EP1103849A1 - Elément radiographique avec pouvoir opacifiant amélioré et un ton de l'image noir-bleu - Google Patents

Elément radiographique avec pouvoir opacifiant amélioré et un ton de l'image noir-bleu Download PDF

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Publication number
EP1103849A1
EP1103849A1 EP00203918A EP00203918A EP1103849A1 EP 1103849 A1 EP1103849 A1 EP 1103849A1 EP 00203918 A EP00203918 A EP 00203918A EP 00203918 A EP00203918 A EP 00203918A EP 1103849 A1 EP1103849 A1 EP 1103849A1
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EP
European Patent Office
Prior art keywords
film
grains
layer
silver halide
silver
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00203918A
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German (de)
English (en)
Inventor
Ann Verbeeck
Johan Loccufier
Govert De Baecke
Freddy Henderickx
Heinrich Odenwälder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Agfa Gevaert AG
Original Assignee
Agfa Gevaert NV
Agfa Gevaert AG
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Publication date
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Priority to EP00203918A priority Critical patent/EP1103849A1/fr
Publication of EP1103849A1 publication Critical patent/EP1103849A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • G03C1/35—Antiplumming agents, i.e. antibronzing agents; Toners
    • G03C1/355—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
    • G03C1/76—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
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C2005/168—X-ray material or process
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G03C2007/3025—Silver content
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/03—111 crystal face
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/40—Mercapto compound
    • 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

Definitions

  • the present invention relates to a radiographic light-sensitive silver halide film material, a screen/film system with intensifying screens relied thereupon and a black-and-white image forming method.
  • 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.
  • a radiographic film material comprising a transparent film support having first and second major surfaces coated with a subbing layer, optionally overcoated with a antihalation undercoat, further coated adjacent to said subbing layer or said antihalation layer, on each side of said film support a light-sensitive silver halide emulsion overcoated with a protective antistress layer, said emulsion layer having chemically and spectrally sensitized (111 ⁇ tabular hexagonal grains or crystals having silver iodide in an amount of at most 3 mole %, based on silver, covering at least 50 %, preferably at least 70 % and most preferably at least 90 % of the total projective surface of all grains, the said tabular 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, wherein said film material is coated with a total amount of silver halide, expressed as an equivalent amount of silver nitrate of less than 7 g/m 2
  • a radiographic screen/film combination or system comprising a radiographic film material according to the claims, sandwiched between a pair of supported or self-supporting X-ray intensifying screens, wherein said pair of supported or self-supporting X-ray intensifying screens comprises luminescent phosphor particles emitting at least 50 % of their emitted radiation in the wavelength range for which said material has been made spectrally sensitive as well as a black-and-white image-forming method comprising the steps of contacting the film material as set forth with X-ray intensifying screens by putting it in a sandwich of a pair of said X-ray intensifying screens in order to get a radiographic screen/film combination as disclosed herein, exposing the film material to X-rays passing a subject to be examined, while being in contact with the said screens; and processing the film material by the steps of developing, fixing, rinsing and drying.
  • the amino mercapto-triazole compound present in at least one hydrophilic non-light-sensitive layer (being a protective antistress layer or a antihalation undercoat, if present) of the material according to the present invention preferably has a N-amino mercapto-triazole structure according to the general formula (II) given hereinafter: wherein the five-membered heterocyclic triazole ring is substituted with a -NR1R2 substituted amino group, a mercapto group in form -SM, M representing a hydrogen atom, an alkali metal atom or an ammonium group; and a substituent R3, wherein each of R1, R2 and R3 independently represents hydrogen, an unsubstituted or substituted alkylene, alkenylene, alkynylene, arylene, heteroarylene, or wherein R1 and R2 together represent a double bond and wherein, optionally, at least one of R1 or R2 or R3 contains one or more alkali soluble group
  • the protective antistress layers of the radiographic material according to the present invention may be the outermost layers of the material but an outermost afterlayer may be optionally present as disclosed e.g. in EP-A's 0 644 454 and 0 644 456, wherein e.g. a synthetic clay is present in favour of pressure resistance.
  • protective antistress layers may be coated as two adjacent layers, wherein one or both can be provided with at least one compound according to the general formula (I). It is however understood that in a preferred embodiment said the layer coated adjacent to the emulsion layer should include such a compound.
  • Protective antistress layers may include compounds providing better antistatic properties has been 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 said compound according to the formula (I) is advantageously present therein, particularly if the said compound would be preferably absent in the protective antistress layers for whatever a reason and may be present therein if said compound is present in the said protective antistress layers.
  • N-amino mercapto-triazole compound more preferably those satisfying formula (I)
  • one or more non-light-sensitive layers like the protective antistress layers and/or antihalation undercoat layers
  • image tone in that a "colder" blue-black image is obtained as desired by medecins examining radiographs for at least the same, and even an increased, covering power.
  • the light-sensitive (photosensitive) layers of the radiographic film material of the present invention coated on each of the major surfaces of the subbed support, optionally provided with a antihalation undercoat thus contain chemically and spectrally sensitized ⁇ 111 ⁇ tabular hexagonal silver halide emulsion grains or crystals in an amount of at least 50 %, more preferably at least 70 % and most preferably at least 90 % of the total projective surface of all grains, wherein the said tabular grains have 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, and more preferably from 0.05 ⁇ m up to 0.25 ⁇ m, wherein said film material is coated with a total amount of silver halide, expressed as an equivalent amount of silver nitrate of less than 7 g/m 2 , more preferably from 3.0 up to 6.0 g/m 2 .
  • 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 radiographic film material according to the present invention comprises light-sensitive layers at both sides of the film support (whereby the film is called a double-side coated or "duplitized" film) wherein ⁇ 111 ⁇ tabular silver halide grains are preferably silver halide grains rich in silver bromide, containing silver iodide in limited amounts of at most 3 mole % and more preferably of at most 1 mole % in favour of developability, although there are no restrictions with respect to the halide composition: any combination of chloride, bromide and iodide (in the previously mentioned limited amounts), leading to ⁇ 111 ⁇ hexagonal tabular silver halide grains suitable for use in radiographic materials according to the present invention is possible.
  • Said ⁇ 111 ⁇ hexagonal tabular grains present in the light-sensitive layers of the radiographic material of the present invention preferably have an average aspect ratio of 2 or more, preferably in the range from 5 to 20, an average grain thickness of less than 0.30 ⁇ m, more preferably from 0.05 ⁇ m up to 0.25 ⁇ m.
  • the ⁇ 111 ⁇ tabular grain population making part of a light-sensitive emulsion 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 grains.
  • ⁇ 111 ⁇ tabular grain emulsions rich in silver bromide Preparation methods for ⁇ 111 ⁇ tabular grain emulsions rich in silver bromide 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 (composed of 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. In a preferred embodiment however silver iodide is present at the surface of all ⁇ 111 ⁇ tabular hexagonal grains. Iodide ions can be provided in the preparation method by addition in a conversion step to silver halide grains of an inorganic iodide salt as potassium iodide to the reaction vessel.
  • More preferred however as providing slower liberation of iodide in the reaction vessel is addition of organic agents releasing iodide ions in order to provide the low silver iodide concentrations, not exceeding 3 mole %, more preferably not 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 proceed as 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 emulsion grains rich in silver bromide and/or chloride is performed by adding fine preformed grains of silver iodide, optionally including bromide and/or chloride in minor amounts, said grains having a grain diameter of not more than 100 nm, and ,more preferably, not more than 50 nm. Such fine grains are so-called "Lippmann" emulsions.
  • Addition of said fine AgI-Lippmann emulsions to the surface of the silver halide crystals in order to get a global iodide content of less than 1 mole % 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. Not only in favour of image tone as set forth in the objects of the present invention but also in favour of developability it may be desirable for said tabular grains, when iodide is present, that all silver iodide is present at the grain surface thereof in an amount in order to get an average amount of iodide over the whole grain volume of less than 1 mole %.
  • Said iodide at the grain surface of the tabular grains, present in order to get an average amount of iodide over the whole grain volume is then preferably present in an amount of at most 3 mole %, more preferably at most 1 mole % based on silver, preferably from 0.05 mole % up to 0.5 mole % of iodide, and even more preferred an average amount of iodide of 0.1 mole % up to 0.4 mole %.
  • 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 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.
  • a crystal habit modifier such as adenine or another aminoazaindene compound
  • 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.
  • 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 Dislosure 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 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.
  • the duplitized film material comprises in its light-sensitive emulsion layers coated on both sides of a subbed 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 J-aggregating blue spectral sensitizer and of at least one dye selected from the group consisting of azacyanine dyes and monomethine cyanine dyes respectively as described hereinafter.
  • the material according to the present invention thus has grains which have been made sensitive to the ultraviolet and/or blue range of the wavelength spectrum in that case.
  • a blue/ultraviolet absorbing dye combination of J-aggregating 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 a blue/UV-intensifying screen.
  • a particularly good image tone is provided offering cold black-bluish images as desired by the medical examiners, according to the objects of the present invention.
  • said film advantageously comprises as spectrally sensitizing J-aggregating dye for the ⁇ 111 ⁇ tabular silver halide grains in order to make them spectrally sensitive to irradiation in the said wavelength range shorter than 420 nm at least one selected zeromethine dye according to the formula (IV.1) or (IV.2) and at least one dye selected from the group consisting of monomethine cyanine dyes and azacyanine dyes.
  • the J-aggregating blue-sensitizing dye or dyes according to the formulae (IV.1) and (IV.2) may be present alone, but are preferably present besides at least one dye selected from the group consisting of azacyanine dyes (the formulae of which are given hereinafter under the formulae (V) and monomethine cyanine dyes further given hereinafter (see formulae VI) in order to reach the objects of the present invention, thereby reducing dye stain after processing and improving speed moreover providing a suitable image tone if applied as spectrally sensitizing combination to the ⁇ 111) hexagonal tabular silver halide, and particularly to the bromoiodide grains having all silver iodide at their grain surface in amounts of not more than 3 mole %, preferably not more than 1 mole %, and still more preferably from 0.1 up to 0.4 mole %, based on silver, over the whole grain volume.
  • azacyanine dyes the formulae of which are given hereinafter under the formulae (V)
  • R and R' independently represents
  • charge compensating cations are Li+, Na+, K+, HN+Et3, wherein Et represents ethyl, whereas preferred charge compensating anions are Cl-, Br-, I-, -OTos, -OMes, CF3S03-, wherein -OTos represents tosylate and -OMes represents mesylate.
  • Preferred (non-J-aggregating) monomethine cyanine dyes mentioned hereinbefore as an alternative for the (non-J-aggregating) azacyanine dyes according to the formulae (V.1) and (V.2), are those represented by the specific formulae (VI.1) and (VI.2) 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 (IV.1) and (IV.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 green sensitizing J-aggregating dye and of at least one dye selected from the group consisting of azacyanine dyes and trimethine cyanine dyes.
  • 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-Q)-9-ethyl-benzoxa-carbocyanine with Q 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-ethyloxa-carbocyanine hydroxide.
  • the total amount of silver halide coated in said film material is less than 7 g/m 2 , preferably in the range from 3 to less than 7 and even more preferably in the range from 3.0 to 6.0 g/m 2 , e.g. about 4.5-5.0 g/m 2 .
  • 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 antihalation undercoat layers of the duplitized radiographic materials of the present invention, wherein said layers, if present, advantageously comprise N-amino mercapto triazole compounds in general and, more particularly, compounds having general formula (I).
  • 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.
  • 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 dispersion 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.
  • 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, etc.
  • 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 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 dioxythiophenes described e.g. in US-A 5,312,681; 5,354,613 and 5,391,472; and in EP-A 1 031 875.
  • Said duplitized film materials for use in radiographic applications are irradiated by the light emitted imagewise by X-ray intensifying screens after conversion of X-ray radiation to the said light by luminescent phosphors coated in the said screens or panels, in intimate contact therewith at 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 between two X-ray intensifying screens each of them making contact with its corresponding light-sensitive side, thus forming a film/screen system.
  • a radiographic screen/film combination or system comprising a radiographic film material, sandwiched between a pair of supported or self-supporting X-ray intensifying screens, characterized in that
  • the radiographic film material as claimed has as least one emulsion comprising ⁇ 111 ⁇ tabular silver halide grains, spectrally sensitive to irradiation in the wavelength range shorter than 420 nm by the presence of at least one spectrally sensitizing dye as the one according to the formula (IV.1) or (IV.2) and of at least one dye selected from the group consisting of azacyanine and monomethine cyanine dyes according to the formulae (V.1-V.2) and (VI.1-VI.2) respectively, the film perfectly matches with the screen emitting said radiation in the wavelength range shorter than 420 nm as in a preferred embodiment of the present invention absorption of radiation in the said wavelength range shorter than 420 nm by the ⁇ 111 ⁇ tabular silver halide, preferably being bromo(chloro)iodide, grains is corresponding with at least 50 % and more preferably at least 80 % of the total radiation absorption by the said grains.
  • 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).
  • Specific intensifying screens emitting ultraviolet-blue radiation have e.g.
  • 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 CaW04 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 (VII): YTaO4:Gd:Nb
  • the radiographic film material has ⁇ 111 ⁇ tabular silver halide emulsions, preferably bromo(chloro)iodide emulsions, spectrally sensitized with spectrally sensitizing dyes absorbing light in the green wavelength range.
  • a radiographic screen/film combination or system comprising a duplitized film material, sandwiched between a pair of supported or self-supporting X-ray intensifying screens, characterized in that
  • azacyanine dyes according to the general formulae (V.1) and (V.2) are advantageously used in the preparation of ⁇ 111 ⁇ tabular grain emulsions as the presence of said dyes permits further addition of J-aggregating spectral sensitizers in lower amounts, without loss in speed, thereby providing better decolouration in the processing.
  • F.M A survey of other useful chemical classes of J-aggregating spectral sensitizers suitable for use in spectrally sensitizing emulsions of the present invention has been described by F.M.
  • the radiation-sensitive emulsion used in the material according to the present invention has one or more azacyanine dye(s) and (a) J-aggregating spectrally sensitizing dye(s), whether providing spectral sensitivity in the blue/UV or in the green light range in a ratio amount of more than 1:4 for a grain coverage exceeding 50 %.
  • said film material (made sensitive to green or blue light by suitable spectral sensitization of its light-sensitive emulsion grains) is arranged in a cassette with two X-ray intensifying screens (emitting green or blue light by suitable luminescent phosphors) making contact with the silver halide emulsion layers at both sides of the film support.
  • said cassette is provided with two X-ray intensifying screens making contact with two X-ray intensifying screens, being the same or different: it is indeed possible to use two identical screens (having same radiation sensitivity), to use two screens emitting the same irradiation but differing in speed, e.g.
  • Specific intensifying screens or conversion screens emitting green or blue light 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 with a tube voltage e.g. from 70 kV up to 100 kV (as in chest radiography as an example of a more specific application of the present invention, without however limiting it thereto).
  • X-ray intensifying screens used in the screen/film systems 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, etc., 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.
  • a black-and-white image-forming method comprising the steps of contacting the film material as claimed with X-ray intensifying screens by putting it in a sandwich of a pair of said X-ray intensifying screens in order to get a radiographic screen/film combination as described hereinbefore; exposing the film material to X-rays passing a subject to be examined, said X-rays (having an energy e.g. from 70 to 100 keV, without however excluding lower irradiation energies) while being in contact with the said screens; and processing the film material by the steps of developing, fixing, rinsing and drying.
  • the said processsing is preferably performed in an automatic processsing 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. Even use thereof in colour photographic applications may be useful.
  • pH was set to a value of 5.0 ⁇ 0.3 and immediately thereafter a solution of 50 g of inert gelatin in 500 ml of demineralized water of 70°C was added.
  • B1 was added at a rate of 7.5 ml/min. during 28 seconds, followed during 1 minute by the simultaneous addition of A1 (at a rate of 7.5 ml/min.) and 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.
  • Consecutively 0.5 g of polyglycol (MW 6000) was added as a development accelerator; 20 ml of polyoxyethylene surfactant H17C8-Phenyl-(O-CH2-CH2)8-O-CH2-COOH and in an amount of 140 mg (per mole of Ag) fluoroglucinol was added as a hardener stabilizer together with polymethyl acrylate latex (in an amount of 140 % by weight, based on the amount of gelatin binder) which was used as a plasticizer.
  • the thus prepared emulsion coating solutions were coated on a blue coloured polyethylene terephthalate support (density of the support measured to be 0.200) in such an amount in order to give a coating weight of 2.75 g/m2 per side in terms of AgNO3 and 1.42 g of gelatin per m2 per side.
  • the following protective layer was coated thereupon (pH value: 6.25) at both sides: Composition of the protective antistress layer Gelatin 1.11 g/m 2 Graft copolymer (1) 14 mg/m 2 Chromium acetic acid 7.3 mg/m 2 Compound (2) 16 mg/m 2 Compound (3) 6.7 mg/m 2 Mobilcer Q (MMM trademarked product) 9 ml/m 2 Compound (4) 15 mg/m 2 Compound (5) 40 mg/m 2
  • Materials have been numbered from 1 to 7, material MT1 representing a comparative material, wherein Emulsion T was coated without N-aminotriazole compound in the protective antistress layer and materials MT2-MT7 representing inventive materials wherein the same light-sensitive coating with Emulsion T was coated but wherein to the protective coating differing N-amino mercaptotriazoles according to the general formula (I) were added, according to the formulae as set forth in the Table 1 hereinafter in an amount of 12 mg/m2.
  • the processing was run in the developer G138i, trademarked product from Agfa-Gevaert N.V., Mortsel, Belgium, followed by fixing in fixer G334i, trademarked product from Agfa-Gevaert N.V., Mortsel, Belgium,and rinsing at the indicated temperature of 35°C for a total processing time of 90 seconds.
  • a silver bromoiodide emulsion having thin tabular crystals was prepared following an analoguous precipitation scheme as in Example 1 hereinbefore, leading to tabular grains having an average diameter of 0.57 ⁇ m and an average thickness of 0.16 ⁇ m.
  • Coating solutions were added as in Example 1 and coating, exposure and processing was also performed in the same way.
  • Sensitometric parameters just as in Table 1 have been given hereinafter in the Table 2, except for the data given with respect to the parameters DLT, expressing density latitude (measured between minimum and maximum density) and

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EP00203918A 1999-11-26 2000-11-07 Elément radiographique avec pouvoir opacifiant amélioré et un ton de l'image noir-bleu Withdrawn EP1103849A1 (fr)

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Cited By (2)

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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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EP0508390A2 (fr) * 1991-04-11 1992-10-14 Konica Corporation Matériau photographique à halogénure d'argent
US5190855A (en) * 1990-02-26 1993-03-02 Fuji Photo Film Co., Ltd. Silver halide photographic material and method for processing the same
JPH07311436A (ja) * 1994-05-18 1995-11-28 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
US5700630A (en) * 1995-03-03 1997-12-23 Fuji Photo Film Co., Ltd. Silver halide photographic material and method for processing the same
US5759759A (en) * 1997-02-18 1998-06-02 Eastman Kodak Company Radiographic elements exhibiting increased covering power and colder image tones
EP0890874A1 (fr) * 1997-07-10 1999-01-13 Agfa-Gevaert N.V. Compositions photographiques à l'halogénure d'argent protégées contre la formation de voile jaune
EP0953867A1 (fr) * 1998-04-29 1999-11-03 Agfa-Gevaert N.V. Procédé à sensibiliser spectralement des grains à l'halogénure d'argent tabulaires

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JPS63155140A (ja) * 1986-12-19 1988-06-28 Konica Corp 銀画像の色調を改良したハロゲン化銀写真感光材料
US5190855A (en) * 1990-02-26 1993-03-02 Fuji Photo Film Co., Ltd. Silver halide photographic material and method for processing the same
EP0508390A2 (fr) * 1991-04-11 1992-10-14 Konica Corporation Matériau photographique à halogénure d'argent
JPH07311436A (ja) * 1994-05-18 1995-11-28 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
US5700630A (en) * 1995-03-03 1997-12-23 Fuji Photo Film Co., Ltd. Silver halide photographic material and method for processing the same
US5759759A (en) * 1997-02-18 1998-06-02 Eastman Kodak Company Radiographic elements exhibiting increased covering power and colder image tones
EP0890874A1 (fr) * 1997-07-10 1999-01-13 Agfa-Gevaert N.V. Compositions photographiques à l'halogénure d'argent protégées contre la formation de voile jaune
EP0953867A1 (fr) * 1998-04-29 1999-11-03 Agfa-Gevaert N.V. Procédé à sensibiliser spectralement des grains à l'halogénure d'argent tabulaires

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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