[go: up one dir, main page]

EP0595031B1 - Process for the production of silver halide emulsions - Google Patents

Process for the production of silver halide emulsions Download PDF

Info

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
Authority
EP
European Patent Office
Prior art keywords
silver halide
mol
emulsion
process according
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP93115452A
Other languages
German (de)
French (fr)
Other versions
EP0595031A1 (en
Inventor
Hans-Ulrich Dr. Borst
Lothar Dr. Endres
Hans Dr. Öhlschläger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0595031A1 publication Critical patent/EP0595031A1/en
Application granted granted Critical
Publication of EP0595031B1 publication Critical patent/EP0595031B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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.

Landscapes

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

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Silberhalogenidemulsionen, bei dem Emulsionen unterschiedlicher Löslichkeit gemischt und umgelöst werden.The invention relates to a method for producing silver halide emulsions, in which emulsions of different solubility are mixed and redissolved.

Silberhalogenidemulsionen werden im allgemeinen durch Fällen von Silberhalogenid in einem Bindemittel hergestellt, wobei als Bindemittel vorzugsweise Gelatine verwendet wird. Die Fällung des Silberhalogenids kann dadurch erfolgen, daß zu einer gelatinehaltigen Halogenidlösung eine wäßrige Lösung eines Silbersalzes zugefügt wird. Die Größe der erhaltenen Silberhalogenidkörner wird u.a. durch die Temperatur der Lösung, die Einlaufzeit und den Halogenidüberschuß gesteuert.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.

Die Korngröße und die Korngrößenverteilung der Silberhalogenidkörner der erhaltenen Emulsionen werden weiterhin vor allem durch die sogenannte Ostwald-Reifung bestimmt. Unter der Ostwald-Reifung wird die Auflösung leichter löslicher Silberhalogenidkörner unter der Einwirkung von Silberhalogenidlösungsmitteln und anschließende Abscheidung des gelösten Silberhalogenids an schwerer löslichen Silberhalogenidkörnern verstanden.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.

Es ist weiterhin bekannt, die wäßrigen Lösungen eines Silbersalzes und eines Halogenids gleichzeitig in eine Vorlage einlaufen zu lassen (Doppelstrahl-Verfahren).It is also known to run the aqueous solutions of a silver salt and a halide into a receiver at the same time (double-jet method).

Zur Herstellung von Silberhalogenidemulsionen sind auch Verfahren bekannt, Emulsionen unterschiedlicher Korngröße zu mischen und in Gegenwart von Silberhalogenidlösungsmitteln eine Umlösung zu bewirken. Eine Voraussetzung für derartige Verfahren ist, daß die bei der Umlösung verwendeten Silberhalogenidkristalle unterschiedliche Löslichkeit aufweisen. Unterschiedliche Löslichkeiten können durch unterschiedliche Korngröße und/oder unterschiedliche Halogenidzusammensetzung hervorgerufen werden. Derartige Verfahren sind aus den US-Patentschriften 2 146 983, 3 206 313, 3 317 322, der deutschen Auslegeschrift 1 207 791, den Referat von D. Markocki und W. Romer in "Korpuskular Photographie", IV (1963), Seiten 149 ff., aus "Zhurnal Nauchnoi Prikladnoi Fotografi Kinematografi 5, No. 2 (1960), Seiten 81-83 und EP-PS 42 060 bekannt.For the production of silver halide emulsions, processes are also known for mixing emulsions of different grain sizes and for effecting a redissolution in the presence of silver halide solvents. A prerequisite for such processes is that the silver halide crystals used in the redissolution have different solubilities. Different solubilities can be caused by different grain size and / or different halide composition. Such methods are described in US Pat. Nos. 2,146,983, 3,206,313, 3,317,322, German Auslegeschrift 1,207,791, D. Markocki and W. Romer in "Korpuskular Photographie", IV (1963), page 149 ff., from "Zhurnal Nauchnoi Prikladnoi Fotografi Kinematografi 5, No. 2 (1960), pages 81-83 and EP-PS 42 060 known.

Die bei diesen Verfahren verwendete leichter lösliche Silberhalogenidemulsion ist vorzugsweise eine feinkörnige Silberhalogenidemulsion mit einem mittleren Korndurchmesser, der kleiner ist als der der schwerer löslichen Silberhalogenidemulsion.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.

Die Vorteile der angegebenen Umlöseverfahren liegen u.a. in der kontrollierten Ostwald-Reifung und vor allem in der Vermeidung örtlicher Silberionenübersättigungen.The advantages of the specified redeployment procedures include: in controlled Ostwald ripening and above all in avoiding local silver ion oversaturation.

Als Silberhalogenidlösungsmittel sind beispielsweise bekannt: Halogenide, vorzugsweise Alkali und Ammoniumhalogenide, insbesondere Bromide oder Chloride; Ammoniak; Thiocyanate, insbesondere Alkali oder Ammoniumthiocyanat; Sulfite, insbesondere Alkali oder Ammoniumsulfite; Thiosulfat; organische Amine; Thioether und Imidazolderivate. Geeignete Thioether sind beispielsweise beschrieben in den US-Patentschriften 3 271 157, 3 507 657, 3 531 289 und 3 574 628. Besonders geeignete Thioether sind weiterhin beschrieben in den deutschen Offenlegungsschriften 2 614 862 und 2 824 249. Geeignete Imidazolderivate sind beschrieben in der deutschen Offenlegungsschrift 27 58 711.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.

Durch die genannten Verfahren lassen sich sowohl hochempfindliche als auch feinkörnige Silberhalogenidemulsionen herstellen, jedoch ist es bisher nicht gelungen, beide Eigenschaften in einem ausreichenden Maß gemeinsam zu realisieren.Both high-sensitivity and fine-grain silver halide emulsions can be produced by the processes mentioned, but it has not hitherto been possible to achieve both properties to a sufficient extent together.

Aufgabe der Erfindung ist daher, ein Verfahren zur Herstellung hochempfindlicher, feinkörniger Silberhalogenidemulsionen zu finden, die niedrigen Schleier aufweisen.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.

Diese Aufgabe wird durch ein verbessertes Umlöseverfahren gelöst.This task is solved by an improved redeployment process.

Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung einer Silberhalogenidemulsion mit bis zu 20 Mol-% AgI durch Fällen einer Silberhalogenidemulsion A mit bis zu 100 Mol-% AgI und Zugabe einer Silberhalogenidemulsion B mit bis zu 40 Mol-% AgI und einer mittleren Korngröße von höchstens 0,25 µm, wobei die Emulsion B in wäßriger Gelatinelösung stets entweder aufgrund iher Korngröße oder aufgrund ihres Iodidgehaltes gegenüber Emulsion A die größere Löslichkeit aufweist, in Gegenwart von wenigstens zwei Verbindungen aus der Reihe Imidazol, Histidin (α-Amino-β-imidazolyl-(5)-propionsäure) und anderen monocyclischen, von SH- Gruppen freien, 5- oder 6-gliedrigen, heterocyclischen Verbindungen mit wenigstens einem Ringstickstoffatom, die in schwach saurer bis neutraler wäßriger Lösung schwerlösliche Silbersalze bilden, die unter Zusatz von Ammoniak bei pH > 9 wieder in Lösung gehen, wobei eine der wenigstens zwei Verbindungen Imidazol oder Histidin und wenigstens eine andere Verbindung nicht Imidazol oder Histidin ist.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 μm, 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 (α-amino-β-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 least two compounds imidazole or histidine and a little Another compound is not imidazole or histidine.

Unter monocyclischen Verbindungen werden solche verstanden, die im gesamten Molekül keine anellierten Ringe besitzen. Unter Korngröße wird stets der Durchmesser der volumengleichen Kugel verstanden.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.

Der Iodidgehalt der Emulsion A beträgt vorzugsweise 10 bis 90 Mol-%,The iodide content of emulsion A is preferably 10 to 90 mol%,

Geeignet sind z.B. Imidazole, Oxazole, Thiazole, Triazole. Thiadiazole, Oxadiazole. Pyridine, Tetrazole und Pyrimidine, die durch Alkyl, vorzugsweise mit bis zu 4 C-Atomen wie Methyl, Ethyl, Isopropyl; Alkenyl wie Allyl; Aryl wie Phenyl, Halogen wie Chlor oder Brom, Carbonsäuregruppen oder Derivate wie Carbalkoxy oder Carbonamido: Sulfonsäuregruppen, Sulfonamid, Sulfone, Thioether wie Methylthio oder Carboxyalkylthio: substituierte oder unsubstituierte Aminogruppen substituiert sein können.Suitable are e.g. Imidazoles, oxazoles, thiazoles, triazoles. Thiadiazoles, oxadiazoles. 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.

Die Umlösung erfolgt vorzusgweise bei einem EAg-Wert von -20 bis -120 mV, insbesondere -40 bis -100 mV, bei einem pH-Wert von 4 bis 10, insbesondere 6 bis 8 und einer Temperatur von 40 bis 90°C, insbesondere 50 bis 75°C. Die Umlösung ist unter diesen Bedingungen üblicherweise nach 20 Minuten abgeschlossen (EAg ist das Potential zwischen einer Silberelektrode und einer gesättigten Kalomelelektrode).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).

Das Gelatine/Silberhalogenid-Gewichtsverhältnis, ausgedrückt als eingesetzte Silbernitratmenge, beträgt bei der Umlösung bevorzugt 0,05 bis 1,0, insbesondere 0,1 bis 0,5.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.

Die Emulsionen A und B, ausgedrückt als eingesetzte Silbernitratmenge, werden vorzusgweise im Gewichtsverhältnis 1:1 bis 1:20 miteinander gemischt, vorzugsweise 1:2 bis 1:10. Die Emulsionen A und B sind im wesentlichen Silberbromidiodidemulsionen. Sie können auch geringe Anteile Silberchlorid enthalten. Die Korngröße der Emulsion A reicht insbesondere von 0,1 bis 1,5 µm, die Korngröße der Emulsion B insbesondere von 0,01 bis 0,2 µm.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 μm, the grain size of emulsion B in particular from 0.01 to 0.2 μm.

Sofern der Iodidgehalt der Emulsion A zwischen 40 und 90 Mol-% liegt, besteht die Emulsion überwiegend aus Körnern mit etwa 40 Mol-% AgI und reinen AgI-Körnern.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.

Der Iodidgehalt der Emulsion A kann durch entsprechende Wahl der für die Fällung vorgesehenen Mischung löslicher Halogenide eingestellt werden. Es kann aber auch zunächst eine Emulsion mit geringerem Iodidanteil gefällt und anschließend unter Zusatz von KI zum gewünschten höheren Iodidgehalt konvertiert werden.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.

Geeignete SH-gruppenfreie N-Heterocyclen sind nachfolgend angegeben:

Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
 Thiadiazolderivate Verbindung R1 R2 I-17 NH2 S-CH2-COOH I-18 S-C2H5 S-CH2-COOH I-19 S-CH2-COOH H I-20 S-CH2-COOH S-CH2-COOH
Figure imgb0011
Figure imgb0012
 Thiazolderivate Verbindung R1 R2 R3 I-30 S-CH2-COOH CH3 COOH I-31 S-CH2-COOCH3 CH3 COOH I-32 NHCOCH3 H H I-33 CH3 CH=CH-COOH H I-34 SCH2COOH H H
Figure imgb0013
 Pyridinderivat Verbindung R1 R2 R3 R4 R5 I-36 S-CH2-COOH H H H H Suitable SH group-free N-heterocycles are given below:
Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
 Thiadiazole derivatives connection R 1 R 2 I-17 NH 2 S-CH 2 -COOH I-18 SC 2 H 5 S-CH 2 -COOH I-19 S-CH 2 -COOH H I-20 S-CH 2 -COOH S-CH 2 -COOH
Figure imgb0011
Figure imgb0012
 Thiazole derivatives connection R 1 R 2 R 3 I-30 S-CH 2 -COOH CH 3 COOH I-31 S-CH 2 -COOCH 3 CH 3 COOH I-32 NHCOCH 3 H H I-33 CH 3 CH = CH-COOH H I-34 SCH 2 COOH H H
Figure imgb0013
 Pyridine derivative connection R 1 R 2 R 3 R 4 R 5 I-36 S-CH 2 -COOH H H H H

Nicht geeignete Verbindungen sind z.B.

Figure imgb0014
Figure imgb0015
 Unsuitable connections are, for example
Figure imgb0014
Figure imgb0015

Diese Verbindungen bilden Silbersalze, die sich unter Zusatz von Ammoniak bei pH > 9 nicht mehr lösen.

Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
 These compounds form silver salts that no longer dissolve when ammonia is added at pH> 9.
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019

Diese Verbindungen besitzen SH-Gruppen oder sind nicht monocyclisch.These compounds have SH groups or are not monocyclic.

In einer bevorzugten Ausführungsform wird zunächst als Vorfällung die Emulsion A hergestellt, die gegebenenfalls konzentriert und entsalzt werden kann. Die weitere Substanzzufuhr, die erfindungsgemäß durch Zugabe der Emulsion B erfolgt, kann dabei so eingerichtet werden, daß mehr als 50 Mol-%, vorzugsweise mehr als 80 Mol-% des eingesetzten Silberhalogenids in der Form der Emulsion B zugesetzt wird. Auch die Emulsion B kann konzentriert und entsalzt werden.In a preferred embodiment, 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.

Die Zugabe der Emulsion B sowie der erfindungsgemäß zu verwendenden Silberhalogenidlösungsmittel kann grundsätzlich gleichzeitig oder zu unterschiedlichen Zeiten, auf einmal oder in mehreren Teilen oder kontinuierlich erfolgen. Die Konzentrationen der benutzten Silberhalogenidemulsionen B und A kann in weiten Grenzen variiert werden. Die Menge der erfindungsgemäß zu verwendenden Silberhalogenidlösungsmittel läßt sich im allgemeinen in einer Versuchsreihe leicht ermitteln und liegt im Fall von Imidazol und Histidin vorzugsweise zwischen 10-5 und 2,0 Mol pro Mol eingesetztem Silberhalogenid, insbesondere zwischen 10-3 und 0,3 Mol pro Mol eingesetztem Silberhalogenid und im Fall der von Imidazol und Histidin verschiedenen Verbindungen vorzugsweise 10-6 und 0,5 Mol pro Mol eingesetzten Silberhalogenid.In principle, 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. The 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.

Erfindungsgemäß können grundsätzlich Emulsionen für die verschiedensten photographischen Materialien hergestellt werden, z.B. negativarbeitende Emulsionen mit hoher Oberflächenempfindlichkeit, negativarbeitende Emulsionen mit hoher Innenempfindlichkeit, direkt positiv arbeitende Emulsionen, die oberflächlich verschleiert oder oberflächlich unverschleiert sein können, Emulsionen mit geschichtetem Kornaufbau, print-out Emulsionen, Umkehremulsionen, Emulsionen für Schwarzweiß und für Colormaterialien sowie mit definierter Kornverteilung und Halogenidtopographie, insbesondere mit definiertem Halogenid-, insbesondere Iodidgradienten.According to the invention, 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.

Die erfindungsgemäß hergestellten Silberhalogenidemulsionen sowie die Ausgangsemulsionen A und B können zur Entfernung der wasserlöslichen Salze entweder in bekannter Weise erstarrt, genudelt und gewässert werden oder auch mit einem Koagulierungsmittel koaguliert und anschließend gewaschen werden, wie es beispielsweise aus der deutschen Offenlegungsschrift 2 614 862 bekannt ist. Die Entsalzung erfolgt besonders vorteilhaft durch Ultrafiltration.To remove the water-soluble salts, 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.

Die erfindungsgemäß hergestellte Emulsion sowie auch gegebenenfalls die Ausgangsemulsionen, insbesondere die Emulsion A können chemisch sensibilisiert werden, z.B. durch Zusatz schwefelhaltiger Verbindungen bei der chemischen Reifung, beispielsweise Allylisothiocyanat, Allylthioharnstoff, Natriumthiosulfat. Als chemische Sensibilisatoren können ferner auch Reduktionsmittel, z.B. die in den belgischen Patentschriften 493 464 oder 568 687 beschriebenen Zinnverbindungen, ferner Polyamine wie Diethylentriamin oder Aminomethylsulfinsäure-Derivate, z.B. gemäß der belgischen Patentschrift 547 323, verwendet werden. Weiterhin geeignet sind Selenverbindungen.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. 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.

Geeignet als chemische Sensibilisatoren sind auch Edelmetalle bzw. Edelmetallverbindungen wie Gold, Platin, Palladium, Iridium, Ruthenium oder Rhodium. Diese Methode der chemischen Sensibilisierung ist in dem Artikel von R. Koslowsky, Z. Wis. Phot. 46, 65-72 (1951), beschrieben.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).

Sowohl der Emulsion A als auch der Emulsion B können während der Fällung Fremdionen zur Dotierung zugefügt werden. Dieser Zusatz ist auch vor, während und nach der Umlösung möglich. Geeignete Verbindungen sind beispielsweise Ir- u. Rh-Verbindungen.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.

Sowohl die Emulsion A als auch die Emulsion B kann während der Fällung einer Reduktionsreifung unterzogen werden. Eine solche Reduktionssensibilisierung ist auch vor, während und nach der Umlösung möglich.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.

Diese Maßnahme und geeignete Verbindungen sind z.B. in EP 348 934, 368 304, 369 424, 371 338, 369 491, 378 841, 404 142, 435 270, 435 355 und US 4 917 997 beschrieben.This measure and suitable connections are described, for example, in EP 348 934, 368 304, 369 424, 371 338, 369 491, 378 841, 404 142, 435 270, 435 355 and US 4 917 997.

Weiterhin kann es vorteilhaft sein, entweder bei nachfolgenden Fallungsschritten oder vor der chemischen Sensibilisierung einen Oxidationsschritt durchzuführen. Geeignete Verbindungen hierzu sind beispielsweise Thiosulfonsäurederivate, H2O2 und Quecksilber(II)-verbindungen.Furthermore, it can be advantageous to carry out an oxidation step either in the subsequent precipitation steps or before chemical sensitization. Suitable compounds for this are, for example, thiosulfonic acid derivatives, H 2 O 2 and mercury (II) compounds.

Es ist ferner möglich, die Emulsionen mit Polyalkylenoxid-Derivaten zu sensibilisieren, z.B. mit Polyethylenoxid eines Molekulargewichtes zwischen 1.000 und 20.000, ferner mit Kondensationsprodukten von Alkylenoxiden und aliphatischen Alkoholen, Glykolen, cyclischen Dehydratisierungsprodukten von Hexitolen, mit alkylsubstituierten Phenolen, aliphatischen Carbonsäuren, aliphatischen Aminen, aliphatischen Diaminen und Amiden. Die Kondensationsprodukte haben ein Molekulargewicht von mindestens 700, vorzugsweise von mehr als 1.000. Zur Erzielung besonderer Effekte kann man diese Sensibilisatoren selbstverständlich kombiniert verwenden, wie in der belgischen Patentschrift 536 278 und in der britischen Patentschrift 727 982 beschrieben.It is also possible to sensitize the emulsions with polyalkylene oxide derivatives, e.g. with polyethylene oxide with a molecular weight between 1,000 and 20,000, also with 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. To achieve special effects, these sensitizers can of course be used in combination, as described in Belgian patent 536 278 and in British patent 727 982.

Die Emulsionen können auch optisch sensibilisiert sein, z.B. mit den üblichen Polymethinfarbstoffen wie Neutrocyaninen, basischen oder sauren Carbocyaninen, Rhodacyaninen, Hemicyaninen, Styrylfarbstoffen, Oxonolen und ähnlichen. Derartige Sensibilisatoren sind in F.M. Hamer: "The Cyanine Dyes and related Compounds" 1964, Interscience Publishers, John Wiley and Sons, beschrieben.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. Such sensitizers are described in FM Hamer: "The Cyanine Dyes and Related Compounds" 1964, Interscience Publishers, John Wiley and Sons.

Die Emulsionen können die üblichen Stabilisatoren enthalten, z.B. homöopolare oder salzartige Verbindungen des Quecksilbers mit aromatischen oder heterocyclischen Ringen wie Mercaptotriazole, einfache Quecksilbersalze, Sulfoniumquecksilberdoppelsalze und andere Quecksilberverbindungen. Als Stabilisatoren sind ferner geeignet Azaindene, vorzugsweise Tetra- oder Pentaazaindene, insbesondere solche, die mit Hydroxyl- oder Aminogruppen substituiert sind. Derartige Verbindungen sind in Birr: Z. Wiss. Phot. 47 (1952), 2-58, beschrieben. Weitere geeignete Stabilisatoren sind u.a. heterocyclische Mercaptoverbindungen, z.B. Phenylmercaptoverbindungen, quaternare Benzthiazol-Derivate und Benzotriazol.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. Also suitable as stabilizers are 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.

Erfindungsgemäß ist es von Vorteil, als Bindemittel oder Schutzkolloid für die erfindungsgemäße photographische Emulsion Gelatine zu verwenden, es können aber auch andere Kolloide verwendet werden. So können beispielsweise verschiedene synthetische hydrophile Materialien mit einem hohen Molekulargewicht, wie Pfropfpolymere von Gelatine und anderen Materialien mit einem hohem Molekulargewicht; Proteine, wie Albumin, Casein und dgl.; Cellulosederivate, wie Hydroxyethylcellulose, Carboxymethylcellulose, Cellulosesulfat und dgl.; Saccharidderivate, wie Natriumalginat, Stärkederivate und dgl.; Homopolymere oder Copolymere, wie Polyvinylalkohol, teilweise acetalisierter Polyvinylalkohol, Poly-N-vinylpyrrolidon, Polyacrylsäure, Polymethacrylsäure, Polyacrylamid, Polyvinylimidazol und Polyvinylpyrazol eingesetzt werden.According to the invention, it is advantageous to use gelatin as a binder or protective colloid for the photographic emulsion according to the invention, but other colloids can also be used. For example, 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.

Geeignete Gelatine-Propfpolmere, die erfindungsgemäß verwendet werden können, sind solche, die erhalten werden durch Aufpfropfen von Homopolymeren oder Copolymeren von Vinylmonomeren, wie Acrylsäure, Methacrylsäure, Derivaten davon, z.B. den Estern, Amiden, Acrylnitril, Styrol auf Gelatine. Bevorzugt sind insbesondere Pfropfpolymere von Gelatine mit Polymeren der Acrylsäure, Methacrylsäure, des Acrylamids, Methacrylamids und der Hydroxyalkylmethacrylate.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.

Die Emulsionen können in üblicher Weise gehärtet sein, beispielsweise mit Formaldehyd oder halogensubstituierten Aldehyden, die eine Carboxylgruppe enthalten wie Mucobromsäure, Diketonen, Methansulfonsäureester und Dialdehyden.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.

Weiterhin können die photographischen Schichten mit Härtern des Epoxidtyps, des heterocyclischen Ethylenimins oder des Acryloyltyps gehärtet werden. Beispiele derartiger Härter sind z.B. in der deutschen Offenlegungsschrift 2 263 602 oder in der britischen Patentschrift 1 266 655 beschrieben. Weiterhin ist es auch möglich, die Schichten gemäß dem Verfahren der deutschen Offenlegungsschrift 2 218 009 zu härten, um farbphotographische Materialien zu erzielen, die für eine Hochtemperaturverarbeitung geeignet sind.Furthermore, the photographic layers can be hardened with hardeners of the epoxy type, the heterocyclic ethylene imine or the acryloyl type. Examples of such hardeners are e.g. in German laid-open specification 2 263 602 or in British patent 1 266 655. Furthermore, it is also possible to harden the layers in accordance with the process of German Offenlegungsschrift 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing.

Es ist ferner möglich, die photographischen Schichten bzw. die farbphotographischen Mehrschichtenmaterialien mit Härtern der Diazin-, Triazin- oder 1,2-Dihydrochinolin-Reihe zu härten, wie in den britischen Patentschriften 1 193 290, 1 251 091, 1 306 544, 1 266 655, der französischen Patentschrift 71 02 716 oder der deutschen Offenlegungsschrift 2 332 317 beschrieben ist. Beispiele derartiger Härter sind alkyl- oder arylsulfonylgruppenhaltige Diazin-Derivate, Derivate von hydrierten Diazinen oder Triazinen, wie z.B. 1,3,5,-Hexahydrotriazin, fluorsubstituierte Diazin-Derivate, z.B. Fluorpyrimidin, Ester von 2-substituierten, 1,2-Dihydrochinolin- oder 1,2-Dihydroisochinolin-N-carbonsäure. Brauchbar sind weiterhin Vinylsulfonsäurehärter, Carbodiimid- oder Carbamoylhärter, wie z.B. in den deutschen Offenlegungsschriften 2 263 602, 2 225 230 und 1 808 685, der französischen Patentschrift 1 491 807, der deutschen Patentschrift 872 153 und der DD-A-7218 beschrieben. Weitere brauchbare Härzer sind bespielsweise in der britischen Patentschrift 1 268 550 beschrieben.It is also possible to coat the photographic layers or the color photographic multilayer materials with hardeners of the diazine, triazine or 1,2-dihydroquinoline series to harden, as described in British Patents 1 193 290, 1 251 091, 1 306 544, 1 266 655, French Patent 71 02 716 or German Laid-Open Specification 2 332 317. Examples of such hardeners are 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. Also useful are 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.

Die vorliegende Erfindung kann sowohl für die Herstellung schwarz-weißer als auch farbiger photographischer Bilder angewendet werden. Farbige photographische Bilder können z.B. nach dem bekannten Prinzip der chromogenen Entwicklung in Anwesenheit von Farbkupplern, die mit dem Oxidationsprodukt von farbgebenenden p-Phenylendiamin-Entwicklern unter Bildung von Farbstoffen reagieren, hergestellt werden.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.

Die Farbkuppler können beispielsweise dem Farbentwickler nach dem Prinzip des sogenannten Einentwicklungsverfahrens zugesetzt werden. In einer bevorzugten Ausführungsform enthält das photographische Material selbst die üblichen Farbkuppler, die in der Regel den Silberhalogenidschichten einverleibt sind. So kann die rotempfindliche Schicht beispielswiese einen nicht-diffundierenden Farbkuppler zur Erzeugung des blaugrünen Teilfarbenbildes enthalten, in der Regel einen Kuppler vom Phenol- oder α-Naphthaltyp, Die grünempfindliche Schicht kann beispielsweise mindestens einen nicht-diffundierenden Farbkuppler zur Erzeugung des purpurnen Teilfarbenbildes enthalten, wobei üblicherweise Farbkuppler vom Typ des 5-Pyrazolons, des Indazolons oder der Pyrazoloazole Verwendung finden. Die blauempfindliche Schicht kann beispielswiese einen nicht-diffundierenden Farbkuppler zur Erzeugung des gelben Teilfarbenbildes, in der Regel einen Farbkuppler mit einer offenkettigen Ketomethylengruppierung enthalten. Farbkuppler dieser Art sind in großer Zahl bekannt und in einer Vielzahl von Patentschriften beschrieben. Beispielhaft sei hier auf die Veröffentlichung "Farbkuppler" von W. Pelz in "Mitteilungen aus den Forschungslaboratorien der Agfa, Leverkusen/München", Band III (1961) und K. Venkataraman in "The Chemistry of Synthetic Cyes", Vol. 4, 341-387, Academic Press, 1971, hingewiesen.The color couplers can, for example, be added to the color developer according to the principle of the so-called development process. In a preferred embodiment the photographic material itself contains the usual color couplers, which are usually incorporated into the silver halide layers. For example, 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 α-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. For example, 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 "Mitteilungen aus dem Forschungslaboratorien der Agfa, Leverkusen / München", Volume III (1961) and K. Venkataraman in "The Chemistry of Synthetic Cyes", Vol. 4, 341 -387, Academic Press, 1971.

Als weitere nicht-diffundierende Farbkuppler können 2-Äquivalentkuppler verwendet werden; diese enthalten in der Kupplungsstelle einen abspaltbaren Substituenten, so daß sie zur Farbbildung nur zwei Äquivalente Silberhalogenid benötigen im Unterschied zu den üblichen 4-Äquivalentkupplern, Zu den einsetzbaren 2-Äquivalent-Kupplern gehören beispielsweise die bekannten DIR-Kuppler, bei denen der abspaltbare Rest nach Reaktion mit Farbentwickleroxidationsprodukten als diffundierender Entwicklungsinhibitor in Freiheit gesetzt wird. Weiterhin können zur Verbesserung der Eigenschaften des photographischen Materials die sogenannten Weißkuppler eingesetzt werden, die ein farbloses Kupplungsprodukt liefern.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. Furthermore, the so-called white couplers can be used to improve the properties of the photographic material, which provide a colorless coupling product.

Die nicht-diffundierenden Farbkuppler und farbgebenden Verbindungen werden den lichtempfindlichen Silberhalogenidemulsionen oder sonstigen Gießlösungen nach üblichen bekannten Methoden zugesetzt. Wenn es sich um wasser- oder alkalilösliche Verbindungen handelt, können sie den Emulsionen in Form von wäßrigen Lösungen, gegebenenfalls unter Zusatz von mit Wasser mischbaren organischen Lösungsmitteln wie Ethanol, Aceton oder Dimethylformamid, zugesetzt werden. Soweit es sich bei den nicht-diffundierenden Farbkupplern und farbgebende Verbindungen um wasser- bzw. alkaliunlösliche Verbindungen handelt, können sie in bekannter Weise emulgiert werden, z.B. indem eine Lösung dieser Verbindungen in einem niedrigsiedenden organischen Lösungsmittel direkt mit der Silberhalogenidemulsion oder zunächst mit einer wäßrigen Gelatinelösung vermischt wird, worauf das organische Lösungsmittel in üblicher Weise entfernt wird. Ein so erhaltenes Gelatineemulgat der jeweiligen Verbindung wird anschließend mit der Silberhalogenidemulsion vermischt. Gegebenenfalls verwendet man zur Einemulgierung derartiger hydrophober Verbindungen zusätzlich noch sogenannte Kupplerlösungsmittel oder Öl-das sind in der Regel höhersiedende organische Verbindungen, die die in den Silberhalogenidemulsionen zu emulgierenden, nicht-diffundierenden Farbkuppler und Entwicklungsinhibitor abspaltenden Verbindungen in Form öliger Tröpfchen einschließen. Verwiesen sei in diesem Zusammenhang beispielsweise auf die US-Patentschriften 2 322 027, 2 533 514, 3 689 271, 3 764 336 und 3 765 897.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. If the 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. If necessary, so-called 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. In this connection, reference is made, for example, to US Pat. Nos. 2,322,027, 2,533,514, 3,689,271, 3,764,336 and 3,765,897.

Die erfindungsgemäß hergestellten Emulsionen können auf die üblichen Schichtträger aufgetragen werden, z.B. Träger aus Celluloseestern wie Celluloseacetat oder Celluloseacetobutyrat, ferner Polyester, insbesondere Polyethylenterephthalat oder Polycarbonate, insbesondere auf Basis von Bisphenylolpropan. Geeignet sind ferner Papierträger, die gegebenenfalls wasserundurchlässige Polyolefinschichten, z.B. aus Polyethylen oder Polypropylen, enthalten können, ferner Träger aus Glas oder Metall.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. Also suitable are paper supports, which can optionally contain water-impermeable polyolefin layers, for example made of polyethylene or polypropylene, and supports made of glass or metal.

Die in den nachstehenden Beispielen eingesetzte Emulsion B ist eine Silberbromidemulsion, die eine mittlere Korngröße von 0,05 µm aufweist und 1,25 mol Silberhalogenid pro kg sowie 18 g Gelatine pro kg enthält.The emulsion B used in the examples below is a silver bromide emulsion which has an average grain size of 0.05 μm and contains 1.25 mol of silver halide per kg and 18 g of gelatin per kg.

Beispiel 1example 1

Die AgBrI-Emulsion A1 wird mit Hilfe eines Doppelstrahlverfahrens hergestellt und enthält 1 mol Silberhalogenid und 32 g Gelatine pro kg. Die mittlere Korngröße liegt bei 0,4 µm, der Iodidgehalt bei 25 mol-%.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 µm, the iodide content is 25 mol%.

Jeweils 3000 g der Emulsion B werden mit 1500 g der Emulsion Al vermischt und in Gegenwart der in Tabelle 1 angegebenen Substanzen bei 65°C, pH 7,5 und einen EAg-Wert von -60 mV digeriert, bis die Umlösung abgeschlossen ist (etwa nach 20 Minuten). Anschließend wird koaguliert, gewaschen und schließlich unter Zusatz von Wasser- und Gelatine redispergiert. Danach wird eine optimale Reifung mit Gold- und Schwefelverbindungen durchgeführt. Die mittlere Korngröße beträgt 0,7 µm, der Iodidgehalt 7 mol-%.In each case 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 µm, the iodide content 7 mol%.

Beispiel 2Example 2

Die AgBrI-Emulsion A2 wird mit Hilfe eines Doppelstrahlverfahrens hergestellt und enthält 1 mol Silberhalogenid und 32 g Gelatine pro kg. Die mittlere Korngröße liegt bei 0,7 µm, der Iodidgehalt bei 40 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 µm, the iodide content is 40 mol%.

Jeweils 9000 g der Emulsion B werden mit 1500 g der Emulsion A2 vermischt und in Gegenwart der in Tabelle 2 angegebenen Substanzen bei 60°C, pH 7,5 und einem EAg-Wert von -60 mV digeriert, bis die Umlösung abgeschlossen ist (nach etwa 20 Minuten). Die weitere Bearbeitung entspricht Beispiel 1. Die mittlere Korngröße beträgt 1,1 µm, der Iodidgehalt 4,7 mol-%.In each case 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 µm, the iodide content 4.7 mol%.

Beispiel 3Example 3

Die AgBrI-Emulsion A3 wird mit Hilfe eines Doppelstrahlverfahrens hergestellt und enthält 1 mol Silberhalogenid und 32 g Gelatine pro kg. Die mittlere Korngröße beträgt 0,5 µm, der Jodidgehalt 70 mol-%, wobei zunächst mit einem Iodidgehalt von 30 mol-% gefällt und anschießend durch Zugabe von KI bis zum angegebenen Iodidgehalt konvertiert wird.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 µm, the iodide content is 70 mol%, with an iodide content of 30 mol% first being precipitated and then converted to the stated iodide content by adding KI.

Jeweils 5800 g der Emulsion B werden mit 1500 g der Emulsion A3 vermischt und in Gegenwart der in Tabelle 3 angegebenen Substanzen bei 70°C, pH 7,5 und EAg-60 mV digeriert, bis die Umlösung nach etwa 20 Minuten abgeschlossen ist. Die weitere Bearbeitung entspricht Beispiel 1.In each case 5800 g of emulsion B are mixed with 1500 g of emulsion A3 and digested in the presence of the substances listed in Table 3 at 70 ° C., pH 7.5 and E Ag -60 mV until the redissolution is complete after about 20 minutes. The further processing corresponds to example 1.

Die mittlere Korngröße beträgt 1,1 µm, der Iodidgehalt 12 mol-X.

Figure imgb0020
Figure imgb0021
Figure imgb0022
 The average grain size is 1.1 µm, the iodide content 12 mol-X.
Figure imgb0020
Figure imgb0021
Figure imgb0022

Beispiel 4Example 4

Sowohl die nach 1.1 als auch nach 1.3 hergestellten Emulsionen werden neben einer optimalen Goldschwefelreifung auch einer optimalen Reifung unterzogen, bei der neben Gold- und Schwefelverbindungen auch Selenverbindungen anwesend sind. Geeignete Selenverbindungen hierfür sind beispielsweise in EP 428 041, 458 278, 476 345 beschrieben. Emulsion Reifung E S 1.1 S/Au 100 21 1.1a S/Se/Au 104 28 1.3 S/Au 165 18 1.3a S/Se/Au 208 26 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. emulsion maturation E S 1.1 S / Au 100 21 1.1a S / Se / Au 104 28 1.3 S / Au 165 18th 1.3a S / Se / Au 208 26

Beim erfindungsgemäßen Beispiel 1.3 findet eine wesentlich größere Steigung der Empfindlichkeit durch den Reifzusatz Selen statt als beim nicht erfindungsgemäßen Beispiel 1.1.In 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.

Claims (10)

  1. Process for the production of a silver halide emulsion containing up to 20 mol.% of AgI by precipitating a silver halide emulsion A containing up to 100 mol.% of AgI and adding a silver halide emulsion B containing up to 40 mol.% of AgI and having an average grain size of at most 0.25 µm, wherein emulsion B, due either to the grain size thereof or to the iodide content thereof, always has the greater solubility in an aqueous gelatine solution in comparison with emulsion A, in the presence of at least two compounds from the range comprising imidazole, histidine (α-amino-β-imidazolyl-(5)-propionic acid) and other monocyclic, 5- or 6-membered heterocyclic compounds containing at least one ring nitrogen atom and containing no SH groups, which compounds form sparingly soluble silver salts in a weakly acidic to neutral aqueous solution, which on addition of ammonia at pH > 9 pass back into solution, wherein one of the compounds of which there are at least two is imidazole or histidine and at least one other compound is neither imidazole nor histidine.
  2. Process according to claim 1, characterised in that the iodide content of emulsion A is 10 to 90 mol.%.
  3. Process according to claim 1, characterised in that recrystallisation proceeds at EAg -20 to -120 mV, pH 4 to 10 and 40 to 90°C.
  4. Process according to claim 1, characterised in that recrystallisation proceeds at EAg -40 to -100 mV, pH 6 to 8 and 50 to 75°C.
  5. Process according to claim 1, characterised in that the gelatine/silver halide weight ratio, expressed as the quantity of silver nitrate used, is 0.05 to 1 during recrystallisation.
  6. Process according to claim 1, characterised in that the gelatine/silver halide weight ratio, expressed as the quantity of silver nitrate used, is 0.1 to 0.5 during recrystallisation.
  7. Process according to claim 1, characterised in that emulsions A and B, expressed as the quantities of silver nitrate used, are used for recrystallisation in a weight ratio of 1:1 to 1:20.
  8. Process according to claim 1, characterised in that emulsions A and B, expressed as the quantities of silver nitrate used, are used for recrystallisation in a weight ratio of 1:2 to 1:10.
  9. Process according to claim 1, characterised in that the heterocyclic compounds containing at least one ring nitrogen atom, containing no SH groups and differing from imidazole and histidine, which compounds form sparingly soluble silver salts in a weakly acidic to neutral aqueous solution, which on addition of ammonia at pH > 9 pass back into solution, belong to the following classes: imidazoles, oxazoles, thiazoles, triazoles, thiadiazoles, oxadiazoles, pyridines, tetrazoles and pyrimidines.
  10. Process according to claim 1, characterised in that imidazole and/or histidine are used in a quantity of 10-5 to 2.0 mol/mol of silver halide and the compounds differing from imidazole and histidine in a quantity of 10-6 to 0.5 mol/mol of silver halide.
EP93115452A 1992-10-07 1993-09-24 Process for the production of silver halide emulsions Expired - Lifetime EP0595031B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4233714A DE4233714A1 (en) 1992-10-07 1992-10-07 Process for the preparation of silver halide emulsions
DE4233714 1992-10-07

Publications (2)

Publication Number Publication Date
EP0595031A1 EP0595031A1 (en) 1994-05-04
EP0595031B1 true EP0595031B1 (en) 1997-12-17

Family

ID=6469851

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93115452A Expired - Lifetime EP0595031B1 (en) 1992-10-07 1993-09-24 Process for the production of silver halide emulsions

Country Status (4)

Country Link
US (1) US5427904A (en)
EP (1) EP0595031B1 (en)
JP (1) JPH06202257A (en)
DE (2) DE4233714A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19933258A1 (en) 1999-07-15 2001-01-18 Agfa Gevaert Ag Preparation of silver halide emulsions
US6451520B1 (en) * 2000-07-29 2002-09-17 Agfa-Gevaert Color photographic silver halide material

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE414540A (en) * 1935-04-05
US3206313A (en) * 1961-05-15 1965-09-14 Eastman Kodak Co Chemically sensitized emulsions having low surface sensitivity and high internal sensitivity
US3317322A (en) * 1965-08-27 1967-05-02 Eastman Kodak Co Photographic emulsions having high internal sensitivity
DE2758711A1 (en) * 1977-12-29 1979-07-19 Agfa Gevaert Ag LIGHT SENSITIVE PHOTOGRAPHIC MATERIAL
DE2828112A1 (en) * 1978-06-27 1980-01-10 Agfa Gevaert Ag LIGHT SENSITIVE PHOTOGRAPHIC MATERIAL
DE3019733A1 (en) * 1980-05-23 1981-12-03 Agfa-Gevaert Ag, 5090 Leverkusen METHOD FOR PRODUCING SILVER HALOGENID EMULSIONS, PHOTOGRAPHIC MATERIALS AND METHOD FOR PRODUCING PHOTOGRAPHIC IMAGES
JPH03120528A (en) * 1989-10-03 1991-05-22 Konica Corp Silver halide emulsion high in sensitivity and improved in fog and graininess and manufacture of the same
US5273871A (en) * 1990-10-03 1993-12-28 Konica Corporation Silver halide photographic emulsion and silver halide color photographic light-sensitive material incorporating it

Also Published As

Publication number Publication date
US5427904A (en) 1995-06-27
JPH06202257A (en) 1994-07-22
EP0595031A1 (en) 1994-05-04
DE59307852D1 (en) 1998-01-29
DE4233714A1 (en) 1994-04-14

Similar Documents

Publication Publication Date Title
EP0042060B1 (en) Process for preparing silver halide emulsions, photographic materials, and process for the production of photographic images
DE2725743A1 (en) PHOTOGRAPHIC SILVER HALOGENIDE EMULSIONS AND METHOD FOR MANUFACTURING AN IMAGE
DE2921817A1 (en) PHOTOGRAPHIC SILVER HALOGENIDE EMULSION AND METHOD OF MANUFACTURING IT
DE3610273C2 (en) Photographic silver halide recording material
DE68906091T2 (en) PHOTOGRAPHIC SILVER HALOGENID MATERIAL.
DE2921164A1 (en) METHOD FOR FORMING METAL SALTS, PHOTOGRAPHIC MATERIALS AND THE USE THEREOF FOR PRODUCING PHOTOGRAPHIC IMAGES
DE2708466A1 (en) EMULSION MIXTURES FOR COLOR REVERSE (SUPERVISORY) MATERIAL
DE69128323T2 (en) Silver halide photographic material and process for processing the same
EP0006543B1 (en) Light-sensitive photographic material, process for making it and its use for realising photographic images
DE3311432A1 (en) COLOR PHOTOGRAPHIC, LIGHT-SENSITIVE SILVER HALOGENIDE MATERIAL
DE2439919A1 (en) PROCESS FOR DEVELOPING AN EXPOSED PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL
EP0040771B1 (en) Photographic material and its use in the formation of images
EP0046871B1 (en) Photographic material, process for its preparation, method for the production of photographic pictures as well as triazols
DE3853596T2 (en) Silver halide photographic materials.
EP0595031B1 (en) Process for the production of silver halide emulsions
DE3614751A1 (en) SILVER HALOGENID EMULSION
DE4039022A1 (en) COLOR PHOTOGRAPHIC RECORDING MATERIAL
DE68917945T2 (en) Process for photographic processing.
DE2419798A1 (en) SENSITIZED PHOTOGRAPHIC SILVER HALOGENIDE EMULSION AND THEIR USE
EP0002476B1 (en) Photographic material and photographic treating baths containing a stabiliser and a process for the fabrication of photographic images in the presence of a stabilising agent
EP0001415B1 (en) Photographic inversion process with chemical fogging, chemical fogging baths therefor, and their use in the production of photographic images
EP0023661B1 (en) Photographic silver halide emulsion with a stabilizer, process for its production, photographic recording materials and method of making photographic images
DE4009181A1 (en) COLOR PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL AND ITS DEVELOPMENT
DE2939016A1 (en) LIGHT SENSITIVE COLOR PHOTOGRAPHIC MATERIAL
DE3331805A1 (en) PHOTOGRAPHIC, LIGHT-SENSITIVE SILVER HALOGENIDE MATERIAL

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19940930

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19970220

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT NL

REF Corresponds to:

Ref document number: 59307852

Country of ref document: DE

Date of ref document: 19980129

ITF It: translation for a ep patent filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19980216

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19980817

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19980930

Year of fee payment: 6

Ref country code: NL

Payment date: 19980930

Year of fee payment: 6

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: 746

Effective date: 19990211

REG Reference to a national code

Ref country code: FR

Ref legal event code: D6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990930

BERE Be: lapsed

Owner name: AGFA-GEVAERT A.G.

Effective date: 19990930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000401

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20000401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000701

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20010829

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20010831

Year of fee payment: 9

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020924

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20020924

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030603

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050924