EP0616256A1 - Colour photographic recording material - Google Patents

Abstract

A colour-photographic silver-halide material having at least one silver-halide emulsion layer which contains, in one layer, a compound of the formula I <IMAGE> in which R1 is H or optionally substituted alkyl, aralkyl or cycloalkyl, R2 is H or optionally substituted alkyl, aryl or aralkyl or a polymer chain, R3 is H, OH, alkyl, aryl, aralkyl, halogen, NHR4, O-CO-R4, O-CO-NHR4 or an optionally substituted oxazoline ring, R4 is optionally substituted or alkyl, aralkyl or aryl, m is 2 or 3, and n is from 2 to 10,000, or a compound of the formula II <IMAGE> in which R1, R3, n and m are as defined above and may be identical or different, and R5 is optionally substituted alkylene, arylene, aralkylene or a polyaddition or polycondensation chain, is distinguished by reduced fogging for the same sensitivity.

Description

worin

R₁

H oder gegebenenfalls substituiertes Alkyl, Aralkyl oder Cycloalkyl

R₂

H oder gegebenenfalls substituiertes Alkyl, Aryl oder Aralkyl oder eine Polymerkette

R₃

H, OH, Alkyl, Aryl, Aralkyl, Halogen, NHR₄, O-CO-R₄, O-CO-NHR₄ oder einen gegebenenfalls substituierten Oxazolinring

R₄

gegebenenfalls substituiertes oder Alkyl, Aralkyl oder Aryl

m

2 oder 3, vorzugsweise 2

n

2 bis 10.000, vorzugsweise 5 bis 2.000 bedeuten

oder eine Verbindung der allgemeinen Formel II enthält

worin R₁, R₃, n und m die oben angegebene Bedeutung haben und gleich oder verschieden sein können und

R₅

gegebenenfalls substituiertes Alkylen, Arylen, Aralkylen oder eine Polyadditions-, Polykondensations- oder ein Polymerisationskette

bedeuten.The invention relates to a color photoaromatic recording material with at least one silver halide emulsion layer, characterized in that it contains a compound of the general formula I before processing:

wherein

R₁

H or optionally substituted alkyl, aralkyl or cycloalkyl

R₂

H or optionally substituted alkyl, aryl or aralkyl or a polymer chain

R₃

H, OH, alkyl, aryl, aralkyl, halogen, NHR₄, O-CO-R₄, O-CO-NHR₄ or an optionally substituted oxazoline ring

R₄

optionally substituted or alkyl, aralkyl or aryl

m

2 or 3, preferably 2

n

2 to 10,000, preferably 5 to 2,000

or contains a compound of general formula II

wherein R₁, R₃, n and m have the meaning given above and may be the same or different and

R₅

optionally substituted alkylene, arylene, aralkylene or a polyaddition, polycondensation or a polymerization chain

mean.

R₁ can be different in a polymer, so that co-, block co- or graft polymers are possible.

The compounds of the formulas (I) and (II) are preferably water-soluble or water-dispersible. Compounds of formula (I) are preferred.

R₁

C₁-C₄-Alkyl, insbesondere CH₃,

R₂

gegebenenfalls substituiertes C₁-C₂₀-Alkyl, wobei als Substituenten insbesondere Phenyl und Sulfamoyl in Betracht kommen,

R₃

OH.

Preferred compounds have the following substituent meanings:

R₁

C₁-C₄ alkyl, especially CH₃,

R₂

optionally substituted C₁-C₂₀-alkyl, phenyl and sulfamoyl being particularly suitable as substituents,

R₃

OH.

The polyaddition, polycondensation or polymerization compounds R₅ are, for example, polyesters, preferably aliphatic polyesters, polyacetals, polyethers, polyamides, polyesteramides, polycarbonates, polyurethanes, polystyrenes, poly (meth) acrylates, optionally substituted polyacrylamides, polyalkylene compounds.

The compounds have a molecular weight of about 300 to 20,000, preferably 500 to 5,000.

Examples of polyethers are the polymerization products of ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide and their mixed or graft polymerization products, and those by condensation of polyvalent ones Alcohols or mixtures thereof obtained condensates and the products obtained by alkoxylation of polyhydric alcohols.

As polyacetals e.g. the compounds that can be prepared from hexanediol and formaldehyde are questionable. The predominantly linear condensates obtained from polyvalent saturated carboxylic acids and polyvalent saturated alcohols, amino alcohols, diamines and their mixtures are suitable as polyesters, polyester amides and polyamides.

Polystyrene, substituted polystyrenes, poly (meth) acrylates such as polybutyl acrylate, polyethyl acrylate, polyhydroxyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, optionally substituted polyacrylamides or polymethacrylamides, polyvinyl ether, polyethylene, polypropylene, polyisobutylene may be mentioned as polymers.

The synthesis of the compounds I and II is in Macromolecules, Vol. 19, No. 6, 1986 p. 1547, Polymer Bulletin 13, 447 (1985), Macromol. Chem., Macromol. Symp. 1 , 23-37 (1986), Macromolecules 1986 , 19, 535 and Macromolecules 1973 , 6, 805.

According to JP-OS 78/124 425, they have hitherto been used in the photographic industry as an additive to bleaching baths in order to improve bleachability.

It has now surprisingly been found that these compounds, a color photographic material before exposure and processing, i.e. added in the course of the production, reducing the veil without deteriorating the sensitivity, improving the storage stability, increasing the proportion of tabular silver halide grains or increasing their aspect ratio and improving the colloid stability of latices and dispersions.

X

= Polyester aus Adipinsäure und Butandiol; M_n (durch Endgruppenbestimmung) ^∼ 2.000

Beispiele für farbfotografische Materialien sind Farbnegativfilme, Farbumkehrfilme, Farbpositivfilme: farbfotografisches Papier, farbumkehrfotografisches Papier, farbempfindliche Materialien für das Farbdiffusionstransfer-Verfahren oder das Silberfarb-Bleichverfahren.Examples of compounds according to the invention are

X

= Polyester from adipic acid and butanediol; M _n (by end group determination) ^∼ 2,000

Examples of color photographic materials are color negative films, color reversal films, color positive films: color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process.

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 and paper laminated with a baryta layer or α-olefin polymer layer (e.g. polyethylene). These carriers 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.

The color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.

Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.

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, which have been 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. 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.

The silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide. For example, the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide. In the case of color negative and color reversal films, silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions with a high chloride content are used up to pure silver chloride emulsions. It can be predominantly compact crystals, which are, for example, regularly cubic or octahedral or can have transitional forms. However, platelet-shaped crystals can preferably also 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 area of the grain.

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 μm and 2.0 μm, the grain size distribution can be either homodisperse or heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ± 30%. 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 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 certain 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 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.

Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe 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.

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 halide and sensitizer concentration - until the optimum sensitivity and fog are reached. The procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).

The chemical sensitization with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII Periodic table (e.g. gold, platinum, palladium, iridium), thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described for example by F. Hamer "The Cyanine Dyes and Related Compounds") , 1964, or Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Vol. 18, pp. 431 ff. And Research Disclosure 17643 (Dec. 1978), Chapter III). As an alternative or in addition, a reduction sensitization can be carried out with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid) using hydrogen, by means of 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 can also be used as antifoggants such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts. 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 17643 (Dec. 1978), Chapter 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 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.). In addition to natural surface-active compounds, e.g. saponin, mainly synthetic surface-active compounds (surfactants) are used: non-ionic surfactants, e.g. alkylene oxide compounds, glycerol compounds or glycidol compounds, cationic surfactants, e.g. higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, containing anionic surfactants 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 as well as sulfuric 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 (Dec. 1978), Chapter IV, provides an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations having a super-sensitizing effect.

• 1. als Rotsensibilisatoren
  9-Ethylcarbocyanine mit Benzthiazol, Benzselenazol oder Naphthothiazol als basische Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy, Carbalkoxy, Aryl substituiert sein können sowie 9-Ethyl-naphthoxathia- bzw. -selencarbocyanine und 9-Ethyl-naphthothiaoxa- bzw. -benzimidazocarbocyanine, vorausgesetzt, daß die Farbstoffe mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff tragen.
• 2. als Grünsensibilisatoren
  9-Ethylcarbocyanine mit Benzoxazol, Naphthoxazol oder einem Benzoxazol und einem Benzthiazol als basische Endgruppen sowie Benzimidazocarbocyanine, die ebenfalls weiter substituiert sein können und ebenfalls mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff enthalten müssen.
• 3. als Blausensibilisatoren
  symmetrische oder asymmetrische Benzimidazo-, Oxa-, Thia- oder Selenacyanine mit mindestens einer Sulfoalkylgruppe am heterocyclischen Stickstoff und gegebenenfalls weiteren Substituenten am aromatischen Kern, sowie Apomerocyanine mit einer Rhodaningruppe.

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

• 1. as red sensitizers
  9-ethylcarbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups, the can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl and 9-ethyl-naphthoxathia or -selenecarbocyanine 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.

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, the red-sensitive layers become cyan couplers, assigned to the green-sensitive layers of purple couplers and the blue-sensitive layers of yellow couplers.

Color couplers for producing the blue-green partial color image are usually couplers of the phenol or α-naphthol type; Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the α-benzoylacetanilide or α-pivaloylacetanilide type.

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 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products. The 2-equivalent couplers also include those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and either directly or after one or after the residue from the primary cleavage group several other groups have been split off (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, for example as Development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.

DIR couplers, the development inhibitors of the azole type, e.g. Release triazoles and benzotriazoles are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281.28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416. Other advantages for color rendering, i.e. Color separation and color purity, and for detail reproduction, i.e. Sharpness and graininess can be achieved with such DIR couplers, e.g. do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further subsequent reaction, which is achieved, for example, with a timing group. Examples of these are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-0 157 146 and 0 204 175, in US-A-4 146 396 and 4 438 393 as well 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-0 167 168 and 0 219 713. This measure ensures trouble-free development and processing consistency.

When using DIR couplers, in particular those which release an easily diffusible development inhibitor, suitable measures can be taken to improve the color rendering, e.g. achieve a more differentiated color rendering, as described, for example, in EP-A-0 115 304, 0 167 173, 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, e.g. also light-insensitive or intermediate layers. However, they are preferably added to the photosensitive silver halide emulsion layers, the characteristics of the silver halide emulsion, e.g. whose iodide content, the structure of the silver halide grains or their grain size distribution influence 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 can 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. links 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-0 089 834, 0 110 511, 0 118 087, 0 147,765 and in U.S.-A-4,618,572 and 4,656,123.

As an example of 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.

Since with DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is 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, as described for example 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 Solvent or dispersant 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-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-AO 130 115, US Pat. 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 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-t-amylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-octoxy-5-butyl-2-butyl , Paraffin, dodecylbenzene and diisopropylnaphthalene.

Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470). In this case, 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, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.

With a suitably low intrinsic sensitivity of the green or Red-sensitive layers can be selected without the yellow filter layer, other layer arrangements 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), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877, 0 125 522.

If there are several sub-layers of the same spectral sensitization, they can be distinguished with regard to their composition, in particular with regard to the type and amount of the silver halide grains. In general, the sublayer with higher sensitivity will be located further away from the support than the sublayer with lower sensitivity. Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, for example through Layers of other spectral sensitization must be separated. 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, 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 μm. The spacers are insoluble in water and can be insoluble in alkali or be alkali-soluble, the alkali-soluble 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 (Dec. 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 which 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 of yellow color images as a result of the development of heat, moisture and light. In order to prevent the deterioration of magenta color images, in particular their impairment as a result of exposure to light, spiroindanes (JP-A-159 644/81) and chromanes which are substituted by hydroquinone diethers or monoethers (JP-A-89 835 / 80) particularly effective.

The layers of the photographic material can be hardened with the usual hardening agents. Suitable curing agents include 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, the reactive halogen contain (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 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 layer thickness and the dry layer 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.

• (a)
  
  worin

  R¹

  Alkyl, Aryl oder Aralkyl bedeutet,

  R²

  die gleiche Bedeutung wie R¹ hat oder Alkylen, Arylen, Aralkylen oder Alkaralkylen bedeutet, wobei die zweite Bindung mit einer Gruppe der Formel

  

  verknüpft ist, oder

  R¹ und R²

  zusammen die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin-oder Morpholinringes erforderlichen Atome bedeuten, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein Kann,

  R³

  für Wasserstoff, Alkyl, Aryl, Alkoxy, -NR⁴-COR⁵, - (CH₂)_m-NR⁸R⁹, - (CH₂)_n-CONR¹³R¹⁴ oder

  

  oder ein Brückenglied oder eine direkte Bindung an eine Polymerkette steht, wobei

  R⁴, R⁶, R⁷, R⁹, R¹⁴, R¹⁵, R¹⁷, R¹⁸ und R¹⁹

  Wasserstoff oder C₁-C₄-Alkyl,

  R⁵

  Wasserstoff, C₁-C₄-Alkyl oder NR⁶R⁷,

  R⁸

  -COR¹⁰

  R¹⁰

  NR¹¹R¹²

  R¹¹

  C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

  R¹²

  Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

  R¹²

  Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

  R¹⁶

  Wasserstoff, C₁-C₄-Alkyl, - COR¹⁸ oder - CONHR¹⁹,

  m

  eine Zahl 1 bis 3,

  n

  eine Zahl 0 bis 3,

  p

  eine Zahl 2 bis 3 und

  Y

  0 oder NR¹⁷ bedeuten oder

  R¹³ und R¹⁴

  gemeinsam die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin-oder Morpholinringes erforderlichen Atome darstellen, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,

  Z

  die zur Vervollständigung eines 5-oder 6-gliedrigen aromatischen heterocyclischen Ringes, gegebenenfalls mit anelliertem Benzolring, erforderlichen C-Atome und

  X^⊖

  ein Anion bedeuten, das entfällt, wenn bereits eine anionische Gruppe mit dem übrigen Molekül verknüpft ist;

• (b)
  
  worin

  R¹, R², R³ und X^⊖

  die für Formel (a) angegebene Bedeutung besitzen.

Suitable examples of instant hardeners are, for example, compounds of the general formulas

• (a)
  
  wherein

  R¹

  Means alkyl, aryl or aralkyl,

  R²

  has the same meaning as R¹ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond being with a group of the formula

  

  is linked, or

  R1 and R2

  together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring being able to be substituted, for example, by C₁-C₃alkyl or halogen,

  R³

  for hydrogen, alkyl, aryl, alkoxy, -NR⁴-COR⁵, - (CH₂) _m -NR⁸R⁹, - (CH₂) _n -CONR¹³R¹⁴ or

  

  or a bridge link or a direct bond to a polymer chain, wherein

  R⁴, R⁶, R⁷, R⁹, R¹⁴, R¹⁵, R¹⁷, R¹⁸ and R¹⁹

  Hydrogen or C₁-C₄ alkyl,

  R⁵

  Hydrogen, C₁-C₄-alkyl or NR⁶R⁷,

  R⁸

  -COR¹⁰

  R¹⁰

  NR¹¹R¹²

  R¹¹

  C₁-C₄ alkyl or aryl, especially phenyl,

  R¹²

  Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,

  R¹²

  Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,

  R¹⁶

  Hydrogen, C₁-C₄-alkyl, - COR¹⁸ or - CONHR¹⁹,

  m

  a number 1 to 3,

  n

  a number 0 to 3,

  p

  a number 2 to 3 and

  Y

  0 or NR¹⁷ mean or

  R¹³ and R¹⁴

  together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring can be substituted, for example, by C₁-C₃alkyl or halogen,

  Z.

  the C atoms required to complete a 5-membered or 6-membered aromatic heterocyclic ring, optionally with a fused-on benzene ring, and

  X ^⊖

  mean an anion which is omitted if an anionic group is already linked to the rest of the molecule;

• (b)
  
  wherein

  R¹, R², R³ and X ^⊖

  have the meaning given for formula (a).

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 weight and high molecular hardness. 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 mechanical layer has to be improved with the protective layer (EP-A-0 114 699).

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. 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.

Usually the material is bleached and fixed immediately after color development. As bleaching agents e.g. 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 are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulfates and peroxides, e.g. Hydrogen peroxide.

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.

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 followed by a diffuse second exposure and then development with a color developer, bleaching and fixing.

example 1 Preparation of the emulsions Emulsion 1 (EM 1)

An aqueous solution of 30 g of inert bone gelatin, 36 g of KBr and 3.2 g of KJ in 3 l of water was placed in a 10 l reaction kettle.

1,200 ml of an aqueous solution of 136 g of AgNO 3 and 1,200 ml of an aqueous solution of 150 g of KBr and 6.8 g of KJ were fed to this template at a temperature of 70 ° C., each with constant dosage over a period of 30 min.

After a break of 10 minutes, a further 1,600 ml of an aqueous solution of 204 g of AgNO 3 and 1,600 ml of an aqueous solution of 130 g of NH₄Br were fed in over a period of 32 minutes with constant metering.

The emulsion was then cooled, flocculated by acidification and with the addition of a flocculant. The flocculate was washed out several times and redispersed with the addition of inert bone gelatin, so that a silver / gelatin weight ratio of 1: 0.3 (based on silver nitrate) resulted.

The emulsion thus obtained had an average grain diameter of 0.8 μm and an iodide content of 3 mol%.

The proportion of tabular crystals in the total projection area was approx. 35% according to electron micrographs. The average aspect ratio of the tabular crystals was 3.5. EM 1 is a comparative emulsion.

EM 2 (according to the invention)

EM 2 was prepared like EM 1 with the change that the initial charge additionally contained 0.34 g of compound P 3. The proportion of tabular crystals in the total projection area was 85% and the average aspect ratio of the tabular crystals was 7.5.

EM 3 (according to the invention)

EM 3 was prepared like EM 1 with the change that the initial charge additionally contained 1.36 g of compound P 3. The proportion of tabular crystals in the total projection area was 95% and the average aspect ratio of the tabular crystals was 17.

EM 4 (according to the invention)

EM 4 was prepared like EM 1 with the change that the initial charge additionally contained 3.4 g of compound P 3. The proportion of tabular crystals in the total projection area was 97% and the average aspect ratio of the tabular crystals was> 25.

Schicht 1

(Antihaloschicht) Schwarzes kolloidales Silbersol aus
0,4 g Ag und
3,0 g Gelatine

Schicht 2

(Zwischenschicht)
0,5 g Gelatine

Schicht 3

(Rotempfindliche Schicht)
rotsensibilisierte Emulsion gemäß Tabelle 1 aus
5,1 g AgNO₃
6,0 g Gelatine
2,4 g Blaugrünkuppler BG 1

Schicht 4

(Zwischenschicht)
1,0 g Gelatine

Schicht 5

(Härtungsschicht)
0,24 g Gelatine
0,3 g Härtungsmittel der Formel

Tabelle 1 Emulsion optimale Belegung mit Rotsensibilisator S 1 [µmol/mol Ag] Schleier rel. Rot-Empfindlichkeit rel.Blau-Empfindlichkeit EM 1 250 0,25 100 100 EM 2 320 0,23 123 102 EM 3 390 0,21 148 100 EM 4 440 0,18 132 98
Rotsensibilisator S 1:

Blaugrünkuppler BG 1

The emulsions EM 1 to EM 4 were optimally ripened with gold and sulfur compounds, stabilized with 5 mmol of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of AgNO₃ and spectrally sensitized with the red sensitizer S 1. Then the following layer structures 1 to 4 were produced, which differed only in the type of emulsion used. The optimal sensitizer occupancy, the fog, the relative red sensitivity and the relative blue sensitivity were checked. The carrier was cellulose triacetate; the quantities refer to 1 m².

Layer 1

(Antihalo layer) Black colloidal silver sol
0.4 g Ag and
3.0 g gelatin

Layer 2

(Intermediate layer)
0.5 g gelatin

Layer 3

(Red sensitive layer)
red-sensitized emulsion according to Table 1
5.1 g AgNO₃
6.0 g gelatin
2.4 g blue-green coupler BG 1

Layer 4

(Intermediate layer)
1.0 g gelatin

Layer 5

(Hardening layer)
0.24 g gelatin
0.3 g hardening agent of the formula

Table 1 emulsion optimal coverage with red sensitizer S 1 [µmol / mol Ag] veil rel. Red sensitivity Relative blue sensitivity EM 1 250 0.25 100 100 EM 2 320 0.23 123 102 EM 3 390 0.21 148 100 EM 4 440 0.18 132 98
Red sensitizer S 1:

Teal Coupler BG 1

Example 2 (Experiments 1-4, Table 2)

To a silver bromide iodide emulsion (A) with an average grain diameter of 1.0 μm, an iodide content of 11.5 mol%, a silver / gelatin weight ratio of 1: 0.3 (based on silver nitrate) and a content of 1.18 mol AgNO₃ per kg of emulsion, which was mixed with 5 mmol of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of AgNO₃, were the amounts given in Table 2 for experiments Nos. 1 to 4 of the compound P 3 / mol AgNO₃ added. Before pouring, 900 g of a 10% by weight gelatin solution and 500 g of a 10% by weight coupler dispersion of the yellow coupler GB 1 as well as wetting agent and water were added to each kg of emulsion.

The emulsions were poured onto the antihalation layer of a cellulose acetate support consisting of a silver dispersion with a silver coating corresponding to 4.6 g AgNO₃ / m².

und ein Netzmittel enthielt, mit einer Auftragsdicke von 2 g Gelatine/m² und 340 mg Härtungsmittel/m² aufgetragen.A protective layer containing a hardening agent of the formula was applied to each of the emulsion layers

and containing a wetting agent, applied at a coating thickness of 2 g gelatin / m² and 340 mg hardening agent / m².

The samples were tested as follows after production, after storage in a heating cabinet (3 days, 60 ° C, 34% relative humidity) and after storage in a tropical cabinet (7 days, 35 ° C, 90% relative humidity):

The samples were exposed in a sensitometer behind a step wedge, developed in the following developer at 38 ° C for 195 seconds and subjected to further processing. developer 1-hydroxyethane-1,1-diphosphonic acid disodium salt 2 g Ethylenediamine-N, N, N ', N'-tetraacetic acid 2 g Potassium carbonate 34.1 g Sodium bicarbonate 1.55 g Sodium disulfite 0.28 g Sodium sulfite 3.46 g Potassium bromide 1.34 g Hydroxylamine sulfate 2.4 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) - aniline 4.7 g Make up to 1 liter with water.

The further processing includes the following baths: Stop bath 1 minute at 38 ° C; Bleach bath 3 1/4 minutes at 38 ° C; Water 3 1/2 minutes at 38 ° C; Fixer 3 1/4 minutes at 38 ° C; Water 5 minutes at 38 ° C.

The stop, bleaching and fixing baths used correspond to those commonly used (British Journal of Photography, 1974 , pages 597 and 598).

The results are shown in Table 2.

The yellow coupler GB 1 had the following structure:

Example 3 (Experiments 5 to 7, Table 2)

Example 3 corresponds in its embodiment to Example 2 with the difference that a silver bromide iodide emulsion with 9 mol% iodide and an average grain diameter of 1.1 μm (emulsion B), and the amounts of the compound given in Table 2 for experiments 5 to 7 P 3 / mol AgNO₃ were used.

Processing and testing corresponded to example 2.

Example 4 (Experiments 8 to 10, Table 2)

The emulsion A used in Example 2 was after the addition of 5 mmol of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of AgNO₃ with 300 µmol red sensitizer S 1 per mole of AgNO₃ and then in each case with those in Table 2 for experiments 8 to 10 specified amounts of the compound P 3 / Mol AgNO₃ added. Before pouring, 700 g of a 10% by weight gelatin solution and 300 g of a 9.8% by weight coupler from the blue-green coupler BG 1 as well as wetting agent and water were added to each kg of emulsion.

The emulsions were poured onto the antihalation layer of a cellulose acetate support consisting of a silver dispersion with a silver coating corresponding to 5.5 g AgNO₃ / m².

und ein Netzmittel enthielt, mit einer Auftragsdicke von 2 g Gelatine/m² und 340 mg Härtungsmittel/m² aufgetragen.

A protective layer containing a hardening agent of the formula was applied to each of the emulsion layers

and containing a wetting agent, applied at a coating thickness of 2 g gelatin / m² and 340 mg hardening agent / m².

As Table 2 shows, the veils are reduced by the substances according to the invention and the storage stability of the photographic material is significantly improved.

Example 5

The compounds P-1, P-4 and P-5 and the magenta couplers PP1 and PP2 are mixed into various samples of a silver bromide iodide emulsion with 3 mol% iodide and an average particle diameter of 0.75 μm spectrally sensitized with the green sensitizer S 2, the 75th g of silver bromide iodide and 72 g of gelatin based on 1 kg of emulsion.

The emulsions prepared in this way were applied to cellulose triacetate layer supports provided with an adhesive layer and dried.

Photographic check:

The individual samples were exposed using a sensitometer and then processed using the color developer described in Example 2. Processing (min) (25 ° C) Color developer 10th Stop bath 4th Intermediate watering 5 Bleach bath 5 Intermediate watering 5 Fixer 5 Final watering 10th

The stop, bleach and fix baths are common bath compositions. A final bath free of formalin was used.

The processed samples were examined sensitometrically and characterized with regard to fog, sensitivity and maximum color yield. The measured values are shown in Table 3.

Kuppler PP1

The green sensitizer S 2 had the structure:

Coupler PP1

a/b/c = 20/40/40 Gew.-%, Mn ^∼ 40.000Coupler PP2

a / b / c = 20/40/40% by weight, Mn ^∼ 40,000

Example 6

A core / shell plasticizer latex is produced according to the method given in US Pat. No. 4,714,671 in Example 1. The latex obtained shows good plasticizer properties, but is unstable when electrolytes are added. By adding the compounds P-4 or P-5, the colloid stability of the latex is significantly improved (Table 4).

The test is carried out by dropping 0.5 ml of the electrolyte solution into 100 ml of the latex in a 150 ml beaker and then assessing the latex stability.

Example 7

The procedure was as in Example 6. Instead of the plasticizer latex, the pyrazolotriazole latex coupler referred to as polymer coupler 1 in EP 237 877 was mixed with the compounds according to the invention and tested for electrolyte stability (Table 5).

The example shows that photographically useful latices can be significantly improved in their stability by adding the polymers according to the invention.

Claims (2)

Color photographic silver halide material with at least one silver halide emulsion layer, characterized in that at least one layer contains a compound of formula I before processing

contains what R₁ H or optionally substituted alkyl, aralkyl or cycloalkyl R₂ H or optionally substituted alkyl, aryl or aralkyl or a polymer chain R₃ H, OH, alkyl, aryl, aralkyl, halogen, NHR₄, O-CO-R₄, O-CO-NHR₄ or an optionally substituted oxazoline ring R₄ optionally substituted or alkyl, aralkyl or aryl m 2 or 3, preferably 2 n 2 to 10,000, preferably 5 to 2,000 or a compound of formula II

contains, wherein R₁, R₃, n and m have the meaning given above and may be the same or different and R₅ optionally substituted alkylene, arylene, aralkylene or a polyaddition, polycondensation or a polymerization chain mean. Color photographic silver halide material according to claim 1, characterized in that at least one layer contains a compound of formula (I) before processing,
wherein R₁ C₁-C₄ alkyl, R₂ optionally substituted C₁-C₂₀ alkyl and R₃ OH mean.