EP1422557B1 - Mammographischer Film und Bildaufzeichnungskombination zur Verwendung mit Rhodium- oder Wolframanoden - Google Patents

Mammographischer Film und Bildaufzeichnungskombination zur Verwendung mit Rhodium- oder Wolframanoden Download PDF

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EP1422557B1
EP1422557B1 EP03078511A EP03078511A EP1422557B1 EP 1422557 B1 EP1422557 B1 EP 1422557B1 EP 03078511 A EP03078511 A EP 03078511A EP 03078511 A EP03078511 A EP 03078511A EP 1422557 B1 EP1422557 B1 EP 1422557B1
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Prior art keywords
silver halide
film
radiographic
cubic
spectral sensitizing
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English (en)
French (fr)
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EP1422557A1 (de
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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 US10/299,941 external-priority patent/US6828077B2/en
Priority claimed from US10/299,765 external-priority patent/US6864045B2/en
Priority claimed from US10/299,759 external-priority patent/US6887641B2/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
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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

  • This invention is directed to radiography.
  • it is directed to a radiographic silver halide film and imaging assembly that are useful for providing medical diagnostic images of soft tissues such as in mammography.
  • These films provide advantages when exposed to X-radiation generated using rhodium or tungsten anodes.
  • the object is to obtain an image of a patient's internal anatomy with as little X-radiation exposure as possible.
  • the fastest imaging speeds are realized by mounting a dual-coated radiographic element between a pair of fluorescent intensifying screens for imagewise exposure. 5% or less of the exposing X-radiation passing through the patient is adsorbed directly by the latent image forming silver halide emulsion layers within the dual-coated radiographic element. Most of the X-radiation that participates in image formation is absorbed by phosphor particles within the fluorescent screens. This stimulates light emission that is more readily absorbed by the silver halide emulsion layers of the radiographic element.
  • radiographic element constructions for medical diagnostic purposes are provided by U. S. Patent 4,425,425 (Abbott et al.) and U.S. Patent 4,425,426 (Abbott et al.), U.S. Patent 4,414,310 (Dickerson), U.S. Patent 4,803,150 (Kelly et al.), U.S. Patent 4,900,652 (Kelly et al.), U.S. Patent 5,252,442 (Tsaur et al.), and Research Disclosure, Vol. 184, August 1979, Item 18431.
  • Mammography film generally contains a single silver halide emulsion layer and is exposed by a single intensifying screen, usually interposed between the film and the source of X-radiation.
  • Mammography utilizes low energy X-radiation, that is, radiation that is predominantly of an energy level less than 40 keV.
  • U.S. Patent 6,033,840 (Dickerson) and U.S. Patent 6,037,112 (Dickerson) describe asymmetric imaging elements and processing methods for imaging soft tissue.
  • Radiographic imaging of soft tissue as in mammography is usually carried out using X-ray imaging equipment that includes an X-ray tube with a rotating anode.
  • the anode is the "source" of the X-radiation that is created when electrons interact with the electrons or nuclei of the metallic atoms in the anode.
  • molybdenum anodes are generally used in such equipment.
  • Rhodium anodes are also known in the art for lowering patient exposure to radiation, but in the case of mammography, poorer image quality is usually the result when they are used.
  • the present invention provides an advance in the art with a radiographic silver halide film that comprises a support having first and second major surfaces and that is capable of transmitting X-radiation, the radiographic silver halide film having disposed on the first major support surface, one or more hydrophilic colloid layers including at least one cubic grain silver halide emulsion layer, and having disposed on the second major support surface, one or more hydrophilic colloid layers including at least one tabular grain silver halide emulsion layer, the film characterized wherein it can be exposed to provide a black-and-white image having a d( ⁇ )/d(log E) value greater than 5, wherein the cubic grain silver halide emulsion layer comprises:
  • Preferred embodiments of the present invention include a radiographic silver halide film having a photographic speed of at least 100 and comprising a transparent film support having first and second major surfaces and that is capable of transmitting X-radiation, the radiographic silver halide film having disposed on the first major support surface, one or more hydrophilic colloid layers including at least one cubic grain silver halide emulsion layer, and having disposed on the second major support surface, one or more hydrophilic colloid layers including at least one tabular grain silver halide emulsion layer, the film also comprising a protective overcoat layer disposed on both sides of the support, the film characterized wherein the cubic grain silver halide emulsion layer comprises:
  • This invention also provides a radiographic imaging assembly comprising:
  • the radiographic imaging assembly of this invention comprises a single fluorescent intensifying screen that comprises an inorganic phosphor coated in admixture with a polymeric binder in a phosphor layer onto a flexible support and has a protective overcoat disposed over the phosphor layer.
  • a method of providing a black-and-white image comprises exposing the radiographic imaging assembly of the present invention to X-radiation generated using rhodium or tungsten anodes in an X-radiation generating device, and processing the radiographic silver halide film, sequentially, with a black-and-white developing composition and a fixing composition, the processing being carried out within 90 seconds, dry-to-dry.
  • a method of providing a black-and-white image comprises exposing the radiographic imaging assembly of the present invention to X-radiation at a peak voltage greater than 28 kVp, and processing the radiographic silver halide film, sequentially, with a black-and-white developing composition and a fixing composition, the processing being carried out within 90 seconds, dry-to-dry.
  • the present invention provides a means for providing radiographic images for mammography unexpectedly exhibiting improved image quality while minimizing radiation dosage to which patients are exposed.
  • image quality can be improved with the present invention by increasing image contrast, decreasing "noise” (for example, film granularity), or both.
  • the radiographic silver halide films of the present invention provide images that exhibit desired contrast in the mid-scale region. This contrast can be evaluated by calculating the derivative (or slope) of a gamma vs. log E curve to obtain a term " d( ⁇ )/d(log E)" that is defined in more detail below.
  • the films exhibit a d( ⁇ )/d(log E) greater than 5 and preferably greater than 5.5.
  • radiographic film can be rapidly processed in the same conventional processing equipment and compositions.
  • patients are exposed at a peak voltage greater than 28 kVp using rhodium or tungsten anodes in an X-radiation generating device, whereby patient dosage is reduced without sacrificing image quality such as image contrast.
  • contrast indicates the average contrast derived from a characteristic curve of a radiographic film using as a first reference point (1) a density (D 1 ) of 0.25 above minimum density and as a second reference point (2) a density (D 2 ) of 2.0 above minimum density, where contrast is ⁇ D (i.e. 1.75) ⁇ ⁇ log E (log E 2 - log E 1 ), E 1 and E 2 being the exposure levels at the reference points (1) and (2).
  • “Gamma” is described as the instantaneous rate of change of a D vs. log E sensitometric curve or the instantaneous contrast at any log E value.
  • Photographic speed for the radiographic films refers to the exposure necessary to obtain a density of at least 1.0 plus D min .
  • Photographic speed for the fluorescent intensifying screens refers to the percentage of photicity relative to a conventional KODAK MinR fluorescent intensifying screen.
  • Image tone can be evaluated using conventional CIELAB (Commission Internationale de l'Eclairage) a* and b* values that can be evaluated using the techniques described by Billmeyer et al., Principles of Color Technology , 2 nd Edition, Wiley & Sons, New York, 1981, Chapter 3.
  • the a* value is a measure of reddish tone (positive a*) or greenish tone (negative a*).
  • the b* value is a measure of bluish tone (negative b*) or yellowish tone (positive b*).
  • d( ⁇ )/d(log E) refers to a mathematical derivative or the slope of a gamma vs. log E sensitometric curve. This term can be obtained by providing a conventional D(density) vs. log E curve, mathematically differentiating that curve to provide a ⁇ (gamma) vs. log E sensitometric curve, and then determining the slope of the "leading edge" (or rising side) of that curve.
  • Exposure latitude refers to the width (in logE terms) of the ⁇ vs. log E sensitometric curve when measured at a specific gamma value.
  • the curve width is measured in log E terms and upon conversion to the appropriate "antilog” provides a ratio of a specific number to 1.
  • rapid access processing is employed to indicate dry-to-dry processing of a radiographic film in 45 seconds or less. That is, 45 seconds or less elapse from the time a dry imagewise exposed radiographic film enters a wet processor until it emerges as a dry fully processed film.
  • the halides are named in order of ascending molar concentrations.
  • ECD equivalent circular diameter
  • COV coefficient of variation
  • covering power is used to indicate 100 times the ratio of maximum density to developed silver measured in mg/dm 2 .
  • dual-coated is used to define a radiographic film having silver halide emulsion layers disposed on both the front- and backsides of the support.
  • the radiographic silver halide films used in the present invention are "dual-coated.”
  • dynamic range refers to the range of exposures over which useful images can be obtained (usually having a gamma greater than 2).
  • the units "kVp" and “MVp” stand for peak voltage applied to an X-ray tube times 10 3 and 10 6 , respectively.
  • fluorescent intensifying screen refers to a screen that absorbs X-radiation and emits light.
  • a “prompt” emitting fluorescent intensifying screen will emit light immediately upon exposure to radiation while a “storage” fluorescent screen can "store” the exposing X-radiation for emission at a later time when the screen is irradiated with other radiation (usually visible light).
  • the screens useful in the practice of the present invention are “prompt” emitting fluorescent intensifying screens.
  • front and back refer to layers, films, or fluorescent intensifying screens nearer to and farther from, respectively, the source of X-radiation.
  • rare earth is used to indicate chemical elements having an atomic number of 39 or 57 through 71.
  • radiographic silver halide films useful in this invention include a flexible support having disposed on both sides thereof, one or more photographic silver halide emulsion layers and optionally one or more non-radiation sensitive hydrophilic layer(s).
  • the photographic silver halide film has a protective overcoat (described below) over all of the layers on each side of the support.
  • the support can take the form of any conventional radiographic film support that is X-radiation and light transmissive.
  • Useful supports for the films of this invention can be chosen from among those described in Research Disclosure, September 1996, Item 38957 XV. Supports and Research Disclosure, Vol. 184, August 1979, Item 18431, XII. Film Supports.
  • the support is preferably a transparent film support.
  • the transparent film support consists of a transparent film chosen to allow direct adhesion of the hydrophilic silver halide emulsion layers or other hydrophilic layers. More commonly, the transparent film is itself hydrophobic and subbing layers are coated on the film to facilitate adhesion of the hydrophilic silver halide emulsion layers.
  • the film support is either colorless or blue tinted (tinting dye being present in one or both of the support film and the subbing layers).
  • Polyethylene terephthalate and polyethylene naphthalate are the preferred transparent film support materials.
  • 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 amount of chloride in the cubic silver halide grains is critical to provide desired processability and image tone while the amount of iodide is critical to provide desired photographic speed. Too much chloride results in poor absorption of spectral sensitizing dyes to the grains.
  • 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.
  • At least one of the cubic grain silver halide emulsion layers comprise a combination of one or more first spectral sensitizing dyes and one or more second spectral sensitizing dyes that provide a combined J-aggregate absorption within the range of from 540 to 560 nm (preferably from 545 to 555 nm) when absorbed on the cubic silver halide grains.
  • the one or more first spectral sensitizing dyes are anionic benzimidazolebenzoxazole carbocyanines and the one or more second spectral sensitizing dyes are anionic oxycarbocyanines.
  • all cubic grain silver halide emulsions in the film contain one or more of these combinations of spectral sensitizing dyes.
  • the combinations of dyes can be the same of different in each cubic grain silver halide emulsion layer.
  • a most preferred combination of spectral sensitizing dyes A-2 and B-1 identified below has a combined J-aggregate absorption ⁇ max of 552 nm when absorbed to cubic silver halide grains.
  • the first and second spectral sensitizing dyes are provided on the cubic silver halide grains in a molar ratio of one or more first spectral sensitizing dyes to one or more second spectral sensitizing dyes of from 0.25:1 to 4:1, preferably at a molar ratio of from 0.5: 1 to 1.5: 1, and more preferably at a molar ratio of from 0.75:1 to 1.25:1.
  • a most preferred combination of spectral sensitizing dyes A-2 and B-1 identified below is a molar ratio of 1:1.
  • the useful total amounts of the first and second dyes in a given cubic grain silver halide emulsion layer are generally and independently within the range of from 0.1 to 1 mmol/mole of silver in the emulsion layer. Optimum amounts will vary with the particular dyes used and a skilled worker in the art would understand how to achieve optimal benefit with the combination of dyes in appropriate amounts.
  • the total amount of both dyes is generally from 0.25 to 0.75 mmol/mol
  • first spectral sensitizing dyes can be represented by the following Structure I
  • second spectral sensitizing dyes can be represented by the following Structure II.
  • 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.
  • R 1 , R 2 , and R 3 are independently alkyl groups having 1 to 4 carbon atoms, phenyl groups, alkoxy groups having 1 to 4 carbon atoms, or alkenyl groups having 2 to 4 carbon atoms. All of these groups can be substituted as described above, and in particular, they can be substituted with a sulfo or carboxy group.
  • R 4 and R 5 are independently defined as noted above for R 1 , R 2 , and R 3 , R 6 is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, each of which groups can be substituted as described above for the other radicals.
  • 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.
  • hexacoordination complex compounds particularly useful in the practice of this invention are represented by the following Structure I: [ML 6 ] n wherein M is a Group VIII polyvalent transition metal ion, L represents six coordination complex ligands that can be the same or different provided that at least four of the ligands are anionic ligands and at least one (preferably at least 3) of the ligands is more electronegative than any halide ligand, and n is -2, -3, or -4. Preferably, n is -3 or -4.
  • 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.
  • Particularly useful dopants are ruthenium coordination complexes comprising at least 4 and more preferably 6 cyanide coordination complex ligands.
  • the metal dopants can be introduced during emulsion precipitation using procedures well known in the art. They can be present in the dispersing medium present in the reaction vessel before grain nucleation. More typically, the metal coordination complexes are introduced at least in part during precipitation through one of the halide ion or silver ion jets or through a separate jet. Such procedures are described in U.S. Patent 4,933,272 (McDugle et al.) and U.S. Patent 5,360,712 (Olm et al.), cited therein.
  • dopants in the art are distributed uniformly throughout 100% of the volume of the silver halide grains, it is desired in the practice of this invention to provide the dopant in only a part of the grain volume, generally within 95% and preferably within 90% of the innermost volume from the center of the cubic silver halide grains. Methods for doing this are known in the art, for example is described in U.S. Patent 4,933,272 and U.S. Patent 5,360,712 (both noted above).
  • 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.
  • U. S. Patent 4,414,310 (Dickerson), U.S. Patent 4,425,425 (Abbott et al.), U.S. Patent 4,425,426 (Abbott et al.), U.S. Patent 4,439,520 (Kofron et al.), U.S. Patent 4,434,226 (Wilgus et al.), U.S. Patent 4,435,501 (Maskasky), U.S. Patent 4,713,320 (Maskasky), U.S. Patent 4,803,150 (Dickerson et al.), U.S. Patent 4,900,355 (Dickerson et al.), U.S. Patent 4,994,355 (Dickerson et al.), U.S.
  • 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.
  • Patent 5,576,168 (Daubendiek et al.), U.S. Patent 5,576,171 (Olm et al.), and U.S. Patent 5,582,965 (Deaton et al.).
  • the patents to Abbott et al., Fenton et al., Dickerson, and Dickerson et al. are also cited to show conventional radiographic film features in addition to gelatino-vehicle, high bromide ( ⁇ 80 mol % bromide based on total silver) tabular grain emulsions and other features useful in the present invention.
  • 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 amounts of such dyes or pigments in the antihalation layer are generally from 1 to 2 mg/dm 2 .
  • a particularly useful antihalation dye is the magenta filter dye M-1 identified as follows:
  • 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.
  • the silver halide emulsion layers and other hydrophilic layers on both sides of the support of the radiographic films generally contain conventional polymer vehicles (peptizers and binders) that include both synthetically prepared and naturally occurring colloids or polymers.
  • the most preferred polymer vehicles include gelatin or gelatin derivatives alone or in combination with other vehicles.
  • Conventional gelatino-vehicles and related layer features are disclosed in Research Disclosure, Item 38957, Section II. Vehicles, vehicle extenders, vehicle-like addenda and vehicle related addenda.
  • the emulsions themselves can contain peptizers of the type set out in Section II, paragraph A. Gelatin and hydrophilic colloid peptizers.
  • the hydrophilic colloid peptizers are also useful as binders and hence are commonly present in much higher concentrations than required to perform the peptizing function alone.
  • the preferred gelatin vehicles include alkali-treated gelatin, acid-treated gelatin or gelatin derivatives (such as acetylated gelatin, deionized gelatin, oxidized gelatin and phthalated gelatin).
  • Cationic starch used as a peptizer for tabular grains is described in U.S. Patent 5,620,840 (Maskasky) and U.S. Patent 5,667,955 (Maskasky). Both hydrophobic and hydrophilic synthetic polymeric vehicles can be used also.
  • 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).
  • Conventional hardeners can be used for this purpose, including but not limited to formaldehyde and free dialdehydes such as succinaldehyde and glutaraldehyde, blocked dialdehydes, ⁇ -diketones, active esters, sulfonate esters, active halogen compounds, s-triazines and diazines, epoxides, aziridines, active olefins having two or more active bonds, blocked active olefins, carbodiimides, isoxazolium salts unsubstituted in the 3-position, esters of 2-alkoxy-N-carboxydihydroquinoline, N-carbamoyl pyridinium salts, carbamoyl oxypyridinium salts, bis(amidino) ether salts, particularly bis(amidino) ether salts, surface-applied carboxyl-activating hardeners in combination with complex-forming salts, carbamoylonium, carb
  • 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.
  • the fluorescent layer contains phosphor particles and a binder, optimally additionally containing a light scattering material, such as titania or light absorbing materials such as particulate carbon, dyes or pigments.
  • a binder any conventional binder (or mixture thereof) can be used but preferably the binder is an aliphatic polyurethane elastomer or another highly transparent elastomeric polymer.
  • 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.
  • Patent 4,387,141 (Patten), U.S. Patent 5,021,327 (Bunch et al.), U.S. Patent 4,865,944 (Roberts et al.), U.S. Patent 4,994,355 (Dickerson et al.), U.S. Patent 4,997,750 (Dickerson et al.), U.S. Patent 5,064,729 (Zegarski), U.S. Patent 5,108,881 (Dickerson et al.), U.S. Patent 5,250,366 (Nakajima et al.), U.S. Patent 5,871,892 (Dickerson et al.), EP-A-0 491,116 (Benzo et al.), the disclosures of all of which are cited with respect to the phosphors.
  • Useful classes of phosphors include, but are not limited to, calcium tungstate (CaWO 4 ), activated or unactivated lithium stannates, niobium and/or rare earth activated or unactivated yttrium, lutetium, or gadolinium tantalates, rare earth (such as terbium, lanthanum, gadolinium, cerium, and lutetium)-activated or unactivated middle chalcogen phosphors such as rare earth oxychalcogenides and oxyhalides, and terbium-activated or unactivated lanthanum and lutetium middle chalcogen phosphors.
  • CaWO 4 calcium tungstate
  • activated or unactivated lithium stannates activated or unactivated lithium stannates
  • rare earth such as terbium, lanthanum, gad
  • 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' 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
  • w is 1 when X' is halogen or 2 when X' is a middle chalcogen
  • 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 (2) 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.
  • FIG. 1 An embodiment of the present invention is illustrated in FIG. 1.
  • fluorescent intensifying screen 20 is arranged in association with radiographic silver halide film 30 in cassette holder 40 .
  • 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-OMAT TM RA 480 processor that can utilize Kodak Rapid Access processing chemistry.
  • Kodak X-OMAT TM 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 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-1,3,3a,7-tetraazaindene 1 g/Ag mole Maleic acid hydrazide 0.00
  • Radiographic Film B (Invention):
  • Radiographic Film B was a dual-coated radiographic film with 2/3 of the silver and gelatin coated on one side of the support and the remainder coated on the opposite side of the support. It also included a halation control layer containing solid particle dyes to provide improved sharpness.
  • the film contained a green-sensitive, high aspect ratio tabular silver bromide grain emulsion on both sides of the support. Thus, at least 50% of the total grain projected area is accounted for by tabular grains having a thickness of less than 0.3 ⁇ m and having an average aspect ratio greater than 8:1.
  • the emulsion average grain diameter was 2.0 ⁇ m and the average grain thickness was 0.10 ⁇ m. It was polydisperse in distribution and had a coefficient of variation of 38.
  • 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.
  • Samples of the films in the imaging assemblies were imaged using a commercially available GE DMR Mammographic X-ray unit equipped with both molybdenum and rhodium anodes. It was capable of accelerating voltages of 25,000-40,000 volts. Images were made using an RMI 156 phantom (available from Gammex-RMI, Middleton, Wisconsin), and RMI phantom 165, and a Kodak-Pathe "Indicateur de Technique Operatoire" phantom.
  • 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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Claims (18)

  1. Radiografischer Silberhalogenidfilm mit einem Träger, der erste und zweite Hauptoberflächen aufweist und Röntgenstrahlung übertragen kann,
    wobei der radiografische Silberhalogenidfilm auf der ersten Träger-Hauptoberfläche ein oder mehrere abgeschiedene, hydrophile Kolloidschichten aufweist, einschließlich mindestens einer Silberhalogenidemulsionsschicht mit kubischen Körnern und auf der zweiten Träger-Hauptoberfläche ein oder mehrere abgeschiedene, hydrophile Kolloidschichten, einschließlich mindestens einer Silberhalogenid-Tafelkorn-Emulsionsschicht aufweist,
    dadurch gekennzeichnet, dass der Film exponiert werden kann, um ein Schwarz-Weiß-Bild mit einem d(γ)/d(log E)-Wert von größer als 5 zu erzeugen,
    wobei die Silberhalogenidemulsionsschicht mit den kubischen Körnern umfasst:
    1) eine Kombination aus ersten und zweiten, spektralen Sensibilisierungsfarbstoffen, die ein kombiniertes J-Aggregat-Absorptions-Maximum auf den kubischen Silberhalogenidkömem von 540 bis 560 nm liefern, und
    worin der erste, spektral sensibilisierende Farbstoff ein anionisches Benzimidazol-Benzoxazolcarbocyanin ist, der zweite, spektral sensibilisierende Farbstoff ein anionisches Oxydcarbocyanin ist und wobei der erste und der zweite, spektral sensibilisierende Farbstoff in einem molaren Verhältnis von 0,25:1 bis 4:1 vorliegen,
    2) eine Mischung aus einem ersten, hydrophilen Bindemittel, das Gelatine oder ein Gelatinederivat ist und einem zweiten, hydrophilen Bindemittel, das von Gelatine oder einem Gelatinederivat verschieden ist, worin das Gew.-Verhältnis von dem ersten, hydrophilen Bindemittel zu dem zweiten, hydrophilen Bindemittel bei 2:1 bis 5:1 liegt und wobei die Menge an Härtungsmittel in der Silberhalogenidemulsionsschicht mit den kubischen Körnern bei 0,4 bis 1,5 Gew.-%, bezogen auf das Gesamtgewicht des ersten hydrophilen Bindemittels in der Silberhalogenidemulsionsschicht mit den kubischen Körnern liegt,
    3) die kubischen Silberhalogenidkörner 1 bis 20 Mol-% Chlorid und 0,25 bis 1,5 Mol-% Iodid enthalten, in beiden Fällen bezogen auf das Gesamtsilber in der Emulsionsschicht mit den kubischen Körnern, wobei die kubischen Silberhalogenidkörner einen mittleren ECD-Wert von 0,65 bis 0,8 µm haben, und
    4) die kubischen Silberhalogenidkörner dotiert sind mit einer Hexakoordinationskomplex-Verbindung innerhalb eines Teils oder sämtlicher 95 % des innersten Volumens vom Zentrum der kubischen Silberhalogenidkörner.
  2. Radiografischer Silberhalogenidfilm nach Anspruch 1, in dem der erste, spektral sensibilisierende Farbstoff durch die folgende Struktur I dargestellt wird:
    Figure imgb0040
     worin Z1 und Z2 die Kohlenstoffatome darstellen, die erforderlich sind zur Bildung eines substituierten oder unsubstituierten Benzol- oder Naphthalinringes, R1, R2 und R3 unabhängig voneinander stehen für substituierte oder unsubstituierte Alkyl-, Alkoxy-, Aryl- oder Alkenylgruppen, X1 - ein Anion ist und n für 1 oder 2 steht, und worin der zweite, spektral sensibilisierende Farbstoff dargestellt wird durch die Struktur II:
    Figure imgb0041
     worin Z1 und Z2 die Kohlenstoffatome darstellen, die zur Bildung eines substituierten oder unsubstituierten Benzol- oder Naphthalinringes erforderlich sind, R4 und R5 unabhängig voneinander für substituierte oder unsubstituierte Alkyl-, Alkoxy-, Aryl- oder Alkenylgruppen stehen, R6 ein Wasserstoffatom ist oder eine substituierte oder unsubstituierte Alkyl- oder Phenylgruppe, X2 - ein Anion ist und n für 1 oder 2 steht.
  3. Radiografischer Silberhalogenidfilm nach Anspruch 1 oder 2, in dem die Gesamtmenge der Kombination aus erstem und zweitem, spektral sensibilisierendem Farbstoff bei 0,25 bis 0,75 Molen/Mol Silber liegt und wobei der erste und der zweite, spektral sensibilisierende Farbstoff in einem molaren Verhältnis von 0,5:1 bis 1,5: 1 vorliegen.
  4. Radiografischer Silberhalogenidfilm nach einem der Ansprüche 1 bis 3, in dem die Kombination aus dem ersten und dem zweiten, spektral sensibilisierenden Farbstoff eine kombinierte J-Aggregat-Absorption von 545 bis 555 nm erzeugen, wenn die Farbstoffe auf den kubischen Silberhalogenidkörnern absorbiert sind.
  5. Radiografischer Silberhalogenidfilm nach einem der Ansprüche 1 bis 4, in dem der erste spektral sensibilisierende Farbstoff ausgewählt ist aus den folgenden Verbindungen A-1 bis A-7 und worin der zweite, spektral sensibilisierende Farbstoff ausgewählt ist aus den folgenden Verbindungen B-1 bis B-5:
    Figure imgb0042
    Figure imgb0043
    Figure imgb0044
    Figure imgb0045
    Figure imgb0046
    Figure imgb0047
    Figure imgb0048
    Figure imgb0049
    Figure imgb0050
    Figure imgb0051
    Figure imgb0052
    Figure imgb0053
  6. Radiografischer Silberhalogenidfilm nach einem der Ansprüche 1 bis 5, in dem die Hexakoordinationskomplex-Verbindung in einer Menge von 1 x 10-6 bis 5 x 10-4 Molen pro Mol Silber in der Silberhalogenidemulsionsschicht vorliegt.
  7. Radiografischer Silberhalogenidfilm nach einem der Ansprüche 1 bis 6, in dem die Hexakoordinationskomplex-Verbindung innerhalb der innersten 90 Volumen-% der kubischen Silberhalogenidkörner vorliegt.
  8. Radiografischer Silberhalogenidfilm nach einem der Ansprüche 1 bis 7, in dem die Hexakoordinationskomplex-Verbindung dargestellt wird durch die folgende Struktur I:

            [ML6]n

    worin M ein polyvalentes Übergangsmetallion der Gruppe 8 ist, L für sechs Koordinationskomplexliganden steht, die gleich oder verschieden sein können, vorausgesetzt, dass mindestens vier der Liganden anionische Liganden sind und mindestens einer der Liganden elektronegativer als irgendein Halogenidligand ist und worin n steht für -2, -3 oder -4.
  9. Radiografischer Silberhalogenidfilm nach einem der Ansprüche 1 bis 8, in dem die kubischen Silberhalogenidkörner zu 10 bis 20 Mol-% aus Chlorid, bezogen auf das Gesamtsilber in der Emulsionsschicht, bestehen und zu 0,5 bis 1 Mol-% aus Iodid, bezogen auf das Gesamtsilber in der Silberhalogenidemulsionsschicht mit den kubischen Körnern.
  10. Radiografischer Silberhalogenidfilm nach einem der Ansprüche 1 bis 9, in dem das Gew.-Verhältnis von dem ersten, hydrophilen Bindemittel zu dem zweiten, hydrophilen Bindemittel bei 2,5:1 bis 3,5:1 liegt und worin die Menge an Härtungsmittel bei 0,5 bis 1,5 Gew.-%, bezogen auf das Gesamtgewicht des ersten, hydrophilen Bindemittels in der Silberhalogenidemulsionsschicht mit den kubischen Körnern liegt.
  11. Radiografischer Silberhalogenidfilm nach einem der Ansprüche 1 bis 10, in dem das zweite, hydrophile Bindemittel ein Dextran oder Polyacrylamid ist.
  12. Radiografischer Silberhalogenidfilm mit einer fotografischen Empfindlichkeit von mindestens 100 und mit einem transparenten Filmträger mit einer ersten und einer zweiten Hauptfläche, der Röntgenstrahlung zu übertragen vermag,
    wobei der radiografische Silberhalogenidfilm auf der ersten Träger-Hauptoberfläche ein oder mehrere hydrophile Kolloidschichten abgeschieden enthält, einschließlich mindestens einer Silberhalogenidemulsionsschicht mit kubischen Körnern und wobei der Film auf der zweiten Träger-Hauptoberfläche ein oder mehrere hydrophile Kolloidschichten abgeschieden enthält, einschließlich mindestens einer Silberhalogenid-Tafelkom-Emulsionsschicht,
    wobei der Film ferner eine schützende Deckschicht auf beiden Seiten des Trägers aufweist,
    wobei der Film dadurch gekennzeichnet ist, dass die Emulsionsschicht mit den kubischen Silberhalogenidkörnern umfasst:
    1) eine Kombination aus ersten und zweiten, spektral sensibilisierenden Farbstoffen, die ein kombiniertes J-Aggregat-Absorptions-Maximum von 545 bis 555 nm liefern, wenn die Farbstoffe auf der Oberfläche der kubischen Silberhalogenidkörner absorbiert sind,
    worin der erste, spektral sensibilisierende Farbstoff der folgende Farbstoff A-2 ist und worin der zweite, spektral sensibilisierende Farbstoff der folgende Farbstoff B-1 ist, wobei der erste und der zweite, spektral sensibilisierende Farbstoff in einem molaren Verhältnis von 0,5:1 bis 1,5:1 vorliegen, und worin die Gesamtmenge an spektral sensibilisierenden Farbstoffen in dem Film bei 0,25 bis 0,75 mMolen/Mol Silber liegt,
    Figure imgb0054
    Figure imgb0055
    2) eine Mischung aus einem ersten, hydrophilen Bindemittel, das Gelatine oder ein Gelatinederivat ist und einem zweiten, hydrophilen Bindemittel, das ein Dextran oder Polyacrylamid ist, worin das Gew.-Verhältnis von dem ersten, hydrophilen Bindemittel zu dem zweiten, hydrophilen Bindemittel bei 2,5:1 bis 3,5:1 liegt und wobei die Menge an Härtungsmittel in der Silberhalogenidemulsion mit den kubischen Körnern bei 0,5 bis 1,5 Gew.-%, bezogen auf das Gesamtgewicht des ersten, hydrophilen Bindemittels in der Silberhalogenidemulsionsschicht mit den kubischen Körnern liegt,
    3) die kubischen Silberhalogenidkörner 10 bis 20 Mol-% Chlorid und 0,5 bis 1 Mol-% Iodid, jeweils bezogen auf das Gesamtsilber in der Silberhalogenidemulsionsschicht mit den kubischen Körnern, enthalten, wobei die kubischen Silberhalogenidkörner einen mittleren ECD-Wert von 0,72 bis 0,76 µm haben, und
    4) die kubischen Silberhalogenidkörner mit einer Hexakoordinationskomplex-Verbindung innerhalb von 75 bis 80 % des innersten Volumens vom Zentrum der kubischen Silberhalogenidkörner aus dotiert sind, wobei die Hexakoordinationskomplex-Verbindung dargestellt wird durch die folgende Struktur I:

            [ML6]n

    worin M steht für Fe+2, Ru+2, Os+2, Co+3, Rh+3, Ir+3, Pd+3 oder Pt+4, L steht für sechs Koordinationskomplexliganden, die gleich oder verschieden sein können, vorausgesetzt, dass mindestens 3 der Liganden Cyanidionen sind und n steht für -2, -3 oder -4.
  13. Radiografische Bildaufzeichnungszusammenstellung mit:
    A) dem radiografischen Silberhalogenidfilm nach einem der Ansprüche 1 bis 12 und
    B) einem fluoreszierenden Verstärkerschirm mit einem anorganischen Leuchtstoff, der Röntgenstrahlung zu absorbieren vermag und elektromagnetische Strahlung mit einer Wellenlänge von größer als 300 nm zu emittieren vermag.
  14. Radiografische Bildaufzeichnungszusammenstellung nach Anspruch 13, in der der anorganische Leuchtstoff in Form von Teilchen vorliegt, wobei mindestens 50 % der Teilchen eine Größe von weniger als 3 µm haben und mindestens 85 % der Teilchen eine Größe von weniger als 5,5 µm, und wobei die Beschichtungsstärke des anorganischen Leuchtstoffes in der Leuchtstoffschicht bei 260 bis 380 g/m2 liegt.
  15. Verfahren zur Herstellung eines Schwarz-Weiß-Bildes, das umfasst die Exponierung der radio grafischen Bildaufzeichnungszusammenstellung nach Anspruch 13 oder 14 mit Röntgenstrahlung, erzeugt unter Verwendung von Rhodium- oder Wolframanoden in einem Röntgenstrahlen erzeugenden Gerät und Entwicklung des radiografischen Silberhalogenidfilmes in Folge mit einer Schwarz-Weiß-Entwicklerzusammensetzung sowie einer Fixier-Zusammensetzung, wobei das Verfahren innerhalb von 90 Sekunden von trocken-zu-trocken durchgeführt wird.
  16. Bildaufzeichnungsverfahren für die Mammografie, das umfasst die Exponierung einer Patientin mit Röntgenstrahlung unter Verwendung eines Röntgenstrahlen erzeugenden Gerätes mit Rhodium- oder Wolframanoden und Bereitstellung eines Schwarz-Weiß-Bildes der exponierten Patientin unter Anwendung der Bildaufzeichnungszusammenstellung nach Anspruch 13 oder 14.
  17. Verfahren nach Anspruch 16, bei dem die Patientin einer Röntgenstrahlung bei einer Spitzenspannung von größer als 28 kVp exponiert wird.
  18. Verfahren zur Bereitstellung eines Schwarz-Weiß-Bildes, das umfasst die Exponierung der radiografischen Bildaufzeichnungszusammenstellung von Anspruch 13 oder 14 mit Röntgenstrahlung bei einer Spitzenspannung von größer als 28 kVp und die Entwicklung des radiografischen Silberhalogenidfilmes in Folge mit einer Schwarz-Weiß-Entwicklerzusammensetzung sowie einer Fixier-Zusammensetzung, wobei die Entwicklung innerhalb von 90 Sekunden von trocken-zu-trocken durchgeführt wird.
EP03078511A 2002-11-19 2003-11-07 Mammographischer Film und Bildaufzeichnungskombination zur Verwendung mit Rhodium- oder Wolframanoden Expired - Lifetime EP1422557B1 (de)

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US299759 2002-11-19
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US10/299,941 US6828077B2 (en) 2002-11-19 2002-11-19 Mammography imaging method using high peak voltage
US10/299,765 US6864045B2 (en) 2002-11-19 2002-11-19 Mammography film and imaging assembly for use with rhodium or tungsten anodes
US299765 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

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US6350554B1 (en) * 2000-11-06 2002-02-26 Eastman Kodak Company High contrast visually adaptive radiographic film and imaging assembly for orthopedic imaging

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EP0212968A3 (de) * 1985-08-20 1990-01-24 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial
IT1230335B (it) * 1989-07-12 1991-10-18 Minnesota Mining & Mfg Cassetta con schermi di rinforzo per uso con un film radiografico.
US5800976A (en) * 1997-02-18 1998-09-01 Eastman Kodak Company Radiographic elements that satisfy image and tone requirements with minimal silver
EP0862083B1 (de) * 1997-03-01 2004-05-12 Agfa-Gevaert System und Verfahren zur Röntgenbild Herstellung
US6033840A (en) * 1998-10-14 2000-03-07 Eastman Kodak Company Medical diagnostic film for soft tissue imaging (i)

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