EP0564910B1 - Matériau d'enregistrement pour la photographie en couleur - Google Patents

Matériau d'enregistrement pour la photographie en couleur Download PDF

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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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German (de)
English (en)
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EP0564910A1 (fr
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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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Claims (8)

  1. Matériau comportant de l'halogénure d'argent pour photographie en couleur, ce matériau comportant un support et, appliqué sur le support, au moins une couche d'émulsion d'halogénure d'argent sensible au bleu et couplant pour du jaune, au moins une couche d'émulsion d'halogénure d'argent sensible au vert et couplant pour du pourpre, au moins une couche d'émulsion d'halogénure d'argent sensible au rouge et couplant pour du bleu-vert, ainsi que des couches intermédiaires et protectrices usuelles, les grains d'halogénure d'argent d'au moins l'une des couches d'émulsion d'halogénure d'argent consistant pour au moins 80 mol % en Agcl et pour un maximum de 0,05 mol % en AgI, et étant additionné ou dopé par un composé de métal du groupe (a), le groupe ou ensemble (a) comprenant les métaux rhodium, iridium, ruthénium, osmium et cadmium, matériau caractérisé en ce que ces grains d'halogénure d'argent sont en outre dopés par au moins un composé de l'or.
  2. Matériau comportant de l'halogénure d'argent pour photographie en couleur selon la revendication 1, caractérisé en ce que les grains d'halogénure d'argent de toutes les couches d'émulsion d'halogénure d'argent consiste pour au moins 80 mol % en AgCl et pour un maximum de 0,5 mol % en AgI.
  3. Matériau comportant de l'halogénure d'argent pour photographie en couleur selon la revendication 1, caractérisé en ce que l'émulsion d'halogénure d'argent dopée par des composés de l'or et des composés de métaux du groupe ou ensemble (a) est une émulsion de AgCl95-100Br0-5.
  4. Matériau comportant de l'halogénure d'argent pour photographie en couleur selon la revendication 1, caractérisé en ce que l'émulsion d'halogénure d'argent de toutes les couches d'émulsion d'halogénure d'argent est constituée par des émulsions de AgCl95-100Br0-5.
  5. Matériau comportant de l'halogénure d'argent pour photographie en couleur selon la revendication 1, caractérisé en ce que l'émulsion d'halogénure d'argent dopée par des composés de l'or et par des composés de métaux du groupe ou ensemble (a) est mûrie avec de l'or et avec du soufre.
  6. Matériau comportant de l'halogénure d'argent pour photographie en couleur selon la revendication 1, caractérisé en ce que l'émulsion d'halogénure d'argent dopée par des composés de l'or et par des composés de métaux du groupe ou ensemble (a) est sensibilisée pour le domaine bleu du spectre.
  7. Matériau comportant de l'halogénure d'argent pour photographie en couleur selon la revendication 1, caractérisé en ce que des émulsions d'halogénure d'argent de toutes les couches d'émulsion d'halogénure d'argent sont dopées par des composés de l'or et par des composés de métaux du groupe ou ensemble (a) et sont mûries en présence d'or et de soufre.
  8. Matériau comportant de l'halogénure d'argent pour photographie en couleur selon la revendication 1, caractérisé en ce que les grains d'halogénure d'argent de toutes les couches d'émulsion d'halogénure d'argent présente la composition AgCl95-100Br0-5, elles sont dopées par un composé d'iridium et sont mûries en présence de soufre et d'or et au moins des grains d'halogénure d'argent d'au moins une couche d'émulsion d'halogénure d'argent sensible au bleu et couplant pour du jaune sont dopés en outre par un composé de l'or.
EP93104865A 1992-04-06 1993-03-24 Matériau d'enregistrement pour la photographie en couleur Expired - Lifetime EP0564910B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4211462 1992-04-06
DE4211462A DE4211462A1 (de) 1992-04-06 1992-04-06 Farbfotografisches Aufzeichnungsmaterial

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EP0564910A1 EP0564910A1 (fr) 1993-10-13
EP0564910B1 true EP0564910B1 (fr) 1996-06-05

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EP93104865A Expired - Lifetime EP0564910B1 (fr) 1992-04-06 1993-03-24 Matériau d'enregistrement pour la photographie en couleur

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JP (1) JPH0643615A (fr)
DE (2) DE4211462A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE69426412T2 (de) * 1994-02-08 2001-04-19 Tulalip Consultoria Com Socied Gehärtete photographische Silberhalogenidelemente

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE69121174T2 (de) * 1990-11-26 1997-01-09 Konishiroku Photo Ind Photographisches lichtempfindliches Silberhalogenidmaterial

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JPH0643615A (ja) 1994-02-18
DE59302792D1 (de) 1996-07-11
DE4211462A1 (de) 1993-10-07
EP0564910A1 (fr) 1993-10-13

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