EP0595031B1 - Méthode de préparation d'émulsions à l'halogénure d'argent - Google Patents

Méthode de préparation d'émulsions à l'halogénure d'argent Download PDF

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Publication number
EP0595031B1
EP0595031B1 EP93115452A EP93115452A EP0595031B1 EP 0595031 B1 EP0595031 B1 EP 0595031B1 EP 93115452 A EP93115452 A EP 93115452A EP 93115452 A EP93115452 A EP 93115452A EP 0595031 B1 EP0595031 B1 EP 0595031B1
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Prior art keywords
silver halide
mol
emulsion
process according
compounds
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EP93115452A
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German (de)
English (en)
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EP0595031A1 (fr
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Hans-Ulrich Dr. Borst
Lothar Dr. Endres
Hans Dr. Öhlschläger
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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
    • 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
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • 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
    • G03C1/07—Substances influencing grain growth during silver salt formation

Definitions

  • the invention relates to a method for producing silver halide emulsions, in which emulsions of different solubility are mixed and redissolved.
  • Silver halide emulsions are generally prepared by precipitating silver halide in a binder, preferably gelatin as the binder.
  • the silver halide can be precipitated by adding an aqueous solution of a silver salt to a gelatin-containing halide solution.
  • the size of the silver halide grains obtained is inter alia controlled by the temperature of the solution, the run-in time and the excess of halide.
  • the grain size and the grain size distribution of the silver halide grains of the emulsions obtained are still determined primarily by the so-called Ostwald ripening. Under the Ostwald ripening is the dissolution Easily soluble silver halide grains are understood to be the action of silver halide solvents and subsequent separation of the dissolved silver halide on less soluble silver halide grains.
  • the more readily soluble silver halide emulsion used in these methods is preferably a fine grain silver halide emulsion with an average grain diameter that is smaller than that of the less soluble silver halide emulsion.
  • the advantages of the specified redeployment procedures include: in controlled Ostwald ripening and above all in avoiding local silver ion oversaturation.
  • Examples of known silver halide solvents are: halides, preferably alkali and ammonium halides, in particular bromides or chlorides; Ammonia; Thiocyanates, especially alkali or ammonium thiocyanate; Sulfites, especially alkali or ammonium sulfites; Thiosulfate; organic amines; Thioether and imidazole derivatives.
  • Suitable thioethers are described, for example, in US Pat. Nos. 3,271,157, 3,507,657, 3,531,289 and 3,574,628. Particularly suitable thioethers are also described in German Offenlegungsschriften 2,614,862 and 2,824,249. Suitable imidazole derivatives are described in US Pat German Offenlegungsschrift 27 58 711.
  • the object of the invention is therefore to find a process for the production of highly sensitive, fine-grained silver halide emulsions which have low fog.
  • the invention therefore relates to a process for the preparation of a silver halide emulsion with up to 20 mol% AgI by precipitation of a silver halide emulsion A with up to 100 mol% AgI and addition of a silver halide emulsion B with up to 40 mol% AgI and an average grain size of at most 0.25 ⁇ m, emulsion B in aqueous gelatin solution always being more soluble than emulsion A either because of its grain size or because of its iodide content, in the presence of at least two compounds from the series imidazole, histidine ( ⁇ -amino- ⁇ -imidazolyl - (5) -propionic acid) and other monocyclic, free of SH groups, 5- or 6-membered, heterocyclic compounds with at least one ring nitrogen atom, which form sparingly soluble silver salts in weakly acidic to neutral aqueous solution, which with the addition of ammonia at pH > 9 go back into solution, one of the at
  • Monocyclic compounds are understood to mean those which have no fused rings in the entire molecule.
  • Grain size is always understood to mean the diameter of the same-volume ball.
  • the iodide content of emulsion A is preferably 10 to 90 mol%
  • Suitable are e.g. Imidazoles, oxazoles, thiazoles, triazoles.
  • Pyridines, tetrazoles and pyrimidines which are substituted by alkyl, preferably with up to 4 carbon atoms such as methyl, ethyl, isopropyl; Alkenyl such as allyl;
  • Aryl such as phenyl, halogen such as chlorine or bromine, carboxylic acid groups or derivatives such as carbalkoxy or carbonamido: sulfonic acid groups, sulfonamide, sulfones, thioethers such as methylthio or carboxyalkylthio: substituted or unsubstituted amino groups can be substituted.
  • the solution is preferably carried out at an E Ag value of -20 to -120 mV, in particular -40 to -100 mV, at a pH of 4 to 10, in particular 6 to 8 and a temperature of 40 to 90 ° C. especially 50 to 75 ° C. Under these conditions, the redissolution is usually complete after 20 minutes (E Ag is the potential between a silver electrode and a saturated calomel electrode).
  • the gelatin / silver halide weight ratio expressed as the amount of silver nitrate used, is preferably 0.05 to 1.0, in particular 0.1 to 0.5, when the solution is redissolved.
  • Emulsions A and B expressed as the amount of silver nitrate used, are preferably mixed with one another in a weight ratio of 1: 1 to 1:20, preferably 1: 2 to 1:10.
  • Emulsions A and B are essentially silver bromoiodide emulsions. They can also contain small amounts of silver chloride.
  • the grain size of emulsion A ranges in particular from 0.1 to 1.5 ⁇ m, the grain size of emulsion B in particular from 0.01 to 0.2 ⁇ m.
  • the emulsion A If the iodide content of emulsion A is between 40 and 90 mol%, the emulsion consists predominantly of grains with about 40 mol% AgI and pure AgI grains.
  • the iodide content of emulsion A can be adjusted by appropriate selection of the mixture of soluble halides intended for the precipitation.
  • An emulsion with a lower iodide content can also be precipitated first and then converted to the desired higher iodide content with the addition of KI.
  • These compounds have SH groups or are not monocyclic.
  • emulsion A is first prepared as a precipitate, which can optionally be concentrated and desalted.
  • the further substance supply, which is carried out according to the invention by adding emulsion B, can be set up in such a way that more than 50 mol%, preferably more than 80 mol%, of the silver halide used is added in the form of emulsion B.
  • Emulsion B can also be concentrated and desalted.
  • emulsion B and the silver halide solvents to be used according to the invention can be added simultaneously or at different times, all at once or in several parts or continuously.
  • concentrations of the silver halide emulsions B and A used can be varied within wide limits.
  • the amount of silver halide solvent to be used according to the invention can generally be easily determined in a series of tests and, in the case of imidazole and histidine, is preferably between 10 -5 and 2.0 mol per mol of silver halide used, in particular between 10 -3 and 0.3 mol per Mol of silver halide used and in the case of the compounds other than imidazole and histidine preferably 10 -6 and 0.5 mol per mol of silver halide used.
  • emulsions can in principle be prepared for a wide variety of photographic materials, e.g. Negative working emulsions with high surface sensitivity, negative working emulsions with high internal sensitivity, directly positive working emulsions that can be superficially veiled or superficially unveiled, emulsions with layered grain structure, print-out emulsions, reverse emulsions, emulsions for black and white and for color materials as well as with defined grain distribution and halide topography , in particular with a defined halide, in particular iodide gradient.
  • photographic materials e.g. Negative working emulsions with high surface sensitivity, negative working emulsions with high internal sensitivity, directly positive working emulsions that can be superficially veiled or superficially unveiled, emulsions with layered grain structure, print-out emulsions, reverse emulsions, emulsions for black and white and for color materials as well as with defined grain distribution and halide
  • the silver halide emulsions prepared according to the invention and the starting emulsions A and B can either be solidified, pasta-coated and soaked in a known manner or can also be coagulated with a coagulating agent and then washed, as is known, for example, from German Offenlegungsschrift 2,614,862. Desalination is particularly advantageously carried out by ultrafiltration.
  • the emulsion produced according to the invention and optionally also the starting emulsions, in particular emulsion A, can be chemically sensitized, for example by adding sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea, sodium thiosulfate.
  • sulfur-containing compounds for example allyl isothiocyanate, allyl thiourea, sodium thiosulfate.
  • Reducing agents for example, the tin compounds described in the Belgian patent specifications 493 464 or 568 687, and also polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, for example in accordance with the Belgian patent specification 547 323, can be used.
  • Selenium compounds are also suitable.
  • Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z. Wis. Phot. 46, 65-72 (1951).
  • Both emulsion A and emulsion B can be added with foreign ions for doping during the precipitation. This addition is also possible before, during and after the redeployment.
  • Suitable compounds are for example Ir- and. Rh compounds.
  • Both emulsion A and emulsion B can be subjected to reduction ripening during the precipitation. Such reduction sensitization is also possible before, during and after the redissolution.
  • Suitable compounds for this are, for example, thiosulfonic acid derivatives, H 2 O 2 and mercury (II) compounds.
  • polyalkylene oxide derivatives e.g. with polyethylene oxide with a molecular weight between 1,000 and 20,000
  • condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides The condensation products have a molecular weight of at least 700, preferably more than 1,000.
  • these sensitizers can of course be used in combination, as described in Belgian patent 536 278 and in British patent 727 982.
  • the emulsions can also be optically sensitized, for example with the customary polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
  • the customary polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
  • sensitizers are described in FM Hamer: "The Cyanine Dyes and Related Compounds" 1964, Interscience Publishers, John Wiley and Sons.
  • the emulsions can contain the usual stabilizers, e.g. homeopolar or salt-like compounds of mercury with aromatic or heterocyclic rings such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • stabilizers e.g. homeopolar or salt-like compounds of mercury with aromatic or heterocyclic rings such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • azaindenes preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are in Birr: Z. Wiss. Phot. 47 (1952), 2-58.
  • Other suitable stabilizers include heterocyclic mercapto compounds, e.g. Phenylmercapto compounds, quaternary benzothiazole derivatives and benzotriazole.
  • gelatin as a binder or protective colloid for the photographic emulsion according to the invention
  • other colloids can also be used.
  • various high molecular weight synthetic hydrophilic materials such as graft polymers of gelatin and other high molecular weight materials; Proteins such as albumin, casein and the like; Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate and the like; Saccharide derivatives such as sodium alginate, starch derivatives and the like; Homopolymers or copolymers, such as polyvinyl alcohol, partially acetalized polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used.
  • Suitable gelatin graft polymers that can be used in the present invention are those obtained by grafting homopolymers or copolymers of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof, e.g. the esters, amides, acrylonitrile, styrene on gelatin. Graft polymers of gelatin with polymers of acrylic acid, methacrylic acid, acrylamide, methacrylamide and hydroxyalkyl methacrylates are particularly preferred.
  • the emulsions can be hardened in a customary manner, for example with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
  • formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
  • the photographic layers can be hardened with hardeners of the epoxy type, the heterocyclic ethylene imine or the acryloyl type.
  • hardeners are e.g. in German laid-open specification 2 263 602 or in British patent 1 266 655.
  • hardeners examples include diazine derivatives containing alkyl or arylsulfonyl groups, derivatives of hydrogenated diazines or triazines, such as, for example, 1,3,5, -hexahydrotriazine, fluorine-substituted diazine derivatives, for example fluoropyrimidine, esters of 2-substituted, 1,2-dihydroquinoline or 1,2-dihydroisoquinoline-N-carboxylic acid.
  • diazine derivatives containing alkyl or arylsulfonyl groups derivatives of hydrogenated diazines or triazines, such as, for example, 1,3,5, -hexahydrotriazine, fluorine-substituted diazine derivatives, for example fluoropyrimidine, esters of 2-substituted, 1,2-dihydroquinoline or 1,2-dihydroisoquinoline-N-carboxylic acid.
  • vinyl sulfonic acid hardeners carbodiimide or carbamoyl hardeners, as described, for example, in German Offenlegungsschriften 2 263 602, 2 225 230 and 1 808 685, French Patent 1,491,807, German Patent 872 153 and DD-A-7218.
  • Other useful resins are described, for example, in British Patent 1,268,550.
  • the present invention can be applied to both black and white and color photographic images.
  • Colored photographic images can e.g. according to the known principle of chromogenic development in the presence of color couplers, which react with the oxidation product of color-giving p-phenylenediamine developers to form dyes.
  • the color couplers can, for example, be added to the color developer according to the principle of the so-called development process.
  • the photographic material itself contains the usual color couplers, which are usually incorporated into the silver halide layers.
  • the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or ⁇ -naphthalene type.
  • the green-sensitive layer can, for example, contain at least one non-diffusing color coupler for producing the purple partial color image, Color couplers of the 5-pyrazolone, indazolone or pyrazoloazole type are usually used.
  • the blue-sensitive layer can contain a non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
  • Color couplers of this type are known in large numbers and are described in a large number of patents. Examples include the publication "Farbkuppler” by W. Pelz in “Mitanderen aus dem Anlagenslaboratorien der Agfa, Leverkusen / Ober", Volume III (1961) and K. Venkataraman in "The Chemistry of Synthetic Cyes", Vol. 4, 341 -387, Academic Press, 1971.
  • 2-equivalent couplers can be used as further non-diffusing color couplers; these contain a removable substituent in the coupling point, so that they only need two equivalents of silver halide to form the color, in contrast to the usual 4-equivalent couplers,
  • the 2-equivalent couplers that can be used include, for example, the known DIR couplers, in which the cleavable residue is released as a diffusing development inhibitor after reaction with color developer oxidation products.
  • the so-called white couplers can be used to improve the properties of the photographic material, which provide a colorless coupling product.
  • the non-diffusing color couplers and coloring compounds are added to the light-sensitive silver halide emulsions or other casting solutions by customary known methods. If the compounds are soluble in water or alkali, they can be added to the emulsions in the form of aqueous solutions, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide.
  • non-diffusing color couplers and coloring compounds are water- or alkali-insoluble compounds, they can be emulsified in a known manner, for example by dissolving these compounds in a low-boiling organic solvent directly with the silver halide emulsion or initially with an aqueous gelatin solution is mixed, whereupon the organic solvent is removed in a conventional manner. A gelatin emulsate of the respective compound thus obtained is then mixed with the silver halide emulsion.
  • coupler solvents or oil das are additionally used to emulsify such hydrophobic compounds are generally higher-boiling organic compounds which include the compounds in the form of oily droplets which split off the non-diffusing color coupler and development inhibitor to be emulsified in the silver halide emulsions.
  • coupler solvents or oil das are generally higher-boiling organic compounds which include the compounds in the form of oily droplets which split off the non-diffusing color coupler and development inhibitor to be emulsified in the silver halide emulsions.
  • the emulsions prepared according to the invention can be applied to the customary layer supports, for example supports made of cellulose esters such as cellulose acetate or cellulose acetobutyrate, furthermore polyesters, in particular polyethylene terephthalate or polycarbonates, in particular based on bisphenylol propane.
  • paper supports which can optionally contain water-impermeable polyolefin layers, for example made of polyethylene or polypropylene, and supports made of glass or metal.
  • the emulsion B used in the examples below is a silver bromide emulsion which has an average grain size of 0.05 ⁇ m and contains 1.25 mol of silver halide per kg and 18 g of gelatin per kg.
  • the AgBrI emulsion A1 is produced using a double jet process and contains 1 mol of silver halide and 32 g of gelatin per kg.
  • the average grain size is 0.4 ⁇ m, the iodide content is 25 mol%.
  • emulsion B 3000 g of emulsion B are mixed with 1500 g of emulsion Al and digested in the presence of the substances listed in Table 1 at 65 ° C., pH 7.5 and an E Ag value of -60 mV until the redissolution is complete ( after about 20 minutes). It is then coagulated, washed and finally redispersed with the addition of water and gelatin. Then an optimal ripening with gold and sulfur compounds is carried out.
  • the average grain size is 0.7 ⁇ m, the iodide content 7 mol%.
  • the AgBrI emulsion A2 is produced using a double jet process and contains 1 mol of silver halide and 32 g of gelatin per kg.
  • the average grain size is 0.7 ⁇ m, the iodide content is 40 mol%.
  • emulsion B 9000 g of emulsion B are mixed with 1500 g of emulsion A2 and digested in the presence of the substances listed in Table 2 at 60 ° C., pH 7.5 and an E Ag value of -60 mV until the redissolution is complete ( after about 20 minutes).
  • the further processing corresponds to Example 1.
  • the average grain size is 1.1 ⁇ m, the iodide content 4.7 mol%.
  • the AgBrI emulsion A3 is produced using a double jet process and contains 1 mol of silver halide and 32 g of gelatin per kg.
  • the average grain size is 0.5 ⁇ m
  • the iodide content is 70 mol%
  • an iodide content of 30 mol% first being precipitated and then converted to the stated iodide content by adding KI.
  • the average grain size is 1.1 ⁇ m, the iodide content 12 mol-X.
  • Both the emulsions produced after 1.1 and after 1.3 are subjected to an optimal ripening of gold sulfur as well as an optimal ripening, in which, in addition to gold and sulfur compounds, selenium compounds are also present. Suitable selenium compounds for this are described for example in EP 428 041, 458 278, 476 345.
  • example 1.3 according to the invention there is a significantly greater increase in sensitivity due to the addition of selenium than in example 1.1 not according to the invention.

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  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
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  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)

Claims (10)

  1. Procédé de préparation d'une émulsion à l'halogénure d'argent avec jusqu'à 20 % molaires d'AgI par précipitation d'une émulsion à l'halogénure d'argent A avec jusqu'à 100 % molaires d'AgI et addition d'une émulsion d'halogénure d'argent B avec jusqu'à 40 % molaires d'AgI et une granulométrie moyenne au plus de 0,25 µm, où l'émulsion B dans la solution aqueuse de gélatine présente toujours soit en raison de sa granulométrie soit en raison de sa teneur en iodure la plus grande solubilité vis-à-vis de l'émulsion A, en présence d'au moins deux composés de la série de l'imidazol, de l'histidine (acide α-amino-β-imidazolyl-(5)-propionique) et d'autres composés monocycliques, exempt de groupes SH, hétérocycliques à 5 ou 6 maillons avec au moins un atome d'azote dans le cycle, qui forment des sels d'argent peu solubles en solution faiblement acide à neutre aqueuse, qui par addition d'ammoniaque à pH > 9 sont redissous, où au moins l'un des deux composés est l'imidazol ou l'histidine et au moins un autre composé n'est pas l'imidazol ni l'histidine.
  2. Procédé selon la revendication 1, caractérisé en ce que la teneur en iodure de l'émulsion est 10 à 90 % molaires.
  3. Procédé selon la revendication 1, caractérisé en ce que la redissolution a lieu à EAg de -20 à -120 mV, à pH 4 à 10 et entre 40 et 90°C.
  4. Procédé selon la revendication 1, caractérisé en ce que la redissolution a lieu à EAg de -40 à -100 mV, de pH 6 à 8 et entre 50 et 75°C.
  5. Procédé selon la revendication 1, caractérisé en ce que le rapport pondéral gélatine/halogénure d'argent, exprimé sous forme de nitrate d'argent mis en oeuvre, représente lors de la redissolution 0,05 à 1.
  6. Procédé selon la revendication 1, caractérisé en ce que le rapport pondéral gélatine/halogénure d'argent, exprimé sous forme de quantité de nitrate d'argent mis en oeuvre, est de 0,1 à 0,5 lors de la redissolution.
  7. Procédé selon la revendication 1, caractérisé en ce qu'on utilise les émulsions A et B, exprimées sous forme de quantité de nitrate d'argent utilisé, dans un rapport pondéral de 1:1 à 1:20 pour la redissolution.
  8. Procédé selon la revendication 1, caractérisé en ce qu'on utilise les émulsions A et B, exprimées sous forme de quantité de nitrate d'argent utilisé, dans un rapport pondéral de 1:2 à 1:10 pour la redissolution.
  9. Procédé selon la revendication 1, caractérisé en ce que les composés hétérocycliques, exempts de groupes SH, monocycliques différents de l'imidazol et de l'histidine avec au moins un atome d'azote dans le cycle, qui forment des sels d'argent peu solubles en solution aqueuse faiblement acide à neutre, qui se redissolvent par addition d'ammoniaque à pH supérieur à 9 dans la solution ammoniacale, font partie des classes suivantes : imidazols, oxazols, thiazols, triazols, thiadiazols, oxadiazols, pyridines, tétrazols et pyrimidines.
  10. Procédé selon la revendication 1, caractérisé en ce qu'on utilise l'imidazol et/ou l'histidine en une quantité de 10-5 à 2,0 mol/mol d'halogénure d'argent et les composés différents de l'imidazol et de l'histidine en une quantité de 10-6 à 0,5 mol/mol d'halogénure d'argent.
EP93115452A 1992-10-07 1993-09-24 Méthode de préparation d'émulsions à l'halogénure d'argent Expired - Lifetime EP0595031B1 (fr)

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DE4233714A DE4233714A1 (de) 1992-10-07 1992-10-07 Verfahren zur Herstellung von Silberhalogenidemulsionen
DE4233714 1992-10-07

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EP0595031B1 true EP0595031B1 (fr) 1997-12-17

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US (1) US5427904A (fr)
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DE (2) DE4233714A1 (fr)

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DE19933258A1 (de) 1999-07-15 2001-01-18 Agfa Gevaert Ag Herstellung von Silberhalogenidemulsionen
US6451520B1 (en) * 2000-07-29 2002-09-17 Agfa-Gevaert Color photographic silver halide material

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BE414540A (fr) * 1935-04-05
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US3317322A (en) * 1965-08-27 1967-05-02 Eastman Kodak Co Photographic emulsions having high internal sensitivity
DE2758711A1 (de) * 1977-12-29 1979-07-19 Agfa Gevaert Ag Lichtempfindliches photographisches material
DE2828112A1 (de) * 1978-06-27 1980-01-10 Agfa Gevaert Ag Lichtempfindliches photographisches material
DE3019733A1 (de) * 1980-05-23 1981-12-03 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur herstellung von silberhalogenidemulsionen, photographische materialien sowie verfahren zur herstellung photographischer bilder
JPH03120528A (ja) * 1989-10-03 1991-05-22 Konica Corp 高感度でカブリ、粒状性の改良されたハロゲン化銀乳剤及びその製造方法
US5273871A (en) * 1990-10-03 1993-12-28 Konica Corporation Silver halide photographic emulsion and silver halide color photographic light-sensitive material incorporating it

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US5427904A (en) 1995-06-27
DE4233714A1 (de) 1994-04-14
JPH06202257A (ja) 1994-07-22
EP0595031A1 (fr) 1994-05-04
DE59307852D1 (de) 1998-01-29

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