EP0554756B1 - Color photographic recording material - Google Patents

Description

The invention relates to a color photographic recording material with improved color stability.

Color photographic materials usually contain at least one yellow coupler, at least one purple coupler and at least one cyan coupler, from which the corresponding dyes are formed by exposure and development. These dyes, in particular the dyes that are constantly exposed to light, are said to have high color stability, with particular emphasis being placed on ensuring that the color stability of all three colors is as good as possible, so that there is no color distortion with a slight fading.

At the same time, the dyes should be as pure as possible. For the purple range, this has led to the pyrazolone couplers which have been customary to date being increasingly replaced by pyrazoloazole couplers, because the latter lead to purer purple tones than the former. From However, dyes obtained from pyrazoloazole couplers are not sufficiently light-stable in comparison with the usual dyes from yellow and cyan couplers.

The object of the present invention was therefore to remedy this lack of light stability.

It has now been found that this object can be achieved by adding a random or alternating copolymer of vinyl alcohol and an unsaturated carboxylic acid, in particular an unsaturated mono-, to the material in a layer closer to and in a more distant layer than the layer containing the magenta coupler. , Di- or tricarboxylic acid or a graft polymer of vinyl acetate on polyalkylene oxide with subsequent saponification of the acetate groups is added and these layers contain gelatin in addition to the graft or copolymer.

The copolymers are obtained by the joint polymerization of vinyl acetate and at least one unsaturated carboxylic acid and subsequent saponification of the acetate groups. The saponification need not be quantitative, so that the copolymer still has acetate groups. The copolymer can also contain other comonomers.

Preferred copolymers contain 50 to 98 mol% of vinyl alcohol units, 0 to 20 mol% of vinyl acetate units, 2 to 30 mol% of units of unsaturated carboxylic acids and 0 to 30 mol% of further comonomers.

The molecular weight M _n should be at least 10,000.

Suitable unsaturated carboxylic acids are e.g. Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid. Suitable further comonomers are vinyl chloride, vinylidene chloride, acrylates and methacrylates, ethylene, propylene, styrene, styrene sulfonic acid, vinyl phosphonic acid and vinyl sulfonic acid.

The graft polymers are described in DE-OS 3 541 162 and can be prepared by the methods given there. The saponification of the acetate groups takes place in a known manner.

wobei

R₃

Wasserstoff oder C₁-C₂-Alkyl, vorzugsweise Wasserstoff,

n

20-1000, vorzugsweise 40-500,

m

1-300, vorzugsweise 2-100, wobei n > m gilt, und

Z

ein Copolymer aus 50 bis 100 Mol-% Vinylalkohol, 0 bis 20 Mol-% Vinylacetat, 0 bis 30 Mol-% ungesättigten Carbonsäuren und 0 bis 30 Mol-% weiteren Comonomeren ist.

The graft polymers preferably have the following structure

in which

R₃

Hydrogen or C₁-C₂-alkyl, preferably hydrogen,

n

20-1000, preferably 40-500,

m

1-300, preferably 2-100, where n> m, and

Z.

is a copolymer of 50 to 100 mol% of vinyl alcohol, 0 to 20 mol% of vinyl acetate, 0 to 30 mol% of unsaturated carboxylic acids and 0 to 30 mol% of further comonomers.

The unsaturated carboxylic acids and the other comonomers of the graft branches are the same as the copolymers.

Examples of suitable vinyl alcohol copolymers and graft polymers are:

worin

R₁

Methyl oder Ethyl und

n

20 bis 2.000 bedeuten.

The polyalkylene oxide preferably corresponds to the formula

wherein

R₁

Methyl or ethyl and

n

20 to 2,000 mean.

Polyethylene oxide is preferred.

The graft polymer preferably contains 2 to 50 mol% of alkylene oxide, 50 to 98 mol% of vinyl alcohol and 0 to 20 mol% of vinyl acetate.

entsprechen, worin

R₁

Wasserstof, Halogen, Alkyl, Aryl, eine heterocyclische Gruppe, Cyan, Alkoxy, Acyloxy, Carbamoyloxy, Acylamino oder ein Polymerrest,

X

Wasserstoff oder eine Abspaltgruppe,

einer der Reste Z₁ und Z₂ ein Stickstoffatom und der andere -CR₂-bedeuten und

R₂

die gleiche Bedeutung wie R₁ hat, wobei einer der Reste R₁ und R₂ eine Ballastgruppe ist oder durch eine Ballastgruppe substituiert ist, wobei die Ballastgruppe auch ein Polymerrest sein kann.

Preferred pyrazoloazole couplers are pyrazolotriazole couplers, in particular those of the formula

correspond to what

R₁

Hydrogen, halogen, alkyl, aryl, a heterocyclic group, cyan, alkoxy, acyloxy, carbamoyloxy, acylamino or a polymer radical,

X

Hydrogen or a leaving group,

one of the radicals Z₁ and Z₂ is a nitrogen atom and the other is -CR₂- and

R₂

has the same meaning as R₁, wherein one of the radicals R₁ and R₂ is a ballast group or is substituted by a ballast group, wherein the ballast group can also be a polymer radical.

Suitable purple couplers are

The graft or copolymer is preferably contained in the layers immediately adjacent to the layer containing the magenta coupler.

Layers designed according to the invention preferably contain 0.3 to 3.0 g of graft or copolymer and 0.1 to 2.0 g of gelatin / m 2.

The material according to the invention is particularly preferably a material which, in the order given, has at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, one intermediate layer, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, one intermediate layer, at least one red-sensitive one , at least one cyan coupler-containing silver halide emulsion layer and at least contains a protective layer, characterized in that the intermediate layer between the green and red-sensitive silver halide emulsion layer and the intermediate layer between the blue and green-sensitive silver halide emulsion layer are designed in the manner according to the invention, and the magenta coupler is a pyrazoloazole coupler.

The support can be reflective or transparent.

AgBr, AgBrCl, AgBrClI and AgCl can be considered as silver halides of the color coupler-containing and the color coupler-free silver halide emulsion layers.

The silver halides of all light-sensitive layers, including the intermediate layers according to the invention, preferably contain at least 80 mol% of chloride, in particular 95 to 100 mol% of chloride, 0 to 5 mol% of bromide and 0 to 1 mol% of iodide. The silver halide emulsions can be directly positive-working or preferably negative-working emulsions.

The silver halide can be predominantly compact crystals which, for example, can have regular cubic or octahedral or transitional forms. However, twinned, for example platelet-shaped crystals can also preferably be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected one Area of the grain. However, the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is greater than 5: 1, for example 12: 1 to 30: 1.

The silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different. The average grain size of the emulsions is preferably between 0.2 »m and 2.0» m, the grain size distribution can be both homo- and heterodisperse. In addition to the silver halide, the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.

Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.

The photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Pysique 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 certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation. In addition to the preferred precipitation with excess halide, so-called inverse precipitation with excess silver ions is also possible. In addition to precipitation, the silver halide crystals can also grow by 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, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.

The silver halide grains can be precipitated in the presence of "growth modifiers", which are substances which influence growth in such a way that special grain shapes and grain surfaces (for example 111 surfaces in AgCl) are formed.

Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe, Pt, Pd, Ru or Os for doping the silver halides may 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.

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. Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers are examples of this.

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. The production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. 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. The gelatin can be partially or completely oxidized.

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

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, (subst.) 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 silver halide layer.

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

The silver halide emulsions are usually chemically ripened, for example by the action of gold compounds or compounds of divalent sulfur.

The photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active 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 ( eg acceleration of development, high contrast, sensitization etc.).

• 1. Rotsensibilisatoren
     Dicarbocyanine mit Naphthothiazol oder Benzthiazol als basischen Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy substituiert sein können sowie 9.11-alkylen-verbrückte, insbesondere 9.11-Neopentylenthiadicarbocyanine mit Alkyl- oder Sulfoalkylsubstituenten am Stickstoff.
• 2. Grünsensibilisatoren
     9-Ethyloxacarbocyanine, die in 5-Stellung durch Chlor oder Phenyl substituiert sind und am Stickstoff der Benzoxazolgruppen Alkyl- oder Sulfoalkylreste, vorzugsweise Sulfoalkylsubstituenten tragen.
• 3. Blausensibilisatoren
     Methincyanine mit Benzoxazol, Benzthiazol, Benzselenazol, Naphthoxazol, Naphthothiazol als basischen Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy substituiert sein können und mindestens eine, vorzugsweise zwei, Sulfoalkylsubstituenten am Stickstoff tragen. Ferner Apomerocyanine mit einer Rhodaningruppe.

Suitable sensitizing dyes are cyanine dyes, in particular of the following classes:

• 1. Red sensitizers
  Dicarbocyanines with naphthothiazole or benzthiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy and 9.11-alkylene-bridged, in particular 9.11-neopentylene thiadicarbocyanines with alkyl or sulfoalkyl substituents on nitrogen.
• 2. Green sensitizers
  9-ethyloxacarbocyanines which are substituted in the 5-position by chlorine or phenyl and carry alkyl or sulfoalkyl radicals, preferably sulfoalkyl substituents, on the nitrogen of the benzoxazole groups.
• 3. Blue sensitizers
  Methine cyanines with benzoxazole, benzthiazole, benzselenazole, naphthoxazole, naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy and carry at least one, preferably two, sulfoalkyl substituents on the nitrogen. Furthermore apomerocyanines with a rhodanine group.

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 bromide iodides.

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 usually couplers of the phenol or α-naphthol type.

In addition to the pyrazoloazole couplers required according to the invention, couplers of the 5-pyrazolone or indazolone type can also be used as color couplers for producing the purple partial color image.

Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the α-acylacetamide type; suitable examples are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers.

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 point, which is split off during the coupling.

The couplers usually contain a ballast residue to prevent diffusion within the material, i.e. both within a layer or from layer to layer, to make impossible. Instead of couplers with a ballast residue, high molecular weight couplers can also be used.

Suitable color couplers or literature references, in which such are described, can be found in Research Disclosure 17 643 (1978), Chapter VII.

High molecular weight color couplers are 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. The selection of the suitable solvent or dispersing agent depends 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-0 043 037.

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-A-0 014 921, EP-A-0 069 671, EP-A-0 130 115, U.S.-A-4,291,113.

The diffusion-resistant incorporation of anionic water-soluble compounds (e.g. dyes) can also be carried out with the help 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 dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert-amylphenol, dioctylacetate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-doxy-5-butyl-2-. -octylaniline, paraffin, dodecylbenzene and diisopropylnaphthalene.

The photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain 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 whiteners 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 »m. 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 dye, coupler and whiteness stability 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, spirochromans, 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 deterioration (degradation) of yellow color images as a result the development of heat, moisture and light. In order to prevent the impairment (deterioration or degradation) of purple color images, in particular their impairment (deterioration or degradation) as a result of exposure to light, Spiroindane (JP-A-159 644/81) and chromanes, which 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-chloroethylurea), 2-Hydroxy-4,6-dichloro-1,3,5-triazine and other compounds containing reactive halogen (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 the layer to be hardened is covered with a layer containing 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 and the swelling of the layer structure occurs as a result of the crosslinking reaction . 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 that react very quickly with gelatin are e.g. to 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 to form peptide bonds and crosslink the gelatin.

There are diffusible curing agents that have the same curing effect on all layers within a layer structure. But there are also layer-limited, non-diffusing, low-molecular and high-molecular hardeners. They can be used to link individual layers, for example the protective layer, particularly strongly. This is important if the silver halide layer is hardened little because of the increase in silver opacity and the protective layer has to improve the mechanical properties (EP-A 0 114 699).

The color photographic materials according to the invention are usually processed by developing, bleaching, fixing and washing or 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 and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine. Other 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.

The material is usually bleached and fixed after color development. As bleaching agents, for example, Fe (III) salts and Fe (III) complex salts such as ferricyanides, Dichromates, water-soluble cobalt complexes can be used. Iron (III) complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, and alkyliminodicarboxylic acids and corresponding phosphonic acids are particularly preferred. 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 acts as a final bath.

The color photographic material according to the invention can also be subjected to a reverse development. The color development is preceded by an initial development with a developer who does not form any dye with the couplers, and a diffuse second exposure or chemical fogging.

example

A color photographic recording material was produced by applying the following layers in the order given on a paper coated on both sides with polyethylene. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given.

Layer structure 1 (comparison)

• 1st layer (substrate layer)
  0.2 g gelatin
• 2nd layer (blue-sensitive layer)
  blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.78 »m) from 0.50 g AgNO₃ with
  1.38 g gelatin
  0.60 g yellow coupler Y-1
  0.48 g tricresyl phosphate (CPM)
• 3rd layer (intermediate layer)
  1.18 g gelatin
  0.08 g 2,5-dioctyl hydroquinone
  0.08 g dibutyl phthalate (DBP)
• 4th layer (green-sensitive layer)
  Green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.37 »m) from 0.40 g AgNO₃ with
  1.02 g gelatin
  0.37 g purple coupler M-1
  0.40 g DBP
• 5th layer (intermediate layer)
  1.20 g gelatin
  0.66 g UV absorber of the formula
  
  0.052 g 2,5-dioctyl hydroquinone
  0.36 g CPM
• 6th layer (red-sensitive layer)
  Red-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.35 »m) from 0.28 g AgNO₃ with
  0.84 g gelatin
  0.39 g of cyan coupler C-1
  0.39 g CPM
• 7th layer (UV protective layer)
  0.65 g gelatin
  0.21 g UV absorber as in 5th layer
  0.11 g CPM
• 8th layer (protective layer)
  0.65 g gelatin
  0.39 g of curing agent of the formula
  
  
  

Layer structure 2 (comparison)

Schicht 3

0,59 g Gelatine
1,77 g Polyvinylalkohol

like layer structure 1 but with the following changes

Layer 3

0.59 g gelatin
1.77 g polyvinyl alcohol

Layer structure 3 comparison

Schicht 3

0,59 g Gelatine
1,77 g Polyvinylalkohol

Schicht 5

0,59 g Gelatine
1,77 g Polyvinylalkohol

like layer structure 1 but with the following changes

Layer 3

0.59 g gelatin
1.77 g polyvinyl alcohol

Layer 5

0.59 g gelatin
1.77 g polyvinyl alcohol

Layer structure 4 (comparison)

Schicht 3

0,59 g Gelatine
1,77 g Polymer P 1

like layer structure 1 but with the following changes

Layer 3

0.59 g gelatin
1.77 g polymer P 1

Layer structure 5 (comparison)

Schicht 5

0,59 g Gelatine
1,77 g Polymer P 1

like layer structure 1 but with the following changes

Layer 5

0.59 g gelatin
1.77 g polymer P 1

Layer structure 6 (according to the invention)

Schicht 3

0,59 g Gelatine
1,77 g Polymer P 1

Schicht 5

0,59 g Gelatine
1,77 g Polymer P 1

like layer structure 1 but with the following changes

Layer 3

0.59 g gelatin
1.77 g polymer P 1

Layer 5

0.59 g gelatin
1.77 g polymer P 1

Layer structure 7 (according to the invention)

Schicht 3

0,82 g Gelatine
1,14 g Polymer P 3

Schicht 5

0,82 g Gelatine
1,14 g Polymer P 3

like layer structure 1 but with the following changes

Layer 3

0.82 g gelatin
1.14 g of polymer P 3

Layer 5

0.82 g gelatin
1.14 g of polymer P 3

Layer structure 8 (according to the invention)

Schicht 2

1,12 g Gelatine
1,18 g Polymer P 3

Schicht 5

0,82 g Gelatine
1,14 g Polymer P 3

like layer structure 1 but with the following changes

Layer 2

1.12 g gelatin
1.18 g polymer P 3

Layer 5

0.82 g gelatin
1.14 g of polymer P 3

Layer structure 9 (according to the invention)

Schicht 2

1,12 g Gelatine
1,18 g Polymer P 4

Schicht 6

0,84 g Gelatine
1,02 g Polymer P 4

like layer structure 1 but with the following changes

Layer 2

1.12 g gelatin
1.18 g polymer P 4

Layer 6

0.84 g gelatin
1.02 g polymer P 4

Layer structure 10 (according to the invention)

Schicht 3

0,82 g Gelatine
1,14 g Polymer P 3

Schicht 7

0,65 g Gelatine
0,65 g Polymer P 3

like layer structure 1 but with the following changes

Layer 3

0.82 g gelatin
1.14 g of polymer P 3

Layer 7

0.65 g gelatin
0.65 g polymer P 3

Layer structure 11 (according to the invention)

Schicht 3

0,94 g Gelatine
1,12 g Polymer P 1

Schicht 5

0,82 g Gelatine
1,14 g Polymer P 5

like layer structure 1 but with the following changes

Layer 3

0.94 g gelatin
1.12 g polymer P 1

Layer 5

0.82 g gelatin
1.14 g polymer P 5

The layered structures were then exposed behind a graduated gray part. The materials were then processed in the customary manner using the processing baths listed below.

The processed samples were exposed to the light of a xenon lamp normalized for daylight and exposed to 4.2 x 10⁶ lx.h. The percentage decrease in density was then measured at an initial density of 1.5 (Table 1).

In addition, the layer structures were viewed in the case of obliquely incident light and the layers were visually assessed for their gloss (Table 1).

• a) Farbentwickler - 45 s - 35°C
  
  auffüllen mit Wasser auf 1000 ml; pH 10,0
• b) Bleichfixierbad - 45 s - 35°C
  
  auffüllen mit Wasser auf 1000 ml; pH 5,5
• c) Wässern - 2 min - 35°C
• d) Trocknen

It can be seen from Table 1 that by using the polymers according to the invention in one layer above and one below the layer containing the purple dye, the light stability of the purple dye is significantly improved and the good transparency of the layers is retained.

• a) Color developer - 45 s - 35 ° C
  
  make up to 1000 ml with water; pH 10.0
• b) bleach-fix bath - 45 s - 35 ° C
  
  make up to 1000 ml with water; pH 5.5
• c) Soak - 2 min - 35 ° C
• d) drying

Claims (7)

1. Colour photographic recording material having a support, at least one photosensitive silver halide emulsion layer containing a pyrazoloazole magenta coupler and at least one other layer arranged closer to the light source and at least one other layer arranged further from the light source than the silver halide emulsion layer containing the pyrazoloazole magenta coupler, characterised in that these other layers contain gelatine and a random or alternating copolymer prepared from vinyl alcohol and an unsaturated carboxylic acid or a graft polymer of vinyl acetate on polyalkylene oxide with subsequent saponification of the acetate groups.
2. Colour photographic recording material according to claim 1, characterised in that the copolymer contains from 50 to 98 mol.% of vinyl alcohol units, from 0 to 20 mol.% of vinyl acetate units, from 2 to 30 mol.% of unsaturated carboxylic acid units and from 0 to 30 mol.% of other comonomers and has a molecular weight M_n of at least 10,000.
3. Colour photographic recording material according to claim 1, characterised in that the pyrazoloazole coupler is of the formula

   

   in which

   R₁   means hydrogen, halogen, alkyl, aryl, a heterocyclic group, cyano, alkoxy, acyloxy, carbamoyloxy, acylamino or a polymer residue,

   X   means hydrogen or an eliminable group,

   one of the residues Z₁ and Z₂ means a nitrogen atom and the other -CR₂- and

   R₂   has the same meaning as R₁, wherein one of the residues R₁ and R₂ is a ballast group or is substituted by a ballast group, wherein the ballast group may also be a polymer residue.
4. Colour photographic recording material according to claim 1, characterised in that the graft copolymer contains from 2 to 50 mol.% of alkylene oxide, from 50 to 98 mol.% of vinyl alcohol and from 0 to 20 mol.% of vinyl acetate.
5. Colour photographic recording material according to claim 1, characterised in that the other layers each contain from 0.3 to 3.0 g of graft polymer or copolymer and from 0.1 to 2.0 g of gelatine per m².
6. Colour photographic recording material which contains in the stated order on a reflective support at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, an interlayer, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, an interlayer, at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler and at least one protective layer, characterised in that the interlayer between the green-sensitive and red-sensitive silver halide emulsion layers and the interlayer between the blue-sensitive and the green-sensitive silver halide emulsion layers contain gelatine and a random or alternating copolymer prepared from vinyl alcohol and an unsaturated carboxylic acid or a graft polymer of vinyl acetate on polyalkylene oxide with subsequent saponification of the acetate groups, and the magenta coupler is a pyrazoloazole coupler.
7. Colour photographic recording material according to claim 6, characterised in that the silver halide emulsions of the silver halide emulsion layers consist to an extent of at least 80 mol.% of silver chloride.