EP0616256B1 - Colour photographic recording material - Google Patents

Description

worin

R₁

H oder gegebenenfalls substituiertes Alkyl, Aralkyl oder Cycloalkyl

R₂

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

R₃

OH

R₄

gegebenenfalls substituiertes 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 photographic recording material having at least one silver halide emulsion layer, characterized in that it contains a compound of the general formula I before processing:

wherein

R ₁

H or optionally substituted alkyl, aralkyl or cycloalkyl

R ₂

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

R ₃

OH

R ₄

optionally substituted 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 R ₁ , R ₃ , n and m have the meaning given above and may be the same or different and

R ₅

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

mean.

R ₁ can be different in one polymer, so that co-, block-co- or graft polymers are possible.

The compounds of formulas (I) and (II) are preferred water soluble or water dispersible. links 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.

Preferred compounds have the following substituent meanings:

R ₁

C ₁ -C ₄ alkyl, especially CH ₃ ,

R ₂

optionally substituted C ₁ -C ₂₀ alkyl, phenyl and sulfamoyl being particularly suitable as substituents.

The polyaddition, polycondensation or polymerization compounds R ₅ 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 300 to 20,000, preferably 500 to 5,000.

As polyethers e.g. the polymerization products of Ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide as well as their mixed or graft polymerization products, as well as the condensation of polyvalent ones Alcohols or mixtures of the same condensates obtained and that by alkoxylation of polyhydric alcohols won products called.

As polyacetals e.g. those made from hexanediol and Formaldehyde-producible compounds in question. As Polyesters, polyester amides and polyamides are made of polyvalent saturated carboxylic acids and polyvalent saturated alcohols, amino alcohols, diamines and their mixtures obtained, mostly linear Suitable for condensates.

Polystyrene, substituted, may be mentioned as polymers Polystyrenes, poly (meth) acrylates such as polybutyl acrylate, Polyethyl acrylate, polyhydroxyethyl acrylate, polymethyl methacrylate, Polyethyl methacrylate, optionally substituted Polyacrylamides or polymethacrylamides, polyvinyl ethers, Polyethylene, polypropylene, polyisobutylene.

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 781124 425 they were used in the photographic Industry previously used as an additive to bleach baths to improve bleachability.

It has now surprisingly been found that this Connections, a color photographic material Exposure and processing, i.e. in the course of manufacturing added, reduce the veil without the Sensitivity deteriorate, storage stability improve the proportion of tabular silver halide grains increase or increase their aspect ratio and the colloid stability of latices and dispersions improve.

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

Beispiele für farbfotografische Materialien sind Farbnegativfilmes Farbumkehrfilme, Farbpositivfilme, farbfotografisches Papier, farbumkehrfotografisches Papier, farbempfindliche Materialien für das Farbdiffusions-transfer-Verfahren oder das Silberfarb-Bleichverfahren.Examples of compounds of the formulas (I) and (II) 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 with a barite layer or α-olefin polymer layer (e.g. polyethylene) laminated paper. These carriers can with dyes and pigments, for example titanium dioxide, be colored. They can also be used for shielding purposes be colored black by light. The surface the carrier is generally subjected to a treatment, the adhesion of the photographic emulsion layer to improve, for example a corona discharge with subsequent application for a substrate layer.

The color photographic materials usually contain at least one red sensitive, green sensitive and blue sensitive silver halide emulsion layer and optionally intermediate layers and Protective layers.

Essential components of the photographic emulsion layers are binders, silver halide grains and Color coupler.

Gelatin is preferably used as the binder. However, this can be done in whole or in part by others synthetic, semi-synthetic or also naturally occurring Polymers to be replaced. Synthetic gelatin substitutes Examples include polyvinyl alcohol, poly-N-vinyl pyrrolidone, Polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are, for example other proteins like 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 as well as gelatin derivatives, which by implementation with alkylating or acylating agents or by Grafting polymerizable monomers obtained are examples of this.

The binders should have a sufficient amount of functional groups so that by implementation sufficiently resistant with suitable hardening agents Layers can be created. Such functional Groups are especially amino groups, but also Carboxyl groups, hydroxyl groups and active methylene groups.

The gelatin which is preferably used can be acidic or alkaline digestion. It can also oxidized gelatin can be used. The production such gelatin 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 should be as possible low level of photographically active impurities included (inert gelatin). Gelatin with high viscosity and low swelling are special advantageous.

That as a light-sensitive component in the photographic Silver halide present as material Halide chloride, bromide or iodide or mixtures of which included. For example, the halide content at least one layer of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% consist of bromide. In the case of color negative and color reversal films usually silver bromide iodide emulsions, in the case of color negative and color reversal paper usually high silver chloride bromide emulsions Chloride content used up to pure silver chloride emulsions. It can be mostly compact crystals act, e.g. are regular cubic or octahedral or can have transitional forms. Preferably however, platelet-shaped crystals can also be present, their average ratio of diameter to Thickness is preferably at least 5: 1, the diameter a grain is 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 be multi-layered Have grain structure, in the simplest case with an inner and an outer grain area (corel shell), the halide composition andloder other modifications, such as Endowments of the individual Grain areas are different. The middle The grain size of the emulsions is preferably between 0.2 µm and 2.0 µm, the grain size distribution can be both be homo- and heterodisperse. Homodisperse grain size distribution means 95% of the grains are not deviate more than ± 30% from the average grain size. In addition to the silver halide, the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.

Two or more types of silher halide emulsions, which are made separately, as a mixture be used.

The photographic emulsions can be different Methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) soluble silver salts and soluble halides become.

The silver halide is preferably precipitated in Presence of the binder, e.g. the gelatin and can carried out in the acidic, neutral or alkaline pH range are, preferably silver halide complexing agents can also be used. The latter belong e.g. Ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The merge the water-soluble silver salts and the halides optionally takes place one after the other after the single-jet or simultaneously using the double-jet process or by any combination of both methods. Prefers the dosage becomes with increasing inflow rates, where the "critical" feed rate at which just no new germs are emerging, not exceeded should be. The pAg range can be changed during the Precipitation can vary within wide limits, preferably uses the so-called pAg-controlled method, in which a certain pAg is kept constant or on Run through the defined pAg profile during the precipitation becomes. In addition to the preferred precipitation with halide excess is also the so-called inverse Precipitation possible with excess of silver ions. Except through The silver halide crystals can also be precipitated by physical ripening (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent to grow. The growth of the emulsion grains can even predominantly through Ostwald ripening take place, preferably a fine-grained, so-called Lippmann emulsion, with a less soluble Emulsion mixed and redissolved on the latter.

During precipitation and / or physical ripening The silver halide grains can also contain salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe to be available.

The precipitation can also be carried out in the presence of sensitizing dyes respectively. Complexing agent and / or dyes can be any Deactivate the point in time, e.g. by changing the pH or by an oxidative treatment.

After crystal formation is complete or already closed the soluble salts are removed at an earlier point in time removed from the emulsion, e.g. by pasta and washing, by flaking and washing, by ultrafiltration or through ion exchangers.

The silver halide emulsion generally becomes one chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until it is reached of the optimum sensitivity and fog. The procedure is e.g. with H. Frieser "The basics of the photographic processes with silver halides " Pages 675-734, Academic Publishing Company (1968).

The chemical sensitization can add of compounds of sulfur, selenium, tellurium andloder Compounds of metals of subgroup VIII Periodic table (e.g. gold, platinum, palladium, iridium) can take place, furthermore thiocyanate compounds, surface-active Compounds such as thioethers, heterocyclic Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described e.g. with F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmann's Encyclopedia of Technical Chemistry, 4th edition, vol. 18, p. 431 ff. And Research Disclosure 17643 (Dec. 1978), Chapter III) can be added. Alternatively or in addition, a reduction sensitization with the addition of reducing agents (tin-II salts, Amines, hydrazine derivatives, aminoboranes, silanes, Formamidine sulfinic acid) by hydrogen, by low pAg (e.g. less than 5) and / or high pH (e.g. above 8) be carried out.

The photographic emulsions can be compounds to Prevention of fog or for stabilization the photographic function during production, the Storage or photographic processing included.

Azaindenes are particularly suitable, preferably tetra and pentaazaindenes, 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 can also be used as antifoggants. Nitroindazole, optionally substituted benzotriazoles or benzthiazolium salts can be used. 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 the silver halide emulsions before, during or after their ripening. Of course, the connections can also be made to others photographic layers that are a layer of halogen silver are assigned.

Mixtures of two or more of the above can also be used Connections are used.

The photographic emulsion layers or other hydrophilic Colloid layers of the one produced according to the invention Photosensitive material can be surface active Contain funds for various purposes, such as coating aids, to prevent electrical charging Improvement of the sliding properties, for emulsifying the Dispersion, to prevent adhesion and to improve the photographic characteristics (e.g. acceleration of development, high contrast, sensitization etc.). In addition to natural surface-active compounds, e.g. Saponin, mainly synthetic surface-active compounds (surfactants) Use: non-ionic surfactants, e.g. Alkylene oxide compounds, Glycerin compounds or glycidol compounds, cationic Surfactants, e.g. higher alkylamines, quaternary ammonium salts, Pyridine compounds and other heterocyclic Compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing one Acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, Sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, e.g. Amino acid and Aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters an amino alcohol.

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

An overview of those suitable as spectral sensitizers Polymethine dyes, their suitable combinations and super-sensitizing combinations contains Research Disclosure 17643 (Dec. 1978), chapter IV.

1. als Rotsensibilisatoren
   9-Ethylcarbocyanine mit Benzthiazol, Benzselenazol oder Naphthothiazol als basische Endgruppen, die in 5- undloder 6-Stellung durch Halogen, Methyl, Methoxy, Carbalkoxy, Aryl substituiert sein können sowie 9-Ethyl-naphthoxathia- bzw. -selencarbo-cyanine und 9-Ethyl-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 benzothiazole, benzselenazole or naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl, and 9-ethyl-naphthoxathia or -selenecarbocyanines and 9- Ethyl-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 become non-diffusing monomeric or polymeric color couplers assigned which is in the same shift or in a layer adjacent to it. Usually, the red-sensitive layers become cyan couplers, the green-sensitive layers of purple couplers and assigned to the blue-sensitive layers yellow couplers.

Color coupler for generating the blue-green partial color image are usually couplers of the phenol or α-naphthol type; Color coupler for the generation of the purple Partial color images are usually couplers of 5-pyrazolone, Indazolone or pyrazoloazole type; Color coupler to generate the yellow partial color image are in the Usually couplers with an open chain ketomethylene grouping, in particular couplers of α-benzoylacetanilide or α-pivaloylacetanilide type,

The color couplers can be 4-equivalent couplers, but also act as 2-equivalent couplers. Latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off at the clutch. To the 2 equivalent couplers colorless ones are to be expected are, as well as those that have an intense intrinsic color have, which disappears with the color coupling or replaced by the color of the image dye generated becomes (mask coupler), and the white couplers that react with color developer oxidation products essentially result in colorless products. To the 2 equivalent couplers such couplers are also to be expected, which in the Coupling point contain a removable residue that when reacting with color developer oxidation products in Freedom is set, either directly or after one or 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, e.g. as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.

DIR couplers, the development inhibitors of the azole type, e.g. Triazoles and benzotriazoles are released 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 are with such DIR couplers to achieve, e.g. the development inhibitor not immediately as a result of coupling with one split off oxidized color developer, but only after a further follow-up reaction, for example with a timing group is reached. Examples of this 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 and in GB-A-2,072,363.

DIR couplers that release a development inhibitor which in the developer bath is essentially photographically ineffective Products are decomposed, for example in DE-A-32 09 486 and in EP-A-0 167 168 and 0 219 713 described. With this measure, a trouble-free Development and processing consistency achieved.

When using DIR couplers, especially those that split off a diffusible development inhibitor, can be taken by taking suitable measures at the optical sensitization improvements in color rendering, e.g. a more differentiated color rendering, achieve, such as 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 used in a multi-layer photographic Material added to different layers e.g. also light-insensitive or intermediate layers. However, they are preferably the photosensitive silver halide emulsion layers added, the characteristic properties the silver halide emulsion, e.g. their iodide content, the Structure of the silver halide grains or their grain size distribution of influence on the photographic achieved Properties are. The influence of the released Inhibitors can be installed, for example an inhibitor scavenger layer according to DE-A-24 31 223 limited become. For reactivity or stability reasons it may be advantageous to use a DIR coupler the one in the respective layer in which it is introduced is one of those to be generated in this layer Color deviates from the color of the coupling.

To increase sensitivity, contrast and DAR or FAR couplers can achieve maximum density be used, which is a development accelerator or split off an fogger. links of this type are described, 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 for the use of BAR couplers (Bleach Accelerator Releasing Coupler) is on EP-A-193 389 referred.

It can be beneficial to combine the effects of one Coupler split off photographically effective group by modifying an intermolecular reaction this group after their release with a another group according to DE-A-35 06 805.

As with the DIR, DAR or FAR couplers mainly the effectiveness of the released at the clutch The rest is desirable and it is less on the color-forming Properties of this coupler that arrives are also such DIR, DAR or FAR couplers suitable for the Coupling result in essentially colorless products (DE-A-15 47,640).

The detachable residue can also be a ballast residue, see above that in the reaction with color developer oxidation products Coupling products are obtained that are diffusible are or at least a weak or restricted one Have mobility (US-A-4 420 556).

The material can still be different from couplers Contain compounds which contain, for example, a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, an fogger or a Free antifoggants, for example so-called DIR hydroquinones and other compounds, as 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 are described. This Connections perform the same function as the DIR, DAR or FAR couplers, except that they are not coupling products form.

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 described. The high molecular color couplers are used in usually by polymerization of ethylenically unsaturated monomeric color couplers. You can but also obtained by polyaddition or polycondensation become.

Incorporation of couplers or other connections in silver halide emulsion layers can in the way done that first of the connection in question a solution, a dispersion or an emulsion and then the pouring solution for that one Layer is added. Choosing the right one Solvent or dispersant depends on the particular Solubility of the compound.

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

Hydrophobic compounds can also be made using high-boiling solvents, so-called oil formers, be introduced into the casting solution. Appropriate methods are 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 Find.

The compounds can also be in the form of loaded latices be introduced into the casting solution. Is referred for example on 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-O 130,115, U.S. 4,291,113.

The diffusion-resistant storage of anionic water-soluble Compounds (e.g. from dyes) can also be used With the help of cationic polymers, so-called pickling polymers respectively.

Suitable oil formers are e.g. Alkyl phthalate, Phosphonic acid esters, phosphoric acid esters, citric acid esters, Benzoic acid esters, amides, fatty acid esters, trimesic acid esters; Alcohols, phenols, aniline derivatives and Hydrocarbons.

Examples of suitable oil formers are dibutyl phthalate, Dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Triphenyl phosphate, tricresyl phosphate, 2-ethyl-hexyldiphenyl phosphate, Tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, Tridecyl phosphate, tributoxyethyl phosphate, Trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate, Diethyldodecanamide, N-tetradecylpyrrolidone, Isostearyl alcohol, 2,4-di-t-amylphenol, Dioctyl acylate, glycerol tributyrate, isostearyl lactate, Trioctyl citrate, N, N-dibutyl-2-butoxy-5-t-octylaniline, Paraffin, dodecylbenzene and diisopropylnaphthalene.

Each of the differently sensitized, photosensitive Layers can consist of a single layer or two or more partial silver halide emulsion layers include (DE-C-1 121 470). Are there red sensitive silver halide emulsion layers Layer supports are often arranged closer than green-sensitive ones Silver halide emulsion layers and these again closer than blue-sensitive, whereby in general between green sensitive layers and blue sensitive layers a non light sensitive yellow filter layer.

With a suitably low intrinsic sensitivity of the green or Red sensitive layers can be avoided the yellow filter layer choose other layer arrangements, where on the carrier e.g. the blue sensitive, then the red sensitive and finally the green-sensitive layers follow.

The usually different between layers Spectral sensitivity arranged non-photosensitive Intermediate layers can contain agents which is an undesirable diffusion of developer oxidation products from a photosensitive to a other photosensitive layer with different prevent spectral sensitization.

Appropriate agents that include scavengers or EOP scavengers are mentioned in Research Disclosure 17,643 (Dec. 1978), Chapter 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 before, so these can look at their Composition, especially what type and amount of silver halide grains concerns differentiate. In general becomes the sub-layer with higher sensitivity be arranged further away from the support than the partial layer with less sensitivity. Sub-layers same spectral sensitization can each other adjacent or through other layers, e.g. by Separate layers of other spectral sensitization be. For example, all highly sensitive and all low-sensitivity layers to form a layer package be summarized (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 said to be on the one hand the image dyes before fading by UV-rich Protect daylight and on the other hand as filter dyes the UV light in daylight during exposure absorb and thus improve the color rendering of a film. Usually for the two tasks Connections of different structures are used. 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 Cyan couplers of the α-naphthol type) and ultraviolet absorbing Polymers are used. These ultraviolet absorbents can be done by pickling in a special Layer fixed.

Include filter dyes suitable for visible light Oxonol dyes, hemioxonol dyes, styryl dyes, Merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, Hemioxonol dyes and merocyanine dyes 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 described.

Certain layers of binder, especially that of Carrier most distant layer, but also occasionally Intermediate layers, especially if they during the manufacturing process the furthest from the wearer represent removed layer, can be photographically inert Contain 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 insoluble in alkali or be alkali-soluble, the alkali-soluble generally in an alkaline development bath the photographic material are removed. Examples suitable polymers are polymethyl methacrylate, copolymers from acrylic acid and methyl methacrylate as well Hydroxypropylmethyl cellulose hexahydrophthalate.

Additives to improve the dye, coupler and White 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-hydroxy-coumarans, Spirochromanes, spiroindanes, p-alkoxyphenols, steric 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 sterically hindered amine partial structure as well as a sterically hindered Have phenol partial structure in one molecule (US-A-4 268 593), are particularly effective in preventing the Impairment of yellow color images as a result of Development of heat, moisture and light. To the Impairment of purple color images, in particular their impairment as a result of exposure to prevent light are spiroindanes (JP-A-159 644181) and chromane by hydroquinone diether or monoethers are substituted (JP-A-89 835/80) particularly effective.

The layers of the photographic material can with the usual hardening agents are hardened. Suitable Hardening agents are e.g. Formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and others 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-di-acryloylhexahydro-1,3,5-triazine and other connections, which contain a reactive olefin bond (US-A-3 635,718, U.S.-A-3,232,763 and GB-A-994,869); N-hydroxymethylphthalimide and other N N-methylol compounds (US-A-2 732,316 and US-A-2,586,168); Isocyanates (U.S.-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 929183); N-carbonyloximide compounds (JP-A-43353181); N-sulfonyloximido compounds (U.S.-A-4 111,926), dihydroquinoline compounds (US-A-4 013 468), 2-sulfonyloxypyridinium salts (JP-A-110 762181), formamidinium salts (EP-A-0 162 308), compounds with 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 that the hardening agent of the casting solution for the hardening layer is added, or in that the Layer to be hardened is covered with a layer which contains a diffusible hardening agent.

Among the classes listed there are slow-acting ones and fast-acting hardeners and so-called Instant hardeners that are particularly beneficial. Under Immediate hardeners are understood as connections that are suitable Crosslink the binder so that immediately after Watering, at the latest after 24 hours, preferably Hardening is completed after 8 hours at the latest is that no more through the crosslinking reaction conditional change in sensitometry and Swelling of the layer structure occurs. Under swell is the difference between the wet film thickness and dry film thickness in the aqueous processing of the film understood (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Closely. (1972), 449).

These hardening agents that react very quickly with gelatin is it e.g. carbamoylpyridinium salts, those with free carboxyl groups of gelatin able to react, so that the latter with free amino groups gelatin to form peptide bonds and crosslinking of the gelatin react.

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 heterocyclischer 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)_mNR⁸R⁹ , - ( 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 Haloaen 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;

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

wherein

R ¹

Means alkyl, aryl or aralkyl,

R ²

has the same meaning as R ¹ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond having a group of the formula

is linked, or

R ¹ and R ²

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 C ₁ -C ₃ alkyl or halogen;

R ³

for hydrogen, alkyl, aryl, alkoxy, -NR ⁴ -COR ⁵ , - (CH ₂ ) _m NR ⁸ R ⁹ , - (CH ₂ ) _n -CONR ¹³ R ¹⁴

or

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

R ⁴ , R ⁶ , R ⁷ , R ⁹ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ¹⁹

Hydrogen or C ₁ -C ₄ alkyl,

R ⁵

Hydrogen, C ₁ -C ₄ alkyl or NR ⁶ R ⁷ ,

R ⁸

-COR ¹⁰

R ¹⁰

NR ¹¹ R ¹²

R ¹¹

C ₁ -C ₄ alkyl or aryl, especially phenyl,

R ¹²

Hydrogen, C ₁ -C ₄ alkyl or aryl, especially phenyl,

R ¹²

Hydrogen, C ₁ -C ₄ alkyl or aryl, especially phenyl,

R ¹⁶

Hydrogen, C ₁ -C ₄ alkyl, -COR ¹⁸ or CONHR ¹⁹ ,

m

a number 1 to 3,

n

a number 0 to 3,

p

a number 2 to 3 and

Y

0 or NR ¹⁷ mean or

R ¹³ and R ¹⁴

together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring may be substituted, for example, by C ₁ -C ₃ alkyl or haloaene,

Z.

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

X ^

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

wherein

R ¹ , R ² , R ³ and X ^⊖

have the meaning given for formula (a).

There are diffusible hardeners that work on everyone Layers within a layer group in the same Wise hardening. But there are also shift-limited ones acting, non-diffusing, low molecular weight and high molecular hardener. With them you can individual Layers, e.g. crosslink the protective layer particularly strongly. This is important when looking at the silver halide layer little hardens due to the increase in silver opacity and with the protective layer the mechanical properties must improve (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 color development, an acidic stop bath or follow a watering.

Usually the material is immediately after the Color development bleached and fixed. As a bleach can e.g. Fe (III) salts and Fe (III) complex salts such as Ferricyanides, dichromates, water-soluble cobalt complexes be used. Iron (III) complexes are particularly preferred of aminopolycarboxylic acids, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid> Diethylenetriaminepentaacetic acid, Nitrilotriacetic acid, iminodiacetic acid; N-hydroxyethyl-ethylenediamine triestric acid; Alkyliminodicarboxylic acids and of corresponding phosphonic acids. Suitable as Bleaching agents are also persulfates and peroxides; e.g. Hydrogen peroxide.

The bleach-fixing bath or fixing bath is usually followed by one Irrigation, which is carried out as countercurrent irrigation or consists of several tanks with their own water supply.

Favorable results can be obtained by using one following final bath, which little or no Contains formaldehyde can be obtained.

However, the watering can be completed by a stabilizing bath to be replaced, usually in countercurrent to be led. This stabilizing bath takes over when formaldehyde is added also the function of a final bath.

In the case of color reversal materials, development initially takes place with a black black and white developer whose oxidation product not able to react with the color couplers is. A diffuse double exposure closes and then developing with a color developer, Bleach and fix.

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

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

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, each with constant metering over a period of 30 minutes, were fed to this template at a temperature of 70 ° C.

After a pause of 10 min, 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 NH ₄ Br were added over a period of 32 min with constant metering.

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

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

The proportion of tabular crystals in the total projection area according to electron microscopy Recordings about 35%. The average aspect ratio the tabular crystals were 3.5. EM 1 is a comparison emulsion.

EM 2 (according to the invention)

EM 2 was produced like EM 1 with the change that the template 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 tabular crystals 7.5.

EM 3 (according to the invention)

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

EM 4 (according to the invention)

EM 4 was produced like EM 1 with the change that the template 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 tabular crystals) 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

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 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 AgNO ₃ 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 relate to 1 m ² .

Layer 1

(Antihalation 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 AgNO ₃
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

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 AgNO ₃ per kg of emulsion to which 5 mmol of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added per mole of AgNO ₃ were the amounts given in Table 2 for experiments Nos. 1 to 4 the compound P 3 / mol AgNO ₃ 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 AgNO ₃ / m ² .

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 with an application thickness of 2 g gelatin / m ² and 340 mg hardening agent / m ² .

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

The samples were placed in a sensitometer behind a Step wedge exposed in the following developer 38 ° C 195 seconds developed and further processing subject.

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 Make up 4-amino-3-methyl-N-ethyl-N- (B-hydroxyethyl) aniline with water to 1 liter. 4.7 g

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 AgNO _{3 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 adding 5 mmol of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of AgNO ₃ with 300 µmol red sensitizer S 1 per mole of AgNO ₃ and then each with the in Table 2 for the experiments 8 to 10 specified amounts of compound P 3 / mol AgNO ₃ 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 AgNO ₃ / m ² .

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

Wie Tabelle 2 zeigt, werden durch die erfindungsgemäßen Substanzen der Schleier vermindert und die Lagerstabilität des fotografischen Materials deutlich verbessert.A protective layer containing a hardening agent of the formula was applied to each of the emulsion layers

and containing a wetting agent, applied with an application thickness of 2 g gelatin / m ² and 340 mg hardening agent / m ² .

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 connections P-1, P-4 and P-5 and the purple couplers PP1 and PP2 are different samples one with the Green sensitizer S 2 spectrally sensitized silver bromoiodide emulsion with 3 mol% iodide and one mixed average particle diameter of 0.75 µm, the 75 g of silver bromide iodide and 72 g of gelatin based on Contains 1 kg of emulsion.

The emulsions prepared in this way were coated with a Cellulose triacetate substrates provided with an adhesive layer applied 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 in terms of fog, sensitivity and characterized 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 wt%, Mn - 40,000

Example 6

According to the procedure given in Example 4,7 in US 4,714,671 a core / shell plasticizer latex is made. The latex obtained shows good plasticizer properties, but is with the addition of electrolytes unstable. By adding compounds P-4 or P-5 the colloidal 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 Plasticizer latex was used in EP 237 877 as a polymer coupler 1 designated pyrazolotriazole latex coupler with the compounds of formula (I) mixed and Electrolyte stability checked (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)

1. Colour photographic silver halide material having at least one silver halide emulsion layer, characterised in that, prior to processing, at least one layer contains a compound of the formula I

   

   in which

   R₁

   means H or optionally substituted alkyl, aralkyl or cycloalkyl

   R₂

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

   R₃

   means OH

   R₄

   means optionally substituted alkyl, aralkyl or aryl

   m

   means 2 or 3, preferably 2

   n

   means 2 to 10000, preferably 5 to 2000

   or a compound of the formula II

   

   in which R₁, R₃, n and m have the above-stated meaning and may be identical or different and

   R₅

   means optionally substituted alkylene, arylene, aralkylene or a polyaddition, polycondensation or polymerisation chain.

2. Colour photographic silver halide material according to claim 1, characterised in that, prior to processing, at least one layer contains a compound of the formula (I)
   in which

   R₁

   means C₁-C₄ alkyl,

   R₂

   means optionally substituted C₁-C₂₀ alkyl.