EP1422557A1 - Pellicule mammographique et assemblage pour la formation d' images pour emploi avec anodes de rhodium ou tungstène - Google Patents

Pellicule mammographique et assemblage pour la formation d' images pour emploi avec anodes de rhodium ou tungstène Download PDF

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Publication number
EP1422557A1
EP1422557A1 EP03078511A EP03078511A EP1422557A1 EP 1422557 A1 EP1422557 A1 EP 1422557A1 EP 03078511 A EP03078511 A EP 03078511A EP 03078511 A EP03078511 A EP 03078511A EP 1422557 A1 EP1422557 A1 EP 1422557A1
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Prior art keywords
silver halide
cubic
radiographic
film
emulsion layer
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EP03078511A
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German (de)
English (en)
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EP1422557B1 (fr
Inventor
Robert E. Eastman Kodak Company Dickerson
William E. Eastman Kodak Company Moore
David J. Eastman Kodak Company Steklenski
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Carestream Health Inc
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Eastman Kodak Co
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Priority claimed from US10/299,759 external-priority patent/US6887641B2/en
Priority claimed from US10/299,765 external-priority patent/US6864045B2/en
Priority claimed from US10/299,941 external-priority patent/US6828077B2/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP1422557A1 publication Critical patent/EP1422557A1/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • 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
    • G03C1/0051—Tabular grain 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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming 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
    • 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
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • 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
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed
    • 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
    • G03C1/46—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein having more than one photosensitive layer
    • 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
    • G03C2001/03541—Cubic grains
    • 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
    • G03C2001/03594—Size of the grains
    • 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
    • G03C2200/52—Rapid processing
    • 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

Definitions

  • ECD equivalent circular diameter
  • COV coefficient of variation
  • At least one non-light sensitive hydrophilic layer is included with the one or more silver halide emulsion layers on each side of the film support. This layer may be called an interlayer or overcoat, or both.
  • the "frontside" of the support comprises one or more silver halide emulsion layers, at least one of which contains predominantly cubic grains (that is, more than 50 weight % of all grains).
  • These cubic silver halide grains include predominantly (at least 78.5 mol %) bromide, and up to 98.75 mol % bromide, based on total silver in the cubic grain silver halide emulsion layer.
  • these cubic grains must have from 1 to 20 mol % chloride (preferably from 10 to 20 mol % chloride) and from 0.25 to 1.5 mol % iodide (preferably from 0.5 to 1 mol % iodide), based on total silver in this cubic grain emulsion layer.
  • the cubic silver halide grains in each silver halide emulsion unit (or silver halide emulsion layers) can be the same or different.
  • the average silver halide grain size can vary within each radiographic silver halide film, and within each emulsion layer within that film.
  • the average grain size in each cubic grain silver halide emulsion layer is generally from 0.65 to 0.8 ⁇ m (preferably from 0.72 to 0.76 ⁇ m), but the average grain size can be different in the various other emulsion layers.
  • the non-cubic silver halide grains (if present) in the cubic grain emulsion layers can have any desirable morphology including, but not limited to, octahedral, tetradecahedral, rounded, spherical or other non-tabular morphologies, or be comprised of a mixture of two or more of such morphologies.
  • Z 1 and Z 2 are independently the carbon atoms that are necessary to form a substituted or unsubstituted benzene or naphthalene ring.
  • each of Z 1 and Z 2 independently represent the carbon atoms necessary to form a substituted or unsubstituted benzene ring.
  • X 1 - and X 2 - are independently anions such as halides, thiocyanate, sulfate, perchlorate, p -toluene sulfonate, ethyl sulfate, and other anions readily apparent to one skilled in the art.
  • "n" is 1 or 2, and it is 1 when the compound is an intermolecular salt.
  • R 1 , R 2 , and R 3 are independently alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms in the aromatic ring, alkenyl groups having 2 to 8 carbon atoms, and other substituents that would be readily apparent to one skilled in the art. Such groups can be substituted with one or more hydroxy, alkyl, carboxy, sulfo, halo, and alkoxy groups.
  • at least one of the R 1 , R 2 , and R 3 groups comprises at least one sulfo or carboxy group.
  • Second spectral sensitizing dyes useful in the practice of this invention include the following Compounds B-1 to B-5:
  • radiographic film of this invention is the presence of one or more hexacoordination complex compounds as silver halide dopants in the cubic silver halide grains of one or more cubic grain emulsions.
  • M examples include but are not limited to, Fe +2 , Ru +2 , Os +2 , Co +3 , Rh +3 , Ir +3 , Pd +3 , and Pt +4 , and preferably M is Ru +2 .
  • useful coordination complex ligands include but are not limited to, cyanide, pyrazine, chloride, iodide, bromide, oxycyanide, water, oxalate, thiocyanide, and carbon monoxide. Cyanide is a preferred coordination complex ligand.
  • the dopants are uniformly distributed in "bands" of the silver halide grains, for example, within a band that is from 50 to 80 innermost volume % (preferably from 75 to 80 innermost volume % for ruthenium hexacoordinating complex compounds) from the center or core of the cubic silver halide grains.
  • band that is from 50 to 80 innermost volume % (preferably from 75 to 80 innermost volume % for ruthenium hexacoordinating complex compounds) from the center or core of the cubic silver halide grains.
  • One skilled in the art would readily know how to achieve these results by planned addition of the doping compounds during only a portion of the process used to prepare the silver halide.
  • the one or more dopants be present within the cubic grains in an amount of at least 1 x 10 -6 mole, preferably from 1 x 10 -6 to 5 x 10 -4 mole, and more preferably from 1 x 10 -5 to 5 x 10 -4 mole, per mole of silver in the cubic grain emulsion layer.
  • the backside of the support also includes one or more silver halide emulsion layers, preferably at least one of which comprises tabular silver halide grains.
  • tabular grains having an average aspect ratio greater than 5, and more preferably greater than 10.
  • the remainder of the silver halide projected area is provided by silver halide grains having one or more non-tabular morphologies.
  • the tabular grains are predominantly (at least 90 mol %) bromide based on the total silver in the emulsion layer and can include up to 1 mol % iodide.
  • the tabular grains are pure silver bromide.
  • Patent 4,997,750 (Dickerson et al.), U.S. Patent 5,021,327 (Bunch et al.), U.S. Patent 5,147,771 (Tsaur et al.), U.S. Patent 5,147,772 (Tsaur et al.), U.S. Patent 5,147,773 (Tsaur et al.), U.S. Patent 5,171,659 (Tsaur et al.), U.S. Patent 5,252,442 (Dickerson et al.), U.S. Patent 5,370,977 (Zietlow), U.S. Patent 5,391,469 (Dickerson), U.S.
  • Patent 5,399,470 (Dickerson et al.), U.S. Patent 5,411,853 (Maskasky), U.S. Patent 5,418,125 (Maskasky), U.S. Patent 5,494,789 (Daubendiek et al.), U.S. Patent 5,503,970 (Olm et al.), U.S. Patent 5,536,632 (Wen et al.), U.S. Patent 5,518,872 (King et al.), U.S. Patent 5,567,580 (Fenton et al.), U.S. Patent 5,573,902 (Daubendiek et al.), U.S. Patent 5,576,156 (Dickerson), U.S.
  • the backside ("second major support surface") of the radiographic silver halide film also preferably includes an antihalation layer disposed over the silver halide emulsion layer(s).
  • This layer comprises one or more antihalation dyes or pigments dispersed on a suitable hydrophilic binder (described below).
  • antihalation dyes or pigments are chosen to absorb whatever radiation the film is likely to be exposed to from a fluorescent intensifying screen.
  • pigments and dyes that can be used as antihalation pigments or dyes include various water-soluble, liquid crystalline, or particulate magenta or yellow filter dyes or pigments including those described for example in U.S. Patent 4,803,150 (Dickerson et al.), U.S.
  • Patent 5,213,956 Diehl et al.
  • U.S. Patent 5,399,690 Diehl et al.
  • U.S. Patent 5,922,523 Helber et al.
  • U.S. Patent 6,214,499 Helber et al.
  • Japanese Kokai 2-123349 all of which cited for pigments and dyes useful in the practice of this invention.
  • One useful class of particulate antihalation dyes includes nonionic polymethine dyes such as merocyanine, oxonol, hemioxonol, styryl, and arylidene dyes as described in U.S. Patent 4,803,150 (noted above) that is cited for the definitions of those dyes.
  • the magenta merocyanine and oxonol dyes are preferred and the oxonol dyes are most preferred.
  • the emulsions can be chemically sensitized by any convenient conventional technique as illustrated by Research Disclosure, Item 38957, Section IV.
  • Chemical Sensitization Sulfur, selenium or gold sensitization (or any combination thereof) are specifically contemplated. Sulfur sensitization is preferred, and can be carried out using for example, thiosulfates, thiosulfonates, thiocyanates, isothiocyanates, thioethers, thioureas, cysteine or rhodanine. A combination of gold and sulfur sensitization is most preferred.
  • one or more silver halide emulsion layers include one or more covering power enhancing compounds adsorbed to surfaces of the silver halide grains.
  • Such compounds include, but are not limited to, 5-mercapotetrazoles, dithioxotriazoles, mercapto-substituted tetraazaindenes, and others described in U.S. Patent 5,800,976 (Dickerson et al.) that is cited for the teaching of the sulfur-containing covering power enhancing compounds.
  • Such materials include, but are not limited to, polyacrylates (including polymethacrylates), polystyrenes and polyacrylamides (including polymethacrylamides).
  • Dextrans can also be used. Examples of such materials are described for example in U.S. Patent 5,876,913 (Dickerson et al.).
  • the silver halide emulsion layers (and other hydrophilic layers) in the radiographic films are generally fully hardened using one or more conventional hardeners.
  • the amount of hardener in each silver halide emulsion and other hydrophilic layer is generally at least 2% and preferably at least 2.5%, based on the total dry weight of the polymer vehicle in each layer (unless otherwise stated herein).
  • An important feature of this invention is the presence of a mixture of hydrophilic binders in at least one of the cubic silver halide grain emulsions on the frontside of the films of this invention.
  • This mixture of hydrophilic binders includes gelatin or a gelatin derivative (as defined above) as a "first" binder (or a mixture of gelatin and gelatin derivatives), and a “second” hydrophilic binder (or mixture thereof) that is not gelatin or a gelatin derivative.
  • this mixture of binders is present in the frontside cubic grain silver halide emulsion layer that also includes the mixture of first and second spectral sensitizing dyes, the hexacoordination complex compounds as dopants, and the unique combination of silver bromide, silver iodide, and silver chloride in the cubic grains described above.
  • Second hydrophilic binders include, but are not limited to, polyacrylates (including polymethacrylates), polystyrenes and polyacrylamides (including polymethacrylamides), dextrans, and various polysaccharides. Examples of such materials are described for example in U.S. Patent 5,876,913 (Dickerson et al.). The dextrans are preferred.
  • the weight ratio of first hydrophilic binder (or mixture thereof) to second hydrophilic binder (or mixture thereof) in the cubic grain silver halide emulsion layer is from 2:1 to 5:1. Preferably, this weight ratio is from 2.5:1 to 3.5:1. A most preferred weight ratio is 3:1.
  • the cubic grain silver halide emulsion layers in the radiographic films are generally hardened to various degrees using one or more conventional hardeners.
  • Conventional hardeners can be used for this purpose, including but not limited to those described above.
  • the cubic grain silver halide emulsion layer comprising the mixture of first and second binders includes a critical amount of one or more hardeners that is at least 0.4 weight % based on the total binder weight in that emulsion layer.
  • the amount of hardener in that emulsion layer is from 0.5 to 1.5 weight % and a most preferred amount is 1 weight %.
  • the preferred hardeners include bisvinylsulfonylmethylether and bisvinylsulfonylmethane.
  • the levels of silver and polymer vehicle in the radiographic silver halide film used in the present invention are not critical.
  • the total amount of silver on each side of each film is at least 10 and no more than 55 mg/dm 2 in one or more emulsion layers.
  • the total amount of polymer vehicle on each side of each film is generally at least 35 and no more than 45 mg/dm 2 in one or more hydrophilic layers.
  • the amounts of silver and polymer vehicle on the two sides of the support in the radiographic silver halide film can be the same or different. Preferably, the amounts are different. These amounts refer to dry weights.
  • the radiographic silver halide films useful in this invention generally include a surface protective overcoat on each side of the support that typically provides physical protection of the emulsion and other hydrophilic layers.
  • Each protective overcoat can be sub-divided into two or more individual layers.
  • protective overcoats can be sub-divided into surface overcoats and interlayers (between the overcoat and silver halide emulsion layers).
  • the protective overcoats can contain various addenda to modify the physical properties of the overcoats. Such addenda are illustrated by Research Disclosure, Item 38957, Section IX. Coating physical property modifying addenda, A. Coating aids, B. Plasticizers and lubricants, C. Antistats, and D. Matting agents.
  • Interlayers that are typically thin hydrophilic colloid layers can be used to provide a separation between the emulsion layers and the surface overcoats.
  • the overcoat on at least one side of the support can also include a blue toning dye or a tetraazaindene (such as 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene) if desired.
  • the protective overcoat is generally comprised of one or more hydrophilic colloid vehicles, chosen from among the same types disclosed above in connection with the emulsion layers.
  • Protective overcoats are provided to perform two basic functions. They provide a layer between the emulsion layers and the surface of the film for physical protection of the emulsion layer during handling and processing. Secondly, they provide a convenient location for the placement of addenda, particularly those that are intended to modify the physical properties of the radiographic film.
  • the protective overcoats of the films of this invention can perform both these basic functions.
  • the various coated layers of radiographic silver halide films used in this invention can also contain tinting dyes to modify the image tone to transmitted or reflected light. These dyes are not decolorized during processing and may be homogeneously or heterogeneously dispersed in the various layers. Preferably, such non-bleachable tinting dyes are in a silver halide emulsion layer.
  • the radiographic imaging assemblies of the present invention are composed of one radiographic silver halide film as described herein and one or more fluorescent intensifying screens.
  • the imaging assembly includes a single fluorescent intensifying screen.
  • Fluorescent intensifying screens are typically designed to absorb X-rays and to emit electromagnetic radiation having a wavelength greater than 300 nm. These screens can take any convenient form providing they meet all of the usual requirements for use in radiographic imaging. Examples of conventional, useful fluorescent intensifying screens and methods of making them are provided by Research Disclosure, Item 18431, cited above, Section IX. X-Ray Screens/Phosphors, and U.S. Patent 5,021,327 (Bunch et al.), U.S.
  • any conventional or useful phosphor can be used, singly or in mixtures, in the intensifying screens used in the practice of this invention.
  • useful phosphors are described in numerous references relating to fluorescent intensifying screens, including but not limited to, Research Disclosure, Vol. 184, August 1979, Item 18431, Section IX, X-ray Screens/Phosphors, and U.S. Patent 2,303,942 (Wynd et al.), U.S. Patent 3,778,615 (Luckey), U.S. Patent 4,032,471 (Luckey), U.S. Patent 4,225,653 (Brixner et al.), U.S. Patent 3,418,246 (Royce), U.S.
  • Patent 3,428,247 (Yocon), U.S. Patent 3,725,704 (Buchanan et al.), U.S. Patent 2,725,704 (Swindells), U.S. Patent 3,617,743 (Rabatin), U.S. Patent 3,974,389 (Ferri et al.), U.S. Patent 3,591,516 (Rabatin), U.S. Patent 3,607,770 (Rabatin), U.S. Patent 3,666,676 (Rabatin), U.S. Patent 3,795,814 (Rabatin), U.S. Patent 4,405,691 (Yale), U.S. Patent 4,311,487 (Luckey et al.), U.S.
  • Still other useful phosphors are those containing hafnium as described for example in U.S. Patent 4,988,880 (Bryan et al.), U.S. Patent 4,988,881 (Bryan et al.), U.S. Patent 4,994,205 (Bryan et al.), U.S. Patent 5,095,218 (Bryan et al.), U.S. Patent 5,112,700 (Lambert et al.), U.S. Patent 5,124,072 (Dole et al.), and U.S. Patent 5,336,893 (Smith et al.).
  • M' (w-n) M" n O w X' wherein M' is at least one of the metals yttrium (Y), lanthanum (La), gadolinium (Gd), or lutetium (Lu), M" is at least one of the rare earth metals, preferably dysprosium (Dy), erbium (Er), europium (Eu), holmium (Ho), neodymium (Nd), praseodymium (Pr), samarium (Sm), tantalum (Ta), terbium (Tb), thulium (Tm), or ytterbium (Yb), X' is a middle chalcogen (S, Se, or Te) or halogen, n is 0.002 to 0.2, and w is 1 when X' is halogen or 2 when X' is a middle chalc
  • Suitable phosphors are described in U.S. Patent 4,835,397 (Arakawa et al.) and U.S. Patent 5,381,015 (Dooms), including for example divalent europium and other rare earth activated alkaline earth metal halide phosphors and rare earth element activated rare earth oxyhalide phosphors.
  • the more preferred phosphors include alkaline earth metal fluorohalide prompt emitting and/or storage phosphors [particularly those containing iodide such as alkaline earth metal fluorobromoiodide storage phosphors as described in U.S. Patent 5,464,568 (Bringley et al.)].
  • Another class of useful phosphors includes rare earth hosts such as rare earth activated mixed alkaline earth metal sulfates such as europium-activated barium strontium sulfate.
  • Particularly useful phosphors are those containing doped or undoped tantalum such as YTaO 4 , YTaO 4 :Nb, Y(Sr)TaO 4 , and Y(Sr)TaO 4 :Nb. These phosphors are described in U.S. Patent 4,226,653 (Brixner), U.S. Patent 5,064,729 (Zegarski), U.S. Patent 5,250,366 (Nakajima et al.), and U.S. Patent 5,626,957 (Benso et al.).
  • alkaline earth metal phosphors that can be the products of firing starting materials comprising optional oxide and a combination of species characterized by the following formula (2): MFX 1-z I z uM a X a :yA: eQ:tD wherein "M” is magnesium (Mg), calcium (Ca), strontium (Sr), or barium (Ba), "F” is fluoride, “X” is chloride (Cl) or bromide (Br), "I” is iodide, M a is sodium (Na), potassium (K), rubidium (Rb), or cesium (Cs), X a is fluoride (F), chloride (Cl), bromide (Br), or iodide (I), "A” is europium (Eu), cerium (Ce), samarium (Sm), or terbium (Tb), "Q” is BeO, MgO, CaO, SrO, BaO, Zn
  • Some fluorescent intensifying screens useful in the present invention have as the preferred phosphor, a gadolinium oxysulfide:terbium phosphor.
  • the particle size distribution of the phosphor particles is an important factor in determining the speed and sharpness of the screen. For example, at least 50% of the particles have a size of less than 3 ⁇ m and 85% of the particles have a size of less than 5.5 ⁇ m.
  • the coverage of phosphor in the dried layer is from 260 to 380g/m 2 , and preferably from 290 to 350 g/m 2 .
  • Flexible support materials for radiographic screens in accordance with the present invention include cardboard, plastic films such as films of cellulose acetate, polyvinyl chloride, polyvinyl acetate, polyacrylonitrile, polystyrene, polyester, polyethylene terephthalate, polyamide, polyimide, cellulose triacetate and polycarbonate, metal sheets such as aluminum foil and aluminum alloy foil, ordinary papers, baryta paper, resin-coated papers, pigmented papers containing titanium dioxide or the like, and papers sized with polyvinyl alcohol or the like.
  • a plastic film is preferably employed as the support material.
  • the plastic film may contain a light-absorbing material such as carbon black, or may contain a light-reflecting material such as titanium dioxide or barium sulfate.
  • the former is appropriate for preparing a high-resolution type radiographic screen, while the latter is appropriate for preparing a high-sensitivity type radiographic screen.
  • the support absorb substantially all of the radiation emitted by the phosphor.
  • particularly preferred supports include polyethylene terephthalate, blue colored or black colored (for example, LUMIRROR C, type X30 supplied by Toray Industries, Tokyo, Japan).
  • These supports may have thickness that is generally between 60 and 1000 ⁇ m, more preferably between 80 and 500 ⁇ m.
  • a representative fluorescent intensifying screen useful in the present invention is described in the example below.
  • Exposure and processing of the radiographic silver halide films can be undertaken in any convenient conventional manner.
  • the exposure and processing techniques of U.S. Patent 5,021,327 and U.S. Patent 5,576,156 are typical for processing radiographic films.
  • Other processing compositions are described in U.S. Patent 5,738,979 (Fitterman et al.), U.S. Patent 5,866,309 (Fitterman et al.), U.S. Patent 5,871,890 (Fitterman et al.), U.S. Patent 5,935,770 (Fitterman et al.), U.S. Patent 5,942,378 (Fitterman et al.).
  • the processing compositions can be supplied as single- or multi-part formulations, and in concentrated form or as more diluted working strength solutions.
  • Exposing X-radiation is generally directed through a fluorescent intensifying screen before it passes through the radiographic silver halide film for imaging soft tissue such as breast tissue.
  • X-radiation can be generated at 28 kVp or less using conventional equipment that comprises rhodium or tungsten anodes. In other embodiments the x-radiation is generated at greater than 28 kVp. Preferably, the peak voltage is 30 kVp or more in such embodiments.
  • the radiographic silver halide films be processed within 90 seconds ("dry-to-dry") and preferably within 60 seconds and at least 20 seconds, for the developing, fixing, any washing (or rinsing) steps, and drying.
  • processing can be carried out in any suitable processing equipment including but not limited to, a Kodak X-OMATTM RA 480 processor that can utilize Kodak Rapid Access processing chemistry.
  • Kodak X-OMATTM RA 480 processor that can utilize Kodak Rapid Access processing chemistry.
  • Other "rapid access processors" are described for example in U.S. Patent 3,545,971 (Barnes et al.) and EP 0 248,390A1 (Akio et al.).
  • the black-and-white developing compositions used during processing are free of any gelatin hardeners, such as glutaraldehyde.
  • the preferred radiographic films satisfying the requirements of the present invention are specifically identified as those that are capable of dry-to-dye processing according to the following reference conditions: Development 11.1 seconds at 35°C, Fixing 9.4 seconds at 35°C, Washing 7.6 seconds at 35°C, Drying 12.2 seconds at 55-65°C. Any additional time is taken up in transport between processing steps.
  • Typical black-and-white developing and fixing compositions are described in the Example below.
  • Radiographic kits can include a radiographic imaging assembly of this invention, one or more additional fluorescent intensifying screens and/or metal screens, and/or one or more suitable processing compositions (for example black-and-white developing and fixing compositions).
  • Radiographic Film A (Control) :
  • Radiographic Film A was a single-coated film having the a silver halide emulsion on one side of a blue-tinted 170 ⁇ m transparent poly(ethylene terephthalate) film support and a pelloid layer on the opposite side.
  • the emulsion was chemically sensitized with sulfur and gold and spectrally sensitized with the following dye A-1:
  • Radiographic Film A had the following layer arrangement:
  • Overcoat Formulation Coverage (mg/dm 2 ) Gelatin vehicle 4.4 Methyl methacrylate matte beads 0.35 Carboxymethyl casein 0.73 Colloidal silica (LUDOX AM) 1.1 Polyacrylamide 0.85 Chrome alum 0.032 Resorcinol 0.073 Dow Corning Silicone 0.153 TRITON X-200 surfactant (Union Carbide) 0.26 LODYNE S-100 surfactant (Ciba Specialty Chem.) 0.0097 Interlayer Formulation Coverage (mg/dm 2 ) Gelatin vehicle 4.4 Emulsion Layer Formulation Coverage (mg/dm 2 ) Cubic grain emulsion [AgBr 0.85 ⁇ m average size] 51.1 Gelatin vehicle 34.9 Spectral sensitizing dye A-1 250 mg/Ag mole 4-Hydroxy-6-methyl-1,3 , 3 a,7-tetraazaindene 1 g/Ag mole Maleic acid hydrazi
  • Radiographic Film B (Invention):
  • the emulsion was spectrally sensitized with anhydro-5,5-dichloro-9-ethyl-3,3'-bis(3-sulfopropyl)oxacarbo-cyanine hydroxide (680 mg/Ag mole), followed by potassium iodide (300 mg/Ag mole).
  • the frontside cubic grain silver halide emulsion comprised cubic grains spectrally sensitized with a 1:1 molar ratio of dyes A-2 and B-1 (noted above). The cubic grains were doped with ruthenium hexacyanide (50 mg/Ag mole).
  • Film B had the following layer arrangement and formulations on the film support:
  • cassettes used in the practice of this invention were those commonly used in mammography.
  • Fluorescent intensifying screen "X” had the same composition and structure as commercially available KODAK Min-R 2000 Screen. It comprised a terbium activated gadolinium oxysulfide phosphor (median particle size of about 4.0 ⁇ m) dispersed in a Permuthane TM polyurethane binder on a blue-tinted poly(ethylene terephthalate) film support. The total phosphor coverage was 315 g/m 2 and the phosphor to binder weight ratio was 21:1.
  • a single screen X was placed in back of the film to form a radiographic imaging assembly.
  • the film samples were processed using a processor commercially available under the trademark KODAK RP X-OMAT® film Processor M6A-N, M6B, or M35A. Development was carried out using the following black-and-white developing composition: Hydroquinone 30 g Phenidone 1.5 g Potassium hydroxide 21 g NaHCO 3 7.5 g K 2 SO 3 44.2 g Na 2 S 2 O 5 12.6 g Sodium bromide 35 g 5-Methylbenzotriazole 0.06 g Glutaraldehyde 4.9 g Water to 1 liter, pH 10
  • the film samples were processed in each instance for less than 90 seconds (dry-to-dry). Fixing was carried out using KODAK RP X-OMAT® LO Fixer and Replenisher fixing composition (Eastman Kodak Company).
  • Optical densities are expressed below in terms of diffuse density as measured by a conventional X-rite Model 310TM densitometer that was calibrated to ANSI standard PH 2.19 and was traceable to a National Bureau of Standards calibration step tablet.
  • the characteristic D vs. log E curve was plotted for each radiographic film that was imaged and processed.
  • Speed was measured at a density of 1.4 + D min .
  • Gamma (contrast) is the slope (derivative) of the noted curves.
  • Entrance Exposure refers to the amount of X-radiation exposure (measured in milliRoentgens) that impinges on the surface of the phantom (or patient) closest to the X-radiation source.
  • ⁇ Density refers to the difference in diffuse optical density between two specified parts of the phantom (or patient).
  • Image noise was determined by a visual comparison of the resulting image to an image obtained using the conventional KODAK Min-R 2000 Mammography film and KODAK Min-R 2000 intensifying screen.
  • the resulting images were rated by an experienced observer on a scale of from 1 to 6 where a rating of "1" represents the lowest noise and a rating of "6" represents the highest noise.
  • Image resolution refers to the ability of an experienced observer to discern discrete lines in a low contrast resolution test pattern. Resolution was measured in a line pair per millimeter. The resulting images were rated by a very experienced observer on a scale of from 1 to 6 where a rating of "1" represents the highest resolution and a rating of "6" represents the lowest resolution.
  • Image quality refers to the ability of a human observer easily and clearly to discern low contrast objects and fine details in the phantoms (or patients). The resulting images were rated by an experienced observer on a scale of from 1 to 6 where a rating of "1" represents the best image quality and a rating of "6" represents the poorest image quality.
  • the film of the present invention (Film B) provided increased contrast in the mid-scale region as indicated by the increase in the "d( ⁇ )/d(log E)" value.
  • Films A and B were imaged and processed as described in Example 1.
  • the following TABLE III shows the results of imaging and processing of Films A and B. It is apparent from the data that image quality is degraded in Film A when the imaging peak voltage was increased from 28 to 32 kVp. However, when the peak voltage was similar increased using Film B, image quality was restored at the lower patient dosage.
  • Film B was a radiographic film having the characteristics required for the present invention.
  • Films A and B were imaged and processed as described in Example 1 using preferred patient imaging conditions.
  • the following TABLE IV shows the results of imaging and processing of Films A and B.
  • Film A was imaged using a conventional dose (28 kVp) and conventional molybdenum anodes.
  • the present invention, using Film B, was practiced using higher kVp and rhodium anodes to provide acceptable image quality but with significantly lower patient dosage.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP03078511A 2002-11-19 2003-11-07 Pellicule mammographique et assemblage pour la formation d' images pour emploi avec anodes de rhodium ou tungstène Expired - Fee Related EP1422557B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US299759 1989-01-23
US299765 1994-09-01
US299941 2002-11-19
US10/299,759 US6887641B2 (en) 2002-11-19 2002-11-19 Mammography imaging method using high peak voltage and rhodium or tungsten anodes
US10/299,765 US6864045B2 (en) 2002-11-19 2002-11-19 Mammography film and imaging assembly for use with rhodium or tungsten anodes
US10/299,941 US6828077B2 (en) 2002-11-19 2002-11-19 Mammography imaging method using high peak voltage

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EP1422557A1 true EP1422557A1 (fr) 2004-05-26
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0212968A2 (fr) * 1985-08-20 1987-03-04 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
EP0407890A2 (fr) * 1989-07-12 1991-01-16 Minnesota Mining And Manufacturing Company Cassette avec feuilles de renforcement à utiliser avec un film radiographique
US5800976A (en) * 1997-02-18 1998-09-01 Eastman Kodak Company Radiographic elements that satisfy image and tone requirements with minimal silver
EP0862083A1 (fr) * 1997-03-01 1998-09-02 Agfa-Gevaert N.V. Système et méthode de formation d'image radiologique
US6033840A (en) * 1998-10-14 2000-03-07 Eastman Kodak Company Medical diagnostic film for soft tissue imaging (i)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6350554B1 (en) * 2000-11-06 2002-02-26 Eastman Kodak Company High contrast visually adaptive radiographic film and imaging assembly for orthopedic imaging

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0212968A2 (fr) * 1985-08-20 1987-03-04 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
EP0407890A2 (fr) * 1989-07-12 1991-01-16 Minnesota Mining And Manufacturing Company Cassette avec feuilles de renforcement à utiliser avec un film radiographique
US5800976A (en) * 1997-02-18 1998-09-01 Eastman Kodak Company Radiographic elements that satisfy image and tone requirements with minimal silver
EP0862083A1 (fr) * 1997-03-01 1998-09-02 Agfa-Gevaert N.V. Système et méthode de formation d'image radiologique
US6033840A (en) * 1998-10-14 2000-03-07 Eastman Kodak Company Medical diagnostic film for soft tissue imaging (i)

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DE60307764D1 (de) 2006-10-05
EP1422557B1 (fr) 2006-08-23
JP2004170987A (ja) 2004-06-17

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