EP1045283A1 - Strahlungsempfindliche Emulsion, lichtempfindlicher photographischer Silberhalogenidfilm und Kombination eines radiographischen Verstärkungsschirms mit einem Film - Google Patents

Strahlungsempfindliche Emulsion, lichtempfindlicher photographischer Silberhalogenidfilm und Kombination eines radiographischen Verstärkungsschirms mit einem Film Download PDF

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Publication number
EP1045283A1
EP1045283A1 EP99201190A EP99201190A EP1045283A1 EP 1045283 A1 EP1045283 A1 EP 1045283A1 EP 99201190 A EP99201190 A EP 99201190A EP 99201190 A EP99201190 A EP 99201190A EP 1045283 A1 EP1045283 A1 EP 1045283A1
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EP
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Prior art keywords
emulsion
silver halide
substituted
unsubstituted
light
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EP99201190A
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English (en)
French (fr)
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EP1045283B1 (de
Inventor
Kathy Elst
Ann Verbeeck
Paul Callant
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to EP99201190A priority Critical patent/EP1045283B1/de
Priority to DE69900812T priority patent/DE69900812D1/de
Priority to US09/533,378 priority patent/US6200743B1/en
Priority to JP2000110072A priority patent/JP2000321701A/ja
Publication of EP1045283A1 publication Critical patent/EP1045283A1/de
Application granted granted Critical
Publication of EP1045283B1 publication Critical patent/EP1045283B1/de
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/122—Azacyanines
    • 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
    • G03C1/07—Substances influencing grain growth during silver salt formation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—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
    • 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

Definitions

  • the present invention relates to a light-sensitive silver halide photographic emulsion, a material comprising said emulsion and a screen-film combination of a radiographic intensifying phosphor screen and said material.
  • Tabular silver halide grains are grains possessing two parallel crystal faces with an aspect ratio of two or more. Said aspect ratio is defined as the ratio between the diameter of a circle having an equivalent surface area as one of these crystal faces, and the thickness, being the distance between the two major faces.
  • Tabular grains are known in the photographic art for quite some time. As early as 1961 Berry et al. described the preparation and growth of tabular silver bromoiodide grains in Photographic Science and Engineering, Vol 5, No 6. A discussion of tabular grains appeared in Duffin, Photographic Emulsion Chemistry, Focal Press, 1966,p.66-72.
  • a common variability coefficient (defined as a ratio between average standard deviation on equivalent circular diameter and the said average equivalent circular diameter) of 0.30 to 0.60 is calculated, partly due to the presence of quite a large number of non-tabular grains having a sphere equivalent diameter of less than 0.3 ⁇ m. Moreover differences in thickness growth are observed, said differences leading to unevenness as a consequence of observed differences in image tone.
  • Heterodispersity of grain morphology further leads to e.g. uncontrolled chemical and spectral sensitization, lower contrast and lower covering power, thereby losing typical advantages of the said grains as referred to hereinbefore.
  • Combinations of intensifying screens provided with luminescent phosphors and light-sensitive silver halide photographic materials are conventionally used for medical diagnosis.
  • the luminescent phosphors in the screen panel or panels are converting X-rays into visible radiation, thereby exposing the film material in contact with the said panel (for single-side coated materials as e.g. in mammography) or panels (for duplitized materials as e.g. in chest imaging).
  • 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.
  • 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.
  • most mammography films today comprise good developable cubic silver halide crystals.
  • cubic crystals show a stable speed and contrast upon varying processing parameters, but said cubic grain emulsions however are characterized by a very high contrast, resulting in a poor skin line perceptibility.
  • tabular grains are mainly concerned with high sensitive silver bromide or silver bromoiodide emulsions.
  • Tabular grain emulsions having a high aspect ratio are known to provide several advantages over more conventional spherical grains as e.g. a high covering power, a high (spectral) sensitivity and a lower coating weight, which saves costs in manufacturing.
  • Said lower coating weight is especially preferred if rapid processing applications, preferably accompanied by low replenishing amounts of developer and fixer, are required, which is nowadays an ever more returning demand.
  • rapid processing applications preferably accompanied by low replenishing amounts of developer and fixer
  • literature is scarce with respect to the use of antihalation dyes and dye stain mostly results from the presence after processing of residual amounts from the normally used high amounts of spectral sensitizing dyes, especially in the presence of tabular grain emulsions having a large surface to volume ratio.
  • Said spectrally sensitizing dyes are well known in the art of photography, especially for green and red sensitization of flat tabular grains, whereas for blue and/or ultraviolet sensitization the number of examples is rather limited. Further it is known to use in mammography combinations of green-emitting phosphor screens with film materials containing green sensitized tabular grain emulsions. After processing of exposed emulsion grains residual amounts of dyes may be present, especially due to the presence of huge amounts of spectral sensitizing dyes as tabular grains have a large specific surface capable of adsorbing said huge amounts. Those huge amounts are further in favour of high speed and image quality (especially sharpness), required in diagnostic imaging where it is further of utmost importance to reduce irradiation of the patient to minimum levels.
  • the present invention is especially useful in mammographic applications, wherein, for reasons of good image definition light-sensitive layers are present on only one side of the film support.
  • Image formation therein proceeds with a system consisting of only one intensifying screen, wherein a high speed, a high contrast (preferably a high "toe contrast") and low residual dye stain are desired.
  • Specific measures taken therefor have e.g. been described in US-A 5,290,655; in EP-A's 0 264 788 and 0 577 027 and in Research Disclosure No. 33487 (1992), p.
  • It is a further object of the present invention to provide a light-sensitive silver halide photographic material comprising a support and on one or both sides thereof at least one light-sensitive hydrophilic layer comprising such grains in order to be applicable in combination with luminescent intensifying screens and more particularly to provide a screen-film image-forming combination or system wherein a light-sensitive silver halide photographic material as set forth before is combined with an intensifying screen in order to obtain an image suitable for medical diagnosis, having a very high image quality, i.e., low fog level, high overall-contrast with an enhanced sharpness (low cross-over) after rapid processing of the said material, and, more particularly, wherein little or no residual colour or dye stain is observed in the processed material.
  • a very high image quality i.e., low fog level, high overall-contrast with an enhanced sharpness (low cross-over) after rapid processing of the said material, and, more particularly, wherein little or no residual colour or dye stain is observed in the processed material.
  • a spectrally sensitized emulsion wherein said emulsion comprises ⁇ 111 ⁇ tabular silver halide grains having an average aspect ratio of at least 2 with two flat parallel ⁇ 111 ⁇ crystal faces accounting for a total projective surface of said parallel crystal faces in said emulsion of at least 50 %, characterized in that a site-directing compound is present at said faces, said formula satisfying general formula I as described hereinafter.
  • a light-sensitive silver halide photographic film material comprising a support and on one or both sides thereof at least one light-sensitive emulsion layer having an emulsion as disclosed has also been claimed as well as a radiographic screen/film combination comprising such a light-sensitive silver halide photographic film material and a supporting or self-supporting X-ray intensifying screen, characterized in that said supported or self-supporting X-ray intensifying screen essentially consists of luminescent phosphor particles emitting green light, more particularly light in the wavelength range between 540 and 555 nm for which the said emulsion having ⁇ 111 ⁇ tabular crystal faces has been made sensitive by the presence of a J-aggregating dye.
  • Said screen/film combination is further particularly suitable for, use in mammographic applications as well as for radiographic chest imaging.
  • the presence of one or more azacyanine dye is favorable as a compound present in the preparation of, preferably green-sensitized, tabular grain emulsions rich in silver bromide, coated in at least one light-sensitive emulsion layer of a silver halide photographic material, wherein said layer or layers has(have) been coated on one or both sides of a support.
  • said material is suitable for use in a screen/film system of the present invention as claimed hereinafter and makes the objects of the present invention to become effectively realized, wherein the said azacyanine dyes are added to the tabular grain emulsions before addition of other dyes or stabilizers and more preferably before starting chemical sensitization.
  • aza- or diazacyanine dyes suitable for use as dyes for silver halide emulsions according to the present invention has been described in US-A 2,307,049.
  • Azamethine dyes made with arylene diamine can be found in US-A 2,368,305 and are suitable for use in the preparation of ⁇ 111 ⁇ tabular emulsions of the present invention as well.
  • Other suitable aza-pseudocyanines originally suitable for use as optical brighteners have been disclosed in US-A 3,130,197, as well as acid substituted azaquino-pseudo-cyanines or cyazines, disclosed in US-A 3,697,282 for use as spectral sensitizers in colour materials.
  • Symmetrical and unsymmetrical quinoline azacyanine dyes can further be used as those disclosed in BE 812431 and in CS 1976695 respectively, or the more recently disclosed pseudo-cyanine or azamethine dyes in US-A 4,977,076.
  • Azacyanines cited in the foregoing references are all suitable for use in the preparation of ⁇ 111 ⁇ tabular emulsions used in the material and the film/screen system according to the present invention.
  • Specific azacyanine dyes particularly suitable for use in the emulsions, materials and in the film-screen system according to the present invention are following:
  • each of R and R' independently represents (CH 2 ) n H or (CH 2 ) n OH, n being an integer having a value from 1 to 4, (CH 2 ) m (SO 3 - ) or (CH 2 ) m O(SO 3 - ), m being an integer having a value from 2 to 4, (CH 2 ) 2 CH(Y)SO 3 - wherein Y represents CH 3 -, -Cl or -OH; (CH 2 ) m N(R)SO 3 - or (CH 2 ) m N(R')SO 3 - (CH 2 ) n (COO - ) or (CH 2 ) n (COOH), (CH 2 ) s SO 2 - (CH 2 ) t H wherein s equals 2 or 3 and t equals 1 or 2; (CH 2 ) x -Phen-W, wherein W represents -COO - or SO 3 - ; Phen represents phenyl which is substituted
  • charge compensating cations are Li + , Na + , K + , HN + Et 3 , wherein Et represents ethyl, whereas preferred charge compensating anions are Cl - , Br - , I - , - OTos, - OMes, CF 3 SO 3 - , wherein - OTos represents tosylate and - OMes represents mesylate.
  • the light emitted imagewise by said X-ray intensifying screen irradiates a contacting photographic silver halide emulsion layer film which after exposure is developed to form therein a silver image in conformity with the X-ray image.
  • the X-ray film for use e.g. in mammographic diagnosis comprises a transparent film support, coated on only one side with a silver halide emulsion layer.
  • said film (made sensitive to green light by spectral sensitization of its light-sensitive emulsion grains) is arranged in a cassette with one X-ray intensifying screen (emitting green light by suitable luminescent phosphors) making contact with the silver halide emulsion layer.
  • Luminescent phosphors suitable for use in the conventional radiographic system must have a high prompt emission of fluorescent light on X-ray irradiation and low afterglow in favour of image sharpness.
  • the relationship between resolution and speed of X-ray intensifying screens has been described e.g. in Med. Phys. 5(3), 205 (1978).
  • Specific intensifying screens emitting green for use in the diagnostic image forming method according to the present invention are the commercially available X-ray generating devices 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 used in the film/screen system according to the present invention is Gd 2 O 2 S:Tb, which emits green light in the wavelength range from 540 tot 555 nm as required for mammographic applications.
  • Said phosphor and its use in intensifying screens have been described extensively in patent literature, e.g. in US-A's. 3,872,309; 4,130,429; 4,912,333; 4,925,594; 4,994,355; 5,021,327; 5,107,125 and 5,259,016 and in GB-Patent 1,489,398 and is suitable for use in the context of the film/screen system according to the present invention.
  • X-ray intensifying screens according to the present invention can be self-supporting or supported.
  • X-ray intensifying screens in accordance with the present invention generally comprise in order: a support (also called substrate), at least one layer comprising phosphor particles dispersed in a suitable binder and a protective coating coated over the phosphor containing layer to protect said layer during use. Further, a primer layer is sometimes provided between the phosphor containing layer and the substrate to closely bond said layer thereto.
  • 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.
  • the emulsion preferably comprises ⁇ 111 ⁇ tabular silver bromide or silver bromoiodide grains or crystals, optionally having from 0 to 10 mole % of chloride ions, have two parallel (hexagonal) (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 or more than 2; an average equivalent crystal diameter of at least 0.3 ⁇ m, and more preferably of at least 0.5 ⁇ m up to 3.0 ⁇ m; an average thickness of from 0.06 to 0.30 ⁇ m and said grains account for a total projected area of at least 50 %, preferably at least 70 % and even more preferably more than 90% with respect to all grains present.
  • said silver halide emulsions have tabular grains with a hexagonal ⁇ 111 ⁇ tabular crystal habit show a habitual 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 according to the present invention 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 0 561 415; 0 563 701; 0 563 708; 0 649 052 and 0 651 284.
  • azacyanines do not work as spectral sensitizers on grains rich in silver bromide. Opposite thereto azacyanines may be successfully applied as blue/ultraviolet sensitizers for ⁇ 111 ⁇ tabular grains rich in silver chloride as has extensively been described in EP-A 0 890 873. As said azacyanines should be considered as non-J-aggregating dyes, the emulsions according to the present invention correspond to a specific embodiment of the emulsions as claimed in EP-Application No. 98201401 filed April 29, 1998.
  • a light-sensitive silver halide emulsion comprising tabular grains having an aspect ratio of at least 2:1 (more preferably between from 5:1 to 50:1 and still more preferably from 8:1 to 20:1, an average crystal diameter between 0.3 ⁇ m and 3.0 ⁇ m (more preferably between 0.5 ⁇ m and 3.0 ⁇ m) and an average thickness of less than 0.50 ⁇ m (more preferably between 0.06 and 0.25 ⁇ m) accounting for at least 50 % (more preferably more than 70 % and even more preferably more than 90 %) of the total projective surface area of said grains, further having at least one J-band aggregating dye and at least one non-J-band aggregating dye.
  • ⁇ 111 ⁇ tabular grain emulsions have 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
  • 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 further 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, followed by one or more washing and redispersion steps.
  • 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, thiourea, selenosulphate, selenocyanate, selenoureas, tellurosulphate, tellurocyanate, 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, Pd, 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.
  • 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.
  • azacyanines according to the general formula (I) are added before addition of other addenda such as the chemical ripening agents and/or spectral sensitizers mentioned hereinbefore.
  • the time between adding said azacyanine dyes and said ripening agents and/or spectral sensitizers is long enough in order to provide the azacyanine dyes perform their (habit) stabilizing action on the grown emulsion crystals.
  • the silver halide emulsion grains present in a radiographic film as in the present application are spectrally sensitized in order to optimally detect the light emitted from the X-ray conversion screen. So in case of a preferred mammography film its spectral sensitivity is 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.
  • the radiation-sensitive emulsion has silver halide grains sensitive to irradiation in the wavelength range between 540 and 555 nm by the presence of a J-aggregating spectrally sensitizing cyanine dye.
  • Preferred (orthochromatic) spectral sensitizers or dyes are J-aggregating dyes corresponding to the general formula (II) wherein
  • the J-aggregating cyanine dye corresponds to the general formula (II) wherein R 7 is -C 2 H 5 , Z and Z' are both representing an oxygen atom, at least one of R 5 and R 6 represents
  • the J-aggregating cyanine dye corresponds to the general formula (II) wherein R 11 is hydrogen, Z is an nitrogen atom, T represents hydrogen, 5-phenyl, 5-Cl, 5-OCH 3 or 5-CH 3 and wherein T' represents 5,6-(Cl) 2 ; 5-CN-6-Cl; 5-CF 3 -6-Cl; 5-Cl; 5-CN, 5-CF 3 , 5-CHF 2 , 5-SO 2 CH 3 or 5-SO 2 R 12 (R 12 representing a fluoro-subsituted or non-fluoro-substituted alkyl group), 5-COOR 13 and 5-SO 2 -N(R x )(R y ) or 5-CO-N(R x )(R y ), wherein R x and R y each independently represents substituted or unsubstited alkyl groups, which may form a ring with the N-atom to which they are attached.
  • each of Z and Z' represents oxygen and each of T and T' represents Cl or, alternatively, T represents Cl and T' represents Phenyl or vice versa and wherein further R 5 and R 6 represent all combinations of the formulae -(CH 2 ) n SO 3 - wherein n equals 2, 3 or 4, -(CH 2 ) 2 -CH(CH 3 )-SO 3 - and -CH 2 -CHY-CH 2 -SO 3 - wherein Y represents -OH or -Cl; and wherein R 5 , corresponding to the formulae given above, is combined with R 6 corresponding to the formulae -(CH 2 ) j H wherein j equals 1, 2, 3 or 4; -CH 2 -Phen-SO 3 - -CH 2 -Phen-COOH -(CH 2 ) k -Phen-COOH wherein k equals 1, 2 or 3. -(CH 2 ) 1 -COOH, wherein 1 equal
  • said J-aggregating spectrally sensitizing dye is a 5,5'-dichloro-3,3'-bis(SO 3 -R)-9-ethyl-benzoxacarbocyanine with R being n-propylene or n-butylene and more particularly anhydro-5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyloxacarbocyanine hydroxide or anhydro-5,5'-dichloro-3,3'-bis(n-sulphopropyl)-9-ethyloxa-carbocyanine hydroxide.
  • 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 with the purpose of obtaining the highest possible photographic speed while reducing dye stain after processing.
  • J-aggregating spectral sensitizers more particularly with respect to the purposes to get reduced dye stain azacyanine dyes are used in the preparation of ⁇ 111 ⁇ tabular grain emulsions as the presence of said dyes permits addition of J-aggregating spectral sensitizers, more preferably green sensitizers, in lower amounts, without loss in speed, thereby providing better decolouration in the processing.
  • J-aggregating spectral sensitizers more preferably green sensitizers
  • spectral sensitization follows the completion of chemical sensitization.
  • the spectral sensitization of tabular grains in particular may occur simultaneously with or even completely precede the chemical sensitization step: it is generally recognized that spectral sensitizers themselves may act as site-directors during the formation of sensitivity specks by the chemical sensitization of tabular grains, thereby enhancing their photographic properties.
  • site-directing action should be performed first by azacyanine dyes before other spectrally sensitizing dyes.
  • the radiation-sensitive emulsion according to the present invention has one or more azacyanine dye(s) and (a) J-aggregating spectrally sensitizing dye(s) in a ratio amount of more than 1:4 for a grain coverage exceeding 50 %.
  • 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 non-diffusible 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
  • fog-inhibiting compounds are those described in Research Disclosure No. 17643 (1978), Chaptre VI. These fog-inhibiting agents or stabilizers can 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 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.
  • a light-sensitive silver halide photographic film material is further provided, wherein said material comprises a support and on one or both sides thereof at least one light-sensitive emulsion layer having an emulsion as disclosed hereinbefore.
  • 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.
  • coating aids as compounds preventing electric charges
  • compounds improving film transport in automatic film handling equipment as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion
  • 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. It may be advantageous to partially substitute the hydrophilic colloid binder, preferably gelatin, of 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.
  • 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 according to the present invention 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 between 0.20 and 0.3 ⁇ m may is not always preferred since thicker grains are characterized by a lower covering power of the developed silver, requiring a large amount of silver halide in the photographic material in order to obtain a satisfactory maximum density. Methods to prepare thicker tabular grains may however be applied as has 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 03100645; 01029838; 01312536; 03103846; 03094249; 03255435; 61285445; EP-A 0 271 309 and in 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 03153234; 03154043 and 03154046 Examples thereof are summarized in JP-A 03153234; 03154043 and 03154046.
  • JP-A's 03156447 and 03157645 the adsorption of a blue coloured dye as a function of exposure has further been disclosed.
  • the photographic material according to the present invention 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.
  • This material may be used in colour photography or black-and-white photography, as in micrographic films, aviation photography, cinéfilm, hardcopy films, nondestructive testing applications, laserfilms, graphic and reprographic films, and in radiography.
  • said photographic material comprises on only one side of the support only one hydrophilic light-sensitive layer comprising an emulsion as disclosed herein, wherein light-sensitive tabular grains have a coverage of from 3.0 to 9.0 g/m 2 , more preferably from 5.0 to 9.0 g/m 2 , expressed as silver nitrate.
  • the said material is particularly suitable for use in radiographic applications, and, more preferably, in mammographic applications.
  • radiographic screen/film combinations comprising a light-sensitive silver halide photographic film material as disclosed hereinbefore is provided and a supporting or self-supporting X-ray intensifying screen, characterized in that said supported or self-supporting X-ray intensifying screen essentially consists of luminescent phosphor particles emitting green light.
  • a radiographic screen/film combination is provided wherein said luminescent phosphor is Gd2O2S:Tb.
  • a radiographic screen/film combination is provided wherein the total amount of coated silver halide in said film, expressed as an equivalent amount of silver nitrate, is less than 7.5 g/m 2 .
  • an automatically operating apparatus is used provided with a system for automatic replenishment of the processing solutions.
  • the processing dry-to-dry within a short processing time of from 30 to 90 seconds and more preferably from 30 seconds to less than 60 seconds of materials coated from low amounts of silver is made possible by the steps of
  • a normally used configuration in the processing apparatus shows the following consecutive tank units corresponding with, as consecutive solutions: developer-fixer-rinse water.
  • developer-fixer-rinse water As consecutive solutions the sequence developer-fixer-fixer-rinse water-rinse water is preferred.
  • One washing step between developing and fixation and one at the end before drying may also be present.
  • a particularly suitable developer solution is the one comprising a reduced amount of sulphite and ascorbic acid which acts as a main developer and anti-oxidant as well and which is called "low-sludge" developer as has e.g. been described in EP-A 0 851 282 and in EP-Applications Nos. 98203412 and 98204079, filed October 8 and November 30, 1998, respectively.
  • a particularly suitable fixer solution comprises an amount of less than 25 g of potassium sulphite per liter without the presence of acetic acid wherein said fixer has a pH value of at least 4.5, in order to make the fixer solution quasi odourless as illustrated in EP-A 0 908 764.
  • preferred minimum regeneration or replenishment amounts are also from about 20 to 200 ml/m 2 , more preferred from 20 to 100 ml/m 2 and still more preferred from 20 to 50 ml/m 2 of developed material.
  • aluminum ions are present in the fixer solution in order to effect hardening, it is necessary to adjust the pH of the fixer in the range from 4.2 to 4.6 in order to get the highest hardening reactivity and to suppress swelling with washing water in the washing or rinsing step.
  • fixer pH For hardened materials having a swelling degree of the hydrophilic layers of less than 250 % and more preferably of less than 200 % it is not required for the fixer pH to held constant in the pH range from 4.2 to 4.6 as mentioned before: in order to reduce irritating smell from sulphite ions in aqueous acidic medium which lead to sulphur dioxide vapour it is recommended to enhance pH to a value of 4.65 up to 5.00.
  • a process whereby the quality of the fixer remains at an optimum level has been described in EP-A 0 872 764.
  • a radiological method for obtaining a diagnostic image for mammography comprising the steps of
  • the same method is applied with respect to e.g. chest-imaging applications, apart for
  • A1 at a constant flow rate of 7.5 ml/min, and B1 at a flow rate, controlled in order to maintain pAg at 8.85, were added in a double jet over a period of 1 minute. This double jet was continued during another period of 2002 seconds, while the flow rate of A1 was linearly increased up to 22.5 ml/min and pAg was maintained at 8.85. This period was called "first growth step”. 5 minutes after the completion of said double jet addition, A1 was added at 7.5 ml/min during 440 seconds.
  • 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.
  • 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
  • the gradation was measured from the characteristic curve over a density range of 1.75 starting from a density value of 0.25 up to 2.00 above fog. Gradation values have been multiplied by a factor of 100.
  • Residual colour can thus be lowered by addition of lower amounts of green-sensitizing dye (see comparative materials TC1-TC3 but, accordingly, speed and contrast also lowered.
  • the presence of azacyanine compounds added before green-sensitizing dyes however permits use of said lower amounts of said green-sensitizing dye without significant loss in speed or contrast.
  • A1 at a rate of 7.5 ml/min.
  • B1 at a rate of 7.6 ml/min.
  • A1 and B1 were added during 2675 seconds at a linearly increasing rate going from 7.5 up to 15 ml/min. for A1 and from 7.6 up to 15.21 ml/min. in order to maintain a constant UAg potential of + 10 mV in the reaction vessel.
  • A1 was added during 263 seconds at a rate of 7.5 ml/min. in order to increase the UAg value to 60 mV.
  • each emulsion was stabilized with 1-p-carboxyphenyl-5-mercaptotetrazole and after addition of the normal coating additives the solutions were coated simultaneously together with a protective layer containing 1.3 g gelatine per m 2 per side on both sides of a polyethylene terephthalate film support having a thickness of 175 ⁇ m.
  • the resulting photographic material contained per side an amount of silver halide corresponding to an amount of x' grams of silver per m 2 as indicated in Table 4. Materials have been numbered from 1 to 15.
  • the density as a function of the light dose was measured and therefrom were determined the following parameters:
  • 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 further added in a double jet precipitation step during 60 seconds at a rate of 10.0 and 10.04 ml/min., followed by double jet addition 4865 seconds at a rate linearly increasing up to 46.49 ml/min. for A1 and up to 46.69 ml/min. for B1 in order to hold a constant Uag potential of + 50 mV in the reaction vessel.
  • An increase of amounts of gold makes speed and contrast increase, more particularly when use has been made from an azacyanine compound (compare sensitometric results obtained for Materials Nos. 16 and 19, 17 and 20 and 18 and 21): no loss in speed is observed and gradation even tends to increase provided that lower amounts of sulphur and selenium are used in the chemical ripening.

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EP99201190A 1999-04-16 1999-04-16 Strahlungsempfindliche Emulsion, lichtempfindlicher photographischer Silberhalogenidfilm und Kombination eines radiographischen Verstärkungsschirms mit einem Film Expired - Lifetime EP1045283B1 (de)

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EP99201190A EP1045283B1 (de) 1999-04-16 1999-04-16 Strahlungsempfindliche Emulsion, lichtempfindlicher photographischer Silberhalogenidfilm und Kombination eines radiographischen Verstärkungsschirms mit einem Film
DE69900812T DE69900812D1 (de) 1999-04-16 1999-04-16 Strahlungsempfindliche Emulsion, lichtempfindlicher photographischer Silberhalogenidfilm und Kombination eines radiographischen Verstärkungsschirms mit einem Film
US09/533,378 US6200743B1 (en) 1999-04-16 2000-03-22 Radiation-sensitive emulsion, light-sensitive silver halide photographic film material and radiographic intensifying screen-film combination
JP2000110072A JP2000321701A (ja) 1999-04-16 2000-04-12 放射線感受性乳剤、感光性ハロゲン化銀写真フィルム材料及び放射線増感スクリーン−フィルム組合せ

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1103848B1 (de) * 1999-11-26 2007-01-17 Agfa-Gevaert Lichtempfindliches photographisches Silberhalogenidfilmmaterial und eine Kombination eines radiographischen Verstärkungsschirms mit diesem Film
WO2023088869A3 (en) * 2021-11-17 2023-07-06 Merck Patent Gmbh Compositions and methods for improving metal structure fabrication by wet chemical etch

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2080050A (en) * 1934-08-03 1937-05-11 Ilford Ltd Sensitization of photographic emulsions
US3850645A (en) * 1973-08-14 1974-11-26 Eastman Kodak Co Non-polymeric peptizers for silver halide suspensions
EP0758760A1 (de) * 1995-08-10 1997-02-19 Eastman Kodak Company Zweiseitigbeschichtete radiographische Elemente enthaltend Emulsionen mit tafelförmigen Körnen, die verbesserte Bindemittel enthalten
EP0890873A1 (de) * 1997-07-11 1999-01-13 Agfa-Gevaert N.V. Kombination von radiographischen UV/blau Verstärkerschirm und Film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2080050A (en) * 1934-08-03 1937-05-11 Ilford Ltd Sensitization of photographic emulsions
US3850645A (en) * 1973-08-14 1974-11-26 Eastman Kodak Co Non-polymeric peptizers for silver halide suspensions
EP0758760A1 (de) * 1995-08-10 1997-02-19 Eastman Kodak Company Zweiseitigbeschichtete radiographische Elemente enthaltend Emulsionen mit tafelförmigen Körnen, die verbesserte Bindemittel enthalten
EP0890873A1 (de) * 1997-07-11 1999-01-13 Agfa-Gevaert N.V. Kombination von radiographischen UV/blau Verstärkerschirm und Film

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1103848B1 (de) * 1999-11-26 2007-01-17 Agfa-Gevaert Lichtempfindliches photographisches Silberhalogenidfilmmaterial und eine Kombination eines radiographischen Verstärkungsschirms mit diesem Film
WO2023088869A3 (en) * 2021-11-17 2023-07-06 Merck Patent Gmbh Compositions and methods for improving metal structure fabrication by wet chemical etch

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