EP0564910B1 - Colour-photographic recording material - Google Patents

Colour-photographic recording material Download PDF

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Publication number
EP0564910B1
EP0564910B1 EP93104865A EP93104865A EP0564910B1 EP 0564910 B1 EP0564910 B1 EP 0564910B1 EP 93104865 A EP93104865 A EP 93104865A EP 93104865 A EP93104865 A EP 93104865A EP 0564910 B1 EP0564910 B1 EP 0564910B1
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EP
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Prior art keywords
silver halide
compounds
emulsion
gold
layers
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EP93104865A
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German (de)
French (fr)
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EP0564910A1 (en
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Sieghart Dipl.-Ing. Klötzer
Bruno Dr. Mücke
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising

Definitions

  • the invention relates to a color photographic recording material which contains at least one blue-sensitive, yellow-coupling, at least one green-sensitive, purple-coupling and at least one red-sensitive, cyan-coupling silver halide emulsion layer and customary intermediate and protective layers, the silver halide grains comprising at least one of the silver halide emulsion layers to at least 80 mol% consist of AgCl and at most 0.5 mol% of AgI; the rest is AgBr.
  • emulsions are usually doped with iridium and / or rhodium salts and chemically ripened for their use. Materials containing these emulsions are processed in short processing steps, with development completed in 45 seconds.
  • the object of the invention was to develop a photographic material which does not have these shortcomings.
  • the material has to be largely developed after a relatively short development time and must not show any change in sensitivity and gradation after prolonged exposure to the developer.
  • the material was developed in the RA4 process for 25 and 45 seconds.
  • the sensitivity difference at development of 25 and 45 sec. was defined as a measure of the development kinetics. The smaller the difference in sensitivity between these two development times, the better the development kinetics.
  • Doping is understood to mean the incorporation of the respective metal atoms into the silver halide during the precipitation. All measures that are carried out after the precipitation to change the emulsion are referred to as ripening. Metals from metal compounds that are added during ripening are therefore only in the surface area of the silver halide grains.
  • the invention thus relates to a color photographic recording material of the type mentioned at the beginning, in which the silver halide grains of the at least one silver halide emulsion layer are doped with at least one metal compound from group (a), where (a) the metals rhodium, iridium, ruthenium, rhenium, osmium and cadmium comprises, characterized in that these silver halide grains are further doped with at least one gold compound.
  • the at least one blue-sensitive layer is preferably doped with iridium and gold compounds, gold compounds in particular being AuCl 3 , HAUCl 4 and Na 3 Au (S 2 O 3 ) 2 .
  • iridium and gold compounds gold compounds in particular being AuCl 3 , HAUCl 4 and Na 3 Au (S 2 O 3 ) 2 .
  • Suitable osmium, rhodium, iridium, ruthenium, rhenium, cadmium and Platinum compounds are described in EP 336 426, 336 427 and 415 481. Preferred metal compounds are mentioned in the examples.
  • the metals of group (a) are preferably used in a total amount of 10 -9 to 10 -3 mol / mol of silver halide. The same applies to gold or doping metal.
  • the doping metal compounds of group (a) and gold can be added during the precipitation so that they are homogeneous in the silver halide crystal or distributed in selected phases of the crystal. Phases are e.g. the core and shells between core and surface. If the metal compounds are only distributed in selected phases, the compounds of group (a) can be distributed in the same or a different phase as the gold compounds.
  • All of the light-sensitive silver halide emulsion layers preferably contain silver halide emulsions according to the invention.
  • the silver halide emulsion contains a binder.
  • 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.
  • 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 of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff.
  • the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
  • the silver halide is preferably AgCl 95-100 Br 0-5 .
  • It can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms.
  • 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 layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, e.g. 12: 1 to 30: 1.
  • the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different.
  • the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be either homodisperse or heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not exceed ⁇ 30%. deviate from the average grain size.
  • 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.
  • 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.
  • so-called inverse precipitation is also involved Silver ion excess possible.
  • the silver halide crystals can also grow by physical ripening (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent.
  • the growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.
  • the 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.
  • 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.
  • 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 described, for example, by H. Frieser "The Basics of Photographic Processes with Silver Halides" page 675-734, Akademische Verlagsgesellschaft (1968).
  • Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroups I and VIII of the periodic table (e.g. gold, platinum, palladium, iridium).
  • Suitable sulfur compounds are e.g. Thiosulfates and thiosulfonates. Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (eg imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Industrial Chemistry, 4. Edition, Vol. 18, p. 431 ff.
  • 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) .
  • reducing agents tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid
  • 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. Can continue as Antifoggant salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts are used.
  • metals such as mercury or cadmium
  • aromatic sulfonic or sulfinic acids such as benzenesulfinic acid
  • nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts are 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.
  • mercaptobenzthiazoles for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
  • 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.
  • the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
  • 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.).
  • non-ionic surfactants for example alkylene oxide compounds, glycerol compounds or glycidol compounds
  • cationic surfactants for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds
  • sulfonium compounds or phosphonium compounds anionic surfactants containing an acid group, for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group
  • ampholytic surfactants for example amino acid and aminosulfonic acid compounds and sulfur or phosphoric acid esters of an amino alcohol.
  • the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
  • Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • the differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, namely the red-sensitive layers cyan couplers, the green-sensitive layers purple couplers and the blue-sensitive layers yellow couplers.
  • the material may further contain compounds other than couplers, which can liberate, for example, 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 Pat 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.
  • couplers can liberate, for example, 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 Pat US-A-4 636 546, 4 345 024, 4 684 60
  • 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.
  • the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
  • 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.
  • oligomers or polymers 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.
  • anionic water-soluble compounds e.g. dyes
  • pickling polymers e.g. acrylic acid
  • 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.
  • 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, dioctyl azate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-octoxy-5-butyl-2-
  • 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).
  • silver halide emulsion partial layers DE-C-1 121 470.
  • red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these in turn are closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • green or red-sensitive layers are suitably low in their own sensitivity, other layer arrangements can be selected without the yellow filter layer, in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.
  • the non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
  • sub-layers of the same spectral sensitization can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains.
  • the sublayer with higher sensitivity will be located further away from the support than the sublayer with lower sensitivity.
  • Sub-layers The same spectral sensitization can be adjacent to one another or separated by other layers, for example by layers of different spectral sensitization. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).
  • the photographic material can also contain UV light-absorbing compounds, 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.
  • 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-di-acryloylhexahydro-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
  • 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.
  • Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction .
  • Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
  • hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.
  • 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 in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound to react.
  • 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.
  • Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used as bleaching agents.
  • Iron (III) complexes of aminopolycarboxylic acids in particular, for example, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, and alkyliminodicarboxylic acids and corresponding phosphonic acids are particularly preferred.
  • Persulphates and peroxides for example hydrogen peroxide, are also suitable as bleaching agents.
  • the bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.
  • the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent.
  • this stabilizing bath also acts as a final bath.
  • the materials according to the invention are processed in particular using a short-term process, such as the Ektacolor RA4 process.
  • Solution 1 400 ml water 30 g gelatin Solution 2: 400 ml water 73 g NaCl 1.2 g KBr Solution 3: 400 ml water 170 g AgNO 3
  • Solutions 2 and 3 are simultaneously added to solution 1 at 50 ° C. in the course of 120 minutes at a pAg of 7.7 with vigorous stirring.
  • An AgCl 99.5 Br 0.5 emulsion with an average particle diameter of 0.8 ⁇ m is obtained.
  • the gelatin / AgNO 3 weight ratio is 0.18.
  • the emulsion is flocked in a known manner, washed and redispersed with the addition of gelatin, so that the gelatin / AgNO 3 ratio is finally 1.0.
  • the emulsion contains 1 mol of silver halide per kg.
  • the mixture is then ripened at a pH of 4.5 with 3.5 ⁇ mol of gold chloride per mole of silver and 1.5 ⁇ mol of sodium thiosulfate / mole of silver.
  • the emulsion (silver halide composition AgCl 0.99 Br 0.01 ) is sensitized and stabilized for the blue spectral range.
  • Emulsion EM-2 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.026 mg RhCl 3
  • Emulsion EM-3 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.056 mg K 2 IrCl 6
  • Emulsion EM-4 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.065 mg PtCl 4
  • Emulsion EM-5 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.062 mg HAuCl 4
  • Emulsion EM-6 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.034 mg K 2 IrCl 6 0.010 mg RhCl 3
  • Emulsion EM-7 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.026 mg RhCl 3 0.060 mg HAuCl 4
  • Emulsion EM-8 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.056 mg K 2 IrCl 6 0.060 mg HAuCl 4
  • Emulsion EM-9 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.056 mg K 2 IrCl 6 0.050 mg PtCl 4
  • Emulsion EM-10 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.034 mg K 2 IrCl 6 0.010 mg RhCl 3 0.060 mg HAuCl 4
  • Table 2 shows the differences in the sensitivities and gradations, formed from the development times of 25 and 45 seconds in the RA4 process, Table 2 emulsion Diff. Sensitivity log I ⁇ t Diff. gradation EM-1 comparison 0.200 1.5 EM-2 comparison 0.230 2.2 EM-3 comparison 0.250 2.0 EM-4 comparison 0.220 1.7 EM-5 comparison 0.190 1.4 EM-6 comparison 0.240 2.0 EM-7 invention 0.050 0.6 EM-8 invention 0.060 1.0 EM-9 comparison 0.080 0.8 EM-10 invention 0.065 0.7
  • the table clearly shows the better development kinetics of the emulsions according to the invention, which are documented here by the lower sensitivity and gradation differences.
  • a color photographic recording material was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene. The amounts given relate in each case to 1 m 2 . The corresponding amounts of AgNO 3 are given for the silver halide application.
  • Table 3 below contains the relevant sensitometric data for layer structures 1 and 2. It can be seen that the emulsion EM-8 according to the invention has significantly better development kinetics than EM-3.

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Description

Die Erfindung betrifft ein farbfotografisches Aufzeichnungsmaterial, das auf einem Träger wenigstens eine blauempfindliche, gelbkuppelnde, wenigstens eine grünempfindliche, purpurkuppelnde und wenigstens eine rotempfindliche, blaugrünkuppelnde Silberhalogenidemulsionsschicht sowie übliche Zwischen- und Schutzschichten enthält, wobei die Silberhalogenidkörner wenigstens einer der Silberhalogenidemulsionsschichten zu wenigstens 80 Mol-% aus AgCl und zu höchstens 0,5 Mol-% aus AgI bestehen; der Rest ist AgBr.The invention relates to a color photographic recording material which contains at least one blue-sensitive, yellow-coupling, at least one green-sensitive, purple-coupling and at least one red-sensitive, cyan-coupling silver halide emulsion layer and customary intermediate and protective layers, the silver halide grains comprising at least one of the silver halide emulsion layers to at least 80 mol% consist of AgCl and at most 0.5 mol% of AgI; the rest is AgBr.

Diese Emulsionen sind für ihren Einsatz üblicherweise mit Iridium- undloder Rhodiumsalzen dotiert und chemisch gereift. Materialien, die diese Emulsionen enthalten, werden in kurzen Verarbeitungsprozessen verarbeitet, wobei die Entwicklung in 45 sec abgeschlossen ist.These emulsions are usually doped with iridium and / or rhodium salts and chemically ripened for their use. Materials containing these emulsions are processed in short processing steps, with development completed in 45 seconds.

Diese kurzen Entwicklungsprozesse, wie der Ektacolor RA4-Prozeß, stellen an das zu verarbeitende fotografische Material hohe Qualitätsansprüche. So hat ein etwas zu langsam entwickelndes Material bei leichten Abweichungen des Entwicklungsprozesses von den Standardwerten (Temperaturschwankungen, geringere Aktivität durch Alterung des Entwicklers) nicht zu tolerierende Qualitätsschwankungen bezüglich Empfindlichkeit und Gradation zur Folge.These short development processes, such as the Ektacolor RA4 process, place high quality demands on the photographic material to be processed. So a material that develops a little too slowly with slight deviations the development process from the standard values (temperature fluctuations, less activity due to aging of the developer) result in unacceptable quality fluctuations with regard to sensitivity and gradation.

Aufgabe der Erfindung war es, ein fotografisches Material auszuarbeiten, das diese Mängel nicht aufweist. Das Material muß nach einer relativ kurzen Entwicklungszeit weitgehend entwickelt sein und darf bei längerer Einwirkung des Entwicklers keine Veränderung bezüglich Empfindlichkeit und Gradation aufweisen.The object of the invention was to develop a photographic material which does not have these shortcomings. The material has to be largely developed after a relatively short development time and must not show any change in sensitivity and gradation after prolonged exposure to the developer.

Zur Beurteilung der Entwicklungsgeschwindigkeit wurde das Material im RA4-Prozeß 25 und 45 sec. entwickelt. Die Empfindlichkeitsdifferenz bei Entwicklung von 25 und 45 sec. wurde als Maß für die Entwicklungskinetik definiert. Je geringer die Differenz der Empfindlichkeiten nach diesen beiden Entwicklungszeiten ist, umso besser ist die Entwicklungskinetik.To assess the development speed, the material was developed in the RA4 process for 25 and 45 seconds. The sensitivity difference at development of 25 and 45 sec. Was defined as a measure of the development kinetics. The smaller the difference in sensitivity between these two development times, the better the development kinetics.

Es ist bekannt, daß durch die Dotierung der silberchloridreichen Emulsion mit Rhodium-, Iridium-, Ruthenium-, Osmium-, Rhenium- und Cadmiumverbindungen Empfindlichkeit, Gradation, Schleier- und Schwarzschildverhalten verbessert werden können. Durch diese Metalldotierungen wird aber in vielen Fällen die Entwicklungskinetik entscheidend verschlechtert.It is known that the doping of the silver chloride-rich emulsion with rhodium, iridium, ruthenium, osmium, rhenium and cadmium compounds can improve sensitivity, gradation, fog and Schwarzschild behavior. In many cases, however, the developmental kinetics are significantly impaired by these metal doping.

Überraschenderweise wurde nun gefunden, daß die durch Metalldotierungen bedingte Verschlechterung der Entwicklungskinetik erheblich verbessert wird, wenn die Emulsion zusätzlich mit Goldverbindungen dotiert wird.Surprisingly, it has now been found that the deterioration in development kinetics caused by metal doping is considerably improved when the emulsion is additionally doped with gold compounds.

Dies gilt insbesondere für die blauempfindliche, gelbkuppelnde Schicht.This applies in particular to the blue-sensitive, yellow-coupling layer.

Unter Dotierung wird dabei der Einbau der jeweiligen Metallatome in das Silberhalogenid während der Fällung verstanden. Alle Maßnahmen, die nach der Fällung zur Veränderung der Emulsion vorgenommen werden, werden als Reifung bezeichnet. Metalle aus Metallverbindungen, die während der Reifung zugegeben werden, befinden sich daher nur im Oberflächenbereich der Silberhalogenidkörner.Doping is understood to mean the incorporation of the respective metal atoms into the silver halide during the precipitation. All measures that are carried out after the precipitation to change the emulsion are referred to as ripening. Metals from metal compounds that are added during ripening are therefore only in the surface area of the silver halide grains.

Gegenstand der Erfindung ist somit ein farbfotografisches Aufzeichnungsmaterial der eingangs genannten Art, bei dem die Silberhalogenidkörner der wenigstens einen Silberhalogenidemulsionsschicht mit wenigstens einer Metallverbindung der Gruppe (a) dotiert sind, wobei (a) die Metalle Rhodium, Iridium, Ruthenium, Rhenium, Osmium und Cadmium umfaßt, dadurch gekennzeichnet, daß diese Silberhalogenidkörner weiterhin mit wenigtens einer Goldverbindung dotiert sind.The invention thus relates to a color photographic recording material of the type mentioned at the beginning, in which the silver halide grains of the at least one silver halide emulsion layer are doped with at least one metal compound from group (a), where (a) the metals rhodium, iridium, ruthenium, rhenium, osmium and cadmium comprises, characterized in that these silver halide grains are further doped with at least one gold compound.

Vorzugsweise wird die wenigstens eine blauempfindliche Schicht mit Iridium- und Goldverbindungen dotiert, wobei als Goldverbindungen insbesondere AuCl3, HAUCl4 und Na3Au (S2O3)2 in betracht kommen. Geeignete Osmium-, Rhodium-, Iridium-, Ruthenium-, Rhenium-, Cadmium- und Platinverbindungen sind in EP 336 426, 336 427 und 415 481 beschrieben. Bevorzugte Metallverbindungen werden in den Beispielen genannt.The at least one blue-sensitive layer is preferably doped with iridium and gold compounds, gold compounds in particular being AuCl 3 , HAUCl 4 and Na 3 Au (S 2 O 3 ) 2 . Suitable osmium, rhodium, iridium, ruthenium, rhenium, cadmium and Platinum compounds are described in EP 336 426, 336 427 and 415 481. Preferred metal compounds are mentioned in the examples.

Vorzugsweise werden die Metalle der Gruppe (a) in einer Gesamtmenge von 10-9 bis 10-3 Mol/Mol Silberhalogenid eingesetzt. Das gleiche gilt für Gold oder Dotierungsmetall.The metals of group (a) are preferably used in a total amount of 10 -9 to 10 -3 mol / mol of silver halide. The same applies to gold or doping metal.

Die Dotierungsmetallverbindungen der Gruppe (a) und des Goldes können während der Fällung so zugegeben werden, daß sie im Silberhalogenidkristall homogen oder in ausgewählten Phasen des Kristalls verteilt sind. Phasen sind z.B. der Kern und Schalen zwischen Kern und Oberfläche. Sind die Metallverbindungen nur in ausgewählten Phasen verteilt, so können die Verbindungen der Gruppe (a) in der gleichen oder einer anderen Phase als die Goldverbindungen verteilt sein.The doping metal compounds of group (a) and gold can be added during the precipitation so that they are homogeneous in the silver halide crystal or distributed in selected phases of the crystal. Phases are e.g. the core and shells between core and surface. If the metal compounds are only distributed in selected phases, the compounds of group (a) can be distributed in the same or a different phase as the gold compounds.

Vorzugsweise enthalten alle lichtempfindlichen Silberhalogenidemulsionsschichten erfindungsgemäße Silberhalogenidemulsionen.All of the light-sensitive silver halide emulsion layers preferably contain silver halide emulsions according to the invention.

Die Silberhalogenidemulsion enthält ein Bindemittel. Als Bindemittel wird vorzugsweise Gelatine verwendet. Diese kann jedoch ganz oder teilweise durch andere synthetische, halbsynthetische oder auch natürlich vorkommende Polymere ersetzt werden. Synthetische Gelatineersatzstoffe sind beispielsweise Polyvinylalkohol, Poly- N-vinylpyrrolidon, Polyacrylamide, Polyacrylsäure und deren Derivate, insbesondere deren Mischpolymerisate.The silver halide emulsion contains a binder. 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.

Natürlich vorkommende Gelatineersatzstoffe sind beispielsweise andere Proteine wie Albumin oder Casein, Cellulose, Zucker, Stärke oder Alginate. Halbsynthetische Gelatineersatzstoffe sind in der Regel modifizierte Naturprodukte. Cellulosederivate wie Hydroxyalkylcellulose, Carboxymethylcellulose und Phthalylcellulose sowie Gelatinederivate, die durch Umsetzung mit Alkylierungs- oder Acylierungsmitteln oder durch Aufpfropfung von polymerisierbaren Monomeren erhalten worden sind, sind Beispiele hierfür.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.

Die Bindemittel sollen über eine ausreichende Menge an funktionellen Gruppen verfügen, so daß durch Umsetzung mit geeigneten Härtungsmitteln genügend widerstandsfähige Schichten erzeugt werden können. Solche funktionellen Gruppen sind insbesondere Aminogruppen, aber auch Carboxylgruppen, Hydroxylgruppen und aktive Methylengruppen.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.

Die vorzugsweise verwendete Gelatine kann durch sauren oder alkalischen Aufschluß erhalten sein. Es kann auch oxidierte Gelatine verwendet werden. Die Herstellung solcher Gelatinen wird beispielsweise in The Science and Technology of Gelatine, herausgegeben von A.G. Ward und A. Courts, Academic Press 1977, Seite 295 ff beschrieben. Die jeweils eingesetzte Gelatine soll einen möglichst geringen Gehalt an fotografisch aktiven Verunreinigungen enthalten (Inertgelatine). Gelatinen mit hoher Viskosität und niedriger Quellung sind besonders vorteilhaft.The gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. The production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff. The gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.

Das Silberhalogenid ist vorzugsweise AgCl95-100Br0-5.The silver halide is preferably AgCl 95-100 Br 0-5 .

Es kann sich um überwiegend kompakte Kristalle handeln, die z.B. regulär kubisch oder oktaedrisch sind oder Übergangsformen aufweisen können. Vorzugsweise können aber auch plättchenförmige Kristalle vorliegen, deren durchschnittliches Verhältnis von Durchmesser zu Dicke bevorzugt wenigstens 5:1 ist, wobei der Durchmesser eines Kornes definiert ist als der Durchmesser eines Kreises mit einem Kreisinhalt entsprechend der projizierten Fläche des Kornes. Die Schichten können aber auch tafelförmige Silberhalogenidkristalle aufweisen, bei denen das Verhältnis von Durchmesser zu Dicke wesentlich größer als 5:1 ist, z.B. 12:1 bis 30:1.It can be predominantly compact crystals, e.g. are regular 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. However, the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, e.g. 12: 1 to 30: 1.

Die Silberhalogenidkörner können auch einen mehrfach geschichteten Kornaufbau aufweisen, im einfachsten Fall mit einem inneren und einem äußeren Kornbereich (core/ shell), wobei die Halogenidzusammensetzung und/oder sonstige Modifizierungen, wie z.B. Dotierungen der einzelnen Kornbereiche unterschiedlich sind. Die mittlere Korngröße der Emulsionen liegt vorzugsweise zwischen 0,2 µm und 2,0 µm, die Korngrößenverteilung kann sowohl homo- als auch heterodispers sein. Homodisperse Korngrößenverteilung bedeutet, daß 95 % der Körner nicht mehr als ± 30%. von der mittleren Korngröße abweichen. Die Emulsionen können neben dem Silberhalogenid auch organische Silbersalze enthalten, z.B. Silberbenztriazolat oder Silberbehenat.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 exceed ± 30%. deviate 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.

Es können zwei oder mehrere Arten von Silberhalogenidemulsionen, die getrennt hergestellt werden, als Mischung verwendet werden.Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.

Die fotografischen Emulsionen können nach verschiedenen Methoden (z.B. 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) aus löslichen Silbersalzen und löslichen Halogeniden hergestellt werden.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.

Die Fällung des Silberhalogenids erfolgt bevorzugt in Gegenwart des Bindemittels, z.B. der Gelatine und kann im sauren, neutralen oder alkalischen pH-Bereich durchgeführt werden, wobei vorzugsweise Silberhalogenidkomplexbildner zusätzlich verwendet werden. Zu letzteren gehören z.B. Ammoniak, Thioether, Imidazol, Ammoniumthiocyanat oder überschüssiges Halogenid. Die Zusammenführung der wasserlöslichen Silbersalze und der Halogenide erfolgt wahlweise nacheinander nach dem singlejet- oder gleichzeitig nach dem double-jet-Verfahren oder nach beliebiger Kombination beider Verfahren. Bevorzugt wird die Dosierung mit steigenden Zuflußraten, wobei die "kritische" Zufuhrgeschwindigkeit, bei der gerade noch keine Neukeime entstehen, nicht überschritten werden sollte. Der pAg-Bereich kann während der Fällung in weiten Grenzen variieren, vorzugsweise wird das sogenannte pAg-gesteuerte Verfahren benutzt, bei dem ein bestimmter pAg-Wert konstant gehalten oder ein definiertes pAg-Profil während der Fällung durchfahren wird. Neben der bevorzugten Fällung bei Halogenidüberschuß ist aber auch die sogenannte inverse Fällung bei Silberionenüberschluß möglich. Außer durch Fällung können die Silberhalogenidkristalle auch durch physikalische Reifung (Ostwaldreifung), in Gegenwart von überschüssigem Halogenid und/oder Silberhalogenidkomplexierungsmittel wachsen. Das Wachstum der Emulsionskörner kann sogar überwiegend durch Ostwaldreifung erfolgen, wobei vorzugsweise eine feinkörnige, sogenannte Lippmann-Emulsion, mit einer schwerer löslichen Emulsion gemischt und auf letzterer umgelöst wird.The silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used. The latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded. The pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation. In addition to the preferred precipitation with excess halide, so-called inverse precipitation is also involved Silver ion excess 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.

Ferner kann die Fällung auch in Gegenwart von Sensibilisierungsfarbstoffen erfolgen. Komplexierungsmittel und/oder Farbstoffe lassen sich zu jedem beliebigen Zeitpunkt unwirksam machen, z.B. durch Änderung des pH-Wertes oder durch eine oxidative Behandlung.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.

Nach abgeschlossener Kristallbildung oder auch schon zu einem früheren Zeitpunkt werden die löslichen Salze aus der Emulsion entfernt, z.B. durch Nudeln und Waschen, durch Flocken und Waschen, durch Ultrafiltration oder durch Ionenaustauscher.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.

Die Silberhalogenidemulsion wird im allgemeinen einer chemischen Sensibilisierung unter definierten Bedingungen - pH, pAg, Temperatur, Gelatine-, Silberhalogenid- und Sensibilisatorkonzentration - bis zum Erreichen des Empfindlichkeits- und Schleieroptimums unterworfen. Die Verfahrensweise ist z.B. bei H. Frieser "Die Grundlagen der Photographischen Prozesse mit Silberhalogeniden" Seite 675-734, Akademische Verlagsgesellschaft (1968) beschrieben.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 described, for example, by H. Frieser "The Basics of Photographic Processes with Silver Halides" page 675-734, Akademische Verlagsgesellschaft (1968).

Dabei kann die chemische Sensibilisierung unter Zusatz von Verbindungen von Schwefel, Selen, Tellur und/oder Verbindungen der Metalle der I. und VIII. Nebengruppe des Periodensystems (z.B. Gold, Platin, Palladium, Iridium) erfolgen. Geeignete Schwefelverbindungen sind z.B. Thiosulfate und Thiosulfonate. Weiterhin können Thiocyanatverbindungen, oberflächenaktive Verbindungen, wie Thioether, heterocyclische Stickstoffverbindungen (z.B. Imidazole, Azaindene) oder auch spektrale Sensibilisatoren (beschrieben z.B. bei F. Hamer "The Cyanine Dyes and Related Compounds", 1964, bzw. Ullmanns Encyclopädie der technischen Chemie, 4. Auflage, Bd. 18, S. 431 ff. und Research Disclosure 17643 (Dez. 1978), Kapitel III) zugegeben werden. Ersatzweise oder zusätzlich kann eine Reduktionssensibilisierung unter Zugabe von Reduktionsmitteln (Zinn-II-Salze, Amine, Hydrazinderivate, Aminoborane, Silane, Formamidinsulfinsäure) durch Wasserstoff, durch niedrigen pAg (z.B. kleiner 5) und/oder hohen pH (z.B. über 8) durchgeführt werden.Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroups I and VIII of the periodic table (e.g. gold, platinum, palladium, iridium). Suitable sulfur compounds are e.g. Thiosulfates and thiosulfonates. Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (eg imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Industrial Chemistry, 4. Edition, Vol. 18, p. 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) .

Die fotografischen Emulsionen können Verbindungen zur Verhinderung der Schleierbildung oder zur Stabilisierung der fotografischen Funktion während der Produktion, der Lagerung oder der fotografischen Verarbeitung enthalten.The photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.

Besonders geeignet sind Azaindene, vorzugsweise Tetra- und Pentaazaindene, insbesondere solche, die mit Hydroxyl- oder Aminogruppen substituiert sind. Derartige Verbindungen sind z.B. von Birr, Z. Wiss. Phot. 47 (1952), S. 2-58 beschrieben worden. Weiter können als Antischleiermittel Salze von Metallen wie Quecksilber oder Cadmium, aromatische Sulfon- oder Sulfinsäuren wie Benzolsulfinsäure, oder stickstoffhaltige Heterocyclen wie Nitrobenzimidazol, Nitroindazol, gegebenenfalls substituierte Benztriazole oder Benzthiazoliumsalze eingesetzt werden. Besonders geeignet sind Mercaptogruppen enthaltende Heterocyclen, z.B. Mercaptobenzthiazole, Mercaptobenzimidazole, Mercaptotetrazole, Mercaptothiadiazole, Mercaptopyrimidine, wobei diese Mercaptoazole auch eine wasserlöslichmachende Gruppe, z.B. eine Carboxylgruppe oder Sulfogruppe, enthalten können. Weitere geeignete Verbindungen sind in Research Disclosure 17643 (Dez. 1978), Kapitel VI, veröffentlicht.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. Can continue as Antifoggant salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts are 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.

Die Stabilisatoren können den Silberhalogenidemulsionen vor, während oder nach deren Reifung zugesetzt werden. Selbstverständlich kann man die Verbindungen auch anderen fotografischen Schichten, die einer Halogensilberschicht zugeordnet sind, zusetzen.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.

Es können auch Mischungen aus zwei oder mehreren der genannten Verbindungen eingesetzt werden.Mixtures of two or more of the compounds mentioned can also be used.

Die fotografischen Emulsionsschichten oder andere hydrophile Kolloidschichten des erfindungsgemäß hergestellten lichtempfindlichen Materials können oberflächenaktive Mittel für verschiedene Zwecke enthalten, wie Überzugshilfen, zur Verhinderung der elektrischen Aufladung, zur Verbesserung der Gleiteigenschaften, zum Emulgieren der Dispersion, zur Verhinderung der Adhäsion und zur Verbesserung der fotografischen Charakteristika (z.B. Entwicklungsbeschleunigung, hoher Kontrast, Sensibilisierung usw.). Neben natürlichen oberflächenaktiven Verbindungen, z.B. Saponin, finden hauptsächlich synthetische oberflächenaktive Verbindungen (Tenside) Verwendung: nicht-ionische Tenside, z.B. Alkylenoxidverbindungen, Glycerinverbindungen oder Glycidolverbindungen, kationische Tenside, z.B. höhere Alkylamine, quartäre Ammoniumsalze, Pyridinverbindungen und andere heterocyclische Verbindungen, Sulfoniumverbindungen oder Phosphoniumverbindungen, anionische Tenside, enthaltend eine Säuregruppe, z.B. Carbonsäure-, Sulfonsäure-, eine Phosphorsäure-, Schwefelsäureester- oder Phosphorsäureestergruppe, ampholytische Tenside, z.B. Aminosäure- und Aminosulfonsäureverbindungen sowie Schwefel- oder Phosphorsäureester eines Aminoalkohols.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, for example saponin, synthetic surface-active compounds (surfactants) are mainly used: non-ionic surfactants, for example alkylene oxide compounds, glycerol compounds or glycidol compounds, cationic surfactants, for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, for example amino acid and aminosulfonic acid compounds and sulfur or phosphoric acid esters of an amino alcohol.

Die fotografischen Emulsionen können unter Verwendung von Methinfarbstoffen oder anderen Farbstoffen spektral sensibilisiert werden. Besonders geeignete Farbstoffe sind Cyaninfarbstoffe, Merocyaninfarbstoffe und komplexe Merocyaninfarbstoffe.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.

Eine Übersicht über die als Spektralsensibilisatoren geeigneten Polymethinfarbstoffe, deren geeignete Kombinationen und supersensibilisierend wirkenden Kombinationen enthält Research Disclosure 17643 (Dez. 1978),Kapitel IV.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.

Insbesondere sind die folgenden Farbstoffe - geordnet nach Spektralgebieten - geeignet:

  • 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. -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, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl and 9-ethyl-naphthoxathia or -selencarbocyanines and 9-ethyl- naphthothiaoxa- or -benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.
  • 2. as green sensitizers
    9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzothiazole 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.

Den unterschiedlich sensibilisierten Emulsionsschichten werden nicht diffundierende monomere oder polymere Farbkuppler zugeordnet, und zwar den rotempfindlichen Schichten Blaugrünkuppler, den grünempfindlichen Schichten Purpurkuppler und den blauempfindlichen Schichten Gelbkuppler.The differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, namely the red-sensitive layers cyan couplers, the green-sensitive layers purple couplers and the blue-sensitive layers yellow couplers.

Das Material kann weiterhin von Kupplern verschiedene Verbindungen enthalten, die beispielsweise einen Entwicklungsinhibitor, einen Entwicklungsbeschleuniger, einen Bleichbeschleuniger, einen Entwickler, ein Silberhalogenidlösungsmittel, ein Schleiermittel oder ein Antischleiermittel in Freiheit setzen können, beispielsweise sogenannte DIR-Hydrochinone und andere Verbindungen, wie sie beispielsweise in US-A-4 636 546, 4 345 024, 4 684 604 und in DE-A-31 45 640, 25 15 213, 24 47 079 und in EP-A-198 438 beschrieben sind. Diese Verbindungen erfüllen die gleiche Funktion wie die DIR-, DAR- oder FAR-Kuppler, außer daß sie keine Kupplungsprodukte bilden.The material may further contain compounds other than couplers, which can liberate, for example, 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 Pat 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.

Hochmolekulare Farbkuppler sind beispielsweise 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 beschrieben. Die hochmolekularen Farbkuppler werden in der Regel durch Polymerisation von ethylenisch ungesättigten monomeren Farbkupplern hergestellt. Sie können aber auch durch Polyaddition oder Polykondensation erhalten werden.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.

Die Einarbeitung der Kuppler oder anderer Verbindungen in Silberhalogenidemulsionsschichten kann in der Weise erfolgen, daß zunächst von der betreffenden Verbindung eine Lösung, eine Dispersion oder eine Emulsion hergestellt und dann der Gießlösung für die betreffende Schicht zugefügt wird. Die Auswahl des geeigneten Lösungs- oder Dispersionsmittels hängt von der jeweiligen Löslichkeit der Verbindung ab.The couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question. The selection of the suitable solvent or dispersing agent depends on the solubility of the compound.

Methoden zum Einbringen von in Wasser im wesentlichen unlöslichen Verbindungen durch Mahlverfahren sind beispielsweise in DE-A-26 09 741 und DE-A-26 09 742 beschrieben.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.

Hydrophobe Verbindungen können auch unter Verwendung von hochsiedenden Lösungsmitteln, sogenannten Ölbildnern, in die Gießlösung eingebracht werden. Entsprechende Methoden sind beispielsweise in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 und EP-A-O 043 037 beschrieben.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.

Anstelle der hochsiedenden Lösungsmitteln können Oligomere oder Polymere, sogenannte polymere Ölbildner Verwendung finden.Instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.

Die Verbindungen können auch in Form beladener Latices in die Gießlösung eingebracht werden. Verwiesen wird beispielsweise auf DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-0 130 115, US-A-4 291 113.The compounds can also be introduced into the casting solution in the form of loaded latices. Reference is made, for example, to DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-0 130 115, U.S.-A-4,291,113.

Die diffusionsfeste Einlagerung anionischer wasserlöslicher Verbindungen (z.B. von Farbstoffen) kann auch mit Hilfe von kationischen Polymeren, sogenannten Beizenpolymeren erfolgen.The diffusion-resistant incorporation of anionic water-soluble compounds (e.g. dyes) can also be carried out with the help of cationic polymers, so-called pickling polymers.

Geeignete Ölbildner sind z.B. Phthalsäurealkylester, Phosphonsäureester, Phosphorsäureester, Citronensäureester, Benzoesäureester, Amide, Fettsäureester, Trimesinsäureester, Alkohole, Phenole, Anilinderivate und Kohlenwasserstoffe.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.

Beispiele für geeignete Ölbildner sind Dibutylphthalat, Dicyclohexylphthalat, Di-2-ethylhexylphthalat, Decylphthalat, Triphenylphosphat, Tricresylphosphat, 2-Ethylhexyldiphenylphosphat, Tricyclohexylphosphat, Tri-2-ethylhexylphosphat, Tridecylphosphat, Tributoxyethylphosphat, Trichlorpropylphosphat, Di-2-ethylhexylphenylphosphat, 2-Ethylhexylbenzoat, Dodecylbenzoat, 2-Ethylhexyl-p-hydroxybenzoat, Diethyldodecanamid, N-Tetradecylpyrrolidon, Isostearylalkohol, 2,4-Di-t-amylphenol, Dioctylacelat, Glycerintributyrat, Isostearyllactat, Trioctylcitrat, N,N-Dibutyl-2-butoxy-5-t-octylanilin, Paraffin, Dodecylbenzol und Diisopropylnaphthalin.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, dioctyl azate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-octoxy-5-butyl-2-butyl , Paraffin, dodecylbenzene and diisopropylnaphthalene.

Jede der unterschiedlich sensibilisierten, lichtempfindlichen Schichten kann aus einer einzigen Schicht bestehen oder auch zwei oder mehr Silberhalogenidemulsionsteilschichten umfassen (DE-C-1 121 470). Dabei sind rotempfindliche Silberhalogenidemulsionsschichten dem Schichtträger häufig näher angeordnet als grünempfindliche Silberhalogenidemulsionsschichten und diese wiederum näher als blauempfindliche, wobei sich im allgemeinen zwischen grünempfindlichen Schichten und blauempfindlichen Schichten eine nicht lichtempfindliche gelbe Filterschicht befindet.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). Are there red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these in turn are closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.

Bei geeignet geringer Eigenempfindlichkeit der grün- bzw. rotempfindlichen Schichten kann man unter Verzicht auf die Gelbfilterschicht andere Schichtanordnungen wählen, bei denen auf den Träger z.B. die blauempfindlichen, dann die rotempfindlichen und schließlich die grünempfindlichen Schichten folgen.If the green or red-sensitive layers are suitably low in their own sensitivity, other layer arrangements can be selected without the yellow filter layer, in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.

Die in der Regel zwischen Schichten unterschiedlicher Spektralempfindlichkeit angeordneten nicht lichtempfindlichen Zwischenschichten können Mittel enthalten, die eine unerwünschte Diffusion von Entwickleroxidationsprodukten aus einer lichtempfindlichen in eine andere lichtempfindliche Schicht mit unterschiedlicher spektraler Sensibilisierung verhindern.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.

Liegen mehrere Teilschichten gleicher spektraler Sensibilisierung vor, so können sich diese hinsichtlich ihrer Zusammensetzung, insbesondere was Art und Menge der Silberhalogenidkörnchen betrifft unterscheiden. Im allgemeinen wird die Teilschicht mit höherer Empfindlichkeit von Träger entfernter angeordnet sein als die Teilschicht mit geringerer Empfindlichkeit. Teilschichten gleicher spektraler Sensibilisierung können zueinander benachbart oder durch andere Schichten, z.B. durch Schichten anderer spektraler Sensibilisierung getrennt sein. So können z.B. alle hochempfindlichen und alle niedrigempfindlichen Schichten jeweils zu einem Schichtpaket zusammengefaßt sein (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).If there are several sub-layers of the same spectral sensitization, these can differ 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. Sub-layers The same spectral sensitization can be adjacent to one another or separated by other layers, for example by layers of different spectral sensitization. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).

Das fotografische Material kann weiterhin UV-Licht absorbierende Verbindungen, Weißtöner, Abstandshalter, Filterfarbstoffe, Formalinfänger, Lichtschutzmittel, Antioxidantien, DMin-Farbstoffe, Zusätze zur Verbesserung der Farbstoff-, Kuppler- und Weißenstabilisierung sowie zur Verringerung des Farbschleiers, Weichmacher (Latices), Biocide und anderes enthalten.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.

UV-Licht absorbierende Verbindungen sollen einerseits die Bildfarbstoffe vor dem Ausbleichen durch UV-reiches Tageslicht schützen und andererseits als Filterfarbstoffe das UV-Licht im Tageslicht bei der Belichtung absorbieren und so die Farbwiedergabe eines Films verbessern.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.

Die Schichten des fotografischen Materials können mit den üblichen Härtungsmitteln gehärtet werden. Geeignete Härtungsmittel sind z.B. Formaldehyd, Glutaraldehyd und ähnliche Aldehydverbindungen, Diacetyl, Cyclopentadion und ähnliche Ketonverbindungen, Bis-(2-chlorethylharnstoff), 2-Hydroxy-4,6-dichlor-1,3,5-triazin und andere Verbindungen, die reaktives Halogen enthalten (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 und GB-A-1 167 207), Divinylsulfonverbindungen, 5-Acetyl-1,3-di-acryloylhexahydro-1,3,5-triazin und andere Verbindungen, die eine reaktive Olefinbindung enthalten (US-A-3 635 718, US-A-3 232 763 und GB-A-994 869); N-Hydroxymethylphthalimid und andere N-Methylolverbindungen (US-A-2 732 316 und US-A-2 586 168); Isocyanate (US-A-3 103 437); Aziridinverbindungen (US-A-3 017 280 und US-A-2 983 611); Säurederivate (US-A-2 725 294 und US-A-2 725 295); Verbindungen vom Carbodiimidtyp (US-A-3 100 704); Carbamoylpyridiniumsalze (DE-A-22 25 230 und DE-A-24 39 551); Carbamoyloxypyridiniumverbindungen (DE-A-24 08 814); Verbindungen mit einer Phosphor-Halogen-Bindung (JP-A-113 929/83); N-Carbonyloximid-Verbindungen (JP-A-43353/81); N-Sulfonyloximido-Verbindungen (US-A-4 111 926), Dihydrochinolinverbindungen (US-A-4 013 468), Z-Sulfonyloxypyridiniumsalze (JP-A-110 762/81), Formamidiniumsalze (EP-A-0 162 308), Verbindungen mit zwei oder mehr N-Acyloximino-Gruppen (US-A-4 052 373), Epoxyverbindungen (US-A-3 091 537), Verbindungen vom Isoxazoltyp (US-A-3 321 313 und US-A-3 543 292); Halogencarboxyaldehyde, wie Mucochlorsäure; Dioxanderivate, wie Dihydroxydioxan und Di-chlordioxan; und anorganische Härter, wie Chromalaun und Zirkonsulfat,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-di-acryloylhexahydro-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), Z-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,

Die Härtung kann in bekannter Weise dadurch bewirkt werden, daß das Härtungsmittel der Gießlösung für die zu härtende Schicht zugesetzt wird, oder dadurch, daß die zu härtende Schicht mit einer Schicht überschichtet wird, die ein diffusionsfähiges Härtungsmittel enthält.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.

Unter den aufgeführten Klassen gibt es langsam wirkende und schnell wirkende Härtungsmittel sowie sogenannte Soforthärter, die besonders vorteilhaft sind. Unter Soforthärtern werden Verbindungen verstanden, die geeignete Bindemittel so vernetzen, daß unmittelbar nach Beguß, spätestens nach 24 Stunden, vorzugsweise spätestens nach 8 Stunden die Härtung so weit abgeschlossen ist, daß keine weitere durch die Vernetzungsreaktion bedingte Änderung der Sensitometrie und der Quellung des Schichtverbandes auftritt. Unter Quellung wird die Differenz von Naßschichtdicke und Trockenschichtdicke bei der wäßrigen Verarbeitung des Films verstanden (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).There are slow-acting and fast-acting hardeners and so-called instant hardeners, which are particularly advantageous, in the classes listed. Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction . Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).

Bei diesen mit Gelatine sehr schnell reagierenden Härtungsmitteln handelt es sich z.B. um Carbamoylpyridiniumsalze, die mit freien Carboxylgruppen der Gelatine zu reagieren vermögen, so daß letztere mit freien Aminogruppen der Gelatine unter Ausbildung von Peptidbindungen und Vernetzung der Gelatine reagieren.These hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.

Farbfotografische Negativmaterialien werden üblicherweise durch Entwickeln, Bleichen, Fixieren und Wässern oder durch Entwickeln, Bleichen, Fixieren und Stabilisieren ohne nachfolgende Wässerung verarbeitet, wobei Bleichen und Fixieren zu einem Verarbeitungsschritt zusammengefaßt sein können. Als Farbentwicklerverbindung lassen sich sämtliche Entwicklerverbindungen verwenden, die die Fähigkeit besitzen, in Form ihres Oxidationsproduktes mit Farbkupplern zu Azomethin- bzw. Indophenolfarbstoffen zu reagieren. Geeignete Farbentwicklerverbindungen sind aromatische, mindestens eine primäre Aminogruppe enthaltende Verbindungen vom p-Phenylendiamintyp, beispielsweise N,N-Dialkyl-p-phenylendiamine wie N,N-Diethyl-p-phenylendiamin, 1-(N-Ethyl-N-methansulfonamidoethyl)-3-methyl-p-phenylendiamin, 1-(N-Ethyl-N-hydroxyethyl)-3-methyl-p-phenylendiamin und 1-(N-Ethyl-N-methoxyethyl)-3-methyl-p-phenylendiamin. Weitere brauchbare Farbentwickler sind beispielsweise in J. Amer. Chem. Soc. 73, 3106 (1951) und G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, Seite 545 ff. beschrieben.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 in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound to react. 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.

Nach der Farbentwicklung kann ein saures Stoppbad oder eine Wässerung folgen.After the color development, an acidic stop bath or watering can follow.

Üblicherweise wird das Material unmittelbar nach der Farbentwicklung gebleicht und fixiert. Als Bleichmittel können z.B. Fe(III)-Salze und Fe(III)-Komplexsalze wie Ferricyanide, Dichromate, wasserlösliche Kobaltkomplexe verwendet werden. Besonders bevorzugt sind Eisen-(III)-Komplexe von Aminopolycarbonsäuren, insbesondere z.B. von Ethylendiamintetraessigsäure, Propylendiamintetraessigsäure, Diethylentriaminpentaessigsäure, Nitrilotriessigsäure, Iminodiessigsäure, N-Hydroxyethyl-ethylendiamintriessigsäure, Alkyliminodicarbonsäuren und von entsprechenden Phosphonsäuren. Geeignete als Bleichmittel sind weiterhin Persulfate und Peroxide, z.B. Wasserstoffperoxid.Usually the material is bleached and fixed immediately after color development. For example, Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used as bleaching agents. Iron (III) complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, and alkyliminodicarboxylic acids and corresponding phosphonic acids are particularly preferred. Persulphates and peroxides, for example hydrogen peroxide, are also suitable as bleaching agents.

Auf das Bleichfixierbad oder Fixierbad folgt meist eine Wässerung, die als Gegenstromwässerung ausgeführt ist oder aus mehreren Tanks mit eigener Wasserzufuhr besteht.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.

Günstige Ergebnisse können bei Verwendung eines darauf folgenden Schlußbades, das keinen oder nur wenig Formaldehyd enthält, erhalten werden.Favorable results can be obtained using a subsequent final bath which contains little or no formaldehyde.

Die Wässerung kann aber durch ein Stabilisierbad vollständig ersetzt werden, das üblicherweise im Gegenstrom geführt wird. Dieses Stabilisierbad übernimmt bei Formaldehydzusatz auch die Funktion eines Schlußbades.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.

Die erfindungsgemäßen Materialien werden insbesondere nach einem Kurzzeitprozeß, wie dem Ektacolor RA4-Prozeß verarbeitet.The materials according to the invention are processed in particular using a short-term process, such as the Ektacolor RA4 process.

Beispiel 1example 1 Herstellung der Emulsion EM-1Preparation of the EM-1 emulsion

Es werden die folgenden Lösungen jeweils mit demineralisiertem Wasser angesetzt: Lösung 1: 400 ml Wasser 30 g Gelatine Lösung 2: 400 ml Wasser 73 g NaCl 1,2 g KBr Lösung 3: 400 ml Wasser 170 g AgNO3 The following solutions are made up with demineralized water: Solution 1: 400 ml water 30 g gelatin Solution 2: 400 ml water 73 g NaCl 1.2 g KBr Solution 3: 400 ml water 170 g AgNO 3

Lösungen 2 und 3 werden bei 50°C im Laufe von 120 Minuten bei einem pAg von 7,7 gleichzeitig unter intensivem Rühren zur Lösung 1 gegeben. Es wird eine AgCl99,5Br0,5-emulsion mit einem mittleren Teilchendurchmesser von 0,8 µm erhalten. Das Gelatine/AgNO3-Gewichtsverhältnis beträgt 0,18, Die Emulsion wird in bekannter Weise geflockt, gewaschen und unter Gelatinezugabe redispergiert, so daß das Gelatine/AgNO3-Verhältnis schließlich 1,0 beträgt. Die Emulsion enthält pro kg 1 Mol Silberhalogenid. Anschließend wird bei einem pH von 4,5 mit 3,5 µMol Goldchlorid pro Mol Silber und 1,5 µMol Natriumthiosulfat/Mol Silber gereift. Nach der chemischen Reifung wird die Emulsion (Silberhalogenidzusammensetzung AgCl0,99Br0,01) für den blauen Spektralbereich sensibilisiert und stabilisiert.Solutions 2 and 3 are simultaneously added to solution 1 at 50 ° C. in the course of 120 minutes at a pAg of 7.7 with vigorous stirring. An AgCl 99.5 Br 0.5 emulsion with an average particle diameter of 0.8 μm is obtained. The gelatin / AgNO 3 weight ratio is 0.18. The emulsion is flocked in a known manner, washed and redispersed with the addition of gelatin, so that the gelatin / AgNO 3 ratio is finally 1.0. The emulsion contains 1 mol of silver halide per kg. The mixture is then ripened at a pH of 4.5 with 3.5 μmol of gold chloride per mole of silver and 1.5 μmol of sodium thiosulfate / mole of silver. After chemical ripening, the emulsion (silver halide composition AgCl 0.99 Br 0.01 ) is sensitized and stabilized for the blue spectral range.

Anschließend wird die oben beschriebene Emulsion mit einer Lösung des Gelbkupplers der Formel

Figure imgb0001
und des Weißkupplers der Formel
Figure imgb0002
 in Trikresylphosphat versetzt und auf einen Schichtträger aus beidseitig mit Polyethylen beschichtetem Papier aufgetragen.Then the emulsion described above with a solution of the yellow coupler of the formula
Figure imgb0001
 and the white coupler of the formula
Figure imgb0002
 in tricresyl phosphate and applied to a substrate made of paper coated on both sides with polyethylene.

Die Schicht enthält pro m2

  • 0,63 g AgCl99,5Br0,5
  • 1,38 g Gelatine
  • 0,95 g Gelbkuppler
  • 0,2 g Weißkuppler
  • 0,29 g Trikresylphosphat
Über diese Schicht wird eine Schutzschicht aus 0,2 g Gelatine und 0,3 g Härtungsmittel der Formel
Figure imgb0003
 pro m2 gegossen. Das Material wird bildmäßig belichtet und nach dem Ektacolor RA4-Prozeß verarbeitet.The layer contains per m 2
  • 0.63 g AgCl 99.5 Br 0.5
  • 1.38 g gelatin
  • 0.95 g yellow coupler
  • 0.2 g white coupler
  • 0.29 g tricresyl phosphate
A protective layer of 0.2 g of gelatin and 0.3 g of hardening agent of the formula is applied over this layer
Figure imgb0003
 cast per m 2 . The material is exposed imagewise and processed using the Ektacolor RA4 process.

Beispiel 2Example 2 Herstellung der Emulsion EM-2Preparation of the EM-2 emulsion

Die Emulsion EM-2 wird hergestellt und verarbeitet wie in Beispiel 1 beschrieben, jedoch mit der Änderung, daß die Lösung 2 die folgende Zusammensetzung aufweist: Lösung 2: 400 ml Wasser 73 g NaCl 1,2 g KBr 0,026 mg RhCl3 Emulsion EM-2 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.026 mg RhCl 3

Beispiel 3Example 3 Herstellung der Emulsion EM-3Preparation of the EM-3 emulsion

Die Emulsion EM-3 wird hergestellt und verarbeitet wie in Beispiel 1 beschrieben, jedoch mit der Änderung, daß die Lösung 2 die folgende Zusammensetzung aufweist: Lösung 2: 400 ml Wasser 73 g NaCl 1,2 g KBr 0,056 mg K2IrCl6 Emulsion EM-3 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.056 mg K 2 IrCl 6

Beispiel 4Example 4 Herstellung der Emulsion EM-4Preparation of the EM-4 emulsion

Die Emulsion EM-4 wird hergestellt und verarbeitet wie in Beispiel 1 beschrieben, jedoch mit der Änderung, daß die Lösung 2 die folgende Zusammensetzung aufweist: Lösung 2: 400 ml Wasser 73 g NaCl 1,2 g KBr 0,065 mg PtCl4 Emulsion EM-4 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.065 mg PtCl 4

Beispiel 5Example 5 Herstellung der Emulsion EM-5Preparation of the EM-5 emulsion

Die Emulsion EM-5 wird hergestellt und verarbeitet wie in Beispiel 1 beschrieben, jedoch mit der Änderung, daß die Lösung 2 die folgende Zusammensetzung aufweist: Lösung 2: 400 ml Wasser 73 g NaCl 1,2 g KBr 0,062 mg HAuCl4 Emulsion EM-5 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.062 mg HAuCl 4

Beispiel 6Example 6 Herstellung der Emulsion EM-6Preparation of the EM-6 emulsion

Die Emulsion EM-6 wird hergestellt und verarbeitet wie in Beispiel 1 beschrieben, jedoch mit der Änderung, daß die Lösung 2 die folgende Zusammensetzung aufweist: Lösung 2: 400 ml Wasser 73 g NaCl 1,2 g KBr 0,034 mg K2IrCl6 0,010 mg RhCl3 Emulsion EM-6 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.034 mg K 2 IrCl 6 0.010 mg RhCl 3

Beispiel 7Example 7 Herstellung der Emulsion EM-7Preparation of the EM-7 emulsion

Die Emulsion EM-7 wird hergestellt und verarbeitet wie in Beispiel 1 beschrieben, jedoch mit der Änderung, daß die Lösung 2 die folgende Zusammensetzung aufweist: Lösung 2: 400 ml Wasser 73 g NaCl 1,2 g KBr 0,026 mg RhCl3 0,060 mg HAuCl4 Emulsion EM-7 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.026 mg RhCl 3 0.060 mg HAuCl 4

Beispiel 8Example 8 Herstellung der Emulsion EM-8Preparation of the EM-8 emulsion

Die Emulsion EM-8 wird hergestellt und verarbeitet wie in Beispiel 1 beschrieben, jedoch mit der Änderung, daß die Lösung 2 die folgende Zusammensetzung aufweist: Lösung 2: 400 ml Wasser 73 g NaCl 1,2 g KBr 0,056 mg K2IrCl6 0,060 mg HAuCl4 Emulsion EM-8 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.056 mg K 2 IrCl 6 0.060 mg HAuCl 4

Beispiel 9Example 9 Herstellung der Emulsion EM-9Preparation of the EM-9 emulsion

Die Emulsion EM-9 wird hergestellt und verarbeitet wie in Beispiel 1 beschrieben, jedoch mit der Änderung, daß die Lösung 2 die folgende Zusammensetzung aufweist: Lösung 2: 400 ml Wasser 73 g NaCl 1,2 g KBr 0,056 mg K2IrCl6 0,050 mg PtCl4 Emulsion EM-9 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.056 mg K 2 IrCl 6 0.050 mg PtCl 4

Beispiel 10Example 10 Herstellung der Emulsion EM-10Preparation of the EM-10 emulsion

Die Emulsion EM-10 wird hergestellt und verarbeitet wie in Beispiel 1 beschrieben, jedoch mit der Änderung, daß die Lösung 2 die folgende Zusammensetzung aufweist: Lösung 2: 400 ml Wasser 73 g NaCl 1,2 g KBr 0,034 mg K2IrCl6 0,010 mg RhCl3 0,060 mg HAuCl4

Figure imgb0004
Emulsion EM-10 is prepared and processed as described in Example 1, but with the change that Solution 2 has the following composition: Solution 2: 400 ml water 73 g NaCl 1.2 g KBr 0.034 mg K 2 IrCl 6 0.010 mg RhCl 3 0.060 mg HAuCl 4
Figure imgb0004

Aus der Tabelle 1 ist zu ersehen, daß die Emulsionen aus den erfindungsgemäßen Beispielen (EM-7, EM-8 und EM-10) eine eindeutig höhere Empfindlichkeit aufweisen, als die Vergleichsemulsionen EM-1 bis EM-6 und EM-9.It can be seen from Table 1 that the emulsions from the examples according to the invention (EM-7, EM-8 and EM-10) have a clearly higher sensitivity than the comparative emulsions EM-1 to EM-6 and EM-9.

In der nachfolgenden Tabelle 2 sind die Differenzen der Empfindlichkeiten und Gradationen, gebildet aus den Entwicklungszeiten von 25 und 45 sec. im RA4-Prozeß, zusammengestellt, Tabelle 2 Emulsion Diff.Empfindlichkeit log I·t Diff. Gradation EM-1 Vergleich 0,200 1,5 EM-2 Vergleich 0,230 2,2 EM-3 Vergleich 0,250 2,0 EM-4 Vergleich 0,220 1,7 EM-5 Vergleich 0,190 1,4 EM-6 Vergleich 0,240 2,0 EM-7 Erfindung 0,050 0,6 EM-8 Erfindung 0,060 1,0 EM-9 Vergleich 0,080 0,8 EM-10 Erfindung 0,065 0,7 Table 2 below shows the differences in the sensitivities and gradations, formed from the development times of 25 and 45 seconds in the RA4 process, Table 2 emulsion Diff. Sensitivity log I · t Diff. gradation EM-1 comparison 0.200 1.5 EM-2 comparison 0.230 2.2 EM-3 comparison 0.250 2.0 EM-4 comparison 0.220 1.7 EM-5 comparison 0.190 1.4 EM-6 comparison 0.240 2.0 EM-7 invention 0.050 0.6 EM-8 invention 0.060 1.0 EM-9 comparison 0.080 0.8 EM-10 invention 0.065 0.7

Aus der Tabelle ist deutlich die bessere Entwicklungskinetik der erfindungsgemäßen Emulsionen zu ersehen, die hier durch die geringeren Empfindlichkeits- und Gradationsdifferenzen dokumentiert sind.The table clearly shows the better development kinetics of the emulsions according to the invention, which are documented here by the lower sensitivity and gradation differences.

Beispiel 11Example 11

Ein farbfotografisches Aufzeichnungsmaterial wurde hergestellt, indem auf einen Schichtträger aus beidseitig mit Polyethylen beschichtetem Papier die folgenden Schichten in der angegebenen Reihenfolge aufgetragen wurden, Die Mengenangaben beziehen sich jeweils auf 1 m2. Für den Silberhalogenidauftrag werden die entsprechenden Mengen AgNO3 angegeben.A color photographic recording material was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene. The amounts given relate in each case to 1 m 2 . The corresponding amounts of AgNO 3 are given for the silver halide application.

Schichtaufbau 1Layer structure 1

  • 1. Schicht (Substratschicht):
       0,3 g Gelatine    1st layer (substrate layer):
    0.3 g gelatin
  • 2. Schicht (blauempfindliche Schicht):
    • blauempfindliche Silberhalogenidemulsion EM-3 aus 0,63 g AgNO3 mit
    • 1,38 g Gelatine
    • 0,95 g Gelbkuppler gemäß Beispiel 1
    • 0,29 g Trikresylphosphat (TKP)
    2nd layer (blue-sensitive layer):
    • blue-sensitive silver halide emulsion EM-3 from 0.63 g AgNO 3 with
    • 1.38 g gelatin
    • 0.95 g yellow coupler according to example 1
    • 0.29 g tricresyl phosphate (CPM)
  • 3. Schicht (Zwischenschicht):
    • 1,1 g Gelatine
    • 0,06 g 2,5-Dioctylhydrochinon
    • 0,06 g Dibutylphthalat (DBP)
    3rd layer (intermediate layer):
    • 1.1 g gelatin
    • 0.06 g 2,5-dioctyl hydroquinone
    • 0.06 g dibutyl phthalate (DBP)
  • 4. Schicht (grünempfindliche Schicht)
    • grünsensibilisierte Silberhalogenidemulsion (99,5 Mol-%. AgCl, 0,5 Mol-% AgBr, mittlerer Korndurchmesser 0,4 µm, mit 1x10-7 Mol K4IrCl6/Mol Silberhalogenid dotiert)
    • aus 0,45 g AgNO3 mit
    • 1,08 g Gelatine
    • 0,45 g Purpurkuppler (s. nachstehende Formel)
    • 0,08 g 2,5-Dioctylhydrochinon
    • 0,5 g DBP
    • 0,4 g TKP
    4th layer (green-sensitive layer)
    • green-sensitized silver halide emulsion (99.5 mol%. AgCl, 0.5 mol% AgBr, average grain diameter 0.4 µm, doped with 1x10 -7 mol K 4 IrCl 6 / mol silver halide)
    • from 0.45 g AgNO 3 with
    • 1.08 g gelatin
    • 0.45 g purple coupler (see formula below)
    • 0.08 g 2,5-dioctyl hydroquinone
    • 0.5 g DBP
    • 0.4 g CPM
  • 5. Schicht (UV-Schutzschicht)
    • 1,15 g Gelatine
    • 0,6 g UV-Absorber der Formel
      Figure imgb0005
    • 0,045 g 2,5-Dioctylhydrochinon
    • 0,3 g TKP
    5th layer (UV protective layer)
    • 1.15 g gelatin
    • 0.6 g UV absorber of the formula
      Figure imgb0005
    • 0.045 g 2,5-dioctyl hydroquinone
    • 0.3 g CPM
  • 6. Schicht (rotempfindliche Schicht)
    • rotsensibilisierte Silberhalogenidemulsion (99,5 Mol-% AgCl, 0,5 Mol-% AgBr, mittlerer Korndurchmesser 0,4 µm, mit 1x10-7 Mol K4IrCl6/Mol Silberhalogenid dotiert)
    • aus 0,3 g AgNO3 mit
    • 0,75 g Gelatine
    • 0,36 g Blaugrünkuppler (s. nachstehende Formel)
    • 0,36 g TKP
    6th layer (red-sensitive layer)
    • Red-sensitized silver halide emulsion (99.5 mol% AgCl, 0.5 mol% AgBr, average grain diameter 0.4 µm, doped with 1x10 -7 mol K 4 IrCl 6 / mol silver halide)
    • from 0.3 g of AgNO 3 with
    • 0.75 g gelatin
    • 0.36 g cyan coupler (see formula below)
    • 0.36 g CPM
  • 7. Schicht (UV-Schutzschicht)
    • 0,35 g Gelatine
    • 0,15 g UV-Absorber wie 5. Schicht
    • 0,075 g TKP
    7th layer (UV protective layer)
    • 0.35 g gelatin
    • 0.15 g UV absorber as 5th layer
    • 0.075 g CPM
  • 8. Schicht (Schutzschicht)
    • 0,9 g Gelatine
    • 0,3 g Härtungsittel der Formel
      Figure imgb0006
    8th layer (protective layer)
    • 0.9 g gelatin
    • 0.3 g hardening agent of the formula
      Figure imgb0006
Schichtaufbau 2Layer structure 2

Wie Schichtaufbau 1, jedoch in der 2. Schicht Emulsion EM-8 in der gleichen Menge AgNO3.Like layer structure 1, but in the second layer Emulsion 8 in the same amount of AgNO 3 .

Die nachfolgende Tabelle 3 enthält die relevanten sensitometrischen Daten der Schichtaufbauten 1 und 2. Es ist zu ersehen, daß die erfindungsgemäße Emulsion EM-8 im Vergleich zu EM-3 die deutlich bessere Entwicklungskinetik aufweist.

Figure imgb0007
Table 3 below contains the relevant sensitometric data for layer structures 1 and 2. It can be seen that the emulsion EM-8 according to the invention has significantly better development kinetics than EM-3.
Figure imgb0007

Als Farbkuppler wurden folgende Verbindungen verwendet:The following connections were used as color couplers:

Purpurkuppler:Purple coupler:

Figure imgb0008
Figure imgb0008

BlaugrünkupplerTeal coupler

Figure imgb0009
Figure imgb0009

Claims (8)

  1. A silver halide material for colour photography, comprising a substrate, at least one blue-sensitive yellow-coupling silver halide emulsion layer, at least one green-sensitive, magenta-coupling silver halide emulsion layer, and at least one red-sensitive, cyan coupling silver halide emulsion layer applied to the substrate and conventional intermediate and protective layers, the silver halide grains in at least one of the silver halide emulsion layers comprising not less than 80 mol-% AgCl and not more than 0.5 mol-% AgI and being doped with at least one compound of a metal in the group (a), where (a) comprises the metals rhodium, iridium, ruthenium, rhenium, osmium and cadmium, characterised in that the silver halide grains are also doped with at least one gold compound.
  2. A silver halide material for colour photography according to claim 1, characterised in that the silver halide grains in all the layers of silver halide emulsion contain not less than 80 mol-% AgCl and not more than 0.5 mol-% AgI.
  3. A silver halide material for colour photography according to claim 1, characterised in that the silver halide emulsion doped with compounds of gold and metals in group (a) is an AgC195-100Br0-5 emulsion.
  4. A silver halide material for colour photography according to claim 1, characterised in that all the silver halide emulsion layers are AgCl95-100Br0-5 emulsions.
  5. A silver halide material for colour photography according to claim 1, characterised in that the silver halide emulsion doped with compounds of gold and metals in group (a) is matured with gold and sulphur.
  6. A silver halide material for colour photography according to claim 1, characterised in that the silver halide emulsion doped with compounds of gold and metals in group (a) is sensitised for the blue spectral range.
  7. A silver halide material for colour photography according to claim 1, characterised in that the silver halide emulsions in all the silver halide emulsion layers are doped with compounds of gold and metals in group (a) and matured with gold and sulphur.
  8. A silver halide material for colour photography according to claim 1, characterised in that the silver halide grains in all the silver halide emulsion layers have the composition AgCl95-100Br0-5, are doped with an iridium compound and matured with sulphur and gold, and at least the silver halide grains in the at least one blue-sensitive yellow-coupling silver halide emulsion layer are additionally doped with a gold compound.
EP93104865A 1992-04-06 1993-03-24 Colour-photographic recording material Expired - Lifetime EP0564910B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4211462 1992-04-06
DE4211462A DE4211462A1 (en) 1992-04-06 1992-04-06 Color photographic recording material

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DE69426412T2 (en) * 1994-02-08 2001-04-19 Tulalip Consultoria Comercial Sociedade Unipessoal S.A., Funchal Hardened silver halide photographic elements

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US4818671A (en) * 1986-07-31 1989-04-04 Konishiroku Photo Industry Co., Ltd. Rapidly processable silver halide color photosensitive material
US5219722A (en) * 1990-09-21 1993-06-15 Konica Corporation Silver halide color photographic light-sensitive material
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