EP0862083A1 - Système et méthode de formation d'image radiologique - Google Patents

Système et méthode de formation d'image radiologique Download PDF

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Publication number
EP0862083A1
EP0862083A1 EP98200468A EP98200468A EP0862083A1 EP 0862083 A1 EP0862083 A1 EP 0862083A1 EP 98200468 A EP98200468 A EP 98200468A EP 98200468 A EP98200468 A EP 98200468A EP 0862083 A1 EP0862083 A1 EP 0862083A1
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Prior art keywords
image
silver
forming system
layers
grains
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German (de)
English (en)
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EP0862083B1 (fr
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Ann Verbeeck
Freddy Henderickx
Dirk Vandenbroucke
Peter Verrept
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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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • 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
    • G03C1/30—Hardeners
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • 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
    • G03C2001/03517—Chloride 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03541—Cubic grains
    • 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
    • G03C2001/03558—Iodide 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03594—Size of the grains
    • 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
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C2005/3007—Ascorbic acid
    • 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
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers

Definitions

  • This invention relates to a system for radiological image formation by means of a suitable film material in operative association with an intensifying screen and a method for image formation.
  • Strongly hardened silver halide photographic materials moreover provide the advantage to use concentrated developing and fixing solutions free from hardening agents as has been set forth e.g. in US-A 5,296,342, which again is in favour of ecology.
  • an image-forming system for radiological imaging consisting of an intensifying screen comprising on a support at least one layer of a green-light emitting phosphor and, in operative association therewith, a prehardened light-sensitive photographic silver halide film material, comprising a support and on both sides thereof one or more hydrophilic colloid layers, said layers being hardened to such an extent that their swelling degree is reduced to less than 200 % after immersing said material for 2 minutes in demineralised water of 35 °C; further comprising in at least one of said hydrophilic layers chemically ripened, monodisperse essentially cubic silver chloroiodide grains having a mean crystal diameter of from 0.40 ⁇ m up to 0.65 ⁇ m; wherein said grains have been spectrally sensitised in the wavelength range between 520 and 580 nm, have a maximum absorption between 540 and 550 nm and have been coated in a total amount of silver per sq.m.
  • said grains have further been spectrally sensitised with a combination of imidacarbocyanine and oxacarbocyanine dyes.
  • a method of image formation is provided by means of the said image-forming system wherein said image formation comprises the step of processing said film material after exposure with light emitted by a green-light emitting phosphor of an intensifying screen after conversion of X-rays having an energy from 60 to 150 kVp, wherein said step of processing proceeds in an automatic processor.
  • said processing is performed within a total processing cycle of less than 90 seconds comprising the steps of developing in a developing solution comprising (iso)ascorbic acid, l-ascorbic acid, reductic acid, salts and/or derivatives thereof; fixing in a fixer solution free from aluminum salts; rinsing and drying.
  • Replenishing of said developing and fixer solution preferably proceeds with amounts of replenisher in the range from 100 up to 200 ml/m 2 and from 50 up to 150 ml/m 2 respectively.
  • a light-sensitive emulsion layer from the material of the image-forming system according to the present invention comprises relatively small cubic silver chloroiodide crystals having an average grain size of from 0.40 up to 0.65 ⁇ m and a monodisperse grain size distribution a sufficient speed was attained without deterioration of image tone, in that no shift to brown coloured silver after development was observed, provided that one or more complex ion compounds according to the general formula (I) represented hereinbefore were added as a dopant to the silver chloroiodide emulsion crystals during precipitation, thereby forming shallow electron traps.
  • the intensity of the electron EPR signal is significantly enhanced (by at least 20 %) when a comparison is made between two emulsion samples being identical, except for the presence or the absence of complex ion compounds according to the general formula (I) given hereinbefore, then the energetic distance between filled higher occupied (HOMO) and lower unoccupied (LUMO) molecular orbital is more than 27000 cm -1 .
  • the LUMO is defined as the "lowest unoccupied molecular orbital" of the related complex, whereas the HOMO is the "highest occupied molecular orbital" as has been described by D.F. Shriver, P.W. Atkins and C.H. Langford in “Inorganic Chemistry”-Oxford Univ. Press (1990), Oxford-Melbourne-Tokyo.
  • the energetic distance between HOMO and LUMO of the compounds is experimentally attainable from spectroscopic measurements. Dissolved in an appropriate solvent and measured by UV-VIS absorption spectroscopy e.g. in tranmission, no absorption may be detected lower than 27000 cm -1 for the compounds satisfying the requirements of the present invention.
  • ligands are e.g. ligands selected from the group consisting of cyanide, cyanate, isocyanate, thiocyanate, carbonyl, nitrosyl and thionitrosyl.
  • spectral sensitisation should be performed with a suitable combination of oxacarbocyanines and an imidacarbocyanines as spectral sensitisers.
  • Metal ions or metal ion complexes are commonly added in significantly lower amounts to the cubic silver chloroiodide crystals coated in emulsion form in one or more hydrophilic layers of the material used in the image-forming system according to the present invention than e.g. spectral sensitisers and are thereby causing much less chemical load of the image-forming system of the present invention.
  • Said dopants can in principle be added in whatever a stage of the emulsion preparation. Generally dopants have little influence on crystal distributions in the emulsions but they may be added to cause advantageous effects with respect to reciprocity, pressure sentisitisation, etc..
  • the cubic silver chloroiodide grains present in coated light-sensitive layers of the material used in the image-forming system of the present invention have been doped with at least one complex ion compound according to the formula (I) wherein M represents Ru 2+ , Os 2+ , Rh 3+ , Ir 3+ , Cr 3+ or Pt 2+ .
  • complex ion compounds of ruthenium are preferred, and more preferably hexacyano-ruthenium salts as dopant(s) for the said cubic silver chloroiodide grain emulsions in the image-forming system of the present invention: at least one complex ion compound being [Ru(CN) 6 ] 4- is present in order to reach the objects of the present invention by modification of the crystal structure, thereby further influencing the physical and chemical properties of the emulsion crystals as well.
  • the metal dopant and the complex ion form e.g. in form of a coordination complex or oligomeric coordination complex
  • the concentration, its valency and its location in the crystal parameters like sensitivity (speed), gradation, stability, developability, pressure sensitisation, dye (de)sensitisation and reciprocity are influenced.
  • the dopants are added after the end of the nucleation step, more preferably after addition of more than 50 % of the total amount of silver (thus during the growth step) and before addition of the last 5 % of silver chloride in order to complete crystal growth of silver chlor(oiod)ide crystals.
  • said solution can be introduced by means of a so-called "third-jet" in order to introduce the dopant in the reaction vessel where rapid incorporation in the growing crystals is performed.
  • said third-jet is adding the dopant solution in the vicinity of the stirrer, where also new rapidly dissolving fine grain nuclei are formed which are precipitated further onto stable growing silver chloride or chloroiodide cubic crystals.
  • dopants in literature are ruthenium, rhodium and iridium. Combinations of one or more dopant(s) may be added, in the same or different preparation steps of silver halide crystals rich in silver chloride having a cubic habit. Just as halide ions the said dopants can be divided homogeneously or heterogeneously over the total crystal volume. So in the core or in the shell or even at the crystal surface, as is e.g. the case when conversion techniques are applied, the said halide ions and/or the said dopants may be concentrated.
  • potassium hexachloroiridate (III) added during chemical ripening, are from 0.5 to 20 ⁇ mole per mole of silver and more preferred from 1 to 5 ⁇ mole per mole as has been described in EP-A 0 754 456.
  • the precipitation conditions are chosen such that said emulsions are emulsions having an essentially cubic crystal habit.
  • the precipitation of such cubic crystals is principally performed by at least one double jet step; but more preferably it consists of a sequence of consecutive double jet steps comprising a nucleation step and at least one growth step.
  • the different steps of the precipitation are commonly alternated by physical ripening steps.
  • said different steps preferably proceed under controlled conditions of pH, pAg, temperature, stirring velocity and addition rates, wherein said addition rates may be held constant or may be increased as precipitation proceeds in order to reduce the total time thereof.
  • a crystal growth accelerator may be added, in favour of crystal growth, further avoiding said renucleation.
  • growth accelerators are thioether compounds as e.g. methionine , 1,8-dihydroxy-3,6-dithiooctane, etc., or polyoxyalkylenes although care should be taken with respect to fog formation.
  • Crystals having an essentially cubic habit, dispersed in an emulsion coated in one or more hydrophilic layers of the material used in the image-forming system of the present invention have an average crystal diameter of from 0.40 up to 0.65 ⁇ m, with a high degree of homogeneity: a variation coefficient on the grain size distribution of less than 0.25, more preferred between 0.10 and 0.20, contributes to the desired sensitometry and image quality. Mixtures of emulsions having grains with homogenous or monodisperse grain size distributions may be useful.
  • Iodide ions should be provided, in order to get a silver chloroiodide composition for the cubic grains, by using aqueous solutions of inorganic salts thereof as e.g. potassium iodide, sodium iodide or ammonium iodide.
  • Iodide ions can however also be provided by organic compounds releasing iodide ions as has e.g. been described in EP-A's 0 561 415, 0 563 701, 0 563 708, 0 649 052 and 0 651 284 and in WO 96/13759.
  • Grain distributions of silver chloroiodide crystals over the light-sensitive emulsion are homogeneous or monodisperse by controlling the precipitation methods used. Therefore it is very important in the precipitation conditions of cubic silver chloride cystals to carefully controll pAg, temperature, dilution of the reaction vessel, presence of growth restrainers or growth accelerators, addition rate of added aqueous soluble silver salt and halide solutions during different precipitation steps (especially during the nucleation step during which e.g. less than 10 % of the total amount of silver salt available is consumed and further during the at least one growth step during which at least 90 % of the said silver salt is consumed), way of mixing and mixing or stirring rate in the reaction vessel during the different precipitation steps.
  • Homogeneous crystal size distributions having variation coefficients (defined as ratio between standard deviation and average diameter) of not more than 0.10 to 0.20 instead of the normally occurring variation coefficients between 0.20 and 0.30 are thus obtained.
  • more heterogeneous distributions may be obtained and may even be more advantageous e.g. from the point of view of exposure latitude a far more better way to obtain the same effect of e.g. an increasing exposure latitude is reached by making mixtures of different homogeneous emulsions having very low variation coefficients e.g. in the range from 0.05 to 0.15.
  • This may lead to even more advantageous sensitometric characteristics (e.g. increased contrast) or image quality (e.g. granularity and/or sharpness) as has been illustrated e.g. in US-A 4,446,228 and in EP-A 0 555 897.
  • Patent literature related with the chemical ripening of emulsion grains rich in silver chloride can be found e.g. in EP-A's 0 443 453, 0 454 278; 0 458 278; 0 513 748; 0 590 593; 0 661 589 and 0 718 674 and in US-A's 4,810,626; 5,306,613 and 5,348,850, wherein said selenium sensitisers are normally used together with other sensitisers as at least gold and optionally sulphur.
  • triphenylphosphorselenide was not a suitable chemical sensitiser for silver chloroiodide emulsion crystals coated in materials used in the image-forming system of that invention, opposite to those selenium compounds selected from the group of compounds consisting of substituted selenoureum, substituted triphenylphosphine selenide and substituted and unsubstituted triphenylorthophosphate selenide.
  • said selenium sensitisers are preferably used together with other sensitisers as at least gold and optionally sulphur.
  • said monodisperse cubic silver chloriodide grains should, besides being chemically ripened with one or more selenium compounds mentioned hereinbefore, further be chemically ripened with one or more sulphur and/or gold compounds.
  • Especially useful labile compounds providing sulphur are therefore e.g. the preferred tetramethyl-thiodithioacetic acid diamide and further dimethylamino-dithiomercaptane, thiosulphates or thiosulphonates.
  • Other useful compounds which may be applied are those as described e.g.
  • chemical sensitisation can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur as e.g. thiosulphate, thiocyanate, thioureas; sulphites, mercapto compounds, rhodamines etc.., wherein combinations of gold-sulphur ripeners together with the required selenium sensitisers are the most preferred.
  • compounds containing sulphur e.g. thiosulphate, thiocyanate, thioureas; sulphites, mercapto compounds, rhodamines etc..
  • combinations of gold-sulphur ripeners together with the required selenium sensitisers are the most preferred.
  • chemically ripened monodisperse cubic silver chloroiodide grains are chemically ripened with one or more sulphur and/or selenium compound(s) and one or more gold compound(s). Addition of tellurium compounds as
  • tellurosulphate, tellurocyanate, telluroureas in very small amounts is thereby however not excluded.
  • Further reductors as e.g. tin compounds as described in GB-Patent 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds may be used, although care should be taken in order to prevent the emulsion from fog formation in an uncontrollable way.
  • Normal amounts of selenium compounds are in the range from 1 x 10 -5 to 1 x 10 -7 moles per mole of silver, whereas normal amounts of gold compounds (as gold chloride or gold thiocyanate) are in the range from 1 x 10 -5 to 2.5 x 10 -5 moles per mole of silver.
  • the surface of the silver chloroioide grains may be treated with slightly oxidising compounds as e.g. toluene thiosulphonic acid and/or corresponding salts thereof in order to reduce small silver specks to grow to fog centers in an uncontrolled manner.
  • slightly oxidising compounds as e.g. toluene thiosulphonic acid and/or corresponding salts thereof in order to reduce small silver specks to grow to fog centers in an uncontrolled manner.
  • light-sensitive cubic silver chloroiodide grains may be spectrally sensitised with methine dyes such as those described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons.
  • Dyes that may be used for the purpose of spectral sensitisation include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • the doped silver chloroiodide grains having a regular, essentially cubic habit are, opposite to the grains described in EP-A 0 336 426, spectrally sensitised with compounds selected from the group consisting of benzimidazoles, benzoxazoles, or a combination thereof.
  • spectral sensitisation with a combination of benzimidazolo- and benzoxazolo-carbocyanines is preferred provided that absorption characteristics of the said combination of those green light-absorbing spectral sensitisers are such that spectral sensitisation occurs in the preferred wavelength range between 520 and 580 nm, with a maximum absorption between 540 and 550 nm.
  • An example of a useful spectral sensitiser of the oxacarbocyanine type is anhydro-5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyloxacarbocyanine hydroxide or anhydro-5,5'-di-chloro-3,3'-bis(n-sulphopropyl)-9-ethyloxacarbocyanine hydroxide.
  • a very suitable mixture or combination of spectral sensitisers of the oxa- and imidacarbocyanine type is anhydro-5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyl oxacarbocyanine hydroxide or anhydro-5,5'-di-chloro-3,3'-bis(n-sulphopropyl)-9-ethyloxacarbocyanine hydroxide together with anhydro-5,5'-dicyano-1,1'-diethyl-3,3'-di(2-acetoxy-ethyl)ethyl-imidacarbocyanine bromide.
  • spectral sensitisation traditionally follows the completion of chemical sensitisation. It can however be advantageous to add a small amount of spectral sensitising dye to the emulsion crystals just before cooling of the dispersion at the end of the growth stage, but in principle the addition of said dye may be performed at any stage of the precipitation, during or after redispersing or before, during or after chemical ripening. The addition can further be performed in one or more portions. So in US-A 5,286,621 it has been shown that spectral sensitiser is added in amounts ranging from 10 -5 to 5 x 10 -3 moles per mole of silver halide as a whole after completion of the precipitation or in several fractions during and after precipitation.
  • An important factor influencing growth of silver nuclei in the preparation of silver chloroiodide grains is the choice of and the amount of protective colloid present in the reaction vessel or added simultaneously with one of the solutions added thereto during nucleation and further, eventually, after nucleation, during physical ripening before and/or during growth of the nuclei formed.
  • gelatin The most well-known and practically used hydrophilic colloidal binder during precipitation of silver chloroiodide crystals is gelatin.
  • the preparation of conventional lime-treated or acid treated gelatin has been described in e.g. "The Science and Technology of Gelatin", edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 and next pages.
  • the gelatin can also be enzyme-treated as described in Bull. Soc. Sci. Phot. Japan, N° 16, page 30 (1966).
  • a preparation method of tabular grain emulsions wherein in the grain growth process use is made of gelatin derivatives with chemically modified NH 2 -groups and wherein said gelatin has a specific methionine content has been described in e.g. EP-A 0 697 618.
  • Gelatin may, however, be replaced in part or integrally by synthetic, semi-synthetic, or natural polymers.
  • Synthetic substitutes for gelatin are e.g. polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl imidazole, polyvinyl pyrazole, polyacrylamide, polyacrylic acid, and derivatives thereof, in particular copolymers thereof.
  • Natural substitutes for gelatin are e.g. other proteins such as zein, albumin and casein, cellulose, saccharides, starch, and alginates.
  • the semi-synthetic substitutes for gelatin are modified natural products e.g.
  • gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents, by grafting of polymerisable monomers on gelatin or prehardened gelatins with blocked functional groups as a consequence of this prehardening treatment, cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates and even potato starch.
  • Part of gelatin may further be replaced with a synthetic or natural high-molecular material.
  • An interesting substitute for gelatin may be silica as has been described in the published EP-A's 0 392 092, 0 517 961, 0 528 476 and 0 649 051 and 0 704 749.
  • EP-A 0 528 476 a method of preparing a silver halide light-sensitive photographic material incorporating layers of silver halide precipitated in colloidal silica serving as a protective colloid is given.
  • the silver halides are prepared in colloidal silica, leading to emulsion crystals that are stable at the end of the precipitation, without however having a predictable mean crystal diameter and crystal size distribution.
  • the emulsion mixture is normally cooled to about 40°C, before or after adding a flocculate being a polymeric compound as e.g. polystyrene sulphonic acid, providing as a anionic polymer a behaviour depending on pH.
  • a flocculate being a polymeric compound as e.g. polystyrene sulphonic acid, providing as a anionic polymer a behaviour depending on pH.
  • a flocculate being a polymeric compound as e.g. polystyrene sulphonic acid, providing as a anionic polymer a behaviour depending on pH.
  • a flocculate being a polymeric compound as e.g. polystyrene sulphonic acid, providing as a anionic polymer a behaviour depending on pH.
  • the pH of the said dispersing medium is adjusted with an acid to a value in order to get a qualitatively good flocculate.
  • Said flocculate may become decanted and
  • adenine to an allowable residual amount preferably at most 0.3 mg/g of gelatin
  • an ultrafiltration washing procedure as disclosed e.g. in Research Disclosure, Vol. 102, Oct. 1972, Item 10208, Research Disclosure Vol. 131, March, Item 13122 and Mignot US-A 4,334,012.
  • Said ultrafiltration technique may be applied on-line during the whole precipitation, in order to reduce the increasing amount of water, thus avoiding dilution of the reaction vessel and increasing amounts of soluble salts like the mainly occurring potassium nitrate. Examples thereof have been described e.g. in EP-A 0 577 886.
  • any useful protective colloid cited hereinbefore as an alternative of gelatin or gelatin in modified form may be used.
  • additional gelatin or anotherhydrophilic colloid suitable as a binder material can be added at a later stage of the emulsion preparation e.g. after washing, to establish optimal coating conditions and/or to establish the required thickness of the coated emulsion layer.
  • a gelatin to silver halide ratio silver halide being expressed as the equivalent amount of silver nitrate, ranging from 0.3 to 1.0 is then obtained.
  • Another binder may also be added instead of or in addition to gelatin.
  • Useful vehicles, vehicle extenders, vehicle-like addenda and vehicle related addenda have been described e.g. in Research Disclosure N° 38957 (1996), Chapter II.
  • any thickening agent may be used in order to regulate the viscosity of the coating solution, provided that they do not particularly affect the photographic characteristics of the silver chloroiodide emulsion in the coated photographic material.
  • Preferred thickening agents include aqueous polymers such as polystyrene sulphonic acid, dextran, sulphuric acid esters, polysaccharides, polymers having a sulphonic acid group, a carboxylic acid group or a phosphoric acid group as well as colloidal silica.
  • Polymeric thickeners well-known from the literature resulting in thickening of the coating solution may even be used in combination with colloidal silica. Patents concerning thickening agents are e.g.
  • hydrophilic colloidal layer compositions on a support by slide-hopper or curtain-coating techniques, wherein said compositions have gelatin in low amounts in order to provide a ratio by weight of gelatin to silver halide expressed as an equivalent amount of silver nitrate in the range from 0.05 to 0.4
  • thickening agents composed of synthetic clay and anionic macromolecular polyelectrolytes wherein said synthetic clay is present in an amount of at least 85 % by weight versus the total amount of thickening agents are recommended as has been disclosed in EP-A 0 813 105.
  • Photographic material having thin emulsion layers e.g. layers with a layer thickness of not more than 6 ⁇ m, containing at most 6 g of gelatin, more preferably from about 2 to 6 g/m 2 and even more preferably to about 3.5 g/m 2 of gelatin offer the advantage that besides rapid processing applicability and the rapid drying of the wet processed material an improvement in sharpness is observed.
  • drying characteristics in the processor are mainly determined by the water absorption of the hydrophilic layers of the photographic material, and since the water absorption is directly proportional to the gelatin content of the layers and inversely proportional to the amount of hardener, added to the layer, its composition is optimised with a low gelatin content and a high hardening degree in order to allow hardener free processing within a total processing time cycle from 30 to at most 60 seconds dry-to-dry.
  • the layer binder In order to reach a high hardening degree the layer binder should of course dispose of an acceptably high number of functional groups, which by reaction with an appropriate hardening agent can provide a sufficiently resistant layer.
  • functional groups are especially the amino groups, but also carboxylic groups, hydroxy groups, and active methylene groups.
  • Hardeners may be added to the antistress layer, covering one or more light-sensitive silver halide emulsion layers rich in chloride before or during the coating procedure, or to one or more of the said emulsion layers.
  • the binders of the photographic element can be hardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type as e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts as e.g. chromium acetate and chromium alum, aldehydes as e.g. formaldehyde, glyoxal and glutaraldehyde, N-methylol compounds as e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives as e.g.
  • appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type as e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts as e.g. chrom
  • 2,3-dihydroxy-dioxan active vinyl compounds as e.g. 1,3,5-triacryloyl-hexa-hydro-s-triazine, active halogen compounds as e.g. 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids as e.g. mucochloric acid and mucophenoxy-chloric acid.
  • These hardeners can be used alone or in combination.
  • the binders can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts.
  • Formaldehyde and phloroglucinol can e.g. be added respectively to the protective layer(s) and to the emulsion layer(s).
  • Preferred hardening agents however in the context of the present invention are bis-(vinyl-sulphonyl)-methane (BVSME) and ethylene bis-(vinyl-sulphone).
  • Materials used in the image-forming system according to the present invention commonly have a hardening degree corresponding with a swelling degree of the layers of the material of less than 200% and even more preferably of not more than 150 % as can be measured from thickness ratios of the layers of the material before and after immersion in demineralised water of 25°C for 3 minutes.
  • sensitometric properties e.g. sensitivity (also called speed), gradation (also called contrast and specified in the toe, the linear part and/or the shoulder of the characteristic curve), fog and maximum density in preferred rapid processing conditions for the materials coated from silver chloroiodide emulsions used in the image-forming system according to the present invention.
  • sensitivity also called speed
  • gradation also called contrast and specified in the toe, the linear part and/or the shoulder of the characteristic curve
  • fog and maximum density in preferred rapid processing conditions for the materials coated from silver chloroiodide emulsions used in the image-forming system according to the present invention.
  • the photographic element may further comprise various kinds of coating physical property modifying addenda as described in RD N° 38957 (1996), Chapter IX, wherein coating aids, plasticisers and lubricants, antistats and matting agents have been described.
  • Development acceleration can be accomplished by incorporating in emulsion layer(s) or adjacent layers various compounds, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-A's 3,038,805; 4,038,075 and 4,292,400 as well as in EP-A's 0 634 688 and 0 674 215.
  • various compounds preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-A's 3,038,805; 4,038,075 and 4,292,400 as well as in EP-A's 0 634 688 and 0 674 215.
  • the photographic element may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, ultraviolet absorbers and spacing agents.
  • Suitable additives for improving the dimensional stability of the photographic element are e.g. dispersions of a water-soluble or hardly soluble synthetic polymer e.g.
  • Suitable UV-absorbers are e.g. aryl-substituted benzotriazole compounds as described in US-A 3,533,794, 4; thiazolidone compounds as described in US-A's 3,314,794 and 3,352,681, benzophenone compounds as described in JP-A 56-2784, cinnamic ester compounds as described in US-A's 3,705,805 and 3,707,375, butadiene compounds as described in US-A 4,045,229, and benzoxazole compounds as described in US-A 3,700,455 and those described in RD N° 38957 (1996), Chapter VI, wherein also suitable optical brighteners are mentioned.
  • Spacing agents may be present of which, in general, the average particle size is comprised between 0.2 and 10 ⁇ m. Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic element, whereas alkali-soluble spacing agents usually are removed therefrom in an alkaline processing bath. Suitable spacing agents can be made e.g. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydrophtha-late. Other suitable spacing agents have been described in US-A 4,614,708.
  • a mixture of two or more emulsions having silver chloroiodide crystals with the same or different crystal sizes, the same or a different crystal habit, a different or the same chemical ripening treatment and/or a different or the same coverage degree with one or more spectral sensitisers being different from each other or the same, as those described hereinbefore may be added to at least one light-sensitive emulsion layer, provided that at least one emulsion is composed of crystals doped with at least one complex metal ion compound corresponding with the general formula (I).
  • the same or different emulsions or emulsion mixtures may be present in the different layers. If the same emulsion or emulsion mixture is present in different emulsion layers distinct amounts of (same or different) spectral sensitiser may have been added during chemical riping and/or preparation for coating in order to get a broader exposure latitude for the material according to the image-forming method of this invention and less sensitometric fluctuations in the processing of the radiographic material.
  • spectral sensitiser If more than one spectral sensitiser is used, wherein at least one of them is absorbing to a differing wavelength region, it is preferred to add them to different layers too, and still more preferred to add them to layers situated at different sides of the support as wandering of spectral sensitizers may form a problem.
  • Such arrangement has e.g. been described in e.g. US-A's 4,978,599 and 5,380,636.
  • the photographic material may contain several light-insensitive layers at the side of the support carrying said light-sensitive emulsion layer(s), e.g. a protective antistress layer which can be split up into two layers, one of them being an underlying interlayer or an outermost afterlayer coated or sprayed on top of the "basic" protective antistress layer, one or more subbing layers, one or more intermediate layers e.g. filter layers and even an afterlayer containing e.g. hardening agent(s), antistatic agent(s), filter dyes for safety-light purposes etc.
  • a protective antistress layer which can be split up into two layers, one of them being an underlying interlayer or an outermost afterlayer coated or sprayed on top of the "basic" protective antistress layer
  • subbing layers one or more intermediate layers e.g. filter layers and even an afterlayer containing e.g. hardening agent(s), antistatic agent(s), filter dyes for safety-light purposes etc.
  • Protective antistress layers preferably contain coating aids and coating physical property modifying addenda mentioned in RD 38957, published September 1996, Chapter IX. Antistatic properties are especially preferred in order to prevent blackening after processing in form of sparks etc. due to abrupt decharging of electrostatic charges during production and/or handling before exposure and/or processing. It is highly preferred to add antistatic agents to the protective antistress layer or to an afterlayer coated thereupon as has been described e.g. in EP-A's 0 534 006, 0 644 454 and 0 644 456 and US-A's 4,670,374 and 4,670,376.
  • Abrasion resistance of these outermost layers may be improved as described in US-A's 4,766,059 and 4,820,615.
  • Spraycoating of afterlayers has been disclosed e.g. in US-A 5,443,640.
  • Non-imagewise blackening occurring as a result of pressure sensitivity of silver halide grains rich in chloride is lowered in the present invention due to the presence of iodide ions at the grain surface of the cubic silver chloroiodide crystals.
  • Measures in order to further suppress pressure sensitivity may be coating of enhanced amounts of binder as e.g. gelatin. This however is disadvantageous with respect to rapid processing and therefore as an alternative silver chloroiodide prepared in silica may offer an alternative as has been disclosed e.g.
  • the support of the photographic materials comprising silver halide emulsions with cubic silver chloroiodide crystals used for X-ray imaging may be a transparent resin, preferably a blue coloured polyester support like polyethylene terephthalate.
  • the thickness of such organic resin film is preferably about 175 ⁇ m.
  • Other hydrophobic resin supports are well known to those skilled in the art and are made e.g. of polystyrene, polyvinyl chloride, polycarbonate and polyethylene naphthalate.
  • the support is further provided with a substrate layer at both sides to have good adhesion properties between the adjacent layers and said support: one or more subbing layers known to those skilled in the art for adhering thereto a hydrophilic colloid layer may be present.
  • Suitable subbing layers for polyethylene terephthalate supports are described e.g. in US-A's 3,397,988, 3,649,336, 4,123,278 and 4,478,907.
  • a preferred layer arrangement wherein a subbing layer composition comprising as a latex copolymer vinylidene chloride, methylacrylate and itaconic acid has been covered with hydrophilic layers being 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 has been described in EP-A 0 752 617.
  • said hydrophilic layers have a swelling ratio of not more than 200 % and in said hydrophilic layers are coated simultaneously by the slide-hopper coating or by the slide-hopper curtain coating technique. Further information on suitable supports can be found in RD 38957, Chapter XV, published September 1996.
  • penetrating radiation which is high energy radiation belonging to the class of X-rays, ⁇ -rays and high energy elementary particle radiation, e.g. ⁇ -rays, electron beam or neutron radiation.
  • penetrating radiation For the conversion of penetrating radiation into visible light and/or ultraviolet radiation luminescent substances are used called phosphors.
  • an X-ray radiograph is obtained by X-rays transmitted imagewise through an object and converted into light of corresponding intensity in a so-called intensifying screen (X-ray conversion screen) wherein phosphor particles absorb the transmitted X-rays and convert them into visible light and/or ultraviolet radiation whereto a photographic film is made more sensitive: it is clear that spectral sensitisers are chosen as a function of and in order to absorb light of about the same wavelength range as the one emitted by luminescent phosphors coated in phosphor layers of intensifying screens brought into contact with the double-side coated film materials during X-ray exposure.
  • intensifying screen X-ray conversion screen
  • silver chloroiodide crystals are spectrally sensitised in the green-wavelength range of the spectrum as e.g. described in GB-Patent 1,489,398 and in US-A's 4,431,922 and 4,710,637. More particlarly silver chloroiodide crystals are spectrally sensitised between 520 and 580 nm, and have a maximum absorption between 540 and 550 nm in order to absorb light emitted from X-ray exposed screens coated from the preferred green-light emitting gadolinium oxisulphide phosphors used in the phosphor screens according to the image-forming system of the present invention.
  • Such phosphors suitable for use in a conventional radiographic system must have a high prompt emission on X-ray irradiation and low afterglow in favour of image-sharpness.
  • terbium activated gadolinium oxisulphide crystals are particularly suitable for use in the image-forming system according to the present invention.
  • Screen-film systems wherein green-light emitting screens are used in contact with green sensitised silver halide films have been described e.g. in EP-A 0 678 772.
  • an X-ray radiation source is used having an energy of from 60 to 150 kVp, e.g. 80 kVp for the detection of bone.
  • the type of binder and the high volume ratio of phosphor to binder it is possible to obtain thin phosphor coatings offering not only high resolution but also high sensitivity without the need for increasing the packing density by compressing so as to reduce the voids as defined in EP-A 0 393 662 to a value of not less than 70%. Moreover the phosphor layer retains high protection against mechanical damage and thus high ease of manipulation.
  • a practically useful binder medium for the phosphor particles has further been disclosed in WO94000530.
  • the binding medium substantially consists of one or more hydrogenated styrenediene block copolymers, having a saturated rubber block, as rubbery and/or elastomeric polymers.
  • the polymer can be represented by the formula A-B-A (tri-block) or by the formula A-B (di-block), wherein A represents styrene and B represents the hydrogenated diene block e.g. ethylene-butylene or ethylene-propylene.
  • Screen/film combinations may be symmetric or asymmetric: this means that screens differing in speed and/or radiation emitted therefrom are differing and/or that there is a difference in speed and/or contrast and/or spectral sensitivity at both sides of the film support.
  • a method of image formation offered as described in the present invention comprises the step of processing said film material after exposure with light emitted by a green-light emitting phosphor of an intensifying screen after conversion of X-rays having an energy from 60 to 150 kVp, wherein said step of processing proceeds in an automatic processor.
  • the image-forming method of the present invention further comprises the step of processing said film material used in the image-forming system described hereinbefore, wherein said processing comprises the steps of developing in a developing solution comprising (iso)ascorbic acid, l-ascorbic acid, reductic acid, salts and/or derivatives thereof; fixing in a fixer solution free from aluminum salts; rinsing and drying.
  • Replenishing of said developing and fixer solution preferably proceeds with amounts of replenisher in the range from 100 up to 200 ml/m 2 and from 50 up to 150 ml/m 2 respectively.
  • an automatically operating apparatus is used provided with a system for automatic replenishment of the processing solutions.
  • the processing therein proceeds within a short processing time of from 30 up to 60 seconds from dry-to-dry for materials used in the image forming system of the present invention.
  • a normally used configuration in the automatic processing apparatus shows the following consecutive tank units corresponding with, as consecutive solutions: developer-fixer-rinse water.
  • the ecologically questionable "hydroquinone" (iso)ascorbic acid, l-ascorbic acid and tetramethyl reductic acid are preferred as main developing agent in the developer.
  • Said developing agents have been described in EP-A's 0 461 783, 0 498 968, 0 690 343, 0 696 759, 0 704 756, 0 732 619, 0 731 381 and 0 731 382; in US-A's 5,474,879 and 5,498,511 and in Research Disclosure No 371052, published March 1, 1995, wherein a more general formula covering the formula of said developing agents has been represented.
  • 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.
  • the presence of ⁇ -ketocarboxylic acid compounds may be useful as described in EP-A's 0 620 483, 0 726 491 and in RD 16768, published March 1978.
  • the developer solution used in the method according to this invention should be replenished not only for decrease of the liquid volume due to cross-over into the next processing solution but also for pH-changes due to oxidation of the developer molecules. This can be done on a regular time interval basis or on the basis of the amount of processed film or on a combination of both. In these circumstances, no dilution and mixing procedures are required before the regeneration bottles are adjusted to the processing unit.
  • 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 100 to 200 ml/m 2 and more preferably from 100 to 150 ml/m 2 for the developer and from 50 to 150 ml/m 2 and more preferably from 50 to 100 ml/m 2 for the fixer solution.
  • 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 minimise 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 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, characterised in that the developing cell is a closed cell and the developing liquid contains an ascorbic acid type 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 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, characterised 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 combination of two screens with a double-side coated film may be used, wherein said film comprises cubic silver chloroiodide crystals as defined in the claims and in the description hereinbefore, and, optionally, ⁇ 111 ⁇ tabular silver chloroiodide crystals as disclosed e.g. in EP-A 0 678 772, e.g. in a multilayer arrangement as disclosed in EP-A 0 770 909, in combination with a processing unit, provided that with minimum amounts of silver coated a sufficient covering power (see therefore e.g. EP-A 0 709 730 with respect to cubic crystal rich in silver chloride) is attained for the film in rapid ecological processing (with e.g.
  • This example demonstrates the advantages of emulsions comprising cubic AgCl(I) crystals doped with a ruthenium compound and having been chemically and spectrally sensitised over other chemically sensitising compounds.
  • Emulsions A and B comparative emulsions
  • 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 demineralised 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 demineralised water containing 0.46 g of sodium chloride per litre after flocculation by addition of polystyrene sulphonic acid to the acidified emulsion.
  • a solution of demineralised water containing 0.46 g of sodium chloride per litre after flocculation by addition of polystyrene sulphonic acid to the acidified emulsion.
  • Spectral sensitisation was carried out for part A by means of a mixture of 0.025 mmoles of anhydro-5,5'-diphenyl-3,3'-bis(n-sulphatopropyl)-9-ethyl-oxacarbocyanine hydroxide and 0.8 mmoles of anhydro-5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyloxacarbocyanine hydroxide per mole of silver.
  • Spectral sensitisation was carried out for part B by means of a mixture of 0.015 mmoles of anhydro-5,5'-dicyano-1,1'-diethy1-3,3'-di(2-acetoxyethyl)ethyl-imidacarbocyanine bromide and 0.8 mmoles of anhydro-5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyloxacarbocyanine hydroxide per mole of silver.
  • Consecutively 0.5 g of polyglycol (MW 6000) were added as a development accelerator; 20 ml of polyoxyethylene surfactant H 17 C 8 -Phenyl-(O-CH 2 -CH 2 ) 8 -O-CH 2 -COOH and in an amount of 140 mg (per mole of Ag) floroglucinol were added as a hardener stabiliser together with polymethyl acrylate latex (in an amount of 140 % by weight, based on the amount of gelatin binder) which was used as a plasticizer.
  • Emulsions C and D Inventive emulsions
  • inventive emulsions C and D were prepared in the same way as the comparative emulsions A and B, except for the presence of a ruthenium dopant in the silver chloroiodide crystals of both emulsions: 13.33 ml of a K 2 Ru(CN) 6 solution was added as an aqueous solution having a concentration of 91 mg/liter in order to add ruthenium as a dopant in amounts of 10 ppm vs.
  • the said solution was added in 217 seconds at an addition rate of 3.69 ml/min., wherein the addition of the dopant solution was starting 52 minutes 40 seconds after the growth step was started.
  • the processing of the exposed silver halide emulsion materials A to D proceeded with the following developing liquid INVDEV, followed by fixing in fixing liquid INVFIX and rinsing at the indicated temperature of 35°C and processing time of 45 seconds.
  • fixer INVFIX 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

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EP1213606A2 (fr) * 2000-12-06 2002-06-12 Eastman Kodak Company Pellicule permettant de localiser la partie d'un corps devant être traitée par rayons pour le traitement des cancers et méthode d'utilisation
EP1422558A1 (fr) * 2002-11-19 2004-05-26 Eastman Kodak Company Pellicule radiographique avec détection de signal améliorée pour mammographie
EP1422557A1 (fr) * 2002-11-19 2004-05-26 Eastman Kodak Company Pellicule mammographique et assemblage pour la formation d' images pour emploi avec anodes de rhodium ou tungstène
EP1422547A1 (fr) * 2002-11-19 2004-05-26 Eastman Kodak Company Emulsions de grains cubiques à haut bromure
WO2004109396A1 (fr) * 2003-05-30 2004-12-16 Eastman Kodak Company Ensemble pour imagerie radiographique pour mammographie

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EP0677773A1 (fr) * 1994-04-06 1995-10-18 Agfa-Gevaert N.V. Emulsions à l'halogénure d'argent comprenant des cristaux tabulaires et méthode de traitement de ces émulsions
US5460916A (en) * 1993-05-24 1995-10-24 Fuji Photo Film Co., Ltd. Silver halide photographic material and method of forming radiation image using said material
EP0712036A1 (fr) * 1994-11-11 1996-05-15 Agfa-Gevaert N.V. Système écran/film photographique à l'halogénure d'argent sensible à la lumière avec qualité d'image améliorée pour des applications de traitement rapide en mammographie

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EP0336426A1 (fr) * 1988-04-08 1989-10-11 EASTMAN KODAK COMPANY (a New Jersey corporation) Emulsions photographiques contenant des granules à l'halogénure d'argent modifiés à l'intérieur
US5124242A (en) * 1990-01-16 1992-06-23 Fuji Photo Film Co., Ltd. Silver halide photographic element with hydrophobic undercoat polymer layer and hydrophobic dye layer
US5460916A (en) * 1993-05-24 1995-10-24 Fuji Photo Film Co., Ltd. Silver halide photographic material and method of forming radiation image using said material
EP0677773A1 (fr) * 1994-04-06 1995-10-18 Agfa-Gevaert N.V. Emulsions à l'halogénure d'argent comprenant des cristaux tabulaires et méthode de traitement de ces émulsions
EP0712036A1 (fr) * 1994-11-11 1996-05-15 Agfa-Gevaert N.V. Système écran/film photographique à l'halogénure d'argent sensible à la lumière avec qualité d'image améliorée pour des applications de traitement rapide en mammographie

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1213606A2 (fr) * 2000-12-06 2002-06-12 Eastman Kodak Company Pellicule permettant de localiser la partie d'un corps devant être traitée par rayons pour le traitement des cancers et méthode d'utilisation
EP1213606A3 (fr) * 2000-12-06 2002-06-26 Eastman Kodak Company Pellicule permettant de localiser la partie d'un corps devant être traitée par rayons pour le traitement des cancers et méthode d'utilisation
EP1422558A1 (fr) * 2002-11-19 2004-05-26 Eastman Kodak Company Pellicule radiographique avec détection de signal améliorée pour mammographie
EP1422557A1 (fr) * 2002-11-19 2004-05-26 Eastman Kodak Company Pellicule mammographique et assemblage pour la formation d' images pour emploi avec anodes de rhodium ou tungstène
EP1422547A1 (fr) * 2002-11-19 2004-05-26 Eastman Kodak Company Emulsions de grains cubiques à haut bromure
WO2004109396A1 (fr) * 2003-05-30 2004-12-16 Eastman Kodak Company Ensemble pour imagerie radiographique pour mammographie

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