EP1103847B1 - Pellicule photographique à l'halogénure d'argent ayant un pouvoir opacifiant accru et un ton de l'image noir bleuâtre "plus froid" - Google Patents

Pellicule photographique à l'halogénure d'argent ayant un pouvoir opacifiant accru et un ton de l'image noir bleuâtre "plus froid" Download PDF

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Publication number
EP1103847B1
EP1103847B1 EP00203916A EP00203916A EP1103847B1 EP 1103847 B1 EP1103847 B1 EP 1103847B1 EP 00203916 A EP00203916 A EP 00203916A EP 00203916 A EP00203916 A EP 00203916A EP 1103847 B1 EP1103847 B1 EP 1103847B1
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Prior art keywords
silver
silver halide
coated
layer
grains
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EP00203916A
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German (de)
English (en)
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EP1103847A1 (fr
Inventor
Ann Verbeeck
Govert De Baecke
Johan Loccufier
Freddy Hendrickx
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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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
    • G03C1/0051—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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • 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
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
    • 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
    • G03C1/37—Antiseptic agents
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • G03C2001/7635—Protective layer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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 black-and-white light-sensitive silver halide photographic film material, particularly suitable for use in radiography and a combination of one or two intensifying luminescent phosphor screen(s) and said film material comprising in the light-sensitive emulsion layers hexagonal ⁇ 111 ⁇ tabular emulsion grains.
  • the film materials are coated with relatively high amounts of silver, in order to provide a suitable sensitometry even if a low radiation dose is applied to the patient as is always desirable.
  • ⁇ 111 ⁇ tabular silver halide grains permits coating of lower amounts of silver, if compared e.g. with grains having a more globular shape as applied before practical application of said tabular grains, there remains the need to provide an acceptable image tone after development of materials having light-sensitive silver halide layers containing said tabular grains.
  • EP-A-575262 describes a radiographic element with increased covering power, the element containing fabular silver bromide, bromochloride or bromoiodide grains and a specifically substituted azole compound.
  • a black-and-white silver halide photographic film material (especially for use in radiography)
  • said material comprises a transparent film support having first and second major surfaces coated with a subbing layer, further coated adjacent thereto on one side (for a single-side coated material) or on both sides (for a duplitized material) of said film support, optionally in contact with a hydrophilic undercoat layer and overcoated with a protective antistress layer, a light-sensitive silver halide emulsion layer having chemically and spectrally sensitized ⁇ 111 ⁇ tabular hexagonal grains, accounting for at least 50 %, more preferably at least 70 % and still more preferably at least 90 % of the total projective surface of all grains, with a mean equivalent volume diameter of from 0.3 ⁇ m up to 1.0 ⁇ m and an average grain thickness of less than 0.30 ⁇ m, wherein said film material is coated with a total amount of silver, expressed as an equivalent amount of silver nitrate of less than 7 g/m2,
  • a silver halide photographic film material (especially for use in radiography) has thus been provided, wherein said material comprises a transparent film support having first and second major surfaces coated with a subbing layer, and having on one or both sides a light-sensitive emulsion layer having ⁇ 111 ⁇ tabular hexagonal silver halide emulsions, wherein said layer is overcoated with a protective antistress layer at one or both sides of the film support, leading to a single-side coated or double-side coated (duplitized) material.
  • the light-sensitive layer(s) is (are) in contact with a hydrophilic undercoat layer, e.g. a hydrophilic layer containing antihalation dyes and therefore called a "antihalation undercoat”.
  • a hydrophilic undercoat layer e.g. a hydrophilic layer containing antihalation dyes and therefore called a "antihalation undercoat”.
  • said functional group A' is represented by the formula (II) wherein X2 represents atoms necessary to form a five-or six-membered heterocyclic ring
  • said five- or six-membered ring is substituted with at least one alkali soluble group.
  • the bifunctional structure of the compound thus obtained has 2 heterocyclic centers interacting with silver, and the said compound does substantially not absorb exposure light as spectrally sensitizing dyes do.
  • the said bifunctional structure is represented in the formula (I/II) hereinafter:
  • Representative examples of said compounds as becomes clear from the formulae (I) and (II) are e.g. thiazoles, oxazoles, indoles and imidazoles.
  • linking groups have following structures:
  • each of a and b independently represents an integer having a value of 2 or 3, leading to ethylene and propylene moieties respectively in the divalent linking group.
  • linking group A" is combined with A', according to formula (IV) wherein W and W' may be the same or different and stand for hydrogen or a group substituting the aromatic rings.
  • W and W' each represents same or differing groups, being an alkali soluble group or a substituent having an alkali soluble group.
  • Typical examples of compounds according to the general formula (IV) have been represented by the structures given hereinafter: wherein said structures (IV.1), (IV.2) and (IV.3) have ethylene thio moieties and thiazole, oxazole and imidazole moieties respectively.
  • Even more preferred in the material of the present invention is the presence of a compound according to formula (IV) wherein at least one of W and W', and most preferably each of W and W', if differing from hydrogen, represents an alkali soluble group or a substituent having an alkali soluble group.
  • W and/or W' have an alkali soluble group
  • said group is preferably an acidic group selected from carboxylic acid, sulphonic acid and phosphonic acid as becomes clear from formulae (V.1)-(V.4) given hereinafter, without however being limited thereto.
  • formula (V.1) an aminoalkylene chain is present; wherein said structure (V.2) has an oxyethylene moiety; structure (V.3) having a structural chain directing group; wherein said structure (V.4) has an alkyl chain with end-standing thio moieties.
  • each of a and b independently represents an integer having a value of 2 or 3
  • ethylene groups or propylene groups are present in a polysulfide chain when Z represents S in formula (IV)
  • presence of alkali soluble groups as in the compounds according to the formulae (V.1)-(V.4) leads to a further preferred compounds according to the formulae (VI.1)-(VI.5) as represented hereinafter, again without being limited thereto: structure (VI.3) representing an alkane benzimidazol; structure (VI.4) representing a thiazole compound; and structure (VI.5) having a propylenethio-moiety.
  • the compound(s) according to the formulae set forth hereinbefore are preferally present in an amount of at least 1 mmole up to 5 mmole per mole of coated silver halide.
  • the protective antistress layers of the silver halide photographic material according to the present invention may be the outermost layers of the material but an outermost afterlayer may be optionally present as has been disclosed e.g. in EP-A's 0 644 454 and 0 644 456, wherein a synthetic clay is present in favour of pressure resistance.
  • Protective antistress layers besides their function as protection layer may include compounds providing better antistatic properties as disclosed e.g. in EP-A 0 644 454 (with polyoxyalkylene compounds as antistatic agents), in EP-A's 0 505 626, 0 534 006 and 0 644 456.
  • As said layers are in most cases outermost layers their contribution to satisfactory surface characteristics of the processed film material is very important, e.g. from the point of view of an excellent surface glare as desired by examining medecins, as has been described in EP-A 0 806 705 and in EP-A 0 992 845.
  • the film material of the present invention besides the protective antistress layer(s) and/or undercoat layer(s) containing a polyether moiety as in the general formula (I), thus further comprises a photosensitive layer at one or both sides of the transparent support, said layer containing in an amount of at least 50 %, preferably at least 70% and even more preferably at least 90 % of the total projective surface of all grains a ⁇ 111 ⁇ tabular grain emulsion containing chemically and spectrally sensitized hexagonal grains having a mean equivalent volume diameter of from 0.3 ⁇ m up to 1.0 ⁇ m and an average grain thickness of less than 0.30 ⁇ m, preferably from 0.05 ⁇ m up to 0.25 ⁇ m and wherein said film material is coated with a total amount of silver, expressed as an equivalent amount of silver nitrate of less than 7 g/m2, more preferably from 3.0 up to at most 6.0.
  • Average grain volumes can be determined from calculations, after measurement for each individual grain of its volume determined after having applied electrochemical reduction techniques, wherein electrical signals thus obtained are related with silver halide grain volumes after total reduction thereof to metallic silver at the cathode of an electrochemical cell.
  • the percentage of the total projective area of all tabular grains with respect to the total projective area of all grains present in the emulsion is calculated from electron microscopic photographs.
  • Average grain diameters and thicknesses of the tabular grains are calculated after determination of individual grain thickness and diameter, calculated as equivalent circular diameter of the hexagonal surface, from shadowed electron microscopic photographs or scanning electron microscopic photographs. From the average ratios of (equivalent circular) diameter to thickness for each individual tabular grain aspect ratios are determined in order to get ability to further calculate the mean aspect ratio of the tabular grains in the emulsion distribution.
  • the film material may comprise light-sensitive layers, wherein presence of more than one light-sensitive layer per side is not excluded, at one (single-side coated) or both (double-side coated or duplitized) sides of the film support.
  • said ⁇ 111 ⁇ tabular hexagonal silver halide grains are preferably silver halide grains, containing silver iodide in limited amounts: the film material should contain chemically and spectrally sensitized ⁇ 111 ⁇ tabular hexagonal grains having a composition wherein silver iodide is present in an amount of less than 3.0 mole %; preferably less than 1.0 mole % and even more preferably from 0.1 up to 0.4 mole % of iodide based on silver, without further restrictions with respect to the halide composition of said silver halide grains.
  • ⁇ 111 ⁇ hexagonal tabular silver halide grains suitable for use in the materials according to the present invention is admissible.
  • Said ⁇ 111 ⁇ hexagonal tabular grains preferably have an average aspect ratio of 2 or more, preferably in the range from 5 to 20, with an average grain thickness of less than 0.30 ⁇ m, more preferably from 0.05 up to 0.25 ⁇ m, and account for at least 50 %, more preferably at least 70 % and still more preferably at least 90 % of the total projective area of all grains.
  • the ⁇ 111 ⁇ tabular grain population with hexagonal geometry for the flat tabular grains make part of a light-sensitive emulsion which is homogeneous, i.e., has a variation coeffient of less and 0.40 and more preferably even from 0.10 up to 0.30, based on the equivalent circular diameters calculated for the individual ⁇ 111 ⁇ tabular hexagonal grains.
  • the chemically and spectrally sensitized ⁇ 111 ⁇ tabular hexagonal grains present in at least one light-sensitive layer of the material of the present invention thus have an average grain thickness of from 0.05 up to 0.25 ⁇ m.
  • ⁇ 111 ⁇ tabular grain emulsions rich in silver bromide which are advantageously used in light-sensitive layers of materials of the present invention can be found in Research Dislosure No. 389057, p. 591-639 (1996), more particularly in Chapter I; No. 375042, published July 1, 1995; No. 391021, published November 1, 1996; No. 394023, published February 1, 1997. A very useful method has been described in EP-A 0 843 208.
  • ⁇ 111 ⁇ tabular hexagonal crystals rich in silver bromide are composed of silver bromoiodide or silver bromochloroiodide (with less than 10 mole % of silver chloride, based on silver). Iodide ions may be divided homogeneously or heterogeneously over the grain volume. When divided heterogeneously silver iodide may be present in one or more shells, divided over the grain volume.
  • silver iodide is present at the surface of all ⁇ 111 ⁇ tabular hexagonal grains.
  • Iodide ions can be provided in the preparation method by addition of such grains by adding an inorganic iodide salt as potassium iodide to the reaction vessel. More preferred as providing slower liberation of iodide in the reaction vessel are organic agents releasing iodide ions in order to provide the low silver iodide concentrations, not being equal or exceeding 3 mole %, more preferably not being equal or exceeding 1 mole % and even more preferably not exceeding the range from 0.1 mole % up to 0.4 mole % based on silver over het whole grain volume.
  • Addition of iodide by organic agents releasing iodide ions can thus be applied within the context of the present invention as has been described e.g. in EP-A's 0 561 415, 0 563 701, 0 563 708 and 0 651 284 and in US-A's 5,482,826 and 5,736,312.
  • iodide ions can be released from iodate as has been described in US-A 5,736,312. Release of iodide in the presence of a compound adjusting the rate of iodide release can be applied as described in US-A 5,807,663.
  • addition of iodide to growing or already grown emulsion grains rich in silver bromide and/or chloride is performed by adding fine preformed grains of silver iodide, whether or not including bromide and/or chloride in minor amounts, said grains having a grain diameter of not more than 100 nm, and ,more preferably, even not more than 50 nm.
  • Such fine grains are so-called "Lippmann" emulsions.
  • Addition of iodide making use from such fine grains rich in silver iodide can thus be applied as has been described for the preparation of ⁇ 111 ⁇ tabular grains in JP-A's 04251241 and 08029904 and in EP-A's 0 662 632 and 0 658 805, wherein an outermost phase rich in silver iodide has been added to ⁇ 111 ⁇ tabular grains rich in silver bromide (optionally comprising up to less than 10 mole % of silver chloride).
  • Addition of said fine silver iodide "Lippmann emulsions" to the surface of the silver halide crystals in order to get a global iodide content of less than 3 mole %, preferably less than 1 mole %, and even more preferred from 0.1 mole % up to at most 0.4 mole % based on silver, in the grain may advantageously proceed as disclosed in EP-A 0 475 191, wherein an excellent speed/fog ratio and a high covering power are attained.
  • Preparation methods for ⁇ 111 ⁇ tabular grain emulsions rich in silver chloride which can advantageously be used in the context of the present invention to be coated in the light-sensitive layers of the material as claimed can be found e.g. in EP-A's 0 481 133 and 0 678 772 and in Research Disclosure No. 388046, published August 1, 1996.
  • Preparation of such grains always require use of a crystal habit modifier in favour of stability of the [111 planes as for AgCl [100 planes are much more stable and as [111 planes easily tend to transform into [100 planes when no crystal habit modifying agent (such as adenine or another aminoazaindene compound) is present.
  • Preparation of ⁇ 111 ⁇ tabular grain emulsions is commonly, as is known by anyone skilled in the art, performed in the presence of gelatin.
  • the precipitation of the hexagonal ⁇ 111 ⁇ tabular silver halide crystals according to the present invention is performed in the presence of a protective, hydrophilic colloid, e.g. conventional lime-treated or acid treated gelatin but also oxidized gelatin (see e.g. EP-A 0 843 208) but even a synthetic peptiser may be used.
  • a protective, hydrophilic colloid e.g. conventional lime-treated or acid treated gelatin but also oxidized gelatin (see e.g. EP-A 0 843 208) but even a synthetic peptiser may be used.
  • the preparation of such modified gelatin types, when use would be made thereof, can be found 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). Before and during the formation of the silver halide grains it is common practice to establish a gelatin concentration of from about 0.05 % to 5.0 % by weight in the dispersion medium.
  • tabular silver halide grains used in emulsions for the materials 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 677 773.
  • colloidal silica sol as a binder providing colloidal stability during all preparation steps can indeed be applied as a valuable alternative.
  • grain growth restrainers or accelerators may also be used during the precipitation, together with flow rate variations and/or concentration variations of the silver and halide salt solutions, the temperature, pAg, physical ripening time.
  • 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 can be 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 diafiltration or ultrafiltration.
  • extra gelatin is added to the emulsion in order to obtain a gelatin to silver ratio which is optimized with respect to the coating conditions and/or in order to establish the required thickness of the coated emulsion layer.
  • a gelatin to silver halide weight ratio ranging from 0.3 to 1.0, and more preferably around 0.5, may be envisaged in order to provide low amounts of gelatin to be coated in favour of e.g. rapid processing applicability for the coated materials.
  • ⁇ 111 ⁇ tabular silver halide emulsion grains present in light-sensitive emulsion layers of materials according to the present invention, should, besides being spectrally sensitized, also be chemically sensitized.
  • Said chemical sensitization preferably following spectral sensitization, preferably proceeds at least with a combination of labile sulphur compounds and gold compounds and more preferably with compounds providing sulphur, selenium or even tellurium and gold in favour of attainable sensitivity, also called speed.
  • Chemical sensitization methods for ⁇ 111 ⁇ tabular grain emulsions which can be applied herein can be found in Research Disclosure No. 389057, p. 591-639 (1996), more particularly in Chapter IV.
  • the ⁇ 111 ⁇ tabular hexagonal silver halide emulsion grains present in light-sensitive emulsion layers of materials according to the present invention are preferably spectrally sensitized in the blue to near ultraviolet wavelength range and/or green wavelength range, depending on the requirements as set forth by medecins examining radiological images as especially sharpness (low cross-over percentage), but also contrast (which should be a "dedicated contrast” depending on the density range wherein image details should be discernable), speed and density range.
  • a light-sensitive silver halide photographic film material wherein said emulsion layer comprises an azacyanine dye as a site directing compound. More preferably said azacyanine dye satisfies general formulae (VII.1) or (VII.2) and is preferably present in said layer besides one or more J-aggregating spectrally sensitizing dye(s), wherein a molar ratio amount between said site directing compound and said a J-aggregating spectrally sensitizing dye(s) is preferably at least 1:6 for a grain coverage of said ⁇ 111 ⁇ tabular grains exceeding 50 % and wherein general formulae (VII.1) or (VII.2) are represented as and
  • the material thus has ⁇ 111 ⁇ tabular grains which preferably have been made sensitive to the ultraviolet/blue and/or green range of the wavelength spectrum.
  • the film material comprises in its light-sensitive emulsion layer(s) coated on one or both sides of the subbed transparent support an emulsion having ⁇ 111 ⁇ hexagonal tabular grains, spectrally sensitive to irradiation in the wavelength range shorter than 420 nm by the presence of at least one blue spectral sensitizer and of at least one dye selected from the group consisting of monomethine cyanine dyes and azacyanine dyes.
  • a blue/ultraviolet absorbing dye combination of zeromethine dyes with monomethine or azacyanine sensitizing dyes absorbing blue/UV-radiation as described in EP-A 1 045 282 is particularly suitable for use when the radiographic material according to the present invention is applied in combination with one or two blue/UV-intensifying screens.
  • a particularly good image tone is provided offering cold black-bluish images as desired by the examiners, according to the objects of the present invention.
  • said film thus in one embodiment comprises as spectrally sensitizing dye for the ⁇ 111 ⁇ hexagonal tabular silver bromoiodide or silver bromo(chloro)iodide grains, in order to make them spectrally sensitive to irradiation in the said wavelength range shorter than 420 nm, at least one zeromethine dye according to the general formula as set forth in EP-A 0 712 034 and at least one dye selected from the group consisting of monomethine cyanine dyes (VIII) and azacyanine dyes (VII).
  • Another useful zeromethine dye is represented by its structure (IX.2). 5-(3-methyl-3(3H)-benzothiazolylidene)-4-oxo-2-thioxo-3-thiazolidine acetic acid
  • the zeromethine J-aggregating blue-sensitizing dye or dyes may be present alone, but are thus preferably present besides at least one dye selected from the group consisting of azacyanine dyes (the formulae of which are given hereinbefore under the formulae (VII)) and monomethine cyanine dyes further given hereinafter (see formulae (VIII)) in order to reach the objects of the present invention, thereby reducing dye stain after processing and improving speed.
  • an exceptionally suitable image tone is provided if applied as spectrally sensitizing combination to the ⁇ 111 ⁇ hexagonal tabular silver bromoiodide grains having all silver iodide at their grain surface in the claimed amounts of less than 1 mole %, based on silver over the whole grain volume.
  • Particularly preferred monomethine cyanine dyes suitable for use in emulsions coated in light-sensitive layers of the material used in film/screen systems related with the present invention correspond to the formula (VIII.1) or (VIII.2), represented hereinafter, without however being limited thereto:
  • Said blue-sensitizing dye or dyes are added as first dye during the chemical ripening procedure, before addition of the chemical ripening compounds or agents.
  • Mixtures of blue sensitizing J-aggregating zeromethine dyes as those according to formula (IX.1) and (IX.2) are particularly interesting from the point of view of an increased spectral response in form of speed, which can be achieved at lower total amounts of dyes as becomes clear from US-A 5,707,794.
  • the material according to the present invention has grains which have been made sensitive to the green range of the wavelength spectrum.
  • the film material as claimed thus has at least one emulsion comprising hexagonal ⁇ 111 ⁇ tabular silver halide grains, spectrally sensitive to irradiation in the wavelength range between 500 and 555 nm by the presence of at least one spectrally sensitizing trimethine dye according to the formulae as described e.g. in EP-A 0 678 772 and of at least one dye selected from the group consisting of azacyanine dyes and monomethine cyanine dyes according to the formulae (VII) and (VIII) respectively.
  • the film then provides perfect matching with the screen emitting said radiation in the green wavelength range with a maximum around 540-545 nm as in a preferred embodiment absorption of radiation in the preferred green wavelength range by the ⁇ 111 ⁇ tabular silver halide grains is corresponding with at least 50 % and more preferably at least 80 % of the total radiation absorption by the said grains. Therefore in a preferred embodiment radiation-sensitive emulsions having ⁇ 111 ⁇ tabular hexagonal silver halide grains, as used in light-sensitive layers of materials according to the present invention, are made sensitive to irradiation in the wavelength range between 530 and 555 nm by the presence of a J-aggregating spectrally sensitizing cyanine dye.
  • Preferred (orthochromatic) spectrally sensitizing dyes are J-aggregating dyes as described in EP-A 0 678 772 and 0 953 867, wherein e.g. trimethine benzoxazoles and imidazoles are used apart or in combination.
  • said J-aggregating spectrally sensitizing dye is a 5,5'-dichloro-3,3'-bis(S03-R)-9-ethyl-benzoxa-carbocyanine with R being n-propylene or n-butylene and more particularly anhydro-5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyl-oxacarbocyanine hydroxide or anhydro-5,5'-dichloro-3,3'-bis(n-sulpho-propyl)-9-ethyloxacarbocyanine hydroxide.
  • the total amount of coated silver halide in said film material is less than 7 g/m2, preferably in the range from 3.0 up to 6.0 g.
  • 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) of single-side coated materials, or to a hydrophilic undercoat layer between light-sensitive emulsion layer and subbed support.
  • the presence of such dye(s) in adapted amounts is not only recommended in order 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.
  • these dyes are non-diffusible during coating of the hydrophilic layers.
  • these dyes are the dyes that have been described in e.g. US-A's 3,560,214; 3,647,460; 4,288,534; 4,311,787 and 4,857,446.
  • These dyes may be added to the coating solution as a solid particle dispersions of water insoluble dyes having a mean particle diameter of less than 10 ⁇ m, more preferably less than 1 ⁇ m and still more preferably less than 0.1 ⁇ m.
  • Examples of such dyes are disclosed in EP-A's 0 384 633; 0 351 593; 0 586 748; 0 587 230 and 0 656 401, EP-A's 0 323 729; 0 274 723 and 0 276 566, and in US-A's 4,900,653; 4,904,565; 4,949,654; 4,940,654; 4,948,717; 4,988,611; 4,803,150 and 5,344,749. Said dyes can also be added in form of a solid silica particle dispersion as disclosed in EP-A 0 569 074.
  • film materials may contain such dyes in favour of image definition, but also presence thereof in screens may be advantageous as has been described in US-A 5,381,015.
  • the silver halide emulsions used in light-sensitive layers of the material according to the present invention may also comprise compounds preventing the formation of a high minimum density or stabilizing the photographic properties during the production or storage of photographic materials or during the photographic treatment thereof.
  • Many known compounds 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.
  • 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 Suitable additives for improving the dimensional stability are i.a. dispersions of a water-soluble or hardly soluble synthetic polymer e.g.
  • UV-absorbers are e.g.
  • 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 in order to avoid static discharges during coating, processing and other handling of the material.
  • Such 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 (see e.g. EP-A 0 890 874) or a polymer latex and the like or polymers providing permanent antistatic properties as polyethylene dioxythiophene described e.g. in US-A 5,312,681; 5,354,613 and 5,391,472; and in EP-A 1 031 875.
  • Single-side coated or duplitized film materials of the present invention for use in radiographic applications are irradiated by the light emitted imagewise by one or more X-ray intensifying screen(s) after conversion of X-ray irradiation to the said light by luminescent phosphors coated in the said screen(s) or panel(s), in intimate contact therewith at one or both sides of the coated film support during X-ray exposure of part of a patient.
  • a diagnostic silver image, in conformity with the X-ray image, is obtained after processing of the said film material.
  • said film is arranged in a cassette in contact with the light-sensitive side in contact with one screen or between two X-ray intensifying screens, thus forming a film/screen system.
  • the radiographic screen/film system thus obtained, comprises a single-side coated or a duplitized film as claimed, in contact with one screen or sandwiched between a pair of supported or self-supporting X-ray intensifying screens, wherein said one screen or said pair of supported or self-supporting X-ray intensifying screens comprise(s) luminescent phosphor particles emitting at least 50 % of their emitted radiation in the wavelength range for which said material has been made spectrally sensitive.
  • a radiographic screen/film combination or system comprising a single-side coated film material in contact with one screen or duplitized film material, sandwiched between a pair of supported or self-supporting X-ray intensifying screens, characterized in that
  • Luminescent phosphors suitable for use in a conventional intensifying screen of a radiographic film/screen system as the one according to the present invention 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 is described e.g. in Med. Phys. 5(3), 205 (1978).
  • Typical blue-UV emitting phosphors therein are tantalates as described in PCT-Applications WO 93/1521 and 93/1522, hafnates as described in US-A 5,173,611 and fluorohalides (fluorobromides) of barium and strontium as in WO 91/1357 and US-A 5,629,125, doped with europium and co-doped with samarium as in US-A's 5,422,220 and 5,547,807 and even mixtures of tantalates and fluorohalides as in US-A 5,077,145 and EP-A 0 533 234, replacing CaWO4 as representative for an older well-known generation of luminescent phosphors.
  • Very useful phosphor particles have e.g.been disclosed in EP-A 0 820 069 wherein particles of niobium doped, monoclinic M, yttriumtantalate phosphor and particles of an europium doped bariumfluorohalide phosphor are composing the screen.
  • preferred phosphor particles are niobium and gadolinium doped, monoclinic M, yttriumtantalate (MYT) phosphor corresponding to formula (X) : YTaO4:Gd:Nb
  • the film material has ⁇ 111 ⁇ tabular silver bromo(chloro)iodide emulsions spectrally sensitized with spectrally sensitizing dyes absorbing light in the green wavelength range as has been set forth hereinbefore.
  • a radiographic screen/film combination or system comprising a single-side coated film material in contact with one screen or a duplitized film material, sandwiched between a pair of supported or self-supporting X-ray intensifying screens, characterized in that
  • Specific intensifying screens or conversion screens emitting green or blue/ultraviolet radiation 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 X-rays (e.g. with a tube voltage from 70 kV up to 100 kV as in chest radiography when duplitized film materials of the present invention are used or from 20 kV up to 40 kV as in mammography when single-side coated film materials of the present invention are used, wherefore the relationship between resolution and speed of X-ray intensifying screens has been described e.g. in Med. Phys. 5(3), 205 (1978)).
  • X-ray intensifying screens used in the film/screen system according to the present invention can be self-supporting or supported.
  • X-ray intensifying screens in the screen/film system according to 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.
  • X-ray intensifying screens according 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.
  • a plastic film is preferably employed as the support material.
  • supports characterized by their reflectance properties, expressed as % reflectance over the wavelength range from 350 to 600 nm are particularly used as described e.g. in US-A 5,381,015.
  • Such supports can be highly light reflecting as e.g. polyethylene terephthalate comprising a white pigment, e.g. BaSO4, TiO2, or it can be light absorbing supports, e.g. polyethylene terephthalate comprising a black pigment, e.g. carbon black. Supports comprising dyes or pigments that absorb light of a specific wavelength can also be useful in the preparation of X-ray intensifying screens in the film/screen system according to the present invention. In most applications the phosphor layers contain sufficient binder to give structural coherence to the layer. A mixture of two or more of these binders may be used, e.g., a mixture of polyethyl acrylate and cellulose acetobutyrate.
  • the weight ratio of phosphor to binder is generally within the range of from 50:50 to 89:11, preferably from 80:20 to 89:11.
  • the screen used in a screen/film system according to the present invention may comprise a supported layer of phosphor particles dispersed in a binding medium comprising one or more rubbery and/or elastomeric polymers as described in EP-A's 0 647 258 and 0 648 254.
  • a ratio by weight of pigment to binding medium of more than 90:10 and more preferably of at least 93:7, e.g. 98:2 can be obtained providing besides an excellent image resolution a high ease of manipulation as a result of a good elasticity of the screen and good adhesion properties between the support and the phosphor layer.
  • a protective layer is generally provided on top of the fluorescent layer.
  • the protective coating has a layer thickness d comprised between 1 and 50 ⁇ m and an embossed surface roughness is applied for high ease of manipulation, thereby avoiding sticking, friction and electrostatic attraction with maintenance of an excellent image resolution.
  • the embossed protective layer can be provided on the phosphor layer in order to protect it against mechanical and chemical damage as described in EP-A's 0 510 753 and 0 510 754. Assemblies providing means for reducing cross-over to less than 10 % for radiation longer than 300 nm in wavelength have been described e.g. in US-A 5,259,016.
  • duplitized materials of the present invention have green sensitized emulsion layers on one side and blue/UV sensitized layers on the other side, wherein before X-ray exposure contact is made with a green emitting and a blue/UV-emitting screen for the respective sides of the duplitized material.
  • film materials having e.g. two light-sensitive layers at one or both sides, wherein one layer is made sensitive to the blue-UV wavelength range,whereas the other layer is made sensitive to the green wavelength range may be provided and in the corresponding film/screen combination a screen having a mixture of green- and blue/UV-emitting phosphors may be provided.
  • sensitometry desired sensitometric curve from the point of diagnostic view
  • image quality granularity and/or image definition, particularly sharpness
  • a method of image formation of a black-and-white image may be used by consecutively performing the steps of
  • the said processsing is preferably performed in an automatic processing machine. More in detail for processing the film material of the present invention, preferably 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 developing said material in a developer (preferably) without hardening agent; fixing said material in a fixer, optionally without hardening agent; rinsing and drying said material.
  • 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 als be present.
  • ecology and low replenishing amounts are main topics with respect to the present invention use is made of concentrated hardener free processing solutions in one single package. Examples thereof have been disclosed e.g. in US-A's 5,187,050 and 5,296,342.
  • 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.
  • Suitable measures taken therefore have recently been described in the EP-Applications Nos. 99201891 and 99201892, both filed simultaneously June 14, 1999.
  • 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 odorless. If however aluminum ions are present in the fixer composition for whatever a reason, the presence of -ketocarboxylic acid compounds is recommended as has been described in EP-A's 0 620 483 and 0 726 491 as well as in RD 16768, published March 1978. It is possible to use sodium thiosulphate as a fixing agent, thus avoiding the ecologically undesirable ammonium ions normally used.
  • black-and-white silver halide material used e.g. in micrography, in aviation photography, in black-and-white cinefilms, in laserfilms or hardcopy films and in graphic or reprographic applications.
  • black-and-white images of the selected blue, green and red images each of them being generated apart from an original colour print film after having been printed from digitized images (e.g. by laser exposure) on black-and-white microfilms providing high resolution.
  • UAg should be in the range from - 18 ⁇ 3 mV versus a Ag/AgCl(sat.) reference electrode at a temperature of 65°C ⁇ 0.2°C.
  • solution A1 was added during 26 seconds at a rate of 3.75 ml per minute and UAg was controlled again and should be in the range of - 10 ⁇ 3 mV at a temperature of 65°C.
  • A1 and B1 were run further during 140 seconds at a rate of 5.2 ml/min by double-jet. After 15 minutes 10.18 ml of a 2.94 M solution of potassium iodide was added to the solution B2 having a volume of 805 ml and 2.40 M of potassium bromide.
  • Chemical sensitization was performed at 50°C for about 5 hours after adjustment of the pH in the reaction vessel to a value of 5.5 ⁇ 0.1.
  • a chemically ripened green-sensitized silver bromoiodide emulsion (99 mole % AgBr, 1 mole % AgI) was thus obtained having 160 g AgNO3 and 70.57 g gelatin per kg having ⁇ 111 ⁇ tabular grains with an average equivalent volume diameter of 0.57 ⁇ m and an average grain thickness of 0.22 ⁇ m.
  • the temperature of the reaction vessel was increased up to 70°C in a time interval of 20 minutes.
  • UAg was measured (normal value -25 mV ⁇ 5 mV vs. a Ag/AgCl(sat.) reference electrode)
  • a solution of 475 ml containing 10 wt% of inert gelatin (70°C) was added.
  • A1 and B1 were added by double-jet precipitation at a rate of 7.5 ml/min and 7.9 ml/min. respectively over the next 60 seconds, before linearly increasing said rates of addition up to 14.4 and 15.2 ml/min.
  • A1 was run further during 10 minute at a rate of 7.5 ml/min by single-jet in order to increase UAg to a value of 100 mV at a temperature of 70°C.
  • A1 and B1 were run simultaneously at a rate of 7.5 ml/min., before starting increasing the rate linearly during a time of 59 min. 30 seconds from 7.5 up to 22.5 ml/min.
  • the reaction vessel was cooled from 70°C up to 45°C, the stirring rate was decreased from 400 to 250 r.p.m.
  • Sulphuric acid was added in an amount to make decrease pH to a value of 3.40-3.50.
  • Polystyrene sulphonic acid was added (3 ml 10wt%) in order to make flocculate the emulsion and after washing, gelatin and water were added in order to obtain a silver halide content of 246 g/kg, expressed as AgNO3, and a gelatin content of 74 g/kg.
  • Chemical sensitization was performed at 48°C, for about 4 hours after pH adjustment in the reaction vessel to a value of 5.5 ⁇ 0.1.
  • a chemically ripened green-sensitized silver bromoiodide emulsion (99 mole % AgBr, 1 mole % AgI) was thus obtained having 169.4 g of AgNO3 and 74.9 g of gelatin per kg having ⁇ 111 ⁇ tabular grains with an average equivalent volume diameter of 0.76 ⁇ m and an average grain thickness of 0.22 ⁇ m.
  • a mixture of emulsions A and B was made, wherein relative amounts, expressed as equivalent amounts of silver nitrate were combined in a ratio amount of 1:1, and wherein an average total amount of 6.2 g of silver nitrate per m2 were coated.
  • the processing was run in the developer G138i and in the fixer G334, both trademarketed products from Agfa-Gevaert N.V., Mortsel, Belgium, followed by rinsing at the indicated temperature of 33°C for a total processing time of 90 seconds in an automatic processing machine.
  • B1 was replaced by B2 (aqueous solution, wherein 10.18 ml of an aqueous solution of KI (2.94 M) were added to a solution of 650 ml of KBr (2.94 M)). After 5 minutes A1 and B2 were further added by double-jet during 50 minutes and 23 seconds at rates increasing up to 15.40 ml/min. and 15.45 ml/min. respectively.
  • Ultrafiltration on-line was ended and the temperature was decreased up to 45°C, while stirring was dcreased to 200 rpm.. Washing during ultrafiltration (pressure 1.8 bar) was performed in order to obtain an end mV value (vs. sat. Ag/AgCl reference electrode) of +80 mV, concentrating the washed emulsion up to a volume of 690 ml per 500 g of AgNO3.
  • Peptisation was performed at 45°C in order to obtain an emulsion having 250 g AgNO3 and 16.3 g of gelatin per kg.
  • the average grain size of the silver bromoioide tabular ⁇ 111 ⁇ emulsion grains (composed of 99.0 mole % of AgBr and 1 mole % AgI based on silver) thus prepared, expressed as equivalent volume diameter, was 0.60 ⁇ m, the average thickness was 0.23 ⁇ m.
  • Example 1 After addition of the same coating solutions as for Emulsions A and B in Example 1 the emulsion was coated in the same way, just as for the Materials Nos 1-4 in Example 1.
  • Emulsion B see Example 1 hereinbefore
  • relative amounts, expressed as equivalent amounts of silver nitrate were combined in a ratio amount of 3:1, and wherein an average total amount of 6.2 g of silver nitrate per m2 were coated.
  • Emulsions C and B were coated in Materials Nos. 5-8, wherein differences between the materials as numbered herein were related with amounts of compound (III) added to the coating solutions of the protective antistress layer as indicated in Table 2, just as in Table 1 hereinbefore.
  • Example 1 an increasing covering power without impairing speed and image tone can be obtained when increasing amounts of compound (III) are added to the protective antistress layer of silver halide materials having ⁇ 111 ⁇ tabular silver bromoiodide grain. Moreover contrast becomes enhanced, as could be derived already from the Table 1, inasmuch as fog was not increasing too much.
  • An increased gradation further opens perspectives with respect to decreased coating amounts of silver in favour of ecology: so it has e.g. been established that the processed materials according to the present invention have an increased gradation in the highest densities, even in weak processing circumstances (as in an exhausted developer) which allows a reduction of amounts of coated silver halide of about 10 %.
  • A1 and B1 were added during 2822 seconds at a linearly increasing rate going from 7.0 up to 21.11 ml/min. for A1 and from 7.06 up to 21.29 ml/min. in order to maintain a constant UAg potential of + 40 mV in the reaction vessel.
  • A1 and B1 were simultaneously added by double-jet addition during 60 seconds at a rate of 10.0 and 10.04 ml/min. respectively whereby the UAg value was held at a constant value of 50 mV while increasing the flow rate up to 46.49 ml/min. and 46.69 ml/min. respectively over a total time period of 81 min. and 5 seconds.
  • the emulsion sample was chemically ripened at 50°C during a time in order to get the best compromise between fog and sensitivity. After cooling phenol was added as a preservative.
  • Coatings were made in the same way as in Example 1, as well as exposure of the Material 13 (comparative) and Material 14 (inventive), the only difference being addition to the protective antistress layer of compound (VI.2) in an amount of 18.4 mg/m2.
  • Both materials Nos. 13 and 14 were further processed after the same exposure in a weak hydroquinone developer, the composition of which has been given hereinafter in Table 4, and further fixed in the same G334 fixer.
  • Weak developer H2Q (pH set at 10.0 ⁇ 0.1) Hydroquinone 13.3 g/l Phenidone 0.8 g/l Sodium metabisulphite EDTA Na4-salt.3aq 29.7 g/l Potassium hydroxyde 1.33g/l Sodium tetraborate.10 aq.
  • the material according to the present invention is more stable with respect to differing processing conditions (see especially the lower decrease of the shoulder gradation and the density latitude).

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Claims (12)

  1. Matériau pelliculaire à l'halogénure d'argent pour la photographie en noir et blanc comprenant un support de forme pelliculaire transparent comportant des première et deuxième grandes surfaces enduites d'une couche adhésive, une couche supplémentaire adjacente à la première citée sur un côté (pour un matériau émulsionné sur une seule face) ou sur les deux côtés (pour un matériau émulsionné sur les deux faces) dudit support de forme pelliculaire, le cas échéant en contact avec une couche sous-jacente hydrophile, et recouvert d'une couche supérieure de protection, une couche d'émulsion photosensible à l'halogénure d'argent comportant des grains hexagonaux tabulaires de structure {111} soumis à une sensibilisation par voie chimique et par voie spectrale, représentant au moins 50 % de la surface de projection totale de l'ensemble des grains, avec un diamètre équivalent en volume de 0,3 µm jusqu'à 1,0 µm et une épaisseur moyenne des grains inférieure à 0,30 µm, dans lequel ledit matériau pelliculaire est coulé avec une quantité totale d'argent, exprimée sous la forme d'une quantité équivalente de nitrate d'argent, inférieure à 7 g/m2, caractérisé en ce que ladite ou lesdites couches supérieures de protection et/ou ladite couche sous-jacente hydrophile comprend/comprennent un composé répondant à la formule générale (I) en une quantité d'au moins 0,5 millimole par mole d'halogénure d'argent à l'état coulé
    Figure 00580001
    formule dans laquelle A" représente une fraction de liaison divalente choisie parmi le groupe constitué par une chaíne arylène, une chaíne hétéroarylène, une chaíne alkylène, une chaíne alcénylène et une chaíne alcynylène, lesdites chaínes étant non substituées ou substituées, dans laquelle chacune desdites chaínes arylène, hétéroarylène, alkylène, alcénylène et alcynylène contenant le cas échéant des hétéroatomes, des noyaux aliphatiques ou aromatiques, et des groupes solubles dans les alcalis ; X1 représente les atomes nécessaires pour former un noyau hétérocyclique pentagonal ou hexagonal ; et dans laquelle A' représente un groupe fonctionnel répondant à la formule (II)
    Figure 00590001
    formule dans laquelle X2 représente les atomes nécessaires pour former un noyau hétérocyclique pentagonal ou hexagonal.
  2. Matériau selon la revendication 1, dans lequel, dans la formule (I), A" répond à la formule (III) Y'-Ca-Z-Cb-n-Y'm dans laquelle
    m est égal à 0 ou 1 ;
    n est égal à 0 ou représente un entier possédant une valeur de 1 à 6 ;
    Y' représente un élément choisi parmi le groupe comprenant un atome de soufre, un groupe CR1R2 et un groupe NR3, R1 -R3 représentant un groupe alkyle, un groupe aryle ou un groupe alkyle substitué ou non substitué, et dans laquelle R1 et R2 peuvent former un noyau alicyclique, hétérocyclique ou aromatique substitué ou non substitué ;
    Z représente un atome d'oxygène, un atome de soufre, un groupe CR7R8, un atome d'azote ou encore une fraction de liaison divalente choisie parmi le groupe constitué par une chaíne alkylène, une chaíne alcénylène et une chaíne alcynylène, lesdites chaínes étant non substituées ou substituées, dans laquelle chacune desdites chaínes alkylène, alcénylène et alcynylène contenant le cas échéant des noyaux aliphatiques ou aromatiques et des groupes solubles dans les alcalis ;
    Ca et Cb représentent, chacun indépendamment l'un de l'autre, une chaíne carbonée aliphatique ;
    dans laquelle a et b sont égaux à 0 ou représentent un entier possédant une valeur de 1 à 5.
  3. Matériau selon la revendication 2, dans lequel, dans la formule (III), a et b représentent chacun, indépendamment l'un de l'autre, un entier possédant une valeur de 2 ou 3.
  4. Matériau selon l'une quelconque des revendications 1 23, dans lequel, dans les formules (I) et (II), ledit noyau pentagonal ou hexagonal est substitué avec au moins un groupe soluble dans les alcalis.
  5. Matériau selon la revendication 2, dans lequel ledit composé (III) répond à la formule (IV)
    Figure 00600001
    dans laquelle
    W et W' représentent chacun des groupes identiques ou différents, à savoir un groupe soluble dans les alcalis ou un substituant possédant un groupe soluble dans les alcalis.
  6. Matériau selon l'une quelconque des revendications 1 à 5, dans lequel ledit groupe soluble dans les alcalis est un groupe acide choisi parmi le groupe comprenant un acide carboxylique, l'acide sulfonique et l'acide phosphonique.
  7. Matériau selon l'une quelconque des revendications 1 à 6, dans lequel ledit composé est présent en une quantité d'au moins 1 millimole jusqu'à 5 millimoles par mole de l'halogénure d'argent à l'état coulé.
  8. Matériau selon l'une quelconque des revendications 1 à 7, dans lequel les grains hexagonaux tabulaires de structure {111} soumis à une sensibilisation par voie chimique et par voie spectrale possèdent une épaisseur moyenne des grains de 0,05 jusqu'à 0,25 µm.
  9. Matériau selon l'une quelconque des revendications 1 à 8, dans lequel les grains hexagonaux tabulaires de structure {111} soumis à une sensibilisation par voie chimique et par voie spectrale possèdent une composition dans laquelle l'iodure d'argent est présent en une quantité inférieure à 3,0 moles % d'iode basée sur l'argent.
  10. Matériau selon l'une quelconque des revendications 1 à 9, dans lequel ladite couche d'émulsion photosensible à l'halogénure d'argent comprend un composé d'azacyanine.
  11. Matériau selon l'une quelconque des revendications 1 à 10, dans lequel lesdits grains ont été rendus sensibles aux domaines de longueurs d'ondes émettant dans le domaine ultraviolet/bleu et/ou vert du spectre.
  12. Système ou combinaison d'écran/film radiographique comprenant un film émulsionné sur une seule face ou un film émulsionné sur les deux faces, selon l'une quelconque des revendications 1 à 11, en contact avec un écran ou intercalé entre une paire d'écrans renforçateurs des rayons X autoporteurs ou déposés sur un support, dans lequel ledit écran au ladite paire d'écrans renforçateurs des rayons X autoporteurs ou déposés sur un support comprend/comprennent des particules de luminophores qui émettent au moins 50 % de leur rayonnement dans la gamme de longueurs d'onde pour laquelle ledit matériau a été rendu sensible par voie spectrale.
EP00203916A 1999-11-26 2000-11-07 Pellicule photographique à l'halogénure d'argent ayant un pouvoir opacifiant accru et un ton de l'image noir bleuâtre "plus froid" Expired - Lifetime EP1103847B1 (fr)

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US6737228B2 (en) * 2001-05-22 2004-05-18 Agfa-Gevaert Film material exhibiting a “colder” blue-black image tone and improved preservation characteristics
US7129031B2 (en) 2003-06-19 2006-10-31 Agfa-Gevaert Radiographic silver halide photographic material having a good developing speed, an excellent image tone and low residual color after processing

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US5700630A (en) * 1995-03-03 1997-12-23 Fuji Photo Film Co., Ltd. Silver halide photographic material and method for processing the same
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