EP0413204A2 - Colour photographic silver halide material - Google Patents

Abstract

Color photographic silver halide material with a support and light-sensitive silver halide emulsion layers for the red, green and blue spectral range, to which cyan, magenta and yellow couplers are complementarily assigned, at least three sub-layers of different sensitivity being provided for at least one spectral range, which, seen from the support, include have a higher sensitivity with increasing distance, and in which the highly sensitive partial layer contains tabular silver halide grains and at least one of the medium sensitive partial layers contains silver halide grains with a layered grain structure, is distinguished by improved graininess and improved color rendering.

Description

The invention relates to a color photographic silver halide negative material with improved graininess and improved color rendering.

It is known from DE-A-32 41 635 to increase the sensitivity and sharpness of multi-layer color photographic recording materials by using tabular silver halide grains, that is to say of silver halide grains, the thickness of which - with a diameter of at least 0.6 micrometers - is less than 0.5 microns and which have an average aspect ratio, defined as the ratio of grain diameter to thickness of greater than 8: 1, provided that the diameter of a grain is defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.

Such materials contain at least two layers of different sensitivity to the same Sensitized spectral range, at least the most sensitive layer contains the above-mentioned tabular silver halide grains.

Despite the improved properties, these materials still have disadvantages because graininess and color rendering do not meet the required requirements.

The object of the invention is to provide color photographic silver halide recording materials which, with improved sensitivity and sharpness, are also improved with respect to graininess and color rendering, the inter-image effect (IIE) serving as a measure of the color rendering.

It has now been found that this object is achieved if three layers of different sensitivity are provided for at least one spectral region, which contain different silver halide emulsions, including tabular silver halide emulsions.

The invention therefore relates to a color photographic silver halide material with a support and light-sensitive silver halide emulsion layers for the red, green and blue spectral range, to which cyan, magenta and yellow couplers are complementarily assigned, at least three partial layers of different sensitivity being provided for at least one spectral range. seen from the carrier, have a higher sensitivity with increasing distance, characterized in that the highest sensitive sub-layer containing tabular silver halide grains and at least one of the medium-sensitive sub-layers of silver halide grains with a layered grain structure.

The green- and / or red-sensitive layers are preferably constructed in at least three layers, the lowest-sensitive partial layer containing in particular a fine-grain emulsion, the mean grain-equivalent grain diameter of which is at most 0.40 μm.

Preferably, at least 80% by weight of the silver halide grains of one of the partial layers specified above are grains of the specified habit, the specified structures or the specified size.

In a preferred embodiment of the invention, both the green-sensitive and the red-sensitive layer are split into at least 3 sub-layers. It is also preferred to select the equivalent ratio of color coupler to silver halide larger in the partial layer with the lowest sensitivity and smaller in the partial layer with the highest sensitivity than in at least one of the medium-sensitive partial layers for the same spectral range.

It is also preferred to incorporate couplers in the partial layer of lowest sensitivity and in the partial layer of highest sensitivity, the coupling speed of which is greater than that of the couplers of the medium-sensitive layers for the same spectral range.

The tabular silver halide grains are characterized by an aspect ratio (definition as DE-A-3 241 635) of at least 5: 1, the proportion of such tabular silver halide grains, defined as the proportion of the projection area of such tabular grains on the projection area of all silver halide grains of the emulsion, at least 50 %, preferably at least 70%, in particular at least 90%. The average diameter of tabular silver halide grains (definition as DE-A-32 41 635) is preferably at least 1.5 μm. The halide distribution of the tabular silver halide grains of mixed silver halides can be homogeneous or inhomogeneous, e.g. be divided into at least two zones of different halide composition from the crystal center to the edge of the parallel main crystal surfaces, the zone boundary can be sharp or flowing. The proportion of the zones can be the same or different from one another, a zone only being spoken of when it accounts for at least 1%, preferably at least 5% of the total grain volume and the same halide composition is present everywhere in this partial volume.

The tabular silver halide grains can consist of 0 to 15 mol% of silver iodide, 0 to 100 mol% of silver bromide and 0 to 100 mol% of silver chloride. Silver bromide iodide grains with at most 15 mol% silver iodide are preferred, the silver iodide content being greater than in the grain center or at the grain edge, in particular in a zone which is not the crystal center or the crystal edge.

Silver halide grains with a layered grain structure are those which contain more than one halide and have a non-homogeneous halide distribution in such a way that at least one shell with a halide composition different from the core is fitted around a core. The boundaries between core and shell or between two shells can be sharp or fluid. One can only speak of a core or a shell if it (it) accounts for at least 5% of the total volume and the same halide composition is present everywhere in this partial volume.

r_i die Größe eines einzelnen Körnchens und
n_i die Anzahl an Körnchen einer Größe r_i bedeuten.The grains with layered grain structure can be tabular or compact, for example cubic, octahedral, tetradecahedral or irregular. They preferably have an average ball-equivalent grain diameter (average diameter of the same-volume ball) of at most 0.6 µm. The grain size distribution can be heterodisperse or homodisperse, the homodisperse grain size distribution being used when S / r ≦ is 0.15, where

r _i the size of a single grain and
n _{i is} the number of granules of size r _i .

Homodisperse silver halide emulsions are preferred. The silver halide emulsions with a layered grain structure contain in particular 0 to 10 mol% of silver iodide, 0 to 99.5 mol% of silver bromide and 0 to 99.5 mol% of silver chloride.

Silver bromide iodide emulsions with 0.5 to 10 mol% of silver iodide, in particular 1 to 5 mol% of silver iodide, are preferred.

The crystals of the silver halide emulsion of the partial layer with the lowest sensitivity of the at least three partial layers of different sensitivity for the same spectral range can be tabular or compact with a homogeneous or inhomogeneous halide distribution. In the case of inhomogeneous halide distribution, one also speaks of layered grain structure. The compact crystals can have, for example, cubic, octahedral, tetradecahedral or irregular crystal habit. In the case of the tabular crystals, the average aspect ratio is at least 5: 1 and the average diameter is at most 1 µm (definitions DE-A-32 41 635). The projection area of these grains makes up at least 50% of the projection area of all grains of this layer. The compact or tabular emulsion consists of 0 to 15 mol% of iodide, 0 to 100 mol% of bromide and 0 to 100 mol% of chloride, preferably it is a silver bromide iodide emulsion with up to 15 mol% of silver iodide . Their grain size distribution can be homodisperse or heterodisperse.

Two or more types of silver halide emulsions, which are prepared separately, can also be used as a mixture in each of the individual partial layers.

The photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.

The silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used. The latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded. The pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a specific pAg value is kept constant or a defined pAg profile is traversed during the precipitation. In addition to the preferred precipitation with an excess of halide, so-called inverse precipitation with an excess of silver ions is also possible. In addition to precipitation, the silver halide crystals can also grow through physical ripening (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent. The growth of the emulsion grains can even take place predominantly by Ostwald ripening, a fine-grained, so-called Lippmann emulsion preferably being mixed with a less soluble emulsion and being redissolved on the latter.

Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe can also be present during the precipitation and / or physical ripening of the silver halide grains.

The precipitation can also be carried out in the presence of sensitizing dyes. Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.

After crystal formation has been completed or at an earlier point in time, the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.

The silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halogens nid and sensitizer concentration - subjected to the sensitivity and fog optimum.

The procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).

Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (for example gold, platinum, palladium, iridium). Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic compounds can also be used Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, vol. 18, pp. 431 ff. and Research Disclosure No. 17643, Section III). Alternatively or additionally, a reduction sensitization with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid) can be carried out by hydrogen, by low pAg (eg less than 5) and / or high pH (eg above 8) .

The photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.

Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also be used as antifoggants. Heterocycles containing mercapto groups, for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group. Other suitable compounds are published in Research Disclosure No. 17643 (1978), Section VI.

The stabilizers can be added to the silver halide emulsions before, during or after their ripening. Of course, the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.

Mixtures of two or more of the compounds mentioned can also be used.

The photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can be surface-active Contain agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (e.g. development acceleration, high contrast, sensitization, etc.). In addition to natural surface-active compounds, for example saponin, synthetic surface-active compounds (surfactants) are mainly used: non-ionic surfactants, for example alkylene oxide compounds, glycerol compounds or glycidol compounds, cationic surfactants, for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, for example amino acid and aminosulfonic acid compounds and sulfur or phosphoric acid esters of an amino alcohol.

The photographic emulsions can be spectrally sensitized using methine dyes or other dyes. Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Research Disclosure 17643/1978 in Department IV contains an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations with a super-sensitizing effect.

The following dyes, sorted by spectral range, are particularly suitable:

1. as red sensitizers

9-ethyl carbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl, and 9-ethyl-naphthoxathia or -selencarbocyanines and 9- Ethyl-naphthothiaoxa- or -benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.

2. as green sensitizers

9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzthiazole as basic end groups, and also benzimidazocarbocyanines, which may also be further substituted and must likewise contain at least one sulfoalkyl group on the heterocyclic nitrogen.

3. as blue sensitizers

symmetrical or asymmetrical benzimidazo, oxa, thia or selenacyanines with at least one sulfoalkyl group on the heterocyclic nitrogen and optionally further substituents on the aromatic nucleus, and apomerocyanines with a rhodanine group.

Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers. Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates. Semi-synthetic gelatin substitutes are usually modified natural products. Examples of these are cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers.

The binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents. Such functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.

The gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. The production such gelatins are described, for example, in The Science and Technology of Gelatine, edited by AG Ward and A. Courts, Academic Press 1977, page 295 ff. The gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.

Suitable supports for the production of color photographic materials are e.g. Films and foils of semi-synthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate. These supports can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light. The surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.

Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromides.

The differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it. Usually cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.

Color couplers for producing the blue-green partial color image are generally couplers of the phenol or α-naphthol type, those of the 2-ureidophenol type and / or of the 1,5-aminonaphthol type are preferred for this invention; Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type, those of the acylaminopyrazolone type and / or pyrazoloazole type are preferred for this invention; Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the α-arylacetamide type; those of the α-benzoylacetanilide type and / or α-pivaloylacetanilide type are preferred for this invention.

The color couplers can be 4-equivalent couplers, but also 2-equivalent couplers. The latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling. The 2-equivalent couplers include colorless ones are, as well as those that have an intense intrinsic color, which disappears during the color coupling or is replaced by the color of the image dye produced (mask coupler), and the white couplers, which essentially result in colorless products when reacted with color developer oxidation products. The material according to the invention preferably contains blue-green coupling red mask couplers with an oxygen-bonded escape group. The 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling point, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue ( eg DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, for example as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.

DIR couplers which release development inhibitors of the azole type, for example triazoles and benzotriazoles, are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 27 26 180, 36 26 219, 36 30 564, 36 36 824, 36 44 416 and 28 42 063. Further advantages for color reproduction, ie, color separation and color purity, and for detail reproduction, ie, sharpness and granularity, can be achieved with those DIR couplers which, for example, do not split off the development inhibitor directly as a result of coupling with an oxidized color developer, but instead only after a further follow-up reaction, which is achieved, for example, with a time control group. Examples of these are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-157 146 and 204 175, in US-A-4 146 396 and 4 438 393 and in GB -A-2 072 363.

DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-167 168 and 219 713. This measure ensures trouble-free development and processing consistency.

When using DIR couplers, in particular those which release a well-diffusible development inhibitor, improvements in the color rendering, e.g. achieve a more differentiated color rendering, as described, for example, in EP-A-115 304, 167 173, GB-A-2 165 058, DE-A-37 00 419 and US-A-4 707 436.

The DIR couplers can be added to a wide variety of layers in a multilayer photographic material, for example also light-insensitive or intermediate layers. However, they are preferably added to the light-sensitive silver halide emulsion layers, the characteristic properties of the silver halide emulsion, for example its iodide content, being the Structure of the silver halide grains or their grain size distribution have an influence on the photographic properties achieved. The influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it may be advantageous to use a DIR coupler which forms a color in the coupling in the respective layer in which it is introduced, which color differs from the color to be produced in this layer.

To increase the sensitivity, the contrast and the maximum density, DAR or FAR couplers can be used, which release a development accelerator or an fogger. Compounds of this type are, for example, in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-89 834, 110 511, 118 087, 147 765 and described in US-A-4,618,572 and 4,656,123.

As an example for the use of BAR couplers (Bleach Accelerator Releasing Coupler), reference is made to EP-A-193 389.

It can be advantageous to modify the effect of a photographically active group which is split off from a coupler in that an intermolecular reaction of this group occurs after its release with another group according to DE-A-35 06 805.

In the present invention, DIR couplers in the or one of the medium sensitive silver halide emulsion layers of the at least one are particularly advantageous three sub-layers of different sensitivity but the same spectral sensitization are used, DIR couplers with inhibitors of high diffusibility being particularly preferred.

Examples of DIR couplers are:

Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-15 47 640).

The cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).

The material may further contain compounds other than couplers, which can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds such as those in US -A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.

High molecular weight color couplers are described, for example, 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, US-A-4 080 211. The high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.

The couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question. Choosing the right one Solvents or dispersants depend on the solubility of the compound.

Methods for introducing compounds which are essentially insoluble in water by grinding processes are described, for example, in DE-A-26 09 741 and DE-A-26 09 742.

Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-O 043 037.

Instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.

The compounds can also be introduced into the casting solution in the form of loaded latices. Reference is made, for example, to DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-AO 014 921, EP-A-0 069 671, EP-A-O 130 115, US-A-4,291,113.

The diffusion-resistant incorporation of anionic water-soluble compounds (eg dyes) can also be carried out with the aid of cationic polymers, so-called pickling polymers.

Suitable oil formers are e.g. Alkyl phthalates, 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-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phylate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert-amylphenol, dioctyl acylate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-doxy-5-butyl-2-. -octylaniline, paraffin, dodecylbenzene and diisopropylnaphthalene.

For the two remaining spectral ranges, the material can comprise a single layer or two or more silver halide emulsion partial layers (DE-C-1 121 470). Red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, with a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.

If the green or red-sensitive layers are suitably low in their own sensitivity, other layer arrangements can be selected without the yellow filter layer, in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.

The non-light-sensitive intermediate layers, which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.

Suitable agents, which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), Chapter VII, 17 842/1979, pages 94-97 and 18.716 / 1979, page 650 and in EP-A- 69,070, 98,072, 124,877, 125,522 and in US-A-463,226.

If there are several sub-layers of the same spectral sensitization, sub-layers of the same spectral sensitization can be adjacent to one another or by other layers, e.g. separated by layers of other spectral sensitization. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).

The photographic material can also contain UV light absorbing compounds, white toners, spacers, Filter dyes, formalin scavengers, light stabilizers, antioxidants, D _Min dyes, additives to improve dye, coupler and whiteness stabilization and to reduce the color fog, plasticizers (latices), biocides and others.

Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film. Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).

Ultraviolet absorbing couplers (such as α-naphthol type cyan couplers) and ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.

Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.

Suitable white toners are e.g. in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.

Certain binder layers, in particular the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).

The average particle diameter of the spacers is in particular in the range from 0.2 to 10 μm. The spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath. Examples of suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.

Additives to improve the stability of dyes, couplers and whites and to reduce the color fog (Research Disclosure 17 643/1978, Chapter VII) can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes, p- Alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.

Compounds that have both a hindered amine partial structure and a hindered phenol partial structure in one molecule (US-A-4,268,593) are particularly effective in preventing the degradation (deterioration or degradation) of yellow color images as a result the development of heat, moisture and light. In order to prevent the deterioration (deterioration or degradation) of crimson color images, in particular their impairment (deterioration or degradation) as a result of exposure to light, Spiroindane (JP-A-159 644/81) and chromanes are caused by Hydroquinone diethers or monoethers are particularly effective (JP-A-89 835/80).

The layers of the photographic material can be hardened with the usual hardening agents. Suitable curing agents are, for example, formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen included (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5 triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316 and US-A-2 586 168); Isocyanates (US-A-3 103 437); Aziridine compounds (US-A-3 017 280 and US-A-2 983 611); Acid derivatives (US-A-2 725 294 and US-A-2 725 295); Carbodiimide type compounds (US-A-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-sulfonyloximido compounds (US-A-4 111 926), dihydroquinoline compounds (US-A-4 013 468), 2-sulfonyloxypyridinium salts (JP-A-110 762/81), formamidinium salts (EP-A-0 162 308) , Compounds having two or more N-acyloximino groups (US-A-4 052 373), epoxy compounds (US-A-3 091 537), isoxazole-type compounds (US-A-3 321 313 and US-A-3 543 292); Halocarboxyaldehydes such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane; and inorganic hardeners such as chrome alum and zirconium sulfate.

The hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.

There are slow-acting and fast-acting hardeners and so-called instant hardeners, which are particularly advantageous, in the classes listed. Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry caused by the crosslinking reaction and the swelling of the layer structure occurs . Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).

These hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin with the formation of peptide bonds and crosslinking of the gelatin.

Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step. All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound. Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type 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-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine. Further useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.

After the color development, an acidic stop bath or watering can follow.

Usually the material is bleached and fixed immediately after color development. For example, Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used as bleaching agents. Are particularly preferred Iron (III) complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulphates and peroxides, for example hydrogen peroxide, are also suitable as bleaching agents.

The bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.

Favorable results can be obtained using a subsequent final bath which contains little or no formaldehyde.

However, the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent. When formaldehyde is added, this stabilizing bath also functions as a final bath.

In the case of color reversal materials, development is first carried out using a black and white developer whose oxidation product is not capable of reacting with the color couplers. This is usually followed by chemical fogging and / or a diffuse second exposure and then development with a color developer, bleaching and fixing.

example 1

A color photographic recording material for color negative color development was produced (layer structures 1 A to 1 E) by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given. All silver halide emulsions were stabilized per 100 g of AgNO₃ with 0.1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Layer structure 1 A (comparison)

• Layer 1 (antihalo layer)
  black colloidal silver sol with
  0.2 g Ag
  1.2 g gelatin
• Layer 2 (Mikrat intermediate layer)
  Mikrat-silver bromide iodide emulsion (0.5 mol% iodide; average grain diameter 0.07 µm)
  0.25 g AgNO₃, with
  1.0 g gelatin
  0.05 g RM-1 red mask
• Layer 3 (1st red-sensitized layer, slightly sensitive)
  0.60 g AgNO₃ of the red-sensitized silver bromide iodide emulsion VN (1) with
  1.15 g gelatin
  0.32 g of cyan coupler C-1
  0.03 g RM-1 red mask
  0.35 g tricresyl phosphate (CPM)
  0.25 g dibutyl phthalate (DBP)
• Layer 4 (2nd red-sensitized layer, medium sensitive)
  1.52 g of AgNO₃ the red-sensitized silver bromide iodide emulsion VM (1) with
  1.40 g gelatin
  0.45 g cyan coupler C-2
  0.04 g RM-1 red mask
  0.04 g DIR coupler DIR-3
  0.02 g DIR coupler DIR-1
  0.30 g CPM
  0.25 g DBP
• Layer 5 (3rd red-sensitized layer, highly sensitive)
  1.35 g AgNO₃ of the red-sensitized silver bromide iodide emulsion VH (1) with
  1.24 g gelatin
  0.16 g of cyan coupler C-3
  0.03 g RM-2 red mask
  0.10 g CPM
  0.08 g DBP
• Layer 6 (intermediate layer)
  0.8 g gelatin
  0.05 g 2,5-di-t-pentadecyl hydroquinone
  0.05 g CPM
  0.05 g DBP
• Layer 7 (1st green-sensitized layer, slightly sensitive)
  0.45 g AgNO₃ of the green-sensitized silver bromide iodide emulsion VN (1) with
  0.85 g gelatin
  0.24 g purple coupler M-1
  0.04 g yellow mask YM-1
• Layer 8 (2nd green-sensitized layer, medium-sensitive)
  1.2 g of AgNO₃ the green-sensitized silver bromide iodide emulsion VM (1) with
  1.05 g gelatin
  0.30 g purple coupler M-2
  0.04 g yellow mask YM-2
  0.01 g DIR coupler DIR-9
  0.03 g DIR coupler DIR-18
  0.35 g CPM
  0.15 g DBP
• Layer 9 (3rd green-sensitive layer, highly sensitive)
  1.0 g of AgNO₃ the green-sensitized silver bromide iodide emulsion VH (1) with
  1.1 g gelatin
  0.11 g purple coupler M-3
  0.02 g yellow mask YM-1
  0.10 g CPM
  0.10 g DBP
• Layer 10 (intermediate layer)
  like layer 6
• Layer 11 (yellow filter layer)
  0.04 g Ag with yellow colloidal silver sol
  0.8 g gelatin
  0.15 g of 2,5-di-t-pentadecyl hydroquinone
  0.40 g CPM
• Layer 12 (1st blue-sensitive layer, slightly sensitive)
  0.3 g of AgNO₃ the blue-sensitized silver bromide iodide emulsion VN (1) and
  0.2 g AgNO₃ of the blue-sensitized silver bromide iodide emulsion VM (1)
  1.2 g gelatin
  0.8 g yellow coupler Y-1
  0.20 g DIR coupler DIR-18
  0.70 g CPM
  0.20 g DBP
• Layer 13 (2nd blue-sensitive layer, highly sensitive)
  0.75 g of AgNO₃ the blue-sensitized silver bromide iodide emulsion VH (1) with
  0.25 g yellow coupler Y-1
  1.0 g gelatin
  0.20 g CPM
• Layer 14 (protective and hardening layer)
  Mikrat-silver bromide iodide emulsion (0.5 mol% iodide; average grain diameter 0.04 µm)
  0.5 g of AgNO₃ with
  1.2 g gelatin
  0.4 g of H-1 curing agent
  1.0 g formaldehyde scavenger FF

Table 1.1 Overview of the emulsions used in Example 1 layer Comparison structures Construction according to the invention No. variety 1 A 1 B 1 C. 1 D 1 E 1 Antihalo 2nd Intermediate layer 3rd low red VN (1) VN (1) VN (1) VN (1) EN (1) 4th medium red VM (1) VM (1) EM (1) EM (1) EM (1) 5 crimson VH (1) EH (1) VH (1) EH (1) EH (1) 6 Interface 7 low green VN (1) VN (1) VN (1) VN (1) EN (1) 8th medium green VM (1) VM (1) EM (1) EM (1) EM (1) 9 high green VH (1) EH (1) VH (1) EH (1) EH (1) 10th Interface 11 Filter yellow 12 low blue 60% VN (1) 60% VN (1) 60% VN (1) 60% VN (1) 60% EN (1) 40% VM (1) 40% VM (1) 40% VM (1) 40% EM (1) 40% EM (1) 13 high blue VH (1) VH (1) VH (1) VH (1) VH (1) 14 Protective and hardening layer

The following layer structures 1B, 1C, 1D and 1E were also produced analogously by emulsions VN (1), VM (1) and VH (1) against the emulsions EN (1), EM (1) and EH in the individual sub-layers (1) were replaced as shown in Table 1/1.

A sample of the layer structures 1A to 1E was exposed behind a gray step wedge with white light (exposure time: 0.01 s) and according to a color negative processing method, as in "The British Journal of Photography (1974), pages 597 and 598 The RMS values (= mean squares of fluctuation) were determined with a measuring aperture of 48 µm diameter at different color densities as a measure of the color granularity. The measuring method is described in: TH James, The Theory of the Photographic Process, 4th ed ., Mac Millan Publ. Co., New York (1977) p. 619, numerical values for the five layer structures 1A to 1E are given in Table 1/2.

According to TH James, The Theory of the Photographic Process, 4th edition, Mc Millan Co. NY (1977) pp. 574 and 614, the interimage effect (IIE) was compared as a percentage of the color gradation in color separation exposure with light of the corresponding spectral range in relation measured to the color gradation that occurs with additive exposure to white light. Table 1.2 Color granularity and interimage effects from Example 1 Layer structure (Comparison) (according to the invention) Color density over veil 1 A 1 B 1 C. 1 D 1 E Color granularity (RMS) purple 0.5 16.0 12.0 15.0 10.0 10.0 1.0 14.5 13.0 10.5 9.5 9.0 1.5 12.0 11.5 10.0 9.0 8.0 Granularity (RMS) blue-green 0.5 15.5 14.0 14.5 9.5 9.5 1.0 14.0 13.5 11.0 8.5 8.0 1.5 12.5 12.0 10.5 8.5 8.0 Interimage effect yellow 5% 5% 5% 15% 20% purple 15% 15% 35% 50% 55% blue green 15% 15% 40% 45% 45%

Example 2

Layer support, amounts and stabilization of the emulsions, layers 1 and 2 as in Example 1.

Layer structure 2 A (comparison)

• Layer 3 (1st red-sensitive layer, slightly sensitive
  0.4 g of AgNO₃ the red-sensitized silver bromide iodide emulsion VN (2) with
  0.55 g gelatin
  0.20 g cyan coupler C-4
  0.10 g of cyan coupler C-5
  0.05 g DIR coupler DIR-19
  0.25 g CPM
  0.10 g DBP
• Layer 4 (2nd red sensitive layer, medium sensitive
  1.35 g AgNO₃ of the red-sensitized silver bromide iodide emulsion VM (2) with
  1.55 g gelatin
  0.38 g of cyan coupler C-4
  0.03 g RM-2 red mask
  0.025g DIR coupler DIR-21
  0.015g DIR coupler DIR-22
  0.25 g CPM
  0.20 g DBP
• Layer 5 (intermediate layer)
  like layer 6 from example 1
• Layer 6 (1st green-sensitive layer, slightly sensitive
  0.5 g of AgNO₃ the green-sensitized silver bromide iodide emulsion VN (2) with
  0.75 g gelatin
  0.32 g purple coupler M-4
  0.03 g yellow mask YM-1
  0.04 g DIR coupler DIR-22
  0.05 g CPM
• Layer 7 (2nd green sensitive layer, medium sensitive
  1.1 g AgNO₃ of the green-sensitized silver bromide iodide emulsion VM (2) with
  0.82 g gelatin
  0.26 g purple coupler M-5
  0.05 g yellow mask YM-3
  0.03 g DIR coupler DIR-22
  0.01 g DIR coupler DIR-9
  0.05 g CPM
  0.04 g DBP
• Layer 8 (yellow filter layer)
  yellow colloidal silver sol,
  0.02 g Ag
  0.8 g gelatin
  0.15 g of 2,5-di-t-pentadecyl hydroquinone
  0.20 g CPM
• Layer 9 (1st blue-sensitive layer, slightly sensitive
  0.3 g AgNO₃ of the blue-sensitized silver bromoiodide emulsion VN (2)
  0.85 g gelatin
  0.65 g yellow coupler Y-3
  0.15 g DIR coupler DIR-20
  0.30 g CPM
  0.20 g DBP
• Layer 10 (2nd blue-sensitive layer, medium-sensitive
  0.25 g of AgNO₃ the blue-sensitized silver bromide iodide emulsion VM (2) with
  0.60 g gelatin
  0.45 g yellow coupler Y-2
  0.10 g DIR coupler DIR-20
  0.20 g CPM
  0.15 g DBP
• Layer 11 (intermediate layer)
  like layer 5
• Layer 12 (3rd red-sensitive layer, highly sensitive
  1.35 g AgNO₃ of the red-sensitized silver bromide iodide emulsion VH (2) with
  1.30 g geletine
  0.12 g cyan coupler C-6
  0.01 g red mask RM-2
  0.10 g CPM
  0.05 g DBP
• Layer 13 (intermediate layer)
  like layer 5
• Layer 14 (3rd green-sensitive layer, highly sensitive)
  1.0 g of AgNO₃ of the green-sensitized silver bromide iodide emulsion VH (2)
  1.05 g gelatin
  0.14 g purple coupler M-6
  0.01 g yellow mask YM-1
  0.12 g CPM
  0.05 g DBP
• Layer 15 (yellow filter layer)
  like layer 8
• Layer 16 (2nd blue-sensitive layer, highly sensitive)
  0.80 g AgNO₃ of the blue-sensitized silver bromide iodide emulsion VH (2)
  0.85 g gelatin
  0.12 g yellow coupler Y-3
  0.10 g CPM
• Layer 17 (protective and hardening layer)
  Mikrat-silver bromide iodide emulsion (2.0 mol% iodide; average grain diameter 0.08 µm)
  0.4 g AgNO, with
  1.0 g gelatin
  0.5 g hardening agent of the formula
  

The layer structures 2B, 2C, 2D and 2E were also produced analogously, using the emulsions listed in Table 2/1 instead of those mentioned in the layer structure 2A.

Tabelle 2.1 Übersicht über die eingesetzten Emulsionen in Beispiel 2 Schicht Vergleichs-Aufbauten Erfindungsgemäßer Aufbau Nr. Sorte 2 A 2 B 2 C 2 D 2E 1 Antihalo 2 Zwischenschicht 3 niedrigrotempf. VN(2) VN(2) VN(2) VN(2) EN(2) 4 mittelrotempf. VM(2) EM(2) EM(2) 5 Trennschicht 6 niedriggrünempf. VN(2) VN(2) VN(2) VN(2) EN(2) 7 mittelgrünempf. VM(2) EM(2) EM(2) 8 1. Filtergelb 9 niedrigblauempf. VM(2) VN(2) VN(2) VN(2) EN(2) 10 mittelblauempf. VM(2) EM(2) EM(2) 11 Zwischenschicht 12 hochrotempf. VH(2) EH(2) EH(2) 13 Trennschicht 14 hochgrünempf. VH(2) EH(2) EH(2) 15 2.Filtergelbschicht 16 hochblauempf. VH(2) VH(2) VH(2) 17 Schutz- und Härtungsschicht Tabelle 2.2 Farbkörnigkeiten und Interimage-Effekte von Beispiel 2 Schichtaufbau (Vergleich) (erfindungsgemäß) Farbdichte über Schleier 2 A 2 B 2 C 2 D 2 E Farbkörnigkeit (RMS) purpur 0,5 22,0 20,0 17,0 12,0 11,0 1,0 19,0 19,0 12,5 10,0 10,0 1,5 16,0 15,0 11,0 9,5 9,0 Farbkörnigkeit (RMS) blaugrün 0,5 20,0 19,0 16,0 13,0 12,5 1,0 19,0 18,0 13,0 11,0 10,0 1,5 17,0 16,0 12,0 10,0 9,5 Interimage-Effekt gelb 10 % 10 % 15 % 20 % 20 % purpur 15 % 15 % 40 % 45 % 45 % blaugrün 20 % 20 % 40 % 50 % 50 % Exposure, processing and evaluation of the samples were carried out analogously to Example 1. The image quality data obtained are listed in Table 2/2.

Table 2.1 Overview of the emulsions used in Example 2 layer Comparison structures Construction according to the invention No. variety 2 A 2 B 2 C 2 D 2E 1 Antihalo 2nd Intermediate layer 3rd low red VN (2) VN (2) VN (2) VN (2) EN (2) 4th medium red VM (2) EM (2) EM (2) 5 Interface 6 low green VN (2) VN (2) VN (2) VN (2) EN (2) 7 medium green VM (2) EM (2) EM (2) 8th 1. Filter yellow 9 low blue VM (2) VN (2) VN (2) VN (2) EN (2) 10th medium blue VM (2) EM (2) EM (2) 11 Intermediate layer 12 crimson VH (2) EH (2) EH (2) 13 Interface 14 high green VH (2) EH (2) EH (2) 15 2.Filter yellow layer 16 high blue VH (2) VH (2) VH (2) 17th Protective and hardening layer Color granularity and interimage effects from Example 2 Layer structure (Comparison) (according to the invention) Color density over veil 2 A 2 B 2 C 2 D 2 E Color granularity (RMS) purple 0.5 22.0 20.0 17.0 12.0 11.0 1.0 19.0 19.0 12.5 10.0 10.0 1.5 16.0 15.0 11.0 9.5 9.0 Granularity (RMS) blue-green 0.5 20.0 19.0 16.0 13.0 12.5 1.0 19.0 18.0 13.0 11.0 10.0 1.5 17.0 16.0 12.0 10.0 9.5 Interimage effect yellow 10% 10% 15% 20% 20% purple 15% 15% 40% 45% 45% blue green 20% 20% 40% 50% 50%

Claims (6)

1. Color photographic silver halide material with a support and light-sensitive silver halide emulsion layers for the red, green and blue spectral range, to which cyan, magenta and yellow couplers are complementarily assigned, at least three sub-layers of different sensitivity being provided for at least one spectral range, which, seen from the support , have a higher sensitivity with increasing distance, characterized in that the highly sensitive partial layer contains tabular silver halide grains and at least one of the medium sensitive partial layers contains silver halide grains with a layered grain structure. 2. Color photographic silver halide material according to claim 1, characterized in that the three sub-layers are sensitive to green and / or red. 3. Color photographic silver halide material according to claim 1, characterized in that the lowest-sensitive sub-layer contains a fine grain emulsion, the mean spherical equivalent grain diameter is at most 0.40 µm. 4. Color photographic silver halide material according to claim 1, characterized in that the equivalent ratio of color coupler to silver halide in the sub-layer with the lowest sensitivity is larger and in the sub-layer with the highest sensitivity is smaller than in at least one of the medium-sensitive sub-layers for the same spectral range. 5. Color photographic silver halide material according to claim 1, characterized in that couplers are incorporated into the partial layers with the highest and the lowest sensitivity, the coupling speed of which is greater than that of the coupler of the medium-sensitive layers for the same spectral range. 6. Color photographic silver halide material according to claim 1, characterized in that it a) 2-equivalent yellow coupler of the benzoylacetanilide type and / or pivaloylacetanilide type b) Purple couplers of the pyrazolo-azole type and / or acylaminopyrazolone type c) cyan couplers of the 2-ureidophenol type and / or 1,5-aminonaphthol type and d) contains blue-green coupling red mask couplers with an oxygen-bonded escape group.