EP1045282A1 - Pellicule radiographique sensible dans la région spectrale UV/bleue et structure combinant un film et un écran intensificateur - Google Patents

Pellicule radiographique sensible dans la région spectrale UV/bleue et structure combinant un film et un écran intensificateur Download PDF

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Publication number
EP1045282A1
EP1045282A1 EP00201192A EP00201192A EP1045282A1 EP 1045282 A1 EP1045282 A1 EP 1045282A1 EP 00201192 A EP00201192 A EP 00201192A EP 00201192 A EP00201192 A EP 00201192A EP 1045282 A1 EP1045282 A1 EP 1045282A1
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Prior art keywords
film
substituted
film material
silver
unsubstituted
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German (de)
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EP1045282B1 (fr
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Kathy Elst
Paul Callant
Ann Verbeeck
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • G03C1/005—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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • G03C1/102—Organic substances dyes other than methine dyes
    • 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
    • G03C1/0051—Tabular grain emulsions
    • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03511—Bromide content
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/091—Gold
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/096—Sulphur sensitiser
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/097—Selenium
    • 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

  • This invention relates to a film material and a screen-film combination of a radiographic intensifying phosphor screen and said film material comprising blue-sensitized light-sensitive silver halide photographic emulsions having tabular grains rich in silver bromide.
  • Combinations of intensifying screens provided with luminescent phosphors and light-sensitive silver halide photographic materials are conventionally used for medical diagnosis.
  • the luminescent phosphors in the screen panel or panels are converting X-rays into visible radiation, thereby exposing the film material in contact with the said panel (for single-side coated materials as e.g. in mammography) or panels (for duplitized materials as e.g. in chest imaging).
  • the corresponding spectral sensitizers and optionally present filter or antihalation dyes make arise the problem of insufficient removal from the film material, thereby causing residual color making increase minimum density and deviate image tone from the desired outlook of the processed image.
  • Silver bromide emulsion crystals have an absorption spectrum which is shifted towards longer wavelengths of the radiation spectrum if compared with silver chloride emulsion crystals the spectrum of which is shifted more to the ultraviolet range.
  • Luminescent phosphors however are not completely matching the absorption spectra of non-spectrally sensitized emulsion crystals.
  • the commercially available phosphors as e.g. CaWO 4 (see e.g. US-A 3,300,311) emitting at 410 nm and BaFBr and YTaO 4 .Nb (apart as in e.g.
  • Novel zeromethine-merocyanine dyes have been disclosed in EP-A 0 794 232.
  • the references cited are scarce examples wherein spectral sensitization of tabular grains rich in silver bromide in the blue and/or ultraviolet range of the spectrum is disclosed, opposite to the more frequently published papers with respect to green and red sensitization of said tabular grains, although combinations of blue/UV screen/film combinations are known to lead to a lower cross-over due to less radiation scatter in that wavelength range.
  • Attaining the required sensitometry, particularly speed, even in a rapid processing cycle of less than 90 seconds making use of minimum amounts of replenisher solutions of developer and fixer, and further getting an image having the desired contrast, high definition, covering power and image tone (the improvement of which has e.g. been demonstrated in EP-A 0 770 909, wherein use has been made of a specific multi-layer arrangement with grains having a cubic crystal habit located farther from the support without showing disturbing residual coloration) remains an ever lasting demand.
  • a light-sensitive silver halide photographic material comprising ⁇ 111 ⁇ tabular silver halide grains rich in silver bromide, spectrally sensitive to irradiation in the wavelength range shorter than 420 nm by the presence of at least one blue spectral sensitizer according to the formula (I) and of at least one azacyanine dye according to the formulae given hereinafter in the description and in the claims.
  • 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
  • said film thus comprises ⁇ 111 ⁇ tabular silver halide grains rich in silver bromide, spectrally sensitive to irradiation in the said wavelength range shorter than 420 nm by the presence of at least one dye according to the formula (I) and at least one azacyanine dye wherein in formula (I), representative for said (blue/near ultraviolet-sensitizing) dye given hereinafter wherein:
  • ⁇ 111 ⁇ tabular emulsion crystals rich in silver bromide have been blue-sensitized with one or more dyes corresponding to the formula (I.1) or (I.2)
  • Another dye is represented by its structure (I.3), wherein X is conjugated with a benzene ring in order to get e.g. a benzothiazole nucleus.
  • X is conjugated with a benzene ring in order to get e.g. a benzothiazole nucleus.
  • Other combinations as e.g. with a benzoxazine, with a benzoselenazole or with a benzimidazole nucleus are also possible.
  • the said blue-sensitizing dye or dyes are present besides at least one azacyanine dye (the formulae of which have been given under formulae II) in order to reach the objects of the present invention, thereby reducing dye stain after processing and improving speed.
  • 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 as will further be illustrated in the Examples given hereinafter.
  • Mixtures of blue sensitizing dyes according to formula (I) wherein Q is S for one dye and 0 for the other 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 has been made clear in US-A 5,707,794.
  • dyes according to the formula (II) With respect to dyes according to the formula (II) the synthesis of aza- or diazacyanine dyes, used in light-sensitive emulsion layers of materials according to the present invention besides blue/near-ultraviolet spectrally sensitizing dyes, and use of said azacyanine dyes in silver halide emulsions has been described in US-A 2,307,049. Azamethine spectral sensitizers made with arylene diamine can further be found in US-A 2,368,305. Sensitization of photographic emulsions with dyes comprising azacyanine dyes has been disclosed in US-A 2,080,050.
  • azacyanines do not work as spectral sensitizers on grains rich in silver bromide .
  • presence of one or more azacyanine(s) beside a blue spectral sensitizer of ⁇ 111 ⁇ tabular grains rich in silver bromide is in favor of speed (sensitivity) and in favor of a decrease of dye stain as the presence of said azacyanine dye(s) makes a reduction of amounts of blue-sensitizing dye on the surface of said tabular grains possible.
  • Specific azacyanine dyes suitable for use in the material of the film-screen system according to the present invention are following:
  • R and R' independently represents
  • charge compensating cations are Li + , Na + , K + , HN + Et 3 , wherein Et represents ethyl, whereas preferred charge compensating anions are Cl - , Br - , I - , - OTos, - OMes, CF 3 SO 3 - , wherein - OTos represents tosylate and - OMes represents mesylate.
  • non-J-aggregating monomethine cyanine dyes may be present, e.g., as those represented by the general formula (III) wherein each of R 9 and R 10 independently represents a substituted or unsubstituted C 1 -C 5 alkyl chain, or a substituted or unsubstituted (five- or six-membered) aromatic ring, provided that at least one of R 9 and R 10 has a solubilizing group or a latent solubilizing group; wherein T and T' each independently represents a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl or a substituted or unsubstituted heterocyclic group and wherein X is an anion, providing electrical neutrality.
  • each of R9 and R10 may independently represent
  • monomethine cyanine dyes which may be used as monomethine cyanine dyes in emulsions coated in light-sensitive layers of the material used in the film/screen system of the present invention correspond to the formula (III.1) or (III.2), represented hereinafter:
  • the film material according to the present invention comprises light-sensitive layers at both sides of the film support wherein ⁇ 111 ⁇ tabular silver halide grains rich in silver bromide are present, said grains having an average aspect ratio of 5 or more, an average grain thickness of at most 0.25 ⁇ m, and account for at least 50 % of the total projective area of all grains. More preferably said grains have an average aspect ratio of from 5 up to 20, an average grain thickness of from 0.06 ⁇ m to 0.22 ⁇ m, and account for at least 70 % of the total projective area of all grains.
  • the 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.
  • Said ⁇ 111 ⁇ tabular crystals rich in silver bromide are composed of silver bromide, silver bromochloride, silver bromochloroiodide or silver bromoiodide.
  • iodide it is preferred, in the context of rapid processing (developing and fixing) ability, to have at most 3 mole % of iodide present, more preferably at most 1 mole % and even still more preferably from 0.05 up to 0.5 mole %.
  • Iodide ions can be divided homogeneously over the tabular grain volume, but it can be preferred to build up a core-shell structure wherein the shell is containing more or less iodide than the core or wherein both distinct phases are separated by a silver halide band rich in silver iodide, or even consisting of pure silver iodide, realized e.g. by conversion wherein iodide ions are replacing halides of much more soluble silver halide salts as silver chloride and/or silver bromide.
  • Addition of iodide is normally performed by addition of an inorganic iodide salt as potassium iodide.
  • 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 in order to get a multilayered structure in the silver halide tabular emulsion grains.
  • Addition of iodide to emulsion grains rich in silver bromide is however also possible 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, not more than 50 nm.
  • Such fine grains are so-called "Lippmann" emulsions.
  • ⁇ 111 ⁇ tabular silver halide emulsion grains present in light-sensitive emulsion layers of materials according to the present invention, are, besides spectrally sensitized in the blue to near ultraviolet wavelength range, also chemically sensitized, preferably with compounds providing sulphur, selenium and gold.
  • Chemical sensitization 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 IV.
  • the total amount of coated silver halide in said film is less than 7.5 g/m 2 .
  • the film material according to the present invention preferably is a duplitized material, i.a., a light-sensitive photographic material comprising in its light-sensitive emulsion layers coated on both sides of a subbed support an emulsion having ⁇ 111 ⁇ tabular grains rich in silver bromide, spectrally sensitive to irradiation in the wavelength range shorter than 420 nm by the presence of at least one blue spectral sensitizer according to the formula (I) and of at least one azacyanine dye corresponding to the formulae (II.1) and (II.2) as described hereinbefore.
  • a duplitized material i.a., a light-sensitive photographic material comprising in its light-sensitive emulsion layers coated on both sides of a subbed support an emulsion having ⁇ 111 ⁇ tabular grains rich in silver bromide, spectrally sensitive to irradiation in the wavelength range shorter than 420 nm by the presence of at least one blue spectral sensitizer according to
  • a duplitized material as in the present invention does however not exlude use in a single-side coated material, whether or not in radiographic applications, as such a black-and-white silver halide material can also be used e.g. in micrography, in aviation photography, in black-and-white cinefilms, in laserfilms or hardcopy films and in graphic or reprographic applications.
  • Said duplitized film materials for use in radiographic applications are irradiated by the light emitted imagewise by X-ray intensifying screens 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 thereof, in conformity with the X-ray image, is obtained after processing of the said film material.
  • the X-ray film material comprises a transparent film support, coated on both sides with at least one silver halide emulsion layer, further overcoated with at least one protective antistress layer and, optionnally, an afterlayer as disclosed e.g. in EP-A's 0 644 454 and 0 644 456.
  • 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 duplitized film material, sandwiched between a pair of supported or self-supporting X-ray intensifying screens, characterized in that i) said pair of supported or self-supporting X-ray intensifying screens essentially consists of luminescent phosphor particles emitting at least 50 % and more preferably at least 80 % of their emitted radiation in the wavelength range shorter than 420 nm, as e.g.
  • said film comprises ⁇ 111 ⁇ tabular silver halide grains rich in silver bromide, spectrally sensitive to irradiation in the said wavelength range shorter than 420 nm by the presence of at least one blue spectral sensitizer according to the formula (I) and of at least one azacyanine dye according to the formulae given in the description and in the claims, wherein said emulsion is present in at least one light-sensitive emulsion layer at both sides of the film support.
  • the film material as claimed has as least one emulsion comprising ⁇ 111 ⁇ tabular silver halide grains rich in silver bromide, spectrally sensitive to irradiation in the wavelength range shorter than 420 nm by the presence of at least one spectrally sensitizing dye according to the formula (I) and of at least one azacyanine dye, 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 grains rich in silver bromide is corresponding with at least 50 % and more preferably at least 80 % of the total radiation absorption by the said grains. This does however not exclude the presence in the film material (in minor amounts) of spectrally sensitizing dyes absorbing light in the wavelength range exceeding 420 nm and even, depending on specific needs, in the wavelength range exceeding e.g. 500 nm.
  • 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 CaWO 4 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 (IV): YTaO 4 :Gd:Nb
  • 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.
  • support materials include cardboard, plastic films such as films of cellulose acetate, polyvinyl chloride, polyvinyl acetate, polyacrylonitrile, polystyrene, polyester, polyethylene terephthalate, polyamide, polyimide, cellulose triacetate and polycarbonate; metal sheets such as aluminum foil and aluminum alloy foil; ordinary papers; baryta paper; resin-coated papers; pigment papers containing titanium dioxide or the like; and papers sized with polyvinyl alcohol or the like.
  • 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.
  • Such supports can be highly light reflecting as e.g. polyethylene terephthalate comprising a white pigment, e.g. BaSO 4 , TiO 2 , 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.
  • the phosphor layers contain sufficient binder to give structural coherence to the layer.
  • the binder of the phosphor containing layer is preferably soluble and remains soluble after coating.
  • Useful binders include proteinaceous binders, e.g.
  • gelatin polysaccharides such as dextran, gum arabic, and synthetic polymers such as polyvinyl butyral, polyvinyl acetate, nitrocellulose, ethylcellulose, vinylidene chloride-vinyl chloride copolymer, polyalkyl (meth)acrylate, vinyl chloride-vinyl acetate copolymer, polyurethane, cellulose acetate, cellulose acetate butyrate, polyvinyl alcohol, polystyrene, polyester, etc.
  • These and other useful binders are disclosed e.g. in US-A's 2,502,529; 2,887,379; 3,617,285; 3,300,310; 3,300,311 and 3,743,833.
  • 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 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.
  • the binder used in screens according to the present invention can beneficially be a polymer P having a T g £ 0 °C, an average molecular weight (MG avg ) between 5000 and 10 7 , being soluble in ethylacetate for at least 5 % by weight (% wt/wt).
  • Such polymers have been disclosed in EP-A 0 758 012 and the corresponding US-A 5,663,005.
  • the phosphor layer can be applied to the support by employing a method such as vapour deposition, sputtering and spraying but is usually applied by the following procedure.
  • Phosphor particles and a binder are added to an appropriate solvent as described hereinafter, and are then mixed in order to prepare a coating dispersion comprising the phosphor particles homogeneously dispersed in the binder solution.
  • Said coating dispersion may further comprise a dispersing agent and plasticizer and filler material as described hereinafter.
  • the coating dispersion containing the phosphor particles and the binder is applied uniformly onto the surface of the support to form a layer of the coating dispersion.
  • the coating procedure may proceed according to any conventional method such as doctor blade coating, dip-coating or roll coating.
  • the binder is cured. Curing of the binder may proceed photochemically by means of UV radiation or with electron beam (EB) as described e.g. in Research Disclosure December 1977, item 16435 or proceeds purely chemically as described e.g. in US-A 4,508,636. It may also be cured by moisture as described in EP-A 0 541 146. Curing may also be performed by heating.
  • the primer layer is provided on the substrate beforehand, and then the phosphor dispersion is applied to the primer layer and dried to form the fluorescent layer.
  • the coating dispersion After applying the coating dispersion onto the support, the coating dispersion is then heated slowly to dryness in order to complete the formation of a phosphor layer. In order to remove entrapped air in the phosphor coating composition as much as possible it can be subjected to an ultrasonic treatment before coating.
  • the phosphor-binder layer (as described e.g. in US-A 4,059,768) can be calendered to improve the phosphor packing density in the dried layer.
  • Useful solvents for the binder of the phosphor containing layer, employable in the preparation of the phosphor coating dispersion include lower alcohols such as methanol, ethanol, n-propanol and n-butanol; chlorinated hydrocarbons such as methylene chloride and ethylene chloride; ketones such as acetone, butanone, methyl ethyl ketone and methyl isobutyl ketone; esters of lower alcohols with lower aliphatic acids such as methyl acetate, ethyl acetate and butyl acetate; ethers such as dioxane, ethylene glycol monoethylether; methyl glycol; and mixtures of the above-mentioned solvents.
  • lower alcohols such as methanol, ethanol, n-propanol and n-butanol
  • chlorinated hydrocarbons such as methylene chloride and ethylene chloride
  • ketones such as acetone, butanone,
  • Useful dispersing agents for the phosphor particles in the coating dispersion to improve the dispersibility of the phosphor particles therein may contain a variety of additives such as a plasticizer for increasing the bonding between the binder and the phosphor particles in the phosphor layer.
  • dispersing agent examples include ionic and nonionic well-known dispersing agents or combinations thereof, e.g., DISPERSE AYD (trade name of Daniel Products Company, New Jersey, USA) GAFAC RM 610 (a tradename a polyoxyethylene (20) sorbitan monopalmitate and monolaurate marketed by General Aniline and Film Company (GAF) New York, USA, polymeric surfactants such as the acrylic graft copolymer, PHOSPHOLIPON 90 (trade name) marketed by Nattermann-Phospholipid GmbH, GmbH, W. Germany, silane dispersing agents and surfactants e.g.
  • DISPERSE AYD trade name of Daniel Products Company, New Jersey, USA
  • GAFAC RM 610 a tradename a polyoxyethylene (20) sorbitan monopalmitate and monolaurate marketed by General Aniline and Film Company (GAF) New York, USA
  • polymeric surfactants such as the acrylic graft copolymer,
  • DOW CORNING 190 (trade name) and SILANE Z6040 (trade name) marketed by Dow Corning Corporation, Midland, Michigan, USA or glymo-3-glycidyloxy-propylmethoxysilane or organosulfate polysilanes, unsaturated p-aminamide salts and high molecular acid esters such as ANTI TERRA U 80 (trade name) marketed by BYK-Chemie GmbH, Wesel, W. Germany, high molecular unsaturated polyesters, etc.
  • Dispersing agents are added in an amount of 0.05 to 10 % by weight based on the phosphor.
  • Useful plasticizers include phosphates such as triphenyl phosphate, tricresyl phosphate and diphenyl phosphate; phthalates such as diethyl phthalate and dimethoxyethyl phthalate; glycolates such as ethylphthalyl ethyl glycolate and butylphthalyl butyl glycolate; polymeric plastizers, e.g. and polyesters of polyethylene glycols with aliphatic dicarboxylic acids such as polyester of triethylene glycol with adipic acid and polyester of diethylene glycol with succinic acid.
  • phosphates such as triphenyl phosphate, tricresyl phosphate and diphenyl phosphate
  • phthalates such as diethyl phthalate and dimethoxyethyl phthalate
  • glycolates such as ethylphthalyl ethyl glycolate and butylphthalyl butyl glycolate
  • 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 by the steps of
  • 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 method of image formation is obtained by consecutively performing the steps of -exposing to X-rays the radiographic screen/film combination or system described hereinbefore; followed by -processing the film according to the present invention 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
  • a normally used configuration in the processing apparatus shows the following consecutive tank units corresponding with, as consecutive solutions: developer-fixer-rinse water.
  • 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.
  • 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.
  • preferred minimum regeneration or replenishment amounts are also from about 20 to 200 ml/m 2 , more preferred from 20 to 100 ml/m 2 and still more preferred from 20 to 50 ml/m 2 of developed material.
  • aluminum ions are present in the fixer solution in order to effect hardening, it is necessary to adjust the pH of the fixer in the range from 4.2 to 4.6 in order to get the highest hardening reactivity and to suppress swelling with washing water in the washing or rinsing step.
  • fixer pH For hardened materials having a swelling degree of the hydrophilic layers of less than 250 % and more preferably of less than 200 % it is not required for the fixer pH to held constant in the pH range from 4.2 to 4.6 as mentioned hereinbefore: in order to reduce irritating smell from sulphite ions in aqueous acidic medium which lead to sulphur dioxide vapour it is recommended to enhance pH to a value of 4.65 up to 5.00.
  • a process whereby the quality of the fixer remains at an optimum level has been described in EP-A 0872 764.
  • processing apparatus In a conventional processing apparatus the sheet material is transported along a generally horizontal feed path, the sheet material passing from one vessel to another usually via a circuitous feed path passing under the surface of each treatment liquid and over dividing walls between the vessels.
  • processing machines having a substantially vertical orientation have also been proposed, in which a plurality of vessels are mounted one above the other, each vessel having an opening at the top acting as a sheet material inlet and an opening at the bottom acting as a sheet material outlet or vice versa.
  • substantially vertical is intended to mean that the sheet material moves along a path from the inlet to the outlet which is either exactly vertical, or which has a vertical component greater than any horizontal component.
  • the apparatus occupies only a fraction of the floor space which is occupied by a conventional horizontal arrangement.
  • the sheet transport path in a vertically oriented apparatus may be substantially straight, in contrast to the circuitous feed path which is usual in a horizontally oriented apparatus.
  • the straight path is independent of the stiffness of the sheet material and reduces the risk of scratching compared with a horizontally oriented apparatus.
  • it is important to avoid, or at least minimize leakage of treatment liquid from one vessel to another and carry-over as the sheet material passes through the apparatus.
  • the treatment liquid in one vessel is not contaminated by contents of the adjacent vessels, that is neither by the treatment liquid of the next higher vessel nor by vapours escaping from the next lower vessel.
  • the developing cell of the apparatus is a closed cell and the developing liquid contains an ascorbic acid developing agent as has been described in EP-Application No. 96201753, filed June 24, 1996.
  • a method of processing photographic sheet material by use of an apparatus comprising a plurality of processing cells so arranged to define a sheet material path through the apparatus, at least one of the cells constituting a developing cell containing a developing liquid, characterized in that the developing cell is a closed cell and the developing liquid contains an ascorbic acid developing agent.
  • EP-A 0 819 992 wherein it was an object to provide an apparatus in which operating components can easily be replaced without the need for substantial re-programming of the CPU. This could be achieved when information concerning characteristics of each operating component is stored in separate memory means.
  • a multi-component apparatus was thus provided comprising a plurality of operating components selected from output operating components, input operating components and combinations thereof, and a central processing unit operatively linked to said operating components, said central processing unit containing information concerning at least one desired operating sequence for said apparatus, characterized in that information concerning characteristics of each said operating component is stored in separate memory means.
  • the programme which is typically carried in the CPU, is now seen as comprising two separable elements. Information concerning the desired function of the apparatus, i.e.
  • logical data such as the speed of sheet material through the apparatus, or the volume of liquid being pumped to vessels of the apparatus per unit time, continues to be stored in the CPU.
  • Information concerning the characteristics of the operating components and their location, is separately stored for each operating component.
  • the separate memory means is removable: when the service engineer removes a given operating component, he also removes the store of characteristics information pertaining to that operating component. As he replaces the removed operating component with a new one, he also provides a new information store, containing the characteristics information pertaining to the new operating component. The need for re-programming of the CPU is therefore avoided.
  • the new information store is created off-site, for example as the new operating component is manufactured.
  • the separate memory means is not removable, but is arranged to be by-passed or even re-programmed by the service engineer. Re-programming of the separate memory means is simpler than re-programming of the CPU. Improvements of that invention lie not only in the improved servicing characteristics but also in the quality assurance of replacement components.
  • a processing apparatus for photographic sheet material comprises several treatment cells, most or all of which are in the form of vessels containing a treatment liquid, such as a developer, a fixer or a rinse liquid.
  • a treatment liquid such as a developer, a fixer or a rinse liquid.
  • sheet material includes not only photographic material in the form of cut sheets, but also in the form of a web unwound from a roll.
  • the sheet material to be processed is transported along a sheet material path through these vessels in turn, by transport means such as one or more pairs of path-defining drive rollers, and thereafter optionally to a drying unit.
  • transport means such as one or more pairs of path-defining drive rollers, and thereafter optionally to a drying unit.
  • the time spent by the sheet material in each vessel is determined by the transport speed and the dimensions of the vessel in the sheet feed path direction.
  • a sheet material processing apparatus comprising at least one treatment cell, a pair of rotatable path-defining rollers defining a sheet material path through the cell, the path-defining rollers having a closed position in which the path-defining rollers are biased into contact with each other to form a nip through which the sheet material path extends and an open position in which the path-defining rollers are spaced from each other, characterized in that the path-defining rollers are supported by bearings carried by eccentric sleeves which are stationary in the closed position, and means are provided for partly rotating the sleeves thereby to withdraw the path-defining rollers from each other into the open position.
  • any screen/film combination may be used, wherein said screen comprises at least luminescent monoclinic yttrium tantalate phosphors e.g. doped with niobium and gadolinium, optionally in combination with other suitable UV/blue light emitting phosphors and wherein said film comprises ⁇ 111 ⁇ tabular silver halide crystals rich in silver chloride spectrally sensitized with at least one or more azacyanine dyes in combination with a processing unit, provided that with minimum amounts of silver coated (total amount, expressed as an equivalent amount of silver nitrate of less than 7.5 g /m 2 , particularly for double-side coated materials; and less than 3.75 g/m 2 for single-side coated materials) sufficient covering power is attained in the film in rapid ecological processing (with e.g.
  • Pairs of screens were arranged in the same type of cassette and between the screens and in contact therewith a duplitized (double-side silver halide emulsion coated) film was inserted.
  • the X-ray exposure proceeded according to ISO/DP9236 with 77 median kVp X-rays.
  • the phosphor coating compositions were prepared by intimately mixing the following components : YTaO 4 :Gd:Nb 200 g cellulose acetobutyrate (30 % in 2-butanone) 1.72 g polyethyl acrylate (30 % in ethyl acetate) 15.46 g ethyl acetate 10.70 g methyl glycol 8.72 g methoxypropanol 26.7 g dispersing agent DISPERSE AYD (trade name) 1.02 g
  • compositions were doctor blade coated onto a subbed 200 ⁇ m thick pigmented polyethylene terephthalate supports.
  • a cellulose acetobutyrate layer having a dry thickness of 10 ⁇ m was applied as protective layer.
  • the total amount of phosphor coated was 50 mg/cm 2 .
  • the screen/film(s) combination(s) were used in a cassette, wherein the cassette was the same for each experimental film.
  • Film materials comprising tabular ⁇ 111 ⁇ grains rich in silver bromide were the following.
  • a nucleation step was performed by introducing solution A and solution B simultaneously in dispersion medium C both at a flow rate of 16 ml/min during 30 seconds. After a physical ripening time of 7 minutes, the temperature was raised to 70 °C in 25 minutes and after another 7 minutes pH was adjusted to a value of 5.0, making use from a solution of 2 molar of sodium hydroxide. After addition of 537 ml of a solution of gelatin (10 wt.%) and homogenizing the dispersing liquid in the reaction vessel during 5.5 minutes a first neutralization was performed by addition of solution B at a rate of 7.5 ml per minute for 148 seconds.
  • a second neutralization step was performed by addition of solution A at a rate of 7.5 ml/minute during 60 seconds and of solution B at a rate in order to get a UAg value of 10 mV (mV versus sat. Ag/AgCl reference electrode).
  • Grain growth was performed by addition at a linearly increasing velocity from 7.5 ml/min. up to 15 ml/min. of 502 ml of solution A in 2675 seconds, while adding solution B at a rate in order to get a constant UAg value of 10 mV.
  • a third neutralization step was performed by addition of solution A at a constant rate of 7.5 ml per minute during 263 seconds.
  • a fourth neutralization step was performed by addition of solution A at a rate of 7.5 ml/minute during 100 seconds and of solution B at a rate in order to get a UAg value of 60 mV.
  • Grain growth was performed in a second growth step by addition at a linearly increasing velocity from 7.5 ml/min. up to 36.8 ml/min. of 930 ml of solution A in 2518 seconds, while adding solution B at a rate in order to get a constant UAg value of 60 mV.
  • After 4 minutes 6.4 g of a 100 % silver iodide Lippmann emulsion (containing 79 g, expressed as an equivalent amount of silver nitrate, per kg) were added and stirring continued for another 20 minutes.
  • the said silver bromoiodide tabular emulsion showed the following grain characteristics:
  • the diameter of the grain was defined as the diameter of the circle having an area equal to the projected area of the grain as viewed in the said photographs.
  • Data for E.V.D. were obtained after computing signals obtained from reduction of individual grains and representative for the volume of each grain before reduction.
  • the UAg-value of the emulsion was adjusted at +100 mV (against a silver/silver chloride reference electrode) and the pH-value at 6.0 with sodium hydroxide.
  • Chemical ripening agents were adapted to the crystal size of the emulsions: amounts are given in the Table 1 hereinafter.
  • Chemical ripening agents were gold thiocyanate, sodium thiosulphate as a source of sulphur, N-(carboxyethyl)-2-selenobenzothiazole (see formula VI hereinafter) as a source of selenium and toluene thiosulphonic acid (see formula VII) was used as predigestion agent.
  • As stabilizing agent in the chemical ripening p-carboxy-phenyl-mercaptotetrazole (see formula VIII) was added.
  • each chemical ripening agent (given in Table 1 per 500 ml of an equivalent amount of silver nitrate present in the emulsion) were optimized in order to obtain an optimal fog-sensitivity relationship after 2 hours at 54°C. 5 minutes predigestion time was taken after addition of the toluene thiosulphonic acid predigestion solution (1.29 x 10 -6 mole per mole of silver) before dyes, the formulae of which are given hereinafter, were added:
  • a digestion time of 30 minutes was respected before addition of a KSCN solution (10 wt.% in demineralized water) in an amount of 8.75 x 10 -4 mole per mole of silver.
  • a KSCN solution (10 wt.% in demineralized water) in an amount of 8.75 x 10 -4 mole per mole of silver.
  • another time of 5 minutes was waited before addition of the compounds providing sulphur (Na 2 S 2 O 3 .5aq.: 8.59 x 10 -6 mole per mole of silver), selenium (compound VI: 4.39 x 10 -6 mole per mole of silver) and gold (HAuCl 4 .4H 2 O: : 3.22 x 10 -6 mole per mole of silver).
  • Stabilizing compound VIII was added as last solution in an amount of 1.28 x 10 -4 mole per mole of silver. All amounts given in the Table 1 are given in ml of the added solutions.
  • the resulting photographic material contained per side an amount of silver halide corresponding to 3.5 grams of AgNO 3 per m 2 and an amount of gelatin corresponding to 2.8 g/m 2 .
  • the processing was run in the developer G138®, followed by fixing in fixer G335® and rinsing at the indicated temperature of 35°C for a total processing time of 45 seconds.
  • Example 2 The same emulsion as in Example 1 was chemically ripened in the following way.
  • Chemical ripening agents were gold thiocyanate, sodium thiosulphate as a source of sulphur, N-(carboxyethyl)-2-seleno-benzothiazole (see formula VI hereinbefore) as a source of selenium and toluene thiosulphonic acid (see formula VII hereinbefore) was used as predigestion agent.
  • As stabilizing agent in the chemical ripening p-carboxy-phenyl-mercaptotetrazole (see formula VIII in Example 1) was added.
  • each chemical ripening agent (given in Table 1 per 500 ml of an equivalent amount of silver nitrate present in the emulsion) were optimized in order to obtain an optimal fog-sensitivity relationship after 2 hours at 54°C.
  • a predigestion time of 5 minutes was taken after addition of the toluene thiosulphonic acid predigestion solution (1.29 x 10 -6 mole per mole of silver) before dyes B and A , the formulae of which have been given hereinbefore in Example 1, were added:

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EP00201192A 1999-04-16 2000-03-30 Pellicule radiographique sensible dans la région spectrale UV/bleue et structure combinant un film et un écran intensificateur Expired - Lifetime EP1045282B1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0736143A (ja) * 1993-07-22 1995-02-07 Konica Corp ハロゲン化銀写真感光材料
EP0712034A1 (fr) * 1994-11-11 1996-05-15 Agfa-Gevaert N.V. Procédé à sensibilises spectralement des grains tabulaires à l'halogénure d'argent
EP0890873A1 (fr) * 1997-07-11 1999-01-13 Agfa-Gevaert N.V. Combinaison écran renforçateur à l'UV/bleu-pellicule radiographique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0736143A (ja) * 1993-07-22 1995-02-07 Konica Corp ハロゲン化銀写真感光材料
EP0712034A1 (fr) * 1994-11-11 1996-05-15 Agfa-Gevaert N.V. Procédé à sensibilises spectralement des grains tabulaires à l'halogénure d'argent
EP0890873A1 (fr) * 1997-07-11 1999-01-13 Agfa-Gevaert N.V. Combinaison écran renforçateur à l'UV/bleu-pellicule radiographique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9515, Derwent World Patents Index; Class E23, AN 95-111445, XP002115113 *

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