EP0933670B1 - Lichtempfindliche Emulsion mit bromidreichen Tafelkörnern, die mit Thiocyanatkomplexen des Rhodiums dotiert sind - Google Patents

Lichtempfindliche Emulsion mit bromidreichen Tafelkörnern, die mit Thiocyanatkomplexen des Rhodiums dotiert sind Download PDF

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Publication number
EP0933670B1
EP0933670B1 EP99200086A EP99200086A EP0933670B1 EP 0933670 B1 EP0933670 B1 EP 0933670B1 EP 99200086 A EP99200086 A EP 99200086A EP 99200086 A EP99200086 A EP 99200086A EP 0933670 B1 EP0933670 B1 EP 0933670B1
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Prior art keywords
grains
emulsion
light
silver
silver halide
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EP99200086A
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English (en)
French (fr)
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EP0933670A1 (de
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Kathy Elst
Dirk Vandenbroucke
Gina Delamper
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • G03C1/0051—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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—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
    • G03C1/0051—Tabular grain emulsions
    • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
    • 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/094—Rhodium
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G03C2007/3025—Silver 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
    • G03C2200/00—Details
    • G03C2200/03—111 crystal face
    • 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
    • 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

  • the present invention deals with a light-sensitive silver halide emulsion having tabular silver halide grains rich in silver bromide and silver halide photographic materials comprising said emulsions.
  • a radiological method using said material particularly suitable for mammographic applications is disclosed.
  • 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 the 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.
  • 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 higher than 3.0.
  • 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 visualisation 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 has been described in US-A 5,290,655.
  • 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 classic article Determination of optimum film density range for röntgenograms from visual effect' by H. Kanamori (Acta Radiol.
  • a silver halide photographic material having a total silver coverage from 6.0 to 9.0 g/m 2 expressed as silver nitrate, wherein the emulsion layer(s) comprise(s) cubic or tabular silver halide grains and wherein the silver coverage of the tabular silver halide grains is lower than the silver coverage of the cubic silver halide grains.
  • Said material is further characterized by a sensitometric curve of optical density as a function of relative logarithmic exposure (hereinafter referred to as logE), having an average gradation of at least 3.5 between the two points where the optical density is Dmin+1.0 and Dmin+2.5 (Dmin being defined as the optical density obtained after processing the unexposed film); a local gradient ranging from 0.7 to 1.8 and an optical density not higher than 3.5 at the point where logE equals SP+0.8 (SP being defined as the logE at which the optical density equals Dmin+1.0); and an optical density of at least 3.7 at the point where logE equals SP+1.3.
  • logE sensitometric curve of optical density as a function of relative logarithmic exposure
  • mammography films are preferred 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.
  • an object of the present invention to provide a radiological method making use from said material in mammographic applications wherein after exposing and processing an image is formed having the desired contrast at differing densities, which is of utmost importance with respect to the high requests put on image quality, especially sharpness, in medical diagnosis.
  • a light-sensitive silver halide photographic emulsion comprising a binder and tabular grains rich in silver bromide, characterized in that said grains contain as a dopant RhCl x (SCN) y , wherein each of x and y are integers having a value of at least 1 and less than 6 so that x+y equals 6.
  • the present invention in order to get light-sensitive silver halide photographic emulsions comprising a binder and tabular grains rich in silver bromide, wherein said grains contain as a dopant RhCl x (SCN) y , wherein each of x and y are integers having a value of at least 1 and less than 6 so that x+y equals 6, the said dopant should be prepared before addition to the reaction vessel wherein said grain are formed.
  • the desired dopant as set forth hereinbefore was obtained by the addition of NaSCN in stoechiometric amounts in order to replace chloride ions by thiocyanate ions in order to obtain the required values of x and y for the complex ion in the dopant.
  • Said amounts of dopant present in silver halide photographic emulsions according to the present invention are from 1 ppb up to 1 ppm versus silver, more particularly from 1 ppb up to 100 ppb and still more preferably from 5 ppb up to 75 ppb.
  • 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 Gd 2 O 2 S: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. in US-A's.
  • a preferred intensifying screen used in the method according to the present 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.
  • mammography films comprise one or more light-sensitive silver halide emulsion layer(s) on only one side of a transparent support, which is typically a blue coloured polyethyleneterephtalate film having a thickness of 175 ⁇ m.
  • a transparent support which is typically a blue coloured polyethyleneterephtalate film having a thickness of 175 ⁇ m.
  • backing layer(s) which operate as anti-halation and anti-curl layer, are present on the opposite side of said support.
  • One or more subbing layers may be coated directly on the support to improve the adhesion of the emulsion and backing layer(s) to the support.
  • an undercoat layer between the emulsion and subbing layer(s) and a protective layer on top of the emulsion layer(s) may be present. Additional non light-sensitive intermediate layers are optional.
  • the light-sensitive emulsion layer(s) of the material according to the present invention comprise(s) tabular silver halide grains as will be illustrated in detail by the working examples. More preferably said tabular grains are ⁇ 111 ⁇ tabular silver bromo(iodide) grains as those described in US-A 5,595,864. ⁇ 111 ⁇ tabular silver halide grains are crystals possessing two parallel (111) faces with a ratio of the diameter of a circle having the same area as these faces versus the thickness, being the distance between the two major faces, equal to at least 2.
  • So emulsions according to the present invention have tabular grains with a ⁇ 111 ⁇ crystal habit with an aspect ratio of more than 2, an average equivalent crystal diameter of at least 0.5 ⁇ m, an average thickness of from 0.06 to 0.30 ⁇ m and wherein said grains account for a total projected area of at least 90 % with respect to all grains present.
  • the precipitation methods of tabular silver halide grains are also extensively described in patent literature. Preferred methods, providing relatively narrow grain size distributions with a variation coefficient of less than 0.30 are described in e.g. US-A 5,290,655.
  • said silver halide emulsions have tabular grains with a hexagonal ⁇ 111 ⁇ crystal habit showing amitual variation coefficient on average crystal diameter of the silver halide distribution of less than 20 %.
  • the silver halide emulsions of the present invention may comprise grains having chloride in combination with bromide or bromoiodide
  • the preferred tabular grain emulsions comprise silver bromide or silver iodobromide grains having bromide in an amount of at least 90 mole %, having an average iodide content of at most 3 mole% and more preferably iodide in an amount of at most 1 mole%.
  • the iodide distribution can be homogeneous over the whole crystal volume or may be present as a so-called core-shell crystal structure, i.e. a silver halide crystal having distinct phases characterized by a different iodide to bromide ratio.
  • Iodide ions can be provided by adding aqueous solutions of inorganic salts thereof as e.g. sodium, potassium or ammonium iodide or by adding organic compounds which are capable of releasing iodide ions as described in the EP-A's Nos. 0 561 415; 0 563 701; 0 563 708; C 649 052 and 0 651 284.
  • gelatin or colloidal silica sol as a binder.
  • the precipitation of the tabular silver halide crystals according to the present invention is indeed performed in the presence of a protective, hydrophilic colloid, e.g. conventional lime-treated or acid treated gelatin but also oxidized gelatin or a synthetic peptiser may be used.
  • a protective, hydrophilic colloid e.g. conventional lime-treated or acid treated gelatin but also oxidized gelatin or a synthetic peptiser may be used.
  • 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 can also be an enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan, No. 16, page 30 (1966).
  • a gelatin concentration of from about 0.05 % to 5.0 % by weight in the dispersion medium.
  • tabular silver halide grains used in emulsions according to the present invention are precipitated in the absence of gelatin by using colloidal silica sol as a protective colloid in the presence of an onium compound, preferably a phosphonium compound, as has been described in EP-A 0 677 773.
  • grain growth restrainers or accelerators may be used during the precipitation or the flow rate or concentration of the silver and halide salt solutions, the temperature, pAg, physical ripening time, etc. may be varied.
  • Silver halide solvents such as ammonia, a thioether compound, thiazolidine-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.
  • 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
  • Another well-known washing technique is ultrafiltration.
  • extra gelatin can be added to the emulsion in order to obtain a gelatin to silver ratio which is optimized with respect to the coating conditions and/or to establish the required thickness of the coated emulsion layer.
  • a gelatin to silver halide weight ratio ranging from 0.3 to 1.0 is then obtained.
  • 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, thicurea, selenosulphate, selenocyanate, selenoureas, tellurosulphate, tellurccyanate, sulphites, mercapto compounds, and rhodamines 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-Patent No. 618,061 may be used.
  • 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 ppm 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. Optionally, small amounts of compounds of Rh, Ru, Pb, Cd, Hg, or Tl can be added.
  • reductors may be added as chemical sensitizers e.g. tin compounds as described in GB-Patent No. 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 as in the present application 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 80 microJoules per 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 can be spectrally sensitized by adding one or several cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • suitable orthochromatic spectral sensitizers are 5,5'-dichloro-3,3'-bis(SO 3 -R)-9-ethylbenz-oxacarbocyanines with R being n-propylene or n-butylene.
  • green-light absorbing spectral sensitizers according to the formulae given in JP-A's 06,035,104; 06,035,101; 06,035,102; 62,191,847; 63,249,839; 01,312,536; 03,200,246; US-A 4,777,125 and DE 3,819,241 may be used.
  • the right choice of said sensitizers or combinations thereof is always related to the purpose of obtaining the highest possible photographic speed while reducing dye stain after processing.
  • Another survey of useful chemical classes of spectral sensitizers is described by F.M.
  • spectral sensitization follows the completion of chemical sensitization.
  • the spectral sensicisation of tabular grains in particular may occur simultaneously with or even precede completely the chemical sensitization step: it is generally recognized that spectral sensitizers may act as site-directors during the formation of sensitivity specks by the chemical sensitization of tabular grains, thereby enhancing their photographic properties.
  • Suitable supersensitizers are, i.a. 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/formaldehyde condensation products as described e.g. in US-A 3,743,510 as well as cadmium salts and azaindene compounds.
  • At least one non-spectrally sensitizing dye can be added to an emulsion layer or to one or more non-light-sensitive hydrophilic layers such as the backing layer(s).
  • the 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.
  • Preferred dyes are those that are removed easily from the photographic material during wet processing in order not to leave any residual colour. When said dyes are added to the emulsion side, it may be preferred that these dyes are nondiffusible during coating of the hydrophilic layers. Examples of such dyes, without being limited thereto, are the dyes that have been described in e.g.
  • the silver halide emulsions 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 can 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
  • the binder of the layers 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.
  • N-methylol compounds as e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives e.g. 2,3-dihydroxy-dioxan, active vinyl compounds e.g. 1,3,5-triacryloyl-hexahydro-s-triazine, active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid.
  • These hardeners can be used alone or in combination.
  • the binder can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US-A's 4,063,952 and with the onium compounds as disclosed in EP-A 0 408 143.
  • 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, silicone-polyethylene 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 sulph
  • 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, sensitization 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. 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.
  • Suitable additives for improving the dimensional stability are i.a. dispersions of a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl (meth)acrylates, alkoxy(meth)acrylates.
  • glycidyl (meth)acrylates (meth)acrylamides, vinyl esters, acrylonitriles, olefins and styrenes, or copolymers of the above with acrylic acids, methacrylic acids, ⁇ - ⁇ -unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulphoalkyl (meth)acrylates, and styrene sulphonic acids.
  • 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-A 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 and the like.
  • the photographic materials according to the present invention are characterized by a neutral silver image tone, obtained after exposure and processing. It is well known that thin tabular emulsion grains may produce a brownish, yellow or even reddish image tone and therefore, tabular grains having an average thickness of 0.2 ⁇ m or more are preferred. On the other hand, a thickness less than 0.3 ⁇ m is also preferred since thicker grains are characterized by a lower covering power of the developed silver, requiring a large amount of silver halide to be present in the photographic material in order to obtain a satisfactory maximum density. Methods to prepare thicker tabular grains have already been described in US-A's 4,801,522; 5,028,521 and 5,013,641 and EP-A 0 569 075.
  • the non-neutral silver image colour 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 03,100,645; 01,029,838; 01,312,536; 03,103,846; 03,094,249; 03,255,435; 61,285,445; EP-B 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 03,153,234; 03,154,043 and 03,154,046 Examples thereof are summarized in JP-A's 03,153,234; 03,154,043 and 03,154,046.
  • JP-A's 03,156,447 and 03,157,645 the adsorption of a blue coloured dye as a function of exposure has further been disclosed.
  • Another method to improve the image tone of tabular grain emulsions consists of mixing them with chloride containing cubic grains, as disclosed in EP-A 0 770 909.
  • the photographic material may comprise preferably in the emulsion layer(s) a compound corresponding to the following formula : wherein Z represents a group of atoms necessary to form a 5- or 6-membered ring and M represents a hydrogen atom, an alkali metal atom or an ammonium group.
  • the compounds of the above formula are preferably added in an amount from 10 -6 to 10 -2 , more preferably 10 -5 to 10 -3 mole per mole of silver in the emulsion layer(s). Representative examples of these compounds are given in US-A 5,290,655.
  • a photographic material comprising a support and coated thereon on at least one side one or more hydrophilic light-sensitive layers, wherein at least one of said layers comprises a silver halide emulsion as disclosed hereinbefore. More preferably according to the present invention said photographic material comprises on only one side of the support only one hydrophilic light-sensitive layer comprising an emulsion as deisclosed herein, wherein light-sensitive tabular grains have a coverage of from 5.0 to 9.0 g/m 2 , expressed as silver nitrate.
  • the said material is particularly suitable for use in mammographic applications.
  • a radiological method for obtaining a diagnostic image for mammography comprising the steps of
  • the photographic materials according to these examples comprise one emulsion layer and one protective layer.
  • the coating solutions of the emulsion layers were prepared by adding solutions of the compounds indicated in Table 1 to the melted emulsion while stirring.
  • the coating solution of the protective layer is given in Table 2. After adjusting pH to 6.7, the viscosity and surface tension of the coating solutions were optimised according to the requirements of the coating method.
  • the emulsion layer(s) and the protective layer were coated simultaneously on one side of a substrated polyester support having a thickness of 175 ⁇ m by means of conventional coating techniques.
  • the silver coverage of the emulsions was about 7 g/m 2 , expressed as an equivalent amount of silver nitrate.
  • the starter solution to be added had the following composition: acetic acid 99 % 15.5 ml KBr 16 g demineralized water up to 100 ml
  • the developed photographic strips were fixed in a conventional fixing bath comprising e.g. sodium thiosulfate and potassium metabisulfite, and then rinsed in water and allowed to dry.Sensitometric properties of these film strips are given in Table 3.
  • This table shows the sensitometric results in terms of fog F (fog multiplied with a factor of 1000 in Table 3)., speed S (figures multiplied with a factor of 100: the lower the figure, the more sensitive is the emulsion), "toe” contrast (gradation) TG , overall contrast GG and "shoulder” contrast or gradation SG of the photographic strips prepared and exposed as set forth above and developed in the developing bath the composition of which has been set forth above during an overall developing time of 12 seconds.
  • the values given in Table 3 for the toe contrast TG are the gradation values measured from the sensitometric curve over a density range of 0.90 starting from a density value of 0.10 up to 1.00 above fog.

Claims (10)

  1. Eine lichtempfindliche fotografische Silberhalogenidemulsion, die ein Bindemittel und silberbromidreiche Tafelkörner enthält, dadurch gekennzeichnet, daß die Körner als Dotiermittel RhClx(SCN)y enthalten, wobei x und y jeweils ganze Zahlen von zumindest 1 und weniger als 6 sind, so daß x + y gleich 6 ist.
  2. Emulsion nach Anspruch 1, dadurch gekennzeichnet, daß das Bindemittel Gelatine oder kolloidales Kieselsol ist.
  3. Emulsion nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Körner einen minimalen Bromidgehalt von 90 mol-% aufweisen.
  4. Emulsion nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Körner einen maximalen Iodidgehalt von 3 mol-% aufweisen.
  5. Emulsion nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Tafelkörner einen {111}-Kristallhabitus mit einem Aspektverhältnis von mehr als 2, einem mittleren äquivalenten Kristalldurchmesser von zumindest 0,5 µm und einer mittleren Stärke zwischen 0,06 und 0,30 µm aufweisen, wobei die Tafelkörner zumindest 90% aller Körner einer totalen projizierten Oberfläche verkörpern.
  6. Emulsion nach Anspruch 5, dadurch gekennzeichnet, daß die Tafelkörner einen hexagonalen {111}-Kristallhabitus mit einem prozentualen Variationskoeffizienten des mittleren Kristalldurchmessers von weniger als 20% aufweisen.
  7. Emulsion nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Dotiermittel in einer Menge zwischen 1 ppb und 1 ppm, bezogen auf die Silbermenge, enthalten ist.
  8. Fotografisches Material, das einen Träger und auf zumindest einer Seite des Trägers eine oder mehrere hydrophile lichtempfindliche Schichten enthält, dadurch gekennzeichnet, daß zumindest eine dieser Schichten eine lichtempfindliche Silberhalogenidemulsion nach einem der Ansprüche 1 bis 7 enthält.
  9. Fotografisches Material nach Anspruch 8, das auf nur einer Seite des Trägers nur eine hydrophile lichtempfindliche Schicht enthält, in der lichtempfindliche Tafelkörner ein als äquivalente Menge Silbernitrat ausgedrücktes Deckvermögen zwischen 5,0 und 9,0 g/m2 aufweisen.
  10. Ein durch die nachstehenden Schritte gekennzeichnetes radiologisches Verfahren zum Erhalt eines mammografischen Diagnosebildes :
    (i) Zusammenstellen eines Film-Folien-Systems, indem ein fotografisches Material nach Anspruch 8 oder 9 in Kontakt mit einer Verstärkerfolie gebracht wird, und
    (ii) Belichtung des Film-Folien-Systems mit Röntgenstrahlung, die durch eine Röntgenstrahlung erzeugende Einrichtung mit einer Röhrenspannung zwischen 20 kV und 40 kV emittiert wird, und
    (iii) Verarbeitung des fotografischen Materials innerhalb einer totalen Trocken/Trocken-Verarbeitungszeit zwischen 38 s und 150 s.
EP99200086A 1998-01-30 1999-01-11 Lichtempfindliche Emulsion mit bromidreichen Tafelkörnern, die mit Thiocyanatkomplexen des Rhodiums dotiert sind Expired - Lifetime EP0933670B1 (de)

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EP99200086A EP0933670B1 (de) 1998-01-30 1999-01-11 Lichtempfindliche Emulsion mit bromidreichen Tafelkörnern, die mit Thiocyanatkomplexen des Rhodiums dotiert sind

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US6342338B1 (en) 1999-11-26 2002-01-29 Agfa-Gevaert Silver halide photographic material exhibiting increased covering power and “colder” blue-black image tone
US6190844B1 (en) * 2000-02-28 2001-02-20 Eastman Kodak Company Method of providing digital image in radiographic film having visually adaptive contrast
US6200723B1 (en) * 2000-02-28 2001-03-13 Eastman Kodak Company Rapidly processable and directly viewable radiographic film with visually adaptive contrast
US6190822B1 (en) * 2000-02-28 2001-02-20 Eastman Kodak Company High contrast visually adaptive radiographic film and imaging assembly
US6573036B2 (en) 2000-04-10 2003-06-03 Afga-Gevaert Single-side coated silver halide photographic film material having reduced tendency to curl
EP1148379B1 (de) * 2000-04-10 2005-11-30 Agfa-Gevaert Einseitig beschichtetes photographisches Silberhalogenidmaterial mit reduzierter Tendenz sich zu Rollen
US6361918B1 (en) * 2000-11-06 2002-03-26 Eastman Kodak Company High speed radiographic film and imaging assembly
US6387586B1 (en) * 2000-11-06 2002-05-14 Eastman Kodak Company High contrast visually adaptive radiographic film and imaging assembly for thoracic imaging
US6358661B1 (en) * 2000-11-06 2002-03-19 Eastman Kodak Company Visually adaptive radiographic film and imaging assembly
US6350554B1 (en) * 2000-11-06 2002-02-26 Eastman Kodak Company High contrast visually adaptive radiographic film and imaging assembly for orthopedic imaging
US6737228B2 (en) * 2001-05-22 2004-05-18 Agfa-Gevaert Film material exhibiting a “colder” blue-black image tone and improved preservation characteristics

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EP0677773A1 (de) * 1994-04-06 1995-10-18 Agfa-Gevaert N.V. Tafelförmige Kristalle enthaltende Silberhalogenidemulsionen und Verfahren zu deren Verarbeitung
US5616446A (en) * 1994-09-29 1997-04-01 Konica Corporation Silver halide photographic light-sensitive material
US5567580A (en) * 1994-10-26 1996-10-22 Eastman Kodak Company Radiographic elements for medical diagnostic imaging exhibiting improved speed-granularity characteristics

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