EP0838720B1 - Verfahren zur Sensibilisierung einer photographischen Silberhalogenidemulsion - Google Patents

Verfahren zur Sensibilisierung einer photographischen Silberhalogenidemulsion Download PDF

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Publication number
EP0838720B1
EP0838720B1 EP96116979A EP96116979A EP0838720B1 EP 0838720 B1 EP0838720 B1 EP 0838720B1 EP 96116979 A EP96116979 A EP 96116979A EP 96116979 A EP96116979 A EP 96116979A EP 0838720 B1 EP0838720 B1 EP 0838720B1
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EP
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Prior art keywords
group
silver halide
metals
process according
added
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EP96116979A
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English (en)
French (fr)
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EP0838720A1 (de
Inventor
Alain Sismondi
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to DE69627493T priority Critical patent/DE69627493T2/de
Priority to EP96116979A priority patent/EP0838720B1/de
Priority to JP9289615A priority patent/JPH10133319A/ja
Publication of EP0838720A1 publication Critical patent/EP0838720A1/de
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Publication of EP0838720B1 publication Critical patent/EP0838720B1/de
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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
    • G03C1/08—Sensitivity-increasing substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03588—Polydisperse emulsion
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C2001/0818—Calcium ion content or calcium compound
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C2001/0827—Cobalt
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/091—Gold
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/092—Mercury
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/096—Sulphur sensitiser
    • 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
    • G03C2200/00—Details
    • G03C2200/43—Process
    • 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
    • G03C2200/00—Details
    • G03C2200/58—Sensitometric characteristics
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing

Definitions

  • the present invention relates to a sensitization process of a silver halide photographic emulsion. More particularly, the present invention relates to a chemical sensitization process employing a metal selected from gold, platinum, and palladium, a metal chosen from Groups 2, 8, 9, 10, and 12 of the periodic table and a sulfur chemical sensitizer. The present invention also relates to a radiographic element comprising the silver halide photographic emulsion obtained with the above mentioned chemical sensitization process.
  • Silver halide emulsions are usually prepared by precipitating silver halide (silver bromide, silver iodide, silver chloride or mixture thereof) in the presence of a hydrophilic colloid (normally gelatin).
  • the silver halide emulsions have to be subjected to a sensitization process for increasing their sensitivity to light.
  • the sensitization process mainly involves spectral sensitization and chemical sensitization.
  • Spectral sensitization comprises the addition of spectral sensitizing dyes which can be adsorbed on the silver halide grain surface in order to make the emulsion sensitive to visible or infrared radiation.
  • Chemical sensitization comprises the addition of various chemical substances to obtain a prescribed value of sensitivity and contrast.
  • Typical methods for chemical sensitizing a silver halide photographic emulsion include sulfur sensitization, noble metal sensitization, and reduction sensitization. It is also common in the art to have combination methods, such as sulfur-noble metal sensitization, reduction-noble metal sensitization, and the like.
  • EP 467,106 discloses a silver halide photographic element chemically sensitized by gold and sulfur compounds and further by a mercury compound.
  • JP 4/009,034 discloses silver halide photographic element chemically sensitized by gold in the presence of an iridium or a platinum complex salt.
  • JP 4/009,837 discloses silver halide photographic element chemically sensitized by reduction sensitization and further by a palladium compound.
  • EP 476,345 discloses silver halide photographic element chemically sensitized in the presence of a noble metal, a sulfur sensitizer, a selenium compound and a silver halide solvent.
  • JP 4/051,232 discloses silver halide photographic element chemically sensitized in the presence of a gold compound, an iridium compound, and a Group VIII metal compound.
  • JP 5/045,768 discloses silver halide photographic element chemically sensitized in the presence of a tellurium organic compound and a gold compound. JP 5/053,234 further discloses the possibility of an additional reduction sensitization.
  • JP 5/045,769 discloses silver halide photographic element chemically sensitized in the presence of tellurium, sulfur and noble metal organic compounds.
  • JP 4/335640, 5/027,360, 5/027,388, EP 563,708 and EP 638,840 disclose silver halide photographic element chemically sensitized in the presence of selenium, gold and sulfur sensitizer.
  • EP 568,092 discloses silver halide photographic element chemically sensitized in the presence of a heavy metal and a thiourea compound.
  • JP 6/51,418 discloses silver halide photographic element chemically sensitized in the presence of a mercuric chloride organic derivative, sodium thiocyanate, sodium thiosulfate, and potassium chloroaurate.
  • the present invention provides a process for chemically sensitizing a silver halide photographic emulsion comprising the following steps:
  • a silver halide solvent and/or a stabilizer can be added at any time before the addition of the sulfur sensitizer.
  • Another aspect of the present invention relates to a radiographic element comprising the silver halide photographic emulsion obtained with the above-mentioned chemical sensitization process.
  • the manufacturing process of silver halide elements usually comprises an emulsion-making step, a chemical and optical sensitization step, and a coating step.
  • the silver halide emulsion-making step generally comprises a nucleation step, in which silver halide grain seeds are formed, followed by one or more growing steps, in which the grain seeds achieve their final dimension, and a washing step, in which all soluble salts are removed from the final emulsion.
  • a ripening step is usually performed between the nucleation and growing step and/or between the growing and the washing steps.
  • Silver halide emulsions can be prepared using a single-jet method, a double-jet method, or a combination of these methods and can be ripened using, for instance, an ammonia method, a neutralization method, or an acid method. Parameters which may be adjusted to control grain growth include pH, pAg, temperature, shape and size of reaction vessel, and the reaction method (e.g., accelerated or constant flow rate precipitation, interrupted precipitation, ultrafiltration during precipitation, reverse mixing processes and combinations thereof).
  • a silver halide solvent such as ammonia, thioethers, thioureas, etc., may be used, if desired, for controlling grain size, grain structure, particle size distribution of the grains, and the grain-growth rate.
  • halogen compositions of the silver halide grains can be used.
  • Typical silver halides include silver chloride, silver bromide, silver iodide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide and the like.
  • silver bromide and silver bromoiodide are preferred silver halide compositions for tabular silver halide grains with silver bromoiodide compositions containing from 0 to 10 mol% silver iodide, preferably, from 0.2 to 5 mol% silver iodide, and more preferably, from 0.5 to 1.5mol% silver iodide.
  • the halogen composition of individual grains may be homogeneous or heterogeneous.
  • the grains of these silver halide emulsions may be coarse or fine, and the grain size distribution of them may be narrow or extensive.
  • the silver halide grains may be regular grains having a regular crystal structure such as cube, octahedron, and tetradecahedron, or the spherical or irregular crystal structure, or those having crystal defects such as twin planes, or those having a tabular form, or combination thereof.
  • the grain structure of the silver halides may be uniform from the interior to exterior thereof, or be multilayer.
  • the grains may comprise a core'and a shell, which may have different halide compositions and/or may have undergone different modifications such as the addition of doping agents.
  • the silver halide grains may also comprise different phases in-between.
  • the silver halides may be of such a type as allows a latent image to be formed mainly on the surface thereof or of such type as allows it to be formed inside the grains thereof.
  • tabular silver halide emulsions are employed in the process of the present invention.
  • Tabular silver halide emulsions are characterized by the average diameter:thickness ratio of silver halide grains (often referred to in the art as aspect ratio).
  • Tabular silver halide having an aspect ratio of at least 2:1, preferably, 2:1 to 20:1, more preferably, 2:1 to 14:1, and most preferably, 2:1 to 8:1 are used in the process of the present invention.
  • Average diameters of the tabular silver halide grains suitable for use in the process of the present invention range from about 0.3 to about 5 ⁇ m, preferably, from about 0.5 to about 3 ⁇ m, more preferably, from about 0.8 to about 1.5 ⁇ m.
  • the tabular silver halide grains suitable for use in the process of the present invention have a thickness of less than 0.4 ⁇ m, preferably, less than 0.3 ⁇ m, and more preferably, within 0.1 to 0.3 ⁇ m.
  • the projected area of the tabular silver halide grains accounts for at least 50%, preferably, at least 80%, and more preferably, at least 90% of the projected area of all the silver halide grains of the emulsion.
  • the tabular silver halide grain dimensions and characteristics described above can be readily ascertained by procedures well known to those skilled in the art.
  • the term "diameter” is defined as the diameter of a circle having an area equal to the projected area of the grain.
  • the term “thickness” means the distance between two substantially parallel main planes constituting the tabular silver halide grains. From the measure of diameter and thickness of each grain the diameter:thickness ratio of each grain can be calculated, and the diameter:thickness ratios of all tabular grains can be averaged to obtain their average diameter:thickness ratio.
  • the average diameter:thickness ratio is the average of individual tabular grain diameter:thickness ratios. In practice, it is simpler to obtain an average diameter and an average thickness of the tabular grains and to calculate the average diameter:thickness ratio as the ratio of these two averages. Whatever the method used, the average diameter:thickness ratios obtained do not greatly differ.
  • Silver halide emulsions containing tabular silver halide grains can be prepared by various processes known to those of ordinary skill in the art for the preparation of photographic elements.
  • Suitable washing processes are those wherein the dispersing medium and soluble salts dissolved therein can be removed from the silver halide emulsion on a continuous basis, such as, for example, a combination of dialysis or electrodialysis for the removal of soluble salts or a combination of osmosis or reverse osmosis for the removal of the dispersing medium.
  • ultrafiltration is a particularly advantageous washing processes for the practice of this process.
  • an ultrafiltration unit comprising membranes of inert, non-ionic polymers is used as a washing process. Since silver halide grains are large in comparison with the dispersing medium and the soluble salts or ions, silver halide grains are retained by the membranes while the dispersing medium and the soluble salts dissolved therein are removed.
  • the chemical sensitization of the above described silver halide emulsion is performed by first adding a metal compound wherein metal is selected from gold, platinum, and palladium, and at least one metal selected from the group consisting of Group 2 metals, Group 8 metals, Group 9 metals, Group 10 metals and Group 12 metals, and thereafter adding a sulfur sensitizer.
  • Metal compound wherein metal is selected from gold, platinum, and palladium useful in the practice of the present invention includes gold derivatives (such as, for example, potassium chloroaurate, gold chloride, and the like), platinum derivatives (such as platinum chloride), and palladium derivatives such as sodium hexachloropalladate).
  • Gold derivatives are preferably used in the process of the present invention.
  • Specific examples of gold derivatives include chloroauric acid, potassium chloroaurate, auric trichloride, sodium aurithiosulfate, potassium aurithiocyanate, potassium iodoaurate, tetracyanoauric acid, 2-aurosulfobenzothiazole methochloride and ammonium aurothiocyanate.
  • the amount of metal selected from gold, platinum, and palladium can range from 1x10 -9 to 1x10 -3 moles per mole of Ag, preferably, from 1x10 -7 to 1x10 -4 moles per mole of Ag.
  • Group 2 metals useful in the process of the present invention are Mg, Ca, and Sr; representative examples of Group 8, 9 and 10 metals useful in the process of the present invention are Fe, Co, Ni, Rh, Ir, Pd, and Pt; and representative examples of Group 12 metals useful in the process of the present invention are Zn, Cd, and Hg.
  • the metal is selected from the group consisting of Mg, Ca, Rh, Ir, Pd, Cu, Zn, Cd, and Hg.
  • Preferred metals include metals selected from the group consisting of Mg, Pd, Zn, and Hg.
  • the amount of the additional metal(s) can range from 1x10 -9 to 1x10 -3 moles per mole of Ag, preferably, from 1x10 -7 to 1x10 -4 moles per mole of Ag.
  • All metals can be mixed together and added contemporaneously to the silver halide emulsion, or they can be added following a step-by-step procedure. They can be added in solid form or in solution, preferably in a water solution.
  • a sulfur chemical sensitizer is added in the process of the present invention in an amount of from 1x10 -6 to 1x10 -1 grams per mole of silver, preferably, from 1x10 -4 to 1x10 -2 grams per mole of silver.
  • Suitable sulfur sensitizers include thiosulfates, such as ammonium thiosulfate, thioureas, such as allylthiocarbamidourea, isothiocyanates, such as allyl isothiocyanate, sulfur-containing aminoacids, such as cystine, thiosulfonates, such as p-toluene thiosulfonates and rhodanines.
  • Thiosulfates such as, for example, sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate are the most preferred sulfur sensitizers employed in the process of the present invention.
  • a silver halide solvent is added at any time before the addition of the sulfur sensitizer, preferably before or together with the metal additions.
  • the term "silver halide solvent” as employed herein means a solubilizing agent for silver halide. It is particularly preferred that a silver halide solvent is present before the addition of the metal selected from gold, platinum, and palladium and the at least one additional metal, but the silver halide solvent can be added together with the metal additions. Any kind of silver halide solvent can be used in the practice of the present invention, but silver halide solvents also acting as complexing agents for the metals are preferred.
  • silver halide solvents include ammonia, thiocyanate derivatives and salts thereof, thioether derivatives, and thiourea derivatives.
  • Thiocyanate derivatives and salts thereof are more preferably used, and most preferably, sodium thiocyanate and potassium thiocyanate.
  • the amount of silver halide solvent can range from 0.01 to 10 g per mole of silver halide, preferably, from 0.1 to 5 g per mole of silver halide.
  • a stabilizer is added at any time before the addition of the sulfur sensitizer, preferably together with or after the metal additions. It is particularly preferred that a stabilizer is added between the metal additions and the sulfur sensitizer.
  • a chemical stabilizer after the completion of the chemical sensitization to prevent fog or to stabilize photographic properties of the resulting photographic element during manufacture, storage or photographic processes. Even if the action of the stabilizer in the process of the present invention is not yet fully understood, it is believed that it acts as a digest stabilizer and a site director for the sulfur sensitizer.
  • the stabilizer is added before the addition of sulfur chemical sensitizer in an amount of from 1 to 500 milligrams per mole of silver, preferably, from 10 to 300 milligrams per mole of silver.
  • useful stabilizers include thiazole derivatives; benzothiazole derivatives; mercapto-substituted heterocyclic compounds, such as, for example, mercaptotetrazoles, mercaptotriazoles, mercaptodiazoles, mercaptopyrimidines, mercaptoazoles; azaindenes, such as triazaindenes and tetrazaindenes; triazoles; tetrazoles; and sulfonic and sulfinic benzene derivatives.
  • Azaindenes are preferably used in the process of the present invention, more preferably, tetraazaindenes.
  • the silver halide grain emulsion may be optically sensitized to a desired region of the visible spectrum.
  • the method for spectral sensitization is not particularly limited.
  • optical sensitization may be possible by using an optical sensitizer, including a cyanine dye, a merocyanine dye, complex cyanine and merocyanine dyes, oxonol dyes, hemioxonol dyes, styryl dyes and streptocyanine dyes, either alone or in combination.
  • Useful optical sensitizers include cyanines derived from quinoline, pyridine, isoquinoline, benzindole, oxazole, thiazole, selenazole, imidazole.
  • optical sensitizers are the dyes of the benzoxazole-, benzimidazole- and benzothiazole-carbocyanine type.
  • the addition of the spectral sensitizer is performed after the completion of chemical sensitization.
  • spectral sensitization can be performed concurrently with chemical sensitization, can entirely precede chemical sensitization, and can even commence prior to the completion of silver halide precipitation.
  • the spectral sensitization is performed before the chemical sensitization, it is believed that the preferential absorption of spectral sensitizing dyes on the crystallographic faces of the tabular grains allows chemical sensitization to occur selectively at unlike crystallographic surfaces of the tabular grains.
  • the spectral sensitizers produce J aggregates, if adsorbed on the surface of the silver halide grains, and a sharp absorption band (J-band) with a bathochromic shift with respect to the absorption maximum of the free dye in aqueous solution.
  • J-band sharp absorption band
  • J-band sharp absorption band
  • spectral sensitizing dye absorbed on the surface of the light-sensitive silver halide grains will vary with the quantity of the specific dye chosen as well as the size and chemical composition of the grains.
  • the maximum intensity of J-band has been obtained with silver halide grains having the above described sizes and the chemical compositions absorbed with J-band spectral sensitizing dyes in a concentration of from 25 to 100 percent or more of monolayer coverage of the total available surface area of the silver halide grains.
  • Optimum dye concentration levels can be chosen in the range of 0.5 to 20 millimoles per mole of silver halide, preferably, in the range of 2 to 10 millimoles.
  • Spectral sensitizing dyes producing J aggregates are well known in the art, as illustrated by F. M. Hamer, Cyanine Dyes and Related Compounds , John Wiley and Sons, 1964, Chapter XVII and by T. H. James, The Theory of the Photographic Process , 4th Edition, MacMillan, 1977, Chapter 8.
  • J-band exhibiting dyes are cyanine dyes.
  • Such dyes comprise two basic heterocyclic nuclei joined by a linkage of methine groups.
  • the heterocyclic nuclei preferably include fused benzene rings to enhance J aggregation.
  • the heterocyclic nuclei are preferably quinolinium, benzoxazolium, benzothiazolium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium and naphthoselenazolium quaternary salts.
  • the cyanine dyes which are joined by a methine linkage, include two basic heterocyclic nuclei, such as pyrrolidine, oxazoline, thiazoline, pyrrole, oxazole, thiazole, selenazole, tetrazole and pyridine and nuclei obtained by fusing an alicyclic hydrocarbon ring or an aromatic hydrocarbon ring to each of the above nuclei, such as indolenine, benzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole and quinoline.
  • nuclei can have substituents groups.
  • the merocyanine dyes which arejoined by a methine linkage, include a basic heterocyclic nucleus of the type described above and an acid nucleus, such as a 5-or 6-membered heterocyclic nucleus derived from barbituric add, 2-thiobarbituric acid, rhodanine, hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one, indan-1,3-dione, cyclohexane-1-3-dione, and isoquinolin-4-one.
  • an acid nucleus such as a 5-or 6-membered heterocyclic nucleus derived from barbituric add, 2-thiobarbituric acid, rhodanine, hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5
  • More preferred dyes within the above class are those having an internal salt group and/or derived from benzoxazole and benzimidazole nuclei as indicated before.
  • Typical methine spectral sensitizing dyes for use in the present invention include those listed below.
  • the methine spectral sensitizing dyes are generally known in the art Particular reference can be made to U.S. Pat. Nos. 2,503,776; 2,912,329; 3,148,187; 3,397,060; 3,573,916; and 3,822,136 and FR Pat. No. 1,118,778. Also their use in photographic emulsions is very well known wherein they are used in optimum concentrations corresponding to desired values of sensitivity to fog ratios. Optimum or near optimum concentrations of spectral sensitizing dyes generally go from 10 to 500 mg per mol of silver, preferably, from 50 to 200, and more preferably, from 50 to 100.
  • Spectral sensitizing dyes can be used in combinations which result in supersensitization, i.e., spectral sensitization which is greater in a spectral region than that from any concentration of one dye alone or which would result from an additive effect of the dyes.
  • Supersensitization can be obtained with selected combinations of spectral sensitizing dyes and other addenda, such as stabilizers and antifoggants, development accelerators and inhibitors, optical brighteners, surfactants and antistatic agents, as described by Gilman, Photographic Science and Engineering , 18, pp. 418-430, 1974 and in U.S. Pat. Nos. 2,933,390; 3,635,721; 3,743,510; 3,615,613; 3,615,641; 3,617,295; and 3,635,721.
  • additives may be added to the emulsion depending upon their purpose.
  • stabilizers or antifoggants such as azaindenes, triazoles, tetrazoles, imidazolium salts, polyhydroxy compounds and others; developing promoters such as benzyl alcohol, polyoxyethylene type compounds, etc.; image stabilizers such as compounds of the chromane, cumaran, bisphenol type, etc.; and lubricants such as wax, higher fatty acids glycerides, higher alcohol esters of higher fatty acids, etc.
  • coating aids, modifiers of the permeability in the processing liquids, defoaming agents, antistatic agents and matting agents may be used.
  • Other useful additives are disclosed in Research Disclosure, Item 17643, December 1978 in Research Disclosure , Item 18431, August 1979, in Research Disclosure, Item 308119, Section IV, December 1989, and in Research Disclosure Item 36544, September 1994.
  • gelatin As a binder for silver halide emulsions and other hydrophilic colloid layers, gelatin is preferred, but other hydrophilic colloids can be used, alone or in combination, such as, dextran, cellulose derivatives (e.g., hydroxyethylcellulose, carboxymethyl cellulose), collagen derivatives, colloidal albumin or casein, polysaccharides, synthetic hydrophilic polymers (e.g., polyvinylpyrrolidone, polyacrylamide, polyvinylalcohol, polyvinylpyrazole) and the like.
  • Gelatin derivatives such as, highly deionized gelatin, acetylated gelatin and phthalated gelatin can also be used.
  • hydrophilic colloids in combination with synthetic polymeric binders and peptizers such as acrylamide and methacrylamide polymers, polymers of alkyl and sulfoalkyl acrylates and methacrylates, polyvinyl alcohol and its derivatives, polyvinyl lactams, polyamides, polyamines, polyvinyl acetates, and the like.
  • Highly deionized gelatin is characterized by a higher deionization with respect to the commonly used photographic gelatins.
  • highly deionized gelatin is almost completely deionized which is defined as meaning that it presents less than 50 ppm (parts per million) of Ca ++ and is practically free (less than 5 parts per million) of other ions such as chlorides, phosphates, sulfates and nitrates, compared with commonly used photographic gelatins having up to 5,000 ppm of Ca ++ and the significant presence of other ions.
  • Dye underlayers are particularly useful to reduce the cross-over of the double coated silver halide radiographic element.
  • Reference to well-known dye underlayer can be found in U.S. Pat. Nos. 4,900,652; 4,855,221; 4,857,446; and 4,803,150.
  • a dye underlayer is coated on at least one side of the support, more preferably, on both sides of the support, before the coating of at least two silver halide emulsion.
  • Examples of materials suitable for the preparation of the support include glass, paper, polyethylene-coated paper, metals, polymeric film such as cellulose nitrate, cellulose acetate, polystyrene, polyethylene terephthalate, polyethylene, polypropylene and the like.
  • Another aspect of the present invention relates to a silver halide radiographic element comprising a support and at least one silver halide emulsion layer coated on both sides thereof, wherein said silver halide emulsion was chemically sensitized by the process as described above, wherein the speed/Dmin ratio of the radiographic element is at least 26.00, preferably, at least 27.00, and more preferably, at least 28.00 when the radiographic element is exposed to X-rays under DIN 6867 Section 1, 1995 exposure conditions through a pair of intensifying screens absorbing more than 25% of the total X-ray radiation and processed at 35°C in a developing and fixing solution having the composition of the following tables for 25 and 27 seconds, respectively.
  • Preferred light-sensitive silver halide photographic elements are radiographic light-sensitive elements employed in X-ray imaging comprising a silver halide emulsion layer(s) coated on both surfaces of a support, preferably, a polyethylene terephthalate support.
  • the silver halide emulsions are coated on the support at a silver coverage in the range of 1.5 to 3 g/m 2 per side.
  • the radiographic light-sensitive elements are associated with intensifying screens so as to be exposed to -radiation emitted by the screens.
  • the screens are made of relatively thick phosphor layers which transform the X-rays into more imaging-effective radiation such as light (e.g., visible light).
  • the screens absorb a larger portion of X-rays than the light-sensitive elements do and are used to reduce the X-ray dose necessary to obtain a useful image.
  • Intensifying screens absorbing more than 25% of the total X-radiation are preferably used with the radiographic element of the present invention.
  • the phosphors can emit radiation in the ultraviolet, blue, green or red region of the visible spectrum and the silver halide emulsions are sensitized to the wavelength region of the radiation emitted by the screens. Sensitization is performed by using spectral sensitizing dyes absorbed on the surface of the silver halide grains as described above.
  • More preferred light-sensitive silver halide photographic elements according to this invention are radiographic light-sensitive elements which employ intermediate diameter:thickness ratio tabular grain silver halide emulsions, as described above.
  • the silver halide photographic elements of the present invention are preferably fore-hardened.
  • organic or inorganic hardeners include chrome salts (e.g., chrome alum, chromium acetate), aldehydes (e.g., formaldehyde and glutaraldehyde), isocyanate compounds (hexamethylene diisocyanate), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine), epoxy compounds (e.g., tetramethylene glycol diglycidylether), N-methylol derivatives (e.g., dimethylolurea, methyloldimethyl hydantoin), aziridines, mucohalogeno acids (e.g., mucochloric acid), active vinyl derivatives (e.g., vinylsulfonyl and hydroxy-substituted vinylsulfonyl derivatives) and the like.
  • chrome salts e.g., chrome
  • subbing layers such as subbing layers, surfactants, filter dyes, intermediate layers, protective layers, anti-halation layers, barrier layers, development inhibiting compounds, speed-increasing agents, stabilizers, plasticizers, chemical sensitizers, UV absorbers and the like can be present in the radiographic element.
  • the silver halide photographic element can be exposed and processed by any conventional processing technique.
  • Any known developing agent can be added into the developer, such as, for example, dihydroxybenzenes (e.g., hydroquinone), pyrazolidones (1-phenyl-3-pyrazolidone or 4,4-dimethyl-1-phenyl-3-pyrazolidone), and aminophenols (e.g., N-methyl-p-aminophenol), alone or in combinations thereof.
  • the silver halide photographic elements are developed in a developer comprising dihydroxybenzenes as the main developing agent, and pyrazolidones and p-aminophenols as auxiliary developing agents.
  • additives can be present in the developer, such as, for example, antifoggants (e.g., benzotriazoles, indazoles, tetrazoles), silver halide solvents (e.g., thiosulfates, thiocyanates), sequestering agents (e.g., aminopolycarboxylic acids, aminopolyphosphonic acids), sulfite antioxidants, buffers, restrainers, hardeners, contrast promoting agents, surfactants, and the like.
  • Inorganic alkaline agents such as KOH, NaOH, and LiOH are added to the developer composition to obtain the desired pH which is usually higher than 10.
  • the silver halide photographic element of the present invention can be processed with a fixer of a typical composition for the application required.
  • the fixing agents include thiosulfates, thiocyanates, sulfites, ammonium salts, and the like.
  • the fixer composition can comprise other well known additives, such as, for example, acid compounds (e.g., metabisulfates), buffers (e.g., carbonic acid, acetic acid), hardeners (e.g., aluminum salts), tone improving agents, and the like.
  • the exposed radiographic elements can be processed by any of the conventional processing techniques. Such processing techniques are illustrated for example in Research Disclosure, Item 17643, cited above, and Research Disclosure 36544 September 1994. Roller transport processing is particularly preferred, as illustrated in U.S. Pat. Nos. 3,025,779; 3,515,556; 3,545,971; and 3,647,459 and in UK Patent 1,269,268. Hardening development can be undertaken, as illustrated in U.S. Patent 3,232,761.
  • a silver bromoiodide tabular emulsion comprising less than 0.9mol% of iodide was prepared by double jet method using controlled pAg.
  • the resulting emulsion had a mean grain size of 1.33 ⁇ m and an average grain thickness of 0.21 ⁇ m, thus obtaining an average aspect ratio of about 6.3.
  • the emulsion had a coefficient of variation (COV) of about 37%.
  • the emulsion silver concentration was first adjusted to 17 %, the pH is corrected to 6.5 and the pAg to 8.4
  • the emulsion was chemically and spectrally sensitized with a conventional sulfur-gold sensitization process while keeping the temperature at 60°C.
  • the emulsion was added with 0.22 mg of mercuric chloride, 75.3 mg of LeucophorTM BCF (a polymer of bis(5-triazin-2-yl-amino-4-hydroxy-6-anilino)stilben-2.2'-sulfonic acid disodium salt), 662 mg of triethyl ammonium salt of 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)-oxacarbocyanine as spectral sensitization dye, 265 mg of a supersensitizing copolymer of acrylamide and 4-dicyanbutadiene-diallyl-amine, 20 mg of benzothiazolium ethyl iodide, a blend of 12.4 mg of sodium paratoluenethios
  • the digest was performed during about 120 to 130 minutes at 60°C and stabilized successively with 200 mg of potassium iodide and 1366 mg of 5-methyl-7-hydroxy-2-3-4-triazoindolizine (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene) first to be chilled.
  • the sensitized silver halide emulsion was melted at 45°C and subjected to final coating digest.
  • the resulting silver halide emulsion was immediately coated on the two faces of blue 7 mil polyester support at a coating weight of 2.25 g Ag/m 2 per face.
  • An antistatic top-coat as described in EP 633,496 was provided on both emulsion layers, to obtain the radiographic film sample 1.
  • the fresh film sample 1 was kept 3 days at 38°C before being subjected to X-ray exposure between two Imation TrimaxTM T8 type screens (front and back) having an X-ray absorbing power of 28%.
  • the conditions of X-ray exposure followed the DIN 6867 Section 1 1995.
  • the film was then processed with Imation standard chemistry (XAD-3 developer and XAF-3 fixer) in a Imation XP-515 automatic developer at 34°C. Development and fixing times were 25 and 27 seconds, respectively. Composition of XAD-3 developer and XAF-3 fixer can be found in Table A and B.
  • 5-methyl-7-hydroxy-2-3-4-triazoindolizine (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene) were added after a ripening time of ten minutes; 598 mg of triethyl ammonium salt of 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)-oxacarbocyanine were added as green spectral sensitization dye after further ten minutes; finally 2.74 mg of thiosulfate pentahydrate was added in the vessel as sulfuring agent.
  • the digest was performed at 45° C and stabilized successively with 200 mg of potassium iodide and 1361 mg of 5-methyl-7-hydroxy-2-3-4-triazoindolizine (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene) first to be chilled.
  • the sensitized silver halide emulsion was melted at 45°C and subjected to final coating digest.
  • a radiographic film 2 was prepared, exposed and developed according to the same procedure of Sample 1.
  • a radiographic film 3 was prepared, exposed and developed according to the same procedure of Sample 1.
  • a radiographic film 4 was prepared, exposed and developed according to the same procedure of Sample 1.
  • a radiographic film 5 was prepared, exposed and developed according to the same procedure of Sample 1.
  • a radiographic film 6 was prepared, exposed and developed according to the same procedure of Sample 1.
  • a silver bromoiodide tabular emulsion comprising 0.9mol% of iodide was prepared by double jet method using controlled pAg.
  • the resulting emulsion had a mean grain size of 1.38 ⁇ m and an average grain thickness of 0.21 ⁇ m, thus obtaining an average aspect ratio of about 6.6.
  • the emulsion had a coefficient of variation (COV) of about 37%.
  • the emulsion silver concentration is first adjusted to 17 %, the pH is corrected to 6.5 and the pAg to 8.4
  • the emulsion was chemically and spectrally sensitized with a conventional sulfur-gold sensitization process while keeping the temperature at 60°C.
  • the emulsion was added with 0.22 mg of mercuric chloride, 75.3 mg of Leucophor BCF (a polymer of bis(5-triazin-2-yl-amino-4-hydroxy-6-anilino)stilben-2.2'-sulfonic acid disodium salt), 726 mg of triethyl ammonium salt of 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)-oxacarbocyanine as spectral sensitization dye, 265 mg of supersensitizing copolymer of acrylamide and 4-dicyanbutadiene-diallyl-amine, 20 mg of benzothiazolium ethyl iodide, a blend of 12.4 mg of sodium paratoluenethiosulfon
  • the digest was performed about 120 to 130 minutes at 60°C and stabilized successively with 220 mg of potassium iodide and 1366 mg of 5-methyl-7-hydroxy-2-3-4-triazoindolizine (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene) first to be chilled.
  • the sensitized silver halide emulsion is melted at 45°C and subjected to final coating digest first to be coated.
  • a radiographic film sample 7 was prepared, exposed and developed according to the same procedure of Sample 1.
  • the total digest time was from about 60 to 90 minutes at 50° C and stabilized successively with 200 mg of potassium iodide and 1307 mg of 5-methyl-7-hydroxy-2-3-4-triazoindolizine (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene) first to be chilled.
  • the sensitized silver halide emulsion is melted at 45°C and subjected to final coating digest first to be coated.
  • a radiographic film sample 8 was prepared, exposed and developed according to the same procedure of Sample 1.
  • Sample 8 The procedure of Sample 8 is repeated, except for the following three changes: (1) the first complex solution comprised a mixture of 2.38 mg of gold chloride, 0.11 mg of mercuric chloride, 26 mg of zinc sulfate heptahydrate, and 189 mg of potassium thiocyanate; (2) 747 mg of triethyl ammonium salt of 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)-oxacarbocyanine was used as green spectral sensitization dye; and (3) sodium para-toluene sulfinate tetrahydrate was replaced by 9 mg of benzothiazolium ethyl iodide.
  • the digest time was between about 60 to 90 minutes at 50° C and stabilized successively with 220 mg of potassium iodide and 1307 mg of 5-methyl-7-hydroxy-2-3-4-triazoindolizine (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene) first to be chilled.
  • the sensitized silver halide emulsion is melted at 45°C and subjected to final coating digest first to be coated.
  • a radiographic film sample 9 was prepared, exposed and developed according to the same procedure of Sample 1. The sensitometric results are reported in Table 2.
  • Film Sample Dmin Dmax Speed Average ⁇ Speed/Dmin Ratio 7 (Control) 0.215 3.49 5.43 2.73 25.26 8 (Invention) 0.205 3.66 5.56 2.59 27.12 9 (Invention) 0.200 3.55 5.69 2.65 28.45

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Claims (18)

  1. Verfahren zur chemischen Sensibilisierung einer fotografischen Silberhalogenidemulsion, welches folgende Schritte umfasst:
    (a) Hinzufügen zu einer fotografischen Silberhalogenidemulsion ein aus Gold, Platin oder Palladium ausgewähltes Metall und mindestens ein Metall, das nicht Gold, Platin oder Palladium ist, ausgewählt aus der Gruppe, die aus den Metallen der Gruppe 2, den Metallen der Gruppe 8, den Metallen der Gruppe 9, den Metallen der Gruppe 10 und den Metallen der Gruppe 12 besteht, und anschließend
    (b) Hinzufügen eines Schwefelsensibilisierers zu der fotografischen Silberhalogenidemulsion.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das aus Gold, Platin oder Palladium ausgewählte Metall Gold ist.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Metalle aus der Gruppe 2 aus der Gruppe ausgewählt sind, die aus Mg und Ca besteht.
  4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Metalle aus der Gruppe 9 und 10 aus der Gruppe ausgewählt sind, die aus Pd, Co und Ni besteht.
  5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Metalle aus der Gruppe 12 aus der Gruppe ausgewählt sind, die aus Zn und Hg besteht.
  6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Schwefelsensibilisierer aus der Gruppe ausgewählt ist, die aus Thiosulfat, Thiohamstoff, Rhodanin und Triphenylthiophosphin besteht.
  7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass ein Silberhalogenidlösemittel jederzeit vor Zugabe des Schwefelsensibilisierers zufügbar ist.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass das Silberhalogenidlösemittel jederzeit vor oder zusammen mit der Zugabe gemäß Schritt (a) zufügbar ist.
  9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass das Silberhalogenidlösemittel aus der Gruppe auswählbar ist, die Ammoniak, Tthioetherderivate, Thiocyanatderivate und deren Salze sowie Ammonium- und Alkalihalogenide umfasst.
  10. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass das Silberhalogenidlösemittel ein Thiocyanatderivat oder ein Salz davon ist.
  11. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass mindestens ein Stabilisator jederzeit vor Zugabe des Schwefelsensibilisierers zufügbar ist.
  12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass mindestens ein Stabilisator zusammen mit oder nach der Zugabe gemäß Schritt (a) zufügbar ist.
  13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass mindestens ein Stabilisator aus der Gruppe auswählbar ist, die besteht aus: Thiazolderivaten; Benzothiazolderivaten; mercapto-substituierten heterozyklischen Verbindungen; Azaindenen; Triazolen; Tetrazolen sowie Schwefel- und Sulfinbenzolderivaten.
  14. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass ein Silberhalogenidlösemittel und mindestens ein Stabilisator jederzeit vor Zugabe des Schwefelsensibilisierers zufügbar ist.
  15. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass ein Silberhalogenidlösemittel vor oder zusammen mit der Zugabe nach Schritt (a) zufügbar ist, und dass ein Stabilisator zusammen mit oder nach der Zugabe gemäß Schritt (a) zufügbar ist.
  16. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass die Zusatzkomponenten in folgender Reihenfolge zugegeben werden:
    (i) das Silberhalogenidlösemittel,
    (ii) das aus Gold, Platin und Palladium auswählbare Metall und Metall(e), das/die aus der Gruppe auswählbar ist/sind, die aus Metallen der Gruppe 2, Metallen der Gruppe 8, Metallen der Gruppe 9, Metallen der Gruppe 10 und Metallen der Gruppe 12 bestehen,
    (iii) die/der Stabilisierer, und
    (iv) der Schwefelsensibilisierer.
  17. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass die Zusatzkomponenten in folgender Reihenfolge zugegeben werden:
    (i) das Silberhalogenidlösemittel, das aus Gold, Platin und Palladium auswählbare Metall und Metall(e), das/die aus der Gruppe auswählbar ist/sind, die aus Metallen der Gruppe 2, Metallen der Gruppe 8, Metallen der Gruppe 9, Metallen der Gruppe 10 und Metallen der Gruppe 12 bestehen,
    (ii) die/der Stabilisierer, und
    (iii) der Schwefelsensibilisierer.
  18. Silberhalogenid-Röntgenelement mit einem Träger und mindestens einer Silberhalogenid-Emulsionsschicht, die auf beiden Seiten des Trägers aufgetragen ist, dadurch gekennzeichnet, dass die Silberhalogenid-Emulsion chemisch mit dem Verfahren nach Anspruch 1 bis 17 sensibilisiert ist, und dass das Verhältnis von Empfindlichkeit zu Dmin des Röntgenelements mindestens 26,00 beträgt, wenn das Röntgenelement mit Röntgenstrahlen nach Bedingungen gemäß DIN 6867, Teil 1, 1995 durch zwei Verstärkungsschirme belichtet wird, die mehr als 25% der gesamten Röntgenstrahlung absorbieren, und bei 35°C für 25 bzw. 27 Sekunden in Entwickler- und Fixierlösungen verarbeitet wird, die folgende Zusammensetzung aufweisen:
    Figure 00360001
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US5294532A (en) * 1991-09-19 1994-03-15 Fuji Photo Film Co., Ltd. Silver halide photographic material and method of processing the same
IT1254509B (it) * 1992-03-06 1995-09-25 Minnesota Mining & Mfg Metodo per il trattamento di un materiale radiografico agli alogenuri d'argento
DE69326556T2 (de) * 1993-12-29 2000-05-04 Imation Corp., Saint Paul Radiographischer Zusammenbau für Brustuntersuchung
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