dioctyl 
acelate, glycerol tributyrate, iso-stearyl lactate, trioctyl citrate, 
N,N-dibutyl-2-butoxy-5-t-octyl aniline, paraffin, dodecyl- benzene and 
diisopropylnaphthalene. 
Each of the differently sensitized photosensitive layers may consist of a 
single layer or may also comprise two or more partial layers of silver 
halide emulsion. In colour photographic silver halide materials according 
to the invention the blue-sensitive, yellow-coupling layer is applied 
first to the support, then the green-sensitive, magenta-coupling layer and 
finally the red-sensitive, cyan-coupling layer in a preferred embodiment. 
The non-photosensitive interlayers generally located between layers of 
different spectral sensitivity may contain in addition to the compounds 
according to the invention agents which prevent an undesirable diffusion 
of developer oxidation products from one photosensitive layer into another 
photosensitive layer with a different spectral sensitization. 
Suitable agents, which are also known as scavengers or DOP scavengers, are 
described in Research Disclosure 17 643 (December 1978), section VII, 17 
842 (February 1979) and 18 716 (November 1979 ), page 650 and in EP-A-0 
069 070, 0 098 072, 0 124 877, 0 125 522. 
If there are several partial layers of the same spectral sensitization, 
then they may differ in composition, particularly in terms of the type and 
quantity of silver halide grains. In general, the partial layer with the 
greater sensitivity will be located further from the support than the 
partial layer with lower sensitivity. Partial layers of the same spectral 
sensitization may be adjacent to each other or may be separated by other 
layers, for example layers of different spectral sensitization. 
Preferably, the material according to the invention contains only one 
blue-, one green- and one red-sensitive silver halide emulsion layer which 
contain the complementary couplers. 
The photographic material may also contain UV light absorbing compounds, 
optical whiteners, toothing agents, filter dyes, formalin scavengers, 
light stabilizers, anti-oxidants, D.sub.min dyes, additives to improve 
stabilization of dyes, couplers and whites and to reduce colour fogging, 
plasticisers (latices), biocides and others. 
The layers of the photographic material according to the invention may be 
hardened with customary hardeners. Suitable hardeners are, for example, 
formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, 
cyclopentadione and similar ketone compounds, bis-(2-chloroethylurea), 
2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds containing 
reactive halogen U.S. Pat. No. 3,288,775, U.S. Pat. No. 2,732,303, 
GB-A-974,723 and GB-A-1,167,207), divinylsulphone compounds, 
5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine and other compounds 
containing a reactive olefin bond (U.S. Pat. No. 3,635,718, U.S. Pat. No. 
3,232,763 and GB-A-994,869); N-hydroxymethylphthalimide and other 
N-methylol compounds (U.S. Pat. No. 2,732,316 and U.S. Pat. No. 
2,586,168); isocyanates (U.S. Pat. No. 3,103,437); aziridine compounds 
(U.S. Pat. No. 3,017,280 and U.S. Pat. No. 2,983,611); acid derivatives 
(U.S. Pat. No. 2,725,294 and U.S. Pat. No. 2,725,295); compounds of the 
carbodiimide type U.S. Pat. No. 3,100,704); carbamoylpyridinium salts 
(DE-A-22 25 230 and DE-A-24 39 551); carbamoyloxypyridinium compounds 
(DE-A-24 08 814); compounds with a phosphorus-halogen bond (JP-A-113 
929/83); N-carbonyloximide compounds (JP-A-43353/81); N-sulphonyloximido 
ompounds (U.S. Pat. No. 4,111,926), dihydroquinoline compounds (U.S. Pat. 
No. 4,013,468), 2-sulphonyloxypyridinium salts (JP-A-110 762/81), 
formamidinium salts (EP-A-0 162 308), compounds with two or more 
N-acyloximino groups (U.S. Pat. No. 4,052,373), epoxy ompounds (U.S. Pat. 
No. 3,091,537), compounds of the isoxazole type (U.S. Pat. No. 3,321,313 
and U.S. Pat. No. 3,543,292); halogen carboxyaldehydes, such as 
mucochloric acid; dioxane derivatives, such as dihydroxydioxane and 
dichlorodioxane; and inorganic hardeners such as chrome alum and zirconium 
sulphate. 
Hardening may be effected in a known manner by adding the hardener to the 
coating solution for the layer to be hardened, or by overcoating the layer 
to be hardened with a layer containing a diffusible hardener. 
There are included in the classes listed slow acting and fast acting 
hardeners as well as so-called instant hardeners, which are particularly 
advantageous. Instant hardeners are taken to be compounds which harden 
suitable binders in such a way that immediately after coating, at the 
latest after 24 hours, preferably at the latest after 8 hours, hardening 
is concluded to such an extent that there is no further alteration in the 
sensitometry and swelling of the layered structure determined by the 
crosslinking reaction. Swelling is taken to be the difference between the 
wet layer thickness and the dry layer thickness during aqueous processing 
of the film (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 
449). 
These hardeners which react very rapidly with gelatine are, for example, 
carbamoylpyridinium salts, which are capable of reacting with the free 
carboxyl groups of the gelatine, so that the latter react with free amino 
groups of the gelatine to form peptide bonds crosslinking the gelatine. 
There are diffusible hardeners which have the same hardening effect on all 
the layers in a layered structure. There are, however, also non-diffusing 
low molecular weight and high molecular weight hardeners the action of 
which is restricted within a layer. Using these, individual layers, for 
example the protective layer, may be particularly highly crosslinked. This 
is important if the silver halide layer is sparingly hardened in order to 
increase the silver covering power and the mechanical properties of the 
protective layer must be improved (EP-A-0 114 699). 
The colour photographic materials according to the invention are 
customarily processed by developing, bleaching, fixing and rinsing or by 
developing, bleaching, fixing and stabilising without subsequent rinsing, 
wherein bleaching and fixing may be combined into a single processing 
stage. Colour developer compounds which may be used are all developer 
compounds having the ability to react, in the form of their oxidation 
product, with colour couplers to azomethine or indophenol dyes. Suitable 
colour developer compounds are aromatic compounds containing at least one 
primary amino group of the p-phenylenediamine type, for example 
N,N-dialkyl-p-pheneylenediamines such as N,N-diethyl-p-phenylenediamine, 
1-(N-ethyl-N-methane-sulphonamidoethyl)-3-methyl-p-phenylenediamine, 
1-(N-ethyl-N-hydroxyethyl)-3-methyl-p-phenylenediamine and 
1-(N-ethyl-N-methoxyethyl)-3-methyl-p-phenylenediamine. 
Further usable colour developers are, for example, described in J. Amer. 
Chem. Soc. 73, 3106 (1951) and G. Haist Modern Photographic Processing, 
1979, John Wiley & Sons, New York, pages 545 et seq. 
An acid stop bath or rinsing may follow after colour development. 
Customarily, the material is bleached and fixed immediately after colour 
development. Bleaches which may be used are, for example, Fe(III) salts 
and Fe(III) complex salts such as ferricyanides, dichromates, water 
soluble cobalt complexes. Iron(III) complexes of aminopolycarboxylic acids 
are particularly preferred, in particular for example complexes of 
ethylenediaminetetraacetic acid, propylene-diaminetetraacetic acid, 
diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic 
acid, N-hydroxyethylethylenediaminetriacetic acid, alkylimino-dicarboxylic 
acids and of corresponding phosphonic acids. Persulphates and peroxides, 
for example hydrogen peroxide, are also suitable as bleaches. 
Rinsing usually follows the bleaching-fixing bath or fixing bath, which is 
performed as countercurrent rinsing or comprises several tanks with their 
own water supply. 
Favourable results may be obtained by using a subsequent finishing bath 
which contains no or only a little formaldehyde. 
Rinsing may, however, be completely replaced with a stabilising bath, which 
is customarily performed countercurrently. If formaldehyde is added, this 
stabilising bath also performs the function of a finishing bath. 
Colour photographic negative materials may also be processed using a colour 
intensification process as described in Research Disclosure 34848 (1993).

EXAMPLES 
A colour photographic recording material suitable for rapid processing was 
produced by applying the following layers in the stated sequence to a 
paper coated on both sides with polyethylene. The stated quantities relate 
in each case to 1 m.sup.2. The corresponding quantity of AgNO.sub.3 is 
stated for the quantity of silver halide applied. 
EXAMPLE 1 (Comparison) 
1st Layer (Substrate Layer) 
0.2 g gelatine 
2nd Layer (Blue-Sensitive Layer) 
Blue-sensitive silver halide emulsion (99.5 mol. % chloride, 0.5 mol. % 
bromide, average grain diameter 0.85 .mu.m) prepared from 0.50 g 
AgNO.sub.3, sensitization maximum 480 nm, with 
1.38 g gelatine 
0.60 g yellow coupler Y-1 
0.48 g tricresyl phosphate (TCP) 
3rd Layer (Interlayer) 
1.18 g gelatine 
0.08 g 2,5-dioctylhydroquinone 
0.08 g dibutyl phthalate (DBP) 
4th Layer (Green-Sensitive Layer) 
Green-sensitised silver halide emulsion (99.5 mol. % chloride, 0.5 mol. % 
bromide, average grain diameter 0.50 .mu.m) prepared from 0.40 g 
AgNO.sub.3, sensitization maximum 545 nm, with 
1.02 g gelatine 
0.37 g magenta coupler M-1 
0.40 g DBP 
5th Layer (Interlayer) 
1.20 g gelatine 
0.66 g UV absorber of the formula 
##STR12## 
0.05 g 2,5-dioctylhydroquinone 0.36 g TCP 
6th Layer (Red-Sensitive Layer) 
Red-sensitised silver halide emulsion (99.5 mol. % chloride, 0.5 mol. % 
bromide, average grain diameter 0.50 .mu.m) prepared from 0.28 g 
AgNO.sub.3, sensitization maximum 708 nm, with 
0.84 g gelatine 
0.39 g cyan coupler C-1 
0.39 g TCP 
7th Layer (UV Protective Layer) 
0.65 g gelatine 
0.21 g UV absorber as in 5th layer 
0.11 g TCP 
8th Layer (Protective Layer) 
0.65 g gelatine 
0.39 g hardener of the formula 
##STR13## 
EXAMPLE 2 (Invention) 
A colour photographic recording material was produced differing from the 
material stated in example 1 in the following details: 
3rd Layer (Interlayer) 
Additionally contains a silver halide emulsion (99.5 mol. % chloride, 0.5 
mol. % bromide, average grain diameter 0.30 .mu.m) prepared from 
0.13 g AgNO.sub.3 ; sensitized with S-4 (.lambda..sub.max =605 nm) 
0.003 g DIR-3 
0.08 g gelatine 
0.006 g DBP 
5th Layer (Interlayer) 
Additionally contains a silver halide emulsion (99.5 mol. % chloride, 0.5 
mol. % bromide, average grain diameter 0.30 .mu.m) prepared from 
0.13 g AgNO.sub.3 ; sensitized with S-4 
0.003 g DIR-3 
0.08 g gelatine 
0.006 g DBP 
7th Layer (UV Protective Layer) 
Additionally contains a silver halide emulsion (99.5 mol. % chloride, 0.5 
mol. % bromide, average grain diameter 0.30 .mu.m) prepared from 
0.13 g AgNO.sub.3 ; sensitized with S-4 
0.003 g DIR-3 
0.08 g gelatine 
0.006 g DBP 
EXAMPLE 3 (Invention) 
A colour photographic recording material was produced differing from the 
material stated in example 1 in the following details: 
5th Layer (Interlayer) 
Additionally contains a silver halide emulsion (99.5 mol. % chloride, 0.5 
mol. % bromide, average grain diameter 0.20 .mu.m) prepared from 
0.06 g AgNO.sub.3 ; sensitized with S-4 
0.003 g DIR-3 
0.06 g gelatine 
0.006 g DBP 
7th Layer (UV Protective Layer) 
Additionally contains a silver halide emulsion (99.5 mol. % chloride, 0.5 
mol. % bromide, average grain diameter 0.20 .mu.m) prepared from 
0.08 g AgNO.sub.3 ; sensitized with S-4 
0.005 g DIR-3 
0.11 g gelatine 
0.01 g DBP 
The products of examples 1 to 3 are 
a) given a diffuse exposure of 1 second with white light through an 
interference filter (maximum transmission at 605 nm) and then 
b) exposed with white light through a step wedge, a barrier filter 
(.lambda..sub.max =605 nm with a half-width of 60 nm) and magenta and 
yellow correcting filters such that a neutral grey is produced on the 
material over the entire density range after processing using the process 
stated below. 
Gradation is measured in the density range between 
D=0.2 and D=1.0, denoted by .gamma..sup.I below and between 
D=1.0 and D=1.8, denoted by .gamma..sup.II below. 
The following gradations are found in the processed sample (y=yellow; 
m=magenta; c=cyan): 
______________________________________ 
.gamma..sup.I 
.gamma..sup.II 
Example y m c y m c 
______________________________________ 
1 1.85 1.96 1.82 3.77 3.91 4.00 
2 1.59 1.69 1.58 3.33 3.66 3.65 
3 1.69 1.77 1.62 3.45 3.79 3.44 
______________________________________ 
By way of comparison, the products of examples 1 to 3 are exposed with 
white light through a step wedge, a barrier filter (.lambda..sub.max =605 
nm) and magenta and yellow correcting filters such that a neutral grey is 
produced on the material over the entire density range after processing 
using the stated process. 
The following gradations are found in the processed samples: 
______________________________________ 
.gamma..sup.I 
.gamma..sup.II 
Example y m c y m c 
______________________________________ 
1 1.83 1.91 1.79 3.70 3.91 3.90 
2 1.82 1.89 1.75 3.70 3.88 3.86 
3 1.82 1.90 1.75 3.70 3.89 3.85 
______________________________________ 
The example shows that, due to the diffuse exposure at .lambda.=605 nm, the 
material according to the invention (examples 2 and 3) exhibits distinctly 
flatter gradation. 
The above-described exposure is repeated with the same light source, but 
the exposure time with white light is reduced to 0.1 second. 
______________________________________ 
.gamma..sup.I 
.gamma..sup.II 
Example y m c y m c 
______________________________________ 
1 1.86 1.98 1.86 3.81 3.91 4.06 
2 1.72 1.88 1.76 3.59 3.77 3.80 
3 1.79 1.90 1.81 3.70 3.85 3.61 
______________________________________ 
The comparison shows that a weaker diffuse exposure at 605 nm brings about 
a steeper gradation of the examples according to the invention, which is, 
however, still flatter than in the comparison material. 
The processing steps were carried out as follows: 
______________________________________ 
step time temperature 
______________________________________ 
colour developer 45 sec 35.degree. C. 
bleach-fixing 45 sec 35.degree. C. 
washing 90 sec 33.degree. C. 
______________________________________ 
The composition of the processing solutions were given below. 
______________________________________ 
Colour developer solution 
Tetraethylene glycol 20,0 g 
N,N-Diethylhydroxylamine 4,0 g 
(N-ethyl-N-(2-methanesulphonamido)ethyl))- 
5,0 g 
4-amino-3-methyl-benzene sulfate 
Potassium sulfite 0,2 g 
Potassium carbonate 30,0 g 
Polymaleinic acid anhydride 
2,5 g 
Hydroxyethanediphosphonic acid 
0,2 g 
Fluorescent whitening agent, 
2,0 g 
(a 4,4'-diaminostilbene- 
sulfonic acid derivative) 
Potassium bromide 0,02 g 
add water to make 1000 mL, adjust pH 
with KOH or H.sub.2 SO.sub.4 to be pH 10,2. 
Bleach-fixing solution 
Ammonium thiosulfate 75,0 g 
Sodium hydrogensulfite 13,5 g 
Ethylenediaminetetraacetic acid 
45,0 g 
(Ferric-ammonium-salt) 
add water to make 1000 mL, adjust 
pH with ammonium hydroxide solution 
(25%) or acetic acid to be pH 6,0. 
______________________________________ 
c) Rinsing--2 min--33.degree. C. 
d) Drying