EP0930527A1 - Kombination eines radiographischen Verstärkungsschirms mit einem Film - Google Patents

Kombination eines radiographischen Verstärkungsschirms mit einem Film Download PDF

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Publication number
EP0930527A1
EP0930527A1 EP98200061A EP98200061A EP0930527A1 EP 0930527 A1 EP0930527 A1 EP 0930527A1 EP 98200061 A EP98200061 A EP 98200061A EP 98200061 A EP98200061 A EP 98200061A EP 0930527 A1 EP0930527 A1 EP 0930527A1
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EP
European Patent Office
Prior art keywords
film
silver
silver halide
formula
film combination
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EP98200061A
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English (en)
French (fr)
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to EP98200061A priority Critical patent/EP0930527A1/de
Publication of EP0930527A1 publication Critical patent/EP0930527A1/de
Withdrawn legal-status Critical Current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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • G03C1/0053—Tabular grain emulsions with high content of silver chloride
    • 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
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups

Definitions

  • This invention relates to a screen-film combination of a radiographic intensifying phosphor screen and a light-sensitive silver halide photographic material comprising emulsion grains rich in silver chloride.
  • 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 fixer and especially the corresponding replenishers is advantageously attainable when in the light-sensitive silver halide photographic material use is made of emulsion crystals rich in silver chloride having a much higher solubility (and processability) than e.g. crystals rich in silver bromide (a factor of about 100). Moreover combination with the more "ecologically acceptable" ascorbic acid or derivatives thereof seems to offer an acceptable alternative.
  • the corresponding spectral sensitizers make arise the problem of insufficient removal from the film material, thereby causing residual colour, also called “dye stain", increase minimum density and deviate image tone from the desired outlook of the processed image.
  • Said lower coating weight is especially preferred if rapid processing applications are required, which is nowadays an ever more returning demand.
  • ⁇ 111 ⁇ tabular grains rich in silver chloride are thermodynamically unstable during preparation crystal habit modifiers are required in order to stabilize their crystal habit during precipitation as has e.g. been disclosed in US-A's 5,061,617; 5,176,992; 5,178,998; 5,183,732; 5,185,239; 5,221,602; 5,252,452; 5,286,621; 5,298,388; 5,399,478; 5,411,852 and 5,601,969.
  • radiographic screen/film combination also called screen/film system
  • a radiographic screen/film combination comprising a duplitized film sandwiched between a pair of supported or self-supporting X-ray intensifying screens, characterized in that
  • Said radiographic screen/film combination wherein said pair of supported or self-supporting X-ray intensifying screens comprise luminescent phosphor particles, preferably gadolinium oxisulphide phosphor particles, more preferably emits at least 80 % of the emitted radiation in the wavelength range between 540 and 555 nm.
  • R 2 is trifluoroethyl and R 4 is sulfoethyl, sulfopropyl, 3-sulfobutyl or 4-sulfobutyl, whereas X 1 and X 3 are hydrogen and X 2 and X 4 are each trifluoromethyl.
  • the benzimidazolocarbocyanine and benzoxazolocarbocyanine spectral sensitizers according to the formulae (I) and (II) respectively are added consecutively in a preferred molar ratio amount between 2:100 and 50:100 to the emulsions coated in the film material used in the radiographic screen/film combination of the present invention.
  • the film of the radiographic film-screen combination comprises ⁇ 111 ⁇ tabular silver halide grains rich in silver chloride having an average aspect ratio of 5 or more, an average grain thickness of at most 0.2 ⁇ m, and account for at least 50 % of the total projective area of all grains.
  • said film comprises ⁇ 111 ⁇ tabular silver halide grains rich in silver chloride having an average aspect ratio of from 8 to 20, an average grain thickness of from 0.06 ⁇ m to 0.20 ⁇ m, and account for at least 70 % of the total projective area of all grains.
  • Preparation methods of such ⁇ 111 ⁇ tabular emulsion grains rich in silver chloride have been described in e.g. US-A's 5,494,788; 5,567,580 and 5,601,969; in EP-A's 0 678 772 and 0 770 909 and in Research Disclosure No. 38846, published August 1, 1996.
  • said radiographic screen-film combination comprises ⁇ 100 ⁇ tabular silver halide grains rich in silver chloride in the film; wherein said grains have an average aspect ratio of 2 or more, an average grain thickness of at most 0.3 ⁇ m, and account for at least 40 % of the total projective area of all grains.
  • said film comprises ⁇ 100 ⁇ tabular silver halide grains rich in silver chloride having an average aspect ratio of 5 or more, an average thickness of at most 0.25 ⁇ m, and account for at least 50 % of the total projected area of all grains.
  • the radiographic screen-film combination according to the present invention comprises cubic silver halide grains rich in silver chloride having an average sphere equivalent diameter of from 0.2 up to 1.0 ⁇ m, more preferably from 0.4 up to 1.0 ⁇ m and most preferably from 0.6 up to 1.0 ⁇ m.
  • Preparation methods of such grains have e.g. been given in EP-A 0 709 730 and in US-A's 5,397,687 and 5,543,284, wherein, in the last reference, colloidal silica has been used as a protective colloid in the said preparation method.
  • a combination of silver halide emulsion grains of the same or different types coated in one or in two adjacent layers at one and/or at both sides of the support of the film material is also enclosed in the present invention, provided that at least one, and preferably all of said emulsion grains are spectrally sensitized with the specific combination of both green spectral sensitizers according to the general formulae (I) and (II), representing a benzimazolocarbocyanine and benzoxazolocarbocyanine respectively.
  • the total amount of coated silver halide in said film is less than 8.0 g/m 2 .
  • a conventional radiographic layer arrangement can be provided according to the one described in EP-A 0 770 909.
  • a multilayer light-sensitive silver halide photographic negative image type material comprising on at least one side of a support a multilayer composition of at least two layers of negative image type silver halide emulsions adjacent to each other, wherein the emulsion layer closest to the said support comprises tabular emulsion crystals selected from the group consisting of silver chloride, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide, silver bromide and silver bromoiodide having a ⁇ 111 ⁇ crystal habit and silver chloride, silver chlorobromide, silver chloroiodide and silver chlorobromoiodide having a ⁇ 100 ⁇ crystal habit and wherein the adjacent layer(s) farther from the said support comprise(s) essentially cubic emulsion crystals selected from the group consisting of silver chloride, silver chlorobromide and silver bromide and wherein the halide composition
  • a method in order to get a radiographic silver halide material by coating on at least one side of a support, covered with a hydrophobic subbing layer comprising as a latex copolymer vinylidene chloride, methylacrylate and itaconic acid, following hydrophilic layers: at least one gelatinous dye containing layer comprising one or more dyes, at least one silver halide emulsion layer, at least one protective antistress layer, and optionally an afterlayer, characterised in that said hydrophilic layers have a swelling ratio of not more than 200 % and in that said hydrophilic layers are coated simultaneously by the slide-hopper coating or by the slide-hopper curtain coating technique, opposite to the time consuming technique described in US-A 5,077,184.
  • a layer arrangement as claimed in the said EP-A 0 752 617 has been provided, wherein one or more merostyryl dye is present as antihalation dye(s) in the gelatinous dye containing layer situated between the subbing layer, being in direct contact with the support in order to provide good adhesion of coatings, and the light-sensitive emulsion layer more close to the said subbing layer.
  • Preferred amounts of dyes are chosen in order to get a ratio by weight of dye to gelatinous hydrophilic binder between 0.4 and 1.3.
  • Preferred merostyryl dyes have e.g. been described in US-A 4,311,787.
  • Said merostyryl dyes are further characterized by a solubility at an alkaline pH of at least 8 (as e.g. in processing conditions) and insolubility at pH values less than 6.0.
  • said merostyryl dye is present in form of a microprecipitated dispersion and is preferably prepared according to the methods described in EP-A 0 724 191.
  • a preferred merostyryl dye for use as a so-called antihalation dye, contributing to the lowering of cross-over of the material according to the material in the screen/film combination according to the present invention are the merostyryl dyes having a pyrazolon nucleus the formulae of which are given hereinafter:
  • a radiographic screen-film combination wherein said film further comprises, in order, a support, a subbing layer, a gelatinous dye containing layer, the light-sensitive emulsion layer and a protective antistress layer, wherein in the said dye containing layer said dye(s) is (are) merostyryl dyes having a pyrazolon nucleus, in favour of cross-over percentage.
  • the light emitted imagewise by said X-ray intensifying screen irradiates a contacting photographic silver halide emulsion layer film which after exposure is developed to form therein a silver image in conformity with the X-ray image.
  • the X-ray film comprises a transparent film support, coated on both sides with a silver halide emulsion layer.
  • said film is arranged in a cassette between two X-ray intensifying screens each of them making contact with its corresponding silver halide emulsion layer.
  • Phosphors suitable for use in the conventional radiographic diagnostic image forming system must have a high prompt emission of fluorescent light on X-ray irradiation and low afterglow in favour of image sharpness.
  • the relationship between resolution and speed of X-ray intensifying screens is described e.g. in Med. Phys. 5(3), 205 (1978).
  • a typical green emitting phosphor used therein is a gadolinium oxisulphide phosphor, just as the preferred phosphor used in the screen of the film/screen combination according to the present invention.
  • the 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 between 540 and 555 nm, wherein said luminescent particles have a composition according to the formula (III) Gd 2 O 2 S:Tb
  • X-ray intensifying screens are thus self-supporting or supported X-ray intensifying screens and 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 in order to protect said layer.
  • a primer layer is sometimes provided between the phosphor containing layer and the substrate in order 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. polyethyleneterephthalate 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 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.
  • proteinaceous binders e.g. gelatin, polysaccharides such as dextran, gum arabic
  • synthetic polymers such as polyvinyl butyral, polyvinyl acetate, nitrocellulose, ethylcellulose, vinylidene chloride-vinyl chloride copolymer, polyalkyl (meth)acrylate, vinyl chloride-vinyl acetate copoly
  • 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 0 648 254 and EP-A 0 647 258 or thermoplastic elastomers as described in US-A 5,641,968.
  • 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 Tg ⁇ 0 °C, an average molecular weight (M avg ) between 5000 and 10 7 , being soluble in ethylacetate for at least 5 % by weight (% wt/wt).
  • Such polymers have been disclosed in 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.
  • EB electron beam
  • 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 so as to complete the formation of a phosphor layer.
  • 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-glycidyloxypropylmethoxysilane 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 (1) coating onto said phosphor containing layer a liquid radiation-curable composition having at the coating temperature a viscosity of at least 450 mPa.s, measured with a Hoeppler viscometer,that does not penetrate for a substantial degree into the phosphor containing layer,
  • 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.
  • 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 odourless.
  • said method comprising the steps of developing in a developer solution, followed by fixing in a fixer solution, comprising a hardening agent, preferably a compound providing aluminum ions, and wherein, in running equilibrium conditions, said fixer solution has a pH of at least 4.3, further followed by rinsing and drying,; characterized in that said developing step is performed in a developer comprising, in an amount of from 5 g up to 100 gram per litre, (iso)ascorbic acid, l-ascorbic acid or tetramethyl reductic acid as a developing agent, a precursor and/or a metal salt thereof.
  • a compound having an ⁇ -ketocarboxylic acid structure in an amount of not more than 3 g per litre is present in the said fixer solution while starting processing or in the said fixer replenisher.
  • sodium thiosulphate as a fixing agent, at least partially as described in US-A 5,275,923, in order to maintain rapid fixing ability, thus avoiding an excess of the ecologically undesired but normally used ammonium ions.
  • a fixation time which is reduced to about 2 to 10 seconds can be attained.
  • regeneration is kept to a minimum, especially in the processing of materials coated from very low amounts of emulsion crystals rich in silver chloride.
  • Preferred minimum regeneration or replenishment amounts are from 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. Materials coated from higher amounts of silver will require the higher amounts of replenisher but in most practical cases replenishment amounts of less than 200 ml/m 2 are attainable.
  • 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-Application No. 97201117, filed April 15, 1997.
  • 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 making use of an apparatus comprising a plurality of processing cells arranged in order 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-Application No. 96202032 filed July 17, 1996, 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 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.
  • 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 rol-lers 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 phosphors emitting green light as those according to the formula (III) in the wavelength range between 540 and 555 nm and wherein said film comprises ⁇ 111 ⁇ or ⁇ 100 ⁇ tabular silver halide crystals or cubic crystals rich in silver chloride spectrally sensitized with a combination of at least one benzimidacarbocyanine dye according to the formula (I) and at least one benzoxacarbocyanine dye according to the formula (II) 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 4 g per m 2 and per side) a sufficient covering power is attained in the film material 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.
  • Film materials comprising cubic grains rich in chloride were the following.
  • a silver chloride emulsion was prepared by a double jet technique.
  • the silver halide composition was 100 mole % of chloride and the average grain size was 0.57 ⁇ m. Therefore following solutions were prepared.
  • Solution 1 Water 880 ml Gelatin 46 g
  • Solution 2 Water 1000 ml Silver nitrate 500 g
  • Solution 3 Water 1000 ml Sodium chloride 173 g
  • the UAg value of solution 1 (potential value expressed in mV versus a saturated silver/silver chloride reference electrode) was adjusted at a constant value of + 138 mV ⁇ 2 mV before starting nucleation by dropwise addition of about 7 ml of a solution having 234 grams of sodium chloride after addition of 0.44 ml of a silver nitrate solution having a concentration of 50 g per liter of demineralized water.
  • UAg was readjusted at the same value of + 138 mV while solution 2 was added at an increasing flow rate varying from 3 ml per minute to 30 ml per minute simultaneously with solution 3, the flow rate of which was varied in order to maintain the same constant UAg-value over a period of 59 minutes and 42 seconds, meanwhile maintaining UAg at the same constant UAg value of + 138 mV.
  • the emulsion was washed with a solution of demineralized water containing 0.46 g of sodium chloride per litre after flocculation by addition of polystyrene sulphonic acid to the acidified emulsion.
  • To the washed flocculate gelatin was added, followed by redispersion. So after addition of said gelatin a ratio of gelatin to silver nitrate in the emulsion of about 0.35 was obtained.
  • the pH-value of the said emulsion was adjusted at 5.20; the pAg-value at + 170 mV.
  • a photographic material was prepared having on a subbed polyester base the gelatinous silver halide emulsions rich in silver chloride the preparation of which has been described above.
  • each emulsion was further stabilized with 1-p-carboxyphenyl-5-mercaptotetrazole and after addition of the normal coating additives the solutions were coated simultaneously together with a protective layer containing 1.3 g gelatine per m 2 per side on both sides of a polyethylene terephthalate film support having a thickness of 175 ⁇ m.
  • the resulting photographic material contained per side an amount of silver halide corresponding to 3.8 grams of AgNO 3 per m 2 and an amount of gelatin corresponding to 3.2 g/m 2 .
  • the emulsion layer in the different materials was overcoated with a gelatin covering layer (protective anti-stress layer) of 1.30 g of gelatin per m 2 , having following composition at a coating pH value of 6.1: Protective layer Gelatin 1.1 g/m 2 Polyethyl acrylate latex 500 mg/m 2 Kieselsol 15 mg/m 2 Chromium acetic acid 5.5 mg/m 2 Compound (1) 7.5 mg/m 2 Compound (2) 19 mg/m 2 Mobilcer Q 25 ml/m 2 Compound (3) 8 mg/m 2
  • the processing was run in the developing liquid EXPDEV, followed by fixing in fixing liquid EXPFIX and rinsing at the indicated temperature of 35°C for a total processing time of 45 seconds.
  • Developer EXPDEV demineralized water 700 ml sodium erythorbate laq. 61.5 g 4,4'-hydroxymethyl-methyl-phenidone 2 g potassium bromide 1 g potassium thiocyanate 1 g 5-methyl-benzotriazole 0.03 g potassium metabisulfite 23 g aqueous potassium carbonate (765 g/l) 125 ml aqueous potassium hydroxyde (755 g/l) 10 ml 1-hydroxy ethyl diphosphonic acid di-Na salt 1 g Polyethylene glycol (M.W.: 400) 20 ml pH (adjusted with acetic acid) 9.65 Water to make 1 l.
  • fixer EXPFIX The developed samples were fixed in fixer EXPFIX, followed by rinsing with water.
  • the composition of the said fixer was as follows: Fixer EXPFIX -Ammonium thiosulphate (60 % solution, wherein 1 ml comprises 0.778 g) 710 ml -Sodium metabisulphite 80 g -Sodium acetate 130 g -Acetic acid 31 ml pH ready-for-use (after dilution 1+3) 4.90
  • % C.O. 100/antilog (logE back - logE front) Film F S Dmax Screen Speed Crossover (%) Abs.abs. (545 nm) TC1 0.040 2.11 3.49 27 54 1.11 TC2 0.218 1.91 3.50 49 60 0.93 TC3 0.041 1.89 3.57 38 49 1.13 TI1 0.056 1.83 3.65 50 46 1.17 TI2 0.028 1.82 3.74 53 51 1.13 TI3 0.028 1.76 3.78 56 50 1.15
  • Film materials comprising tabular ⁇ 111 ⁇ grains rich in chloride were the following.
  • a nucleation step was performed by introducing solution A and solution B1 simultaneously in dispersion medium C both at a flow rate of 120 ml/min during 30 seconds.
  • the first growth step was performed by introducing by a double jet during 28 minutes and 50 seconds solution A starting at a flow rate of 10 ml/min and linearly increasing the flow rate to an end value of 27.4 ml/min, and solution B1 at an increasing flow rate in order to maintain a constant mV-value, measured by a silver electrode versus a saturated calomel electrode (S.C.E.), of +115 mV.
  • the flow rate of solution A was immediately decreased to 10 ml/min and the mV-value adjusted to + 135 mV and increased again to a flow rate of 19.8 ml/min during the following 16 minutes and 8 seconds, during which time the mV-value was further held constant at + 135 mV by a controlled increasing flow of B1.
  • a solution of 40 ml having 15 mmoles of potassium iodide was added at a constant flow rate of 2 minutes.
  • the total iodide content of the tabular silver chloroiodide crystals was thereby enhanced to a value of up to 1.0 mole %.
  • the thus obtained silver chloride 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.
  • the mV-value of the emulsion was adjusted at +158 mV (against a silver/silver chloride reference electrode) with sodium chloride and the pH-value at 5.5 with sodium hydroxide.
  • Chemical ripening agents were adapted to the crystal size of the emulsions.
  • Chemical ripening agents were gold thiocyanate, sodium thiosulphate as a source of sulphur and toluene thiosulphonic acid was used as predigestion agent.
  • the amounts of each chemical ripening agent were optimized in order to obtain an optimal fog-sensitivity relationship after 2 hours at 70°C, without the presence of bromide ions, opposite to the required use thereof at a temperature of greater than 80°C as in US-A 5,494,788.
  • a spectral sensitizing combination of a benzoxazole and a benzimidazole sensitizer for the emulsion grains rich in silver chloride, wherein the benzimidazole spectral sensitizing dye offers good adsorbing J-aggregates at the crystal surface, absorbing light at the desired wavelength of 545 nm thus results in an optimal relation between a high speed and a low fog as desired.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Conversion Of X-Rays Into Visible Images (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP98200061A 1998-01-13 1998-01-13 Kombination eines radiographischen Verstärkungsschirms mit einem Film Withdrawn EP0930527A1 (de)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1246000A1 (de) * 2001-03-29 2002-10-02 Agfa-Gevaert Strahlungsempfindliche Emulsion, lichtempfindlicher photographischer Silberhalogenidfilm und Kombination eines radiographischen Verstärkungsschirms mit einem Film
US6686142B2 (en) 2001-03-29 2004-02-03 Agfa-Gevaert Radiation-sensitive emulsion, silver halide photographic film material and radiographic intensifying screen-film combination
EP1422548A1 (de) * 2002-11-19 2004-05-26 Eastman Kodak Company Radiographischer Silberhalogenidfilm zur Mammography mit weniger Farbflecken

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Publication number Priority date Publication date Assignee Title
EP0506584A1 (de) * 1991-03-28 1992-09-30 Eastman Kodak Company Radiographische Elemente mit weniger Farbflecken enthaltende Emulsion aus tafelförmigen Körnern
JPH08262604A (ja) * 1995-03-23 1996-10-11 Konica Corp ハロゲン化銀写真感光材料とその処理方法及び撮影方法
JPH08314048A (ja) * 1995-05-22 1996-11-29 Konica Corp ハロゲン化銀写真感光材料とその撮影方法及び処理方法
JPH09133981A (ja) * 1995-11-08 1997-05-20 Konica Corp ハロゲン化銀写真感光材料及びその撮影方法と処理方法
JPH09211756A (ja) * 1996-02-02 1997-08-15 Konica Corp ハロゲン化銀写真感光材料及びその処理方法並びに放射線撮影体及び撮影方法

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Publication number Priority date Publication date Assignee Title
EP0506584A1 (de) * 1991-03-28 1992-09-30 Eastman Kodak Company Radiographische Elemente mit weniger Farbflecken enthaltende Emulsion aus tafelförmigen Körnern
JPH08262604A (ja) * 1995-03-23 1996-10-11 Konica Corp ハロゲン化銀写真感光材料とその処理方法及び撮影方法
JPH08314048A (ja) * 1995-05-22 1996-11-29 Konica Corp ハロゲン化銀写真感光材料とその撮影方法及び処理方法
JPH09133981A (ja) * 1995-11-08 1997-05-20 Konica Corp ハロゲン化銀写真感光材料及びその撮影方法と処理方法
JPH09211756A (ja) * 1996-02-02 1997-08-15 Konica Corp ハロゲン化銀写真感光材料及びその処理方法並びに放射線撮影体及び撮影方法

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Title
DATABASE WPI Section Ch Week 9743, Derwent World Patents Index; Class E23, AN 97-461706, XP002065763 *
PATENT ABSTRACTS OF JAPAN vol. 097, no. 002 28 February 1997 (1997-02-28) *
PATENT ABSTRACTS OF JAPAN vol. 097, no. 003 31 March 1997 (1997-03-31) *
PATENT ABSTRACTS OF JAPAN vol. 097, no. 009 30 September 1997 (1997-09-30) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1246000A1 (de) * 2001-03-29 2002-10-02 Agfa-Gevaert Strahlungsempfindliche Emulsion, lichtempfindlicher photographischer Silberhalogenidfilm und Kombination eines radiographischen Verstärkungsschirms mit einem Film
US6686142B2 (en) 2001-03-29 2004-02-03 Agfa-Gevaert Radiation-sensitive emulsion, silver halide photographic film material and radiographic intensifying screen-film combination
EP1422548A1 (de) * 2002-11-19 2004-05-26 Eastman Kodak Company Radiographischer Silberhalogenidfilm zur Mammography mit weniger Farbflecken
US6794105B2 (en) 2002-11-19 2004-09-21 Eastman Kodak Company Radiographic silver halide film for mammography with reduced dye stain

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