EP1246005A1 - Matériau photographique à l'halogénure d'argent pour la mammographie - Google Patents

Matériau photographique à l'halogénure d'argent pour la mammographie Download PDF

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Publication number
EP1246005A1
EP1246005A1 EP01000090A EP01000090A EP1246005A1 EP 1246005 A1 EP1246005 A1 EP 1246005A1 EP 01000090 A EP01000090 A EP 01000090A EP 01000090 A EP01000090 A EP 01000090A EP 1246005 A1 EP1246005 A1 EP 1246005A1
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EP
European Patent Office
Prior art keywords
layer unit
silver
density
silver halide
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
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EP01000090A
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German (de)
English (en)
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EP1246005B1 (fr
Inventor
Marc c/o AGFA-GEVAERT Van den Zegel
Francis c/o AGFA-GEVAERT Vanhoudt
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Agfa Gevaert NV
Agfa Gevaert AG
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Agfa Gevaert NV
Agfa Gevaert AG
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Priority to EP20010000090 priority Critical patent/EP1246005B1/fr
Priority to DE60124070T priority patent/DE60124070D1/de
Priority to US10/100,102 priority patent/US6573019B1/en
Publication of EP1246005A1 publication Critical patent/EP1246005A1/fr
Application granted granted Critical
Publication of EP1246005B1 publication Critical patent/EP1246005B1/fr
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/46—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
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03511—Bromide content
    • 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
    • G03C2001/03558—Iodide content
    • 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
    • G03C2200/26—Gamma

Definitions

  • the mortality rate from breast cancer can be decreased significantly by early detection using the radiological mammography technique.
  • the compressed breast is irradiated with soft X-rays emitted from an X-ray generating device and modulated X-rays are detected with a radiographic X-ray conversion screen, also called intensifying screen, fluorescent screen or phosphor screen.
  • the X-ray conversion screen comprises a luminescent phosphor which converts the absorbed X-rays into visible light and the emitted visible light exposes a silver halide film that is brought into contact with said X-ray conversion screen.
  • film processing comprising the steps of developing, fixing, rinsing and drying, a mammogram is obtained which can be read on a light box.
  • Image quality is manifested by a number of features in the image including sharpness, noise, contrast, silver image colour and skin line perceptibility. It is common practice to set the amount of X-ray exposure so that the tissues on the inside of the breast are depicted at medium optical density values, i.e.
  • Dmin in the optical density range from [Dmin+1.0] to [Dmin+2.5]
  • Dmin being defined as the [base+fog]-density obtained after processing the unexposed film
  • the diagnostic perceptibility of small, potentially malignant lesions in these tissues is highly determined by the contrast of the mammography film within said density range.
  • a quantitative measure of the film contrast is the so-called average gradation, defined as the slope of the line drawn by connecting both points of the sensitometric curve of optical density vs. logarithmic exposure at which the optical density is equal to [Dmin+1.0] and [Dmin+2.5].
  • the low contrast type can be characterized by a relatively low average gradation ranging from 2.0 to 2.5, whereas the average gradation of the high contrast type may range from 3.0 to 3.5.
  • high contrast films are preferred because of the higher ability to detect tiny cancers deep in the glandular tissue of the breast. If the contrast is too high, however, it may preclude visualization of both thin (i.e. the skin line) and thick tissues (i.e. the inside of the breast) in the same image due to lack of exposure latitude. Therefore, some radiologists prefer low contrast mammography films. When the contrast is low, skin line perceptibility is excellent, but then the chance of missing possibly malignant breast lesions is high. Thus a balance has to be found between contrast and exposure latitude and an example of this approach is described in US-A 5,290,665.
  • a film characterized by a higher maximum density e.g. a Dmax equal to at least 3.7, preferably even higher than 4.0.
  • Dmax maximum density
  • a film characterized by a higher "Dmax” is only a minor improvement with regard to better skin line perceptibility, since the background density is too high for the skin line to be clearly visible.
  • the local gradient i.e. the slope of the sensitometric curve, must be very high in order to guarantee a reasonable perceptibility as described in the well-known article titled "Determination of optimum film density range for röntgenograms from visual effect" by H.
  • mammography films which comprise silver halide crystals that can be processed rapidly and consistently in a dry-to-dry processing cycle of 90 seconds or less and therefore, most mammography films today comprise good developable cubic silver halide crystals.
  • cubic crystals show a stable speed and contrast upon varying processing parameters. Cubic emulsions however are characterized by a very high contrast, resulting in a poor skin line perceptibility.
  • tabular silver halide emulsion crystals are characterized by a much lower contrast than cubic silver halide emulsions and thus are only applicable for manufacturing low contrast mammography films.
  • Another drawback of these tabular emulsions is the residual color after processing: due to the larger specific area of the tabular grains compared e.g. with cubic crystals having the same crystal volume, these tabular grains require higher amounts of spectrally sensitizing dye(s), which may leave dye stain after the short processing cycle. Also the brownish color of the developed silver image of thin tabular grains, resulting in an undesired image tone, is a disadvantage for mammography making use of the said tabular grains.
  • a high pressure sensitivity as coated minimum amounts of hydrophilic colloidal binder are envisaged on one hand and questionable archivability as a consequence of long fixing times, shortened in order to provide ending processing within shortened rapid processing cycles at the other hand, clearly lay burden on the most critical feature in mammography, being "image quality", and more particularly "sharpness".
  • a radiographic film material for recording medical diagnostic images of soft tissue through exposure to light, emitted by a single intensifying screen, after having been subjecting to exposure with X-rays, emitted from an X-ray generating device with a tube voltage of 20 kV to 40 kV, and processing, including development, fixing and drying, within a time of 120 seconds (and more preferably 90 seconds or less), wherein said film is comprised of a transparent film support, front and back major faces and an image-forming portion for providing, when imagewise exposed by light emitted by said intensifying screen and processed, an average contrast or gradient in the range from 3.0 up to 4.5, measured over a density above fog in the range of from 0.25 to 2.00, and wherein said image-forming portion is comprised of layer units permeable for aqueous processing solutions, said layer units being
  • a process for obtaining a medical diagnostic image of soft tissue comprising the steps of mounting a radiographic film as claimed adjacent to a single intensifying screen, exposing the intensifying screen to an image pattern of X-radiation that has passed through the soft tissue to provoke light emission by the intensifying screen that imagewise exposes the radiographic film, and processing the radiographic film, including development, fixing and drying in less than 120 (and more preferably 90) seconds.
  • a radiographic film for recording medical diagnostic images of soft tissue is thus characterized by the presence, at both sides of a transparent film support, of light-sensitive silver halide emulsion layers, wherein the silver halide emulsions essentially have cubic emulsion crystals.
  • the term "essentially cubic" is indicative for the presence, in an amount of at least 90, more preferably at least 95 and even more preferably at least 99 % by number of crystals having a ⁇ 100 ⁇ crystal habit and thus (100) crystal faces, wherein edges may be sharp or rounded-off (e.g.
  • silver solubilizing growth accelerators such as ammonia or methionine, a thioether compound, thazolidine-2-thione, tetra-substituted thiourea, potassium or ammonium rhodanide and an amine compound may be present during grain precipitation in order to adjust the average grain size) and wherein it is even not excluded that cubo-octaeders are present, provided that (111) crystal faces therein represent not more than 10 %, more preferably not more than 5 % and even more preferably not more than 1 % of the total projective area of all crystal faces present, and wherein (100) faces are clearly representing the majority of the crystal faces present in the emulsions.
  • silver solubilizing growth accelerators such as ammonia or methionine, a thioether compound, thazolidine-2-thione, tetra-substituted thiourea, potassium or ammonium rhodanide and an amine compound may
  • the class of so-called cubic grains embraces (a) perfectly cubic crystals, or (b) cubic crystals with rounded corners, or (c) cubic crystals with small (111) faces at the corners (also known as tetradecahedrical grains), the total area of these (111) faces however being small compared to the total area of the (100) faces. Presence of cubo-octahedral shapes which are not excluded depends on the pAg values applied during the precipitation.
  • so preferred methods for the precipitation of cubic grains are the pAg-balanced double- or triple-jet methods as described in EP-A's 0 712 036 and 0 610 609, since these methods provide monodispersed emulsions characterized by a narrow grain size distribution defined in that at least 95 % by weight or number of the grains have a diameter within about 40 %, preferably within about 30 % of the average grain size and more preferably within about 10% to 20%.
  • the variation coefficient of the emulsion grains according to this invention has preferably a low value of between 0.15 and 0.20, and still more preferably of 0.10, said variation coefficient being defined as the ratio between the standard deviation of the grain size and the average grain size.
  • the silver halide grains are obtained by conventional precipitation techniques which are well known in the art and consist of the addition of aqueous solutions of silver and halide salts, e.g. silver nitrate and sodium, potassium or ammonium halide to a solution comprising a protective colloid.
  • aqueous solutions of silver and halide salts e.g. silver nitrate and sodium, potassium or ammonium halide
  • use is often made of variable flow rates in order to provide (and controll) crystal growth to be performed at a higher rate and to perform precipitation in more concentrated reaction vessels which may even lead to variability coefficients over the grain distributions in the range from 0.10 up to 0.20.
  • the light-sensitive emulsion layer in the back layer unit which, in favour of skin line perceptibility, should contribute to the total density of the processed material, wherein the back layer unit should exhibit an optical density of at least 1.00 in the wavelength region of the exposing radiation.
  • the grain size of the cubic grain emulsions can be determined using conventional techniques, e.g. as described by Trivelli and Smith, The Photographic Journal, vol. 69, 1939, p.330-338, Loveland “ASTM symposium on light microscopy” 1953, p.94-122 and Mees and James “The Theory of the photographic process” (1977), Chapter II.
  • the material is coated with light(radiation)-sensitive emulsion layers having cubic emulsion grains in the front and in the back layer unit, wherein the radiation-sensitive silver halide grains are containing more than 50 mole % of silver bromide and less than 3 mole % of silver iodide, more preferably less than 2 mole % based on total molar silver amounts.
  • the said radiation-sensitive silver halide grains are silver bromide or silver bromoiodide grains, containing up to at most 1 mole % of silver iodide, based on silver.
  • Differences in silver iodide content, if present, between front and back layer units, are preferably directed to a lower iodide content in the back layer unit, in that less than 1 mole % of iodide, and more preferably about 0.5 mole % of iodide is present, based on silver.
  • Silver iodide present in lower amounts than silver bromide can be distributed in a homogeneously (continuously) or heterogeneously (for so-called "core-shell emulsions" having a core wherein iodide concentrations are lower or higher than in the shell or shells adjacent thereto).
  • pure silver bromide cubes may still be "doped" with silver iodide by application of the so-called “conversion"-technique, wherein silver iodide is formed by conversion at the grain surface after addition of organic or inorganic compounds relasing iodide ions, such as potassium iodide or the iodide releasing compounds described in EP-A's 0 563 701, 0 563 708 and 0 651 284.
  • silver iodide is added in form of ultrafine silver iodide grains of about 0.050 ⁇ m or even smaller (also called “micrate emulsions") after stopping precipitation in the precipitation method or after having ended precipitation, so that silver iodide is located at dedicated sites in the cubic grains.
  • Precipitation of silver halide crystals suitable for use in emulsion layers according to the present invention is performed in the presence of a protective, hydrophilic colloid, which should be chosedn with care: e.g. conventional lime-treated or acid treated gelatin can be used, but also oxidized gelatin (generally known as gelatin having less than 30 p.p.m. of methionine) or a synthetic peptizer.
  • a protective, hydrophilic colloid which should be chosedn with care: e.g. conventional lime-treated or acid treated gelatin can be used, but also oxidized gelatin (generally known as gelatin having less than 30 p.p.m. of methionine) or a synthetic peptizer.
  • the preparation of such modified gelatin types has been described in e.g. "The Science and Technology of Gelatin", edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 and next pages.
  • the gelatin may also be an enzyme-treated gelatin as described
  • Cubic silver halide grains may also be precipitated in absence of gelatin, e.g. by making use of colloidal silica as a protective colloid in the presence of an onium compound, as described in EP-A's 0 677 773 and 0 649 051; or in the alternative by making use of cationic oxidized starch as has been disclosed e.g. in EP-A 0 758 759.
  • the emulsion is made free from excess of soluble inorganic salts by a conventional washing technique e.g. flocculation by ammonium sulphate or polystyrene sulphonate, followed by one or more washing and redispersion steps.
  • a conventional washing technique e.g. flocculation by ammonium sulphate or polystyrene sulphonate, followed by one or more washing and redispersion steps.
  • these compounds or combinations thereof are applied in combination with a noble metal salt, preferably a gold complex salt, but also salts of platinum, palladium and iridium as described in US-A 2,448,060 and GB-A 618,061 may be used. Description of chemical sensitization techniques can be found in Research Disclosure, Item 38957, Chapter IV.
  • the amount of gold, used in the chemical ripening of emulsions according to the present invention is preferably in the range of 25 to 45 p.p.m. vs. the amount of metallic silver.
  • Additions of sulphur and/or selenium and/or tellurium and gold may be carried out consecutively or simultaneously. In the latter case the addition of goldthiosulphate, goldselenosulphate or goldtellurosulphate compounds may be recommended.
  • small amounts of dopants in form of complexing agents of Rh, Ru, Os, Pt or Ir can be added if not yet performed in the course of grain precipitation in order to get grain occlusions other than silver and halide as disclosed in Research Disclosure, Item 38957, Section I; or in more general terms of transition metal hexacoordination complexes as dopants for increasing imaging speed by providing or as so-called SET's (shallow electron trapping agents as described in Research Disclosure, Vol. 367, Nov. 1994, Item 36736.
  • reductors may be added as chemical sensitizers as e.g.
  • tin compounds as described in GB-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • the chemical sensitization can also proceed in the presence of phenidone and/or its derivatives, a dihydroxybenzene as hydroquinone, resorcinol, catechol and/or a derivative(s) thereof, one or more stabilizer(s) or antifoggant(s), one or more spectral sensitizer(s) or combinations of said ingredients.
  • the silver halide emulsions may be chemically sensitized according to the procedures described in e.g. "Chimie et Physique Photographique” by P. Glafkides, in “Photographic Emulsion Chemistry” by G.F. Duffin, in “Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in “Die Grundlagen der Photographischen mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
  • chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur,selenium or tellurium e.g.
  • thiosulphate thiocyanate, thiourea, selenosulphate, selenocyanate, selenoureas, tellurosulphate, tellurocyanate, sulphites, mercapto compounds, and rhodamines.
  • these compounds or combinations thereof are applied in combination with a noble metal salt, preferably a gold complex salt, but also salts of platinum, palladium and iridium as described in US-A 2,448,060 and 5,759,760 and in GB-A 618,061 may be used.
  • Amounts of gold, used in the chemical ripening of emulsions in order to get the most preferred contrast in the toe portion of the sensitometric curve have been disclosed e.g. in EP-A's 0 610 609 and 0 712 036. Additions of sulphur and/or selenium and/or tellurium and gold may be carried out consecutively or simultaneously.
  • goldthiosulphate goldselenosulphate or goldtellurosulphate compounds
  • goldtellurosulphate compounds small amounts of compounds (complexing agents) of Rh, Ru, Os or Ir can be added.
  • reductors may be added as chemical sensitizers as e.g. tin compounds as described in GB-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • the chemical sensitization can also proceed in the presence of phenidone and/or its derivatives, a dihydroxybenzene as hydroquinone, resorcinol, catechol and/or a derivative(s) thereof, one or more stabilizer(s) or antifoggant(s), one or more spectral sensitizer(s) or combinations of said ingredients.
  • the silver halide grains present in a mammography film are spectrally sensitized in order to optimally detect the light emitted from the X-ray conversion screen.
  • a preferred mammography film is characterized by a spectral sensitivity ranging from 5 to 130 ⁇ J/m 2 measured at the emission maximum of the X-ray conversion screen, said spectral sensitivity being defined herein as the amount of exposure to light of a given wavelength required to obtain an optical density Dmin + 1.0 after processing.
  • the silver halide emulsion are spectrally sensitized by adding one or several cyanine dyes, merocyanine dyes, complex, cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Preferred examples of suitable orthochromatic (J-aggregating) spectral sensitizers are 5,5'-dichloro-3,3'-bis(SO3-R)-9-ethylbenzoxacarbo-cyanines with R being n-propylene or n-butylene.
  • the silver halide grains present in a mammography film are spectrally sensitized in order to optimally detect the light emitted from the X-ray conversion screen.
  • a preferred mammography film is characterized by a spectral sensitivity ranging from 5 to 130 ⁇ J/m 2 measured at the emission maximum of the X-ray conversion screen, said spectral sensitivity being defined herein as the amount of exposure to light of a given wavelength required to obtain an optical density Dmin + 1.0 after processing.
  • the light-sensitive emulsion layers at both sides of the transparent support which is typically a blue coloured polyethylene terephtalate (PET) film having a thickness of 175 ⁇ m
  • the radiographic material is coated with a hydrophilic front layer unit coated on the front major face of the support (to be contacted with the sole intensifying screen when exposed to "soft" X-rays, generated from a device with a tube voltage of 20 kV to 40 kV, as is typical for mammographic applications) wherein the front layer unit is capable of reaching a maximum density of more than 3.00, and even more preferably more than 3.5, after processing and wherein sensitivity (speed), measured at a density of 0.50 above fog, is higher for the front layer unit than for the back layer unit in an amount of from 0.70 up to 1.70 log (Exposure) and in a more preferred embodiment the back layer unit has a speed ranging from 1.00 log E to 1.50 log E
  • the front layer is coated with cubic silver halide emulsion crystals in an amount, expressed as equivalent amount of silver nitrate, of less than 8.5 g/m2 and more preferably in the range from 6.0 to 7.0 g/m2, but always more than 4.0 g/m2.
  • the radiation-sensitive cubic silver halide emulsion grains therein have an average grain size in the range of from 0.45 ⁇ m up to 0.85 ⁇ m.
  • Coating amounts of hardenable hydrophilic colloid, composing the front layer unit are, in a preferred embodiment, limited to less than 5.0 g/m2 and, more preferably to less than 4.0 g/m2, and coating amounts of non-hardenable hydrophilic colloid are limited to less than 60 weight % thereof; in order to provide the desired sensitometric and drying properties within the short running time (within 120 seconds, and more preferably less than 90 seconds) of the processing cycle as will be described hereinafter.
  • the said back layer unit is coated with radiation-sensitive cubic silver halide grains accounting for less than 40 % (but not less than 1/5) of the total radiation-sensitive silver halide present in the film, preferably in an amount of not more than 3 g/m2, expressed as equivalent amount of silver nitrate, wherein said cubic grains having an average grain size in the range from 0.40 up to 0.60 ⁇ m.
  • the hydrophilic backing layer unit coated on the back major face of the support further contains hardenable hydrophilic colloid limited to less than 4.0 g/m2, (more preferably in the range from 2.0 up to 3.0 g/m2) and non-hardenabe hydrophilic colloid limited to less than 60 weight % thereof.
  • a total amount of silver halide coated in the material (sum of coating amounts at both sides for both - front and back - layer units), expressed as equivalent amount of silver nitrate again, should be in the range from 6.0 up to 10.0 g/m2.
  • the image-forming portion in the material according to the present invention is, as a consequence of its composition, as disclosed hereinbefore, further comprised of a hydrophilic front layer unit coated on the front major face of the support capable of absorbing up to at least 60 %, and more preferably even more than 70 %, of the exposing radiation.
  • the cubic grains in the back layer unit exhibiting a speed that ranges from 0.3 log E to 1.0 log E slower than in the front layer unit, provide facilitating visualization of anatomical features in the region of the skin-line.
  • E stands for "Exposure” and speed (sensitivity) is measured at a density of 1.0 above fog for the front as well as for the back layer unit.
  • hardenable hydrophilic colloid in the whole back layer unit should be limited to less than or at most 3.0 g/m2, and should, more preferably, be situated in the range from 2.0 to 2.5 g/m2, whereas in the whole front layer unit it should be limited to less than 4.0 g/m2, more preferably be situated in the range from 3.5 to 3.9 g/m2.
  • the non-hardenabe hydrophilic colloid In the back layer unit the non-hardenabe hydrophilic colloid, the presence of which is preferably limited to the light-sensitive emulsion layer thereof, should be limited to less than 10 wt %, but more than 5 wt %, versus the total amount of hardenable hydrophilic colloid present in the whole back layer unit.
  • the non-hardenabe hydrophilic colloid is present in the light-sensitive emulsion layer thereof in an amount of more than 50 wt % and even up to 60 wt %, versus the amount of hardenable hydrophilic colloid present in the light-sensitive layer, which means that in the whole front layer unit the said non-hardenable hydrophilic colloid is present in an amount of about 30 wt% (preferably in the range from 25 up to 35 wt%).
  • whole back layer unit it is understood that, according to the present invention, besides the subbed support a density providing layer is present, situated farther from the said support, and adjacent thereto the emulsion layer is present, further covered by an outermost protective antistress layer as a topcoat layer, whereas the terminology “whole front layer unit” is indicative, according to the present invention, besides the subbed support, for a light-sensitive emulsion layer adjacent to the said subbed support, and wherein said emulsion layer is covered by an outermost protective antistress layer as a topcoat layer, wherein this protective layer must be hardened to an extent in order to avoid scratches due to contact made with the intensifying screen during exposure.
  • subbing layers coated directly on the thus provide subbed support it is clear that these layers are coated (preferably during stretching the polyester in order to get the support of the desired thickness) in order to improve the adhesion of the radiation-sensitive emulsion layer of the front layer unit and the non-radiation sensitive dye containing layer of the back layer unit to the support.
  • an undercoat layer between the emulsion and subbing layer(s) and a protective layer on top of the emulsion layer(s) is present.
  • Additional non light-sensitive intermediate layers are optional.
  • a single-side coated light-sensitive silver halide photographic film material comprising, on one side of a subbed support, one or more light-sensitive silver halide emulsion layer(s) overcoated with an outermost protective layer; said emulsion layer(s) having silver halide grains dispersed in binder, wherein said silver halide is coated in a total amount, expressed as an equivalent amount of silver nitrate of more than 5 g per m 2 , a latex polymer present in an amount of less than 30 % by weight versus said binder, and, at the other side of said support, a backing layer, covered with a protective outermost layer, characterized in that at least said backing layer is provided in at least one layer thereof, besides a cross-linked or cross-linkable first binder, with an organic component as a second binder, wherein said organic component is free from cross-linking upon reaction with a hardener and wherein said organic component is a polymer selected from the group consisting
  • a first cross-linkable binder called hardenable hydrophilic colloid in the present invention and present in amounts in the front layer unit and in the back layer unit as disclosed hereinbefore, besides a second binder, called herein "non-hardenable hydrophilic colloid", being a polymer selected from the group consisting of dextran having an average molecular weight from 1000 up to 100000, polyacrylamide having an average molecular weight from 1000 up to 100000, polyvinyl-pyrrolidone, polyvinyl alcohol and gelatin of the type which is free from cross-linking upon reaction with a hardener, more preferably a polymer selected from the group consisting of dextran having a molecular weight of not more than 20000 and polyacrylamide having a molecular weight not more than 20000.
  • Amounts at both sides of the support are differing from those disclosed in the cited EP-Application as an equilibrium in order to prevent the processed material from curling had to be sought, due to the presence of light-sensitive emulsion layers at both sides of that support now, moreover being complicated by the presence of coating amounts of silver (expressed as equivalent amount of silver nitrate) at both sides, clearly differing from each other.
  • topcoat layer of the front layer unit is coated from an amount of gelatin of about 1.0 up to 1.2 g/m2, corresponding with a coating amount twice as high as coated in the topcoat layer of the back layer unit, and wherein, even when the "density providing layer" in the back layer unit contains about 0.5 g/m2 of gelatin amounts of gelatin in the back layer unit are not exceeding 60 wt% of the total amount of gelatin coated in the whole front layer unit.
  • amounts of hardener should be added to the respective layer units in order to get a perfect balance for the material when leaving the processor as a dried film material bearing the image to be examined.
  • amounts of water absorption before processing should be different at the front layer unit side versus at the back layer unit side due to the required differences in hardening degrees, but should become about equal after processing: as dextran is a non-hardenable polymer binder, present in higher amounts in the emulsion layer(s) of the front layer unit - more than 0.5 g/m2, more preferably more than 1.0 g/m2 and even more preferably more than 1.5 g/m2) in an amount of about 10 times the amounts in the emulsion layer(s) of the back layer unit, the highest amounts will leave the photographic material from the front layer unit during processing, and more particularly during the rinsing step, the better for dextran having a lower molecular weight (M.W.
  • gelatin is used as a preferred polymer binder material, which can be forehardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type, e.g. 1,3-vinylsulphonyl-2-propanol or di-(vinylsulphonyl)-methane, vinylsulphonyl-ether compounds, vinylsulphonyl compounds having soluble groups, chromium salts like e.g. chromium acetate and chromium alum, aldehydes as e.g.
  • Topcoat layers present as outermost layers at both sides of the material according to the present invention have a protective function and are coated from hydrophilic colloid in an amount of from about 1.1 g/m2 and 0.5 g/m2 in the front and in the back layer unit respectively, wherein those amounts are not to be considered as being limitative as amounts differing therefrom may be applied.
  • a density providing layer is present as an additional layer in the back layer unit: situated in a layer farther from the support than the emulsion layer(s), it represents a layer containing a dye in an amount in order to provide a density of at most 0.40 (about 0.40 in green light; about 0.30 in white light) before, and less than 0.10 after processing, due to decolorization of said dye in an alkaline developer.
  • the dye exhibits a half peak absorption bandwidth over the spectral region of peak emission by the intensifying screen.
  • dyes suitable for use in the density providing layer have been described in EP-A's 0 489 973, 0 586 748, 0 587 229, 0 587 230, 0 656 401, 0 786 497 and 0 781 816, as well in the US-A's corresponding therewith.
  • dye according to the formula (I) hereinafter the preparation method of which has been described in US-A 5,344,749.
  • Still another technique to obtain ultra fine dye dispersions consists in acidifying a slightly alkaline coating composition "in situ" just before coating it onto the supporting layer. Further useful information about dyes having decolorizing characteristics in alkaline processing solutions can be found in Research Disclosure, Item 38957, Chapter VIII. Presence of such dye(s) in adapted amounts is not only recommended to adjust the sensitivity of the different emulsion layers and eventually the required contrast, but also in order to reduce scattering of exposure radiation and thus to enhance sharpness.
  • the radiographic material according to the present invention has a spectral sensitivity maximum by the adsorption of spectral sensitizers disclosed hereinbefore, absorbing light from the phosphors prompt emitting light in the wavelength range from 540 to 555 nm after having been irradiated with X-rays, said maximum corresponding with an exposure amount from 5 to 130 ⁇ J per m2 required in order to obtain an optical density of Dmin+1.0 after processing.
  • Suitable supersensitizers are e.g. heterocyclic mercapto compounds containing at least one electronegative substituent as described e.g. in US-A 3,457,078, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds as described e.g. in US-A's 2,933,390 and 3,635,721, aromatic organic acid/for-maldehyde condensation products as described e.g. in US-A 3,743,510 as well as cadmium salts, although nowadays to be avoided, due to ecological considerations, and azaindene compounds.
  • heterocyclic mercapto compounds containing at least one electronegative substituent as described e.g. in US-A 3,457,078, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds as described e.g. in US-A's 2,933,390 and 3,635,721, aromatic organic acid/for-maldehyde condensation products as described e.g. in US-A 3,743,
  • the silver halide emulsions suitable for use in hydrophilic layers of the film material according to the present invention may also comprise compounds preventing the formation of a high minimum density or stabilizing the photographic properties during the production or storage of photographic materials or during the photographic treatment thereof.
  • Many known compounds may be added as fog-inhibiting agent or stabilizer to the silver halide emulsion. Suitable examples are i.a.
  • heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles (preferably 5-methyl-benzotriazole), nitrobenzotriazoles, mercaptotetrazoles, in particular 1-phenyl-5-mercapto-tetrazole, mercaptopyrimidines, mercaptotriazines, benzothiazoline-2-thione, oxazoline-thione, triazaindenes, tetrazaindenes and pentazaindenes, especially those described by Birr in Z.
  • benzothiazolium salts such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlor
  • fog-inhibiting agents or stabilizers may be added to the silver halide emulsion prior to, during, or after the ripening thereof and mixtures of two or more of these compounds can be used.
  • the photographic material according to the present invention may further comprise various kinds of surface-active agents in the light-sensitive emulsion layer(s) or in at least one other hydrophilic colloid layer.
  • Suitable surface-active agents include non-ionic agents such as saponins, alkylene oxides, e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, siliconepolyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides, anionic agents comprising an acid group such as a carboxyl, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic
  • Such surface-active agents can be used for various purposes, e.g. as coating aids, as compounds preventing electric charges, as compounds improving film transport in automatic film handling equipment, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving photographic properties such as higher contrast, sensitisation and development acceleration.
  • development acceleration may be useful, which can be accomplished with the aid of various compounds, preferably polyoxyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-A's 3,038,805; 4,038,075 and 4,292,400.
  • Especially preferred developing accelerators are recurrent thioether groups containing polyoxyethylenes as described in DE 2,360,878, EP-A's 0,634,688 and 0,674,215, which are incorporated herein by reference. The same or different or a mixture of different developing accelerators may be added to at least one of the hydrophilic layers at the emulsion side.
  • hydrophilic colloid binder preferably gelatin
  • the hydrophilic colloid binder preferably gelatin
  • the hydrophilic colloid binder preferably gelatin
  • the light-sensitive silver halide emulsion layer or of an hydrophilic colloid layer in water-permeable relationship therewith by suitable amounts of dextran or dextran derivatives to improve the covering power of the silver image formed and to provide a higher resistance to abrasion in wet condition.
  • the photographic material of the present invention may further comprise various other additives such as compounds improving the dimensional stability of the photographic material, UV-absorbers, spacing agents, lubricants, plasticizers, antistatic agents, etc. as those described in Research Disclosure, Item 38957, Chapter IX, particularly referring to coating physical property modifying addenda, as coating aids (A), plasticizers and lubricants (B), antistatic agents (C), and matting agents (D).
  • Suitable additives for improving the dimensional stability are i.a. dispersions of a water-soluble or hardly soluble synthetic polymer e.g.
  • Suitable UV-absorbers are e.g. aryl-substituted benzotriazole compounds as described in US-A 3,533,794, 4-thiazolidone compounds as described in US-A's 3,314,794 and 3,352,681, benzophenone compounds as described in JP-A 2784/71, cinnamic ester compounds as described in US-A's 3,705,805 and 3,707,375, butadiene compounds as described in US-A 4,045,229, and benzoxazole compounds as described in US-P 3,700,455.
  • the average particle size of spacing agents is comprised between 0.2 and 10 ⁇ m.
  • Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic material, whereas alkali-soluble spacing agents usually are removed in an alkaline processing bath.
  • Suitable spacing agents can be made i.a. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydrophthalate. Other suitable spacing agents have been described in US-A 4,614,708.
  • acetamide or polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerine.
  • a polymer latex is preferably incorporated into the hydrophilic colloid layer for the purpose of improving the anti-pressure properties, e.g. a homopolymer of acrylic acid alkyl ester or a copolymer thereof with acrylic acid, a copolymer of styrene and butadiene, and a homopolymer or copolymer consisting of monomers having an active methylene group.
  • the photographic material may comprise an antistatic layer to avoid static discharges during coating, processing and other handling of the material.
  • antistatic layer may be an outermost coating like the protective layer or an afterlayer or a stratum of one or more antistatic agents or a coating applied directly to the film support or other support and overcoated with a barrier or gelatin layer.
  • Antistatic compounds suitable for use in such layers are e.g. vanadium pentoxide soles, tin oxide soles or conductive polymers such as polyethylene oxides or a polymer latex;, polythiopene (and more particularly PEDT) and the like.
  • Non-neutral silver image colours obtained after processing, due to the colour of the silver thus formed, can be corrected by increasing the optical density in the red region of the visible spectrum by adding suitable dyes to the support or any coated layer.
  • This non-image wise colour correction method has been disclosed in references as e.g. JP-A's 03-100645, 01-029838, 01-312536, 03-103846, 03-094249, 03-255435, 61-285445; issued EP-A 0 271 309 and US-A 4,861,702.
  • This method however may result in an excessive base + fog density of the photographic material and therefore, an alternative way consists in an image-wise colour correction by using colour-forming developers, which are blue coloured in their oxidized form.
  • JP-A's 03-153234, 03-154043 and 03-154046 Examples thereof have been summarized in JP-A's 03-153234, 03-154043 and 03-154046.
  • JP-A's 03-156447 and 03-157645 the adsorption of a blue coloured dye as a function of exposure has further been disclosed.
  • the processing of the exposed material includes the steps of developing, fixing and drying, is performed within 120 seconds or less and more preferably within 90 seconds or less.
  • An important advantage of the dual- or double-side coated radiographic elements for soft tissue imaging is that they are much better suited for rapid processing applications than radiographic elements containing a single emulsion layer unit. This suitability for rapid processing is particularly due to the fact that high amounts of silver are not restricted to presence in only one radiation-sensitive emulsion layer and to the fact that, opposite to duplitized films as for chest imaging in radiology, low cross-over can only be attained the presence of two antihalation layers, interposed between the support and each emulsion layer unit.
  • an average contrast or gradient in the range from 3.0 up to 4.5, measured over a density above fog in the range of from 0.25 to 2.00, is thus attained, wherein said image-forming portion is comprised of layer units permeable for aqueous processing solutions, said layer units being a hydrophilic front layer unit coated on the front major face of the support wherein the front layer unit is capable of reaching a maximum density of more than 3.00 and a hydrophilic back layer unit coated on the back major face of the support, wherein sensitivity (speed), measured at a density of 0.50 above fog, is higher for the front layer unit than for the back layer unit in an amount of from 0.70 up to 1.70 log (Exposure), thanks to the presence in both, the front layer unit and the back layer unit, of the presence of one or more light-sensitive silver halide emulsion layer(s) coated with emulsion crystals, essentially having a cubic crystal habit.
  • a radiological method for obtaining a diagnostic image for mammography comprising the steps of mounting a film-screen system by bringing a photographic material as disclosed herein into contact with a radiographic X-ray conversion screen; and processing said photographic material in a total dry-to-dry processing time of from 38 seconds up to less than 120 seconds, and, more preferably, in a dry-to-dry processing time of from 45 up to 90 seconds.
  • Sensitometric curves of processed film materials are known to show the plot of optical density (D) as a function of relative logarithmic exposure (logE).
  • SL skin line point
  • a practical mammogram is normally obtained by subjecting a film-screen system to X-ray exposure.
  • any commercially available X-ray generating device may be used, providing an exposure to soft X-rays with a tube voltage of 20 to 40 kV.
  • a preferred luminescent phosphor coated in the X-ray conversion screen is Gd2O2S:Tb, which emits green light in the wavelength range from 540 tot 555 nm. Said phosphor and its use in intensifying screens have been described extensively in patent literature, e.g.
  • a preferred intensifying screen used in combination with the film material according to this invention is characterized by a phosphor coating weight of at least 45 mg/cm 2 and a phosphor to binder ratio of at least 97:3 as described in EP-A 0 712 036.
  • Protective layer I (amounts in g/m 2 )
  • Emulsion layer I (amounts in g/m 2 ) :
  • Emulsion layer II (amounts in g/m 2 ):
  • Emulsion layer III (amounts in g/m 2 ):
  • Antihalation layer I (amounts in g/m 2 ):
  • Antihalation layer II (amounts expressed in g/m 2 ) :
  • Emulsion preparation of emulsions having cubic/tabular crystals respectively:
  • a solution was prepared of 6.9 g of oxidized gelatin in 3 1 of demineralized water at 51°C, adjusted to a pH of 2.5 by adding H 2 SO 4 , and said solution was stirred at a rate of 600 r.p.m..
  • A1 0.98 M AgNO 3
  • B1 0.98 M KBr
  • UAg was controlled (expressed in mV versus a Ag/AgCl(sat.) reference electrode and should be in the range from 44.5 ⁇ 5 mV at a temperature of 70°C ⁇ 1°C.
  • pH was set to a value of 5.0 ⁇ 0.3 and immediately thereafter a solution of 50 g of inert gelatin in 500 ml of demineralized water of 70°C was added.
  • B1 was added at a rate of 7.06 ml/min. during 120 seconds, while simultaneously adding by double jet A1 at a rate of 7.5 ml/min..
  • A1 and B1 were added during 2822 seconds at a linearly increasing rate going from 7.0 up to 21.11 ml/min. for A1 and from 7.06 up to 21.29 ml/min. in order to maintain a constant UAg potential of + 40 mV in the reaction vessel.
  • A1 and B1 were simultaneously added by double-jet addition during 60 seconds at a rate of 10.0 and 10.04 ml/min. respectively whereby the UAg value was held at a constant value of 50 mV while increasing the flow rate up to 46.49 ml/min. and 46.69 ml/min. respectively over a total time period of 81 min. and 5 seconds.
  • Samples of Film Materials A, B and C, the layer arrangement of which has been given hereinbefore, were identically exposed from the front-side with green light (filter Corning 4010) during 2.0 seconds, making use of a continuous wedge.
  • the samples were processed in a CURIX 530 , tradename of Agfa-Gevaert N.V., automatic processing machine.
  • Processing sequence and conditions in the said CURIX 530 processing machine were following (expressed in seconds(sec.), temperature (in °C) added thereto: loading 3.4 sec. developing 23.4 sec./35°C in developer cross-over 3.8 sec. fixing 15.7 sec./35°C in fixer G334 cross-over 3.8 sec. rinsing 15.7 sec./20°C drying 32.2 sec. (cross-over time included) total time 98.0 sec.
  • Samples of the film materials were processed in an "active" developer and in a "weak” developer, the weak developer being a model for less optimal development conditions:
  • Table I shows values of fog "F”, speed “S”, contrasts "GG” and "GGSKIN” after processing samples of film materials A (comparative), B (inventive) and C (comparative) in the active (AD) and weak developer (WD) respectively.
  • Figures of fog F have been multiplied by a factor of 1000; all other figures have been multiplied by a factor of 100.
  • Film Matl AD WD ⁇ (AD - WD) F S GG GGSKIN F S GG GGSKIN F S GG GGSKIN A 205 138 390 161 198 146 370 141 -7 -8 -20 -20 B 211 141 380 153 203 147 350 148 -8 -7 -30 -5 C 208 145 369 156 201 151 352 128 -7 -6 -17 -28
  • Differences in speed (measured at a density of 0.5 above fog) between the front and back layer unit for inventive material B were calculated before and after washing off the front layer unit from the material B, processed in a G138 developer/G334® fixer combination after exposure to X-rays of the said material, being in intimate contact with an intensifying mammographic screen Mamoray HD® (trademarketed product from Agfa-Gevaert N.V., Mortsel, Belgium, at the front layer side thereof: a difference of 1.30 log E (Exposure) was calculated.
  • Mamoray HD® trademarketed product from Agfa-Gevaert N.V., Mortsel, Belgium
  • the film allows rapid processing by good developability within a cycle of at most 120 seconds and provides high levels of image sharpness and a good image tone in processing cycles having differing activities, thereby showing good archivability and drying capacity.

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  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP20010000090 2001-03-29 2001-03-29 Matériau photographique à l'halogénure d'argent pour la mammographie Expired - Lifetime EP1246005B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP20010000090 EP1246005B1 (fr) 2001-03-29 2001-03-29 Matériau photographique à l'halogénure d'argent pour la mammographie
DE60124070T DE60124070D1 (de) 2001-03-29 2001-03-29 Photographisches Silberhalogenid-Material für die Mammographie
US10/100,102 US6573019B1 (en) 2001-03-29 2002-03-18 Photographic silver halide photographic material for mammography

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0384633A2 (fr) * 1989-02-23 1990-08-29 Eastman Kodak Company Eléments radiographiques avec des rapports de sensibilité sélectionnés
EP0440367A1 (fr) * 1990-01-23 1991-08-07 Konica Corporation Matériau photographique À  l'halogénure d'argent sensible à la lumière ayant une haute sensibilité et une grande finesse
EP0874275A1 (fr) * 1997-04-23 1998-10-28 Agfa-Gevaert N.V. Produit photographique à l'halogénure d'argent pour la mammographie

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0384633A2 (fr) * 1989-02-23 1990-08-29 Eastman Kodak Company Eléments radiographiques avec des rapports de sensibilité sélectionnés
EP0440367A1 (fr) * 1990-01-23 1991-08-07 Konica Corporation Matériau photographique À  l'halogénure d'argent sensible à la lumière ayant une haute sensibilité et une grande finesse
EP0874275A1 (fr) * 1997-04-23 1998-10-28 Agfa-Gevaert N.V. Produit photographique à l'halogénure d'argent pour la mammographie

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