EP0538947B1 - Für Schnellverarbeitungssysteme geeignetes photographisches Silberhalogenidröntgenmaterial - Google Patents

Für Schnellverarbeitungssysteme geeignetes photographisches Silberhalogenidröntgenmaterial Download PDF

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Publication number
EP0538947B1
EP0538947B1 EP92203210A EP92203210A EP0538947B1 EP 0538947 B1 EP0538947 B1 EP 0538947B1 EP 92203210 A EP92203210 A EP 92203210A EP 92203210 A EP92203210 A EP 92203210A EP 0538947 B1 EP0538947 B1 EP 0538947B1
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Prior art keywords
silver halide
silver
photographic material
developer
gelatin
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French (fr)
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EP0538947A1 (de
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Peter Willems
Freddy Henderickx
Gino De Rycke
Romain Bollen
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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners

Definitions

  • the present invention relates to photographic materials for industrial radiography having silver halide emulsion grains rich in chloride and capable of being processed at accelerated speed and with more ecologically safe developer and fixing solutions.
  • industrial non-destructive testing film After exposure with direct-röntgen rays, industrial non-destructive testing film is automatically processed in a cycle, varying from 8 to 12 minutes, the tendency being to reduce the processing time to a maximum of 5 minutes.
  • a normal processing cycle is characterised by the following steps: developing at 28°C and fixing, rinsing and drying at 26°C.
  • the developer is normally composed of three concentrates that should be diluted in the right order: alkaline solution A contains hydroquinone, acidic solution B contains 1-phenyl-3-pyrazolidinone and acidic solution C contains glutaric dialdehyd as hardening agent.
  • alkaline solution A contains hydroquinone
  • acidic solution B contains 1-phenyl-3-pyrazolidinone
  • acidic solution C contains glutaric dialdehyd as hardening agent.
  • the need for the complex three-part packaged developer concentrates has been dictated by the fact that glutaric aldehyd tends to react with 1-phenyl-3-pyrazolidinone, that this pyrazolidinone is unstable in alkaline medium and that glutaric aldehyd tends to polymerize in alkaline medium.
  • the fixer is composed of 2 concentrated solutions, whereby solution A contains the commonly used highly active ammonium thiosulphate as a fixing agent and solution B aluminum sulphate as a hardening agent. Hardening agents are necessary to lead the film through the processor without damages, to reduce the amount of water absorption and, as a consequence, the drying time. This drying time may be considered as the bottle-neck in speeding up the whole processing cycle since the same amount of water has to be evaporated in a shorter time. For rapid processing times shorter than 8 minutes the temperature of the developer would have to be increased in order to obtain satisfactory photographic characteristics and this is to the detriment of the physical characteristics.
  • the bromide and iodide ions released in the developer inhibit further development of the remaining developable silver halide crystals, so that the regeneration capacity of the developer has to be increased resulting in more consumption of chemicals, a higher cost and more environmental load.
  • a fixer containing ammoniumthiosulphate is disadvantageous.
  • the three-part development chemistry and two-part fixing chemistry is also little consumer friendly. In the developer glutaric dialdehyd should be avoided as an undesired ingredient, whereas in the fixer the hardening agent is causing flocculation problems in certain circumstances.
  • a first object of the present invention is to provide a silver halide photographic material for industrial radiography which has a satisfactory photographic performance even in rapid processing, i.e. higher development and fixing efficiency.
  • a second object of the invention is to provide an increased efficiency and capacity in the processing of industrial photographic material while maintaining an excellent image quality, especially image sharpness, and good physical properties.
  • a third object of the invention is to provide a photographic material for industrial radiography which can be subjected to more ecological processing conditions in that less chemicals are consumed in both developing solution and fixer requiring less regeneration and in that the processing solutions are free from hardening agents thus offering the possiblity of using the more customer-friendly one-part packaging.
  • the fixer can be freed from ammonium ions.
  • a photographic silver halide material for industrial radiography comprising a film support and on one or both sides thereof at least one silver halide emulsion layer which is characterised in that each silver halide emulsion layer comprises as silver halide silver chloride or silver chlorobromide the amounts of bromide being at most 25 mole %; has a gelatin to silver halide (expressed as silver nitrate) ratio from 3:10 to 6:10 and an amount of silver halide corresponding to from 5 g to 15 g of silver per sq. m. and in that the photographic material has been fore-hardened to an extent such that when it is immersed in demineralised water of 25°C for 3 minutes there is absorbed less than 2.5 g of water per gram of gelatin.
  • the present invention also provides a method of processing an exposed fore-hardened photographic material for industrial radiography as defined, comprising the steps of development, fixing,rinsing and drying characterised in that the total processing time is less than 5 minutes, preferably less than 3 minutes, and the processing is preferably substantially free from hardening agents.
  • the chloride rich silver halide grains provide satisfactory photographic performance even in rapid processing.
  • a processing sequence free from hardening agents is made possible by reducing the coated amount of gelatin and simultaneously increasing the amount of hardener in the thinner emulsion layer. As a consequence the amount of water being absorbed after rinsing the film with water is reduced, offering the possibility to the film material to be completely dry within the proposed total processing time.
  • the emulsions are emulsions containing silver chloride crystals or silver chlorobromide crystals containing up to 25 mol% bromide-ions.
  • gelatino silver chloride or chlorobromide emulsions used in accordance with the present invention conventional lime - treated or acid treated gelatin can be used.
  • the preparation of such gelatin types 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 an enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan, N° 16, page 30 (1966).
  • the gelatin concentration is kept from about 0.05 % to 5.0 % by weight in the dispersion medium. Additional gelatin is added in a later stage of the emulsion preparation, e.g.
  • the precipitation in connection with the present invention can be principally performed by one double jet step it is preferred to perform a sequence of a nucleation step and at least one growth step.
  • a nucleation step preferably 0.5 % to 5.0 % is added during said nucleation step which consists preferably of an approximately equimolecular addition of silver and halide salts.
  • the rest of the silver and halide salts is added during one or more consecutive double jet growth steps.
  • the different steps of the precipitation can be alternated by physical ripening steps.
  • an increasing flow rate of silver and halide solutions is preferably established, e.g. a linearly increasing flow rate.
  • the flow rate at the end is about 3 to 5 times greater then at the start of the growth step.
  • These flow rates can be monitored by e.g. magnetic valves.
  • an amount of not more than 25 mol% of bromide ions may be built into the silver halide crystals, whether it is built in homogeneously or, as is the case for core-shell emulsions, heterogeneously.
  • the pAg is maintained between 105 and 85 mV during the nucleation step and preferably between 90 and 65 mV during the growth phase and pH is maintained between 5.2 and 5.8 preferably between 5.6 and 5.8.
  • chloride rich silver halide emulsion grains show a cubic morphology with (100) crystal faces offering better developing characteristics than other crystallographic forms, as e.g. octahedral, rhombic dodecahedral or tabular silver chloride crystals, which require the use of so-called “growth modifiers” or "crystal habit modifiers".
  • chloride emulsions having crystallographic form other than cubic can be used.
  • the silver halide grains used in accordance with the present invention preferably have an average grain size from 0.3 to 1.0 ⁇ m.
  • a wash technique in order to remove the excess of soluble salts is applied at a pH value which can vary during washing but remains comprised between 3.7 and 3.3 making use of a flocculating agent like polystyrene sulphonic acid.
  • a flocculating agent like polystyrene sulphonic acid.
  • the emulsion is washed by diafiltration by means of a semipermeable membrane, also called ultrafiltration, so that it is not necessary to use polymeric flocculating agents that may disturb the coating composition stability before, during or after the coating procedure.
  • Such procedures are disclosed e.g. in Research Disclosure Vol. 102, Oct. 1972, Item 10208, Research Disclosure Vol. . 131, March, Item 13122 and Mignot US 4,334,012.
  • pH and pAg are the same as at the end of the preceding precipitation without any adjustment stage.
  • the emulsions present in the industrial radiographic materials of the present invention can be chemically sensitized as described e.g. in "Chimie et Physique Photographique” by P. Glafkides, in “Photographic Emulsion Chemistry” by G.F. Duffin, in “Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in “Die Grundlagen der Photographischen mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
  • chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur e.g.
  • emulsions can be sensitized also by means of gold-sulphur ripeners or by means of reductors e.g. tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids etc.
  • reductors e.g. tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids etc.
  • the silver halide emulsion layer(s) in accordance with the present invention or the non-light-sensitive layers may comprise compounds preventing the formation of fog or stabilizing the photographic characteristics during the production or storage of the photographic elements or during the photographic treatment thereof.
  • Many known compounds can be added as fog-inhibiting agent or stabilizer to the silver halide emulsion at any stage of the emulsion preparation. Suitable examples are e.g.
  • heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles (preferably 5-methyl-benzotriazole), nitrobenzotriazoles, mercaptotetrazoles, in particular 1-phenyl-5-mercapto-tetrazole, mercaptopyrimidines, mercaptotriazines, benzothiazoline-2-thione, oxazoline-thione, triazaindenes, tetrazaindenes and pentazaindenes, especially those described by Birr in Z.
  • benzothiazolium salts such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlor
  • the ratio of gelatin to silver halide (expressed as silver nitrate) in the silver halide emulsion layers of the photographic material according to the present invention is comprised between 0.3 and 0.6, preferably from 0.4 to 0.6.
  • the gelatin binder of the photographic elements according to the present invention can be hardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, aldehydes e.g. formaldehyde, glyoxal, and glutaric aldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives e.g. 2,3-dihydroxy-dioxan, active vinyl compounds e.g.
  • appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, aldehydes e.g. formaldehyde, gly
  • 1,3,5-triacryloyl-hexahydro-s-triazine 1,3,5-triacryloyl-hexahydro-s-triazine, active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid.
  • active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine
  • mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid.
  • the binder can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US 4,063,952 and with the onium compounds as disclosed in European Patent Application No 90.201850.6 Hardening is to such an extent that when the photographic material is immersed in demineralized water of 25°C at most 2.5 g of water is absorbed per gram of gelatin in 3 minutes.
  • fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US 4,063,952 and with the onium compounds as disclosed in European Patent Application No 90.201850.6
  • Hardening is to such an extent that when the photographic material is immersed in demineralized water of 25°C at most 2.5 g of water is absorbed per gram of gelatin in 3 minutes.
  • the photographic elements under consideration may further comprise various kinds of surface-active agents in the photographic emulsion layer and/or in at least one other hydrophilic colloid layer.
  • Preferred surface-active coating agents are compounds containing perfluorinated alkyl groups.
  • the photographic elements may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents and plasticizers.
  • the photographic material according to the present invention is preferably a duplitized material having on both sides of the film support emulsion layers. Both emulsion layers are overcoated with an antistress top layer.
  • the support of the photographic material in accordance with the present invention may be a transparent resin, preferably a blue coloured polyester support like polyethylene terephtalate.
  • the thickness of such organic resin film is preferably about 175 ⁇ m.
  • the support is provided with a substrate layer at both sides to have good adhesion properties between the emulsion layer and said support.
  • the photographic material can be image-wise exposed by means of an x-ray radiation source the energy of which, expressed in kV, depends on the specific application.
  • an x-ray radiation source the energy of which, expressed in kV, depends on the specific application.
  • Another typical radiation source is a radioactive Co 60 source.
  • a metal filter usually a lead filter, is used in combination with the photographic film.
  • an automatically operating apparatus is used provided with a system for automatic replenishment of the processing solutions.
  • Film materials in accordance with this invention may be processed in developer solutions of different compositions as e.g. hydroquinone-1-phenyl-3-pyrazolidinone, 1-phenyl-3-pyrazolidinone-ascorbic acid and ascorbic acid itself.
  • An amount of potassium thiocyanate in the range of 0.1 to 10 g pro liter of the developer solution is recommended to obtain high gradation values.
  • An amount of 25 to 250 mg of potassium iodide pro liter is particularly recommended to obtain a higher speed.
  • the developer solution according to the invention has to 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.
  • the development step can be followed by a washing step, a fixing solution and another washing or stabilization step.
  • 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 0.40 ⁇ m using methionin as a growth accelerator in an amount of 16 g pro 3.3 l starting volume in the vessel, containing 100 g of inert gelatin and 38 mmoles of sodium chloride at 60°C.
  • pAg was about 70 mV and the flocculation procedure could begin: pH was adjusted at a value of 3.3 with sulphuric acid, 3 M, and 6.7 g of polystyrene sulphonic acid was added slowly in 2 minutes. The washing procedure was performed in a discontinous way, adding 3 l of demineralised water, containing up to 8 mmole of sodium chloride pro liter, until pAg was reaching a value of about 100 mV.
  • the emulsion was peptised and was chemically ripened to an optimal fog-sensitivity relationship at 52°C, pAg having a value of about 125 mV.
  • Chemical ripening agents besides gold (in an amount of 0.027 mmole) and sulphur (in an amount of 0.089 mmole), were toluene thiosulphonic acid and iodide ions, both being predigestion agents in amounts of 4 mg and 18 mmoles respectively.
  • Stabilizers as the sodium salt of 7-sulpho-naphto-[2,3-D]-oxazoline-2-thion and 1-phenyl-5-mercaptotetrazole were added in amounts of 40, respectively 30 mg pro 100 g AgNO 3 .
  • the emulsion was coated at both sides of a substrated blue polyester of 175 ⁇ m thickness by means of the slide hopper technique, the emulsion layers each containing silver halide emulsion crystals, expressed as AgNO 3 , in an amount of 10.5 g/m 2 and in an amount of 5.25 g/m 2 gelatin. Both emulsion layers were covered with a protective layer coated at 1.40 g/m 2 of gelatin and hardened with formaldehyd and resorcinol to such an extent that when immersed in demineralized water of 25°C for 3 minutes about 2 g of water was absorbed.
  • the coated and dried films were exposed with a 86 kV x-ray radiation source placed at a distance of 1.50 m and in contact with a copper filter with a thickness of 1 mm (indicated as exposure A in the further examples) or with a 235 kV radiation source placed at a distance of 1.50 m in contact with a copper filter of 8 mm thickness (indicated as exposure B).
  • PQ1 PQ2 PA hydroquinone 20 g 20 g -- ascorbic acid -- -- 50 g 1-phenyl-3-pyrazolidinone 0.8 g 0.8 g -- 4-methyl,4-hydroxymethyl-1-phenyl-3-pyrazolidinone. -- -- 4 g potassium bromide 10 g 10 g 10 g potassium iodide 0.1 g 0.1 g -- phenylmercaptotetrazole 0.03 g 0.03 g 0.03 g potassium thiocyanate 2.5 g 2.5 g 2.5 g 2.5 g polyglycol (M.W.
  • the films were run in a STRUCTURIX NDT-M machine marketed by Agfa-Gevaert and processed with an adapted processing speed at 28°C.
  • the materials according to the invention were run in the PQ1- or PQ2-developer whereas the comparative Structurix-material was run in the commercially available Agfa-Gevaert NDT-developer G135.
  • Sensitometric results are also given for a manual development cycle at 25°C in developer PQ1 and PQ2 for the materials of the invention and in the commercial G128 developer of Agfa-Gevaert.
  • G2 a lower value of log K indicating a higher film speed
  • D 4.0
  • Replenishment rates could be lowered about 50% compared with the comparative conventional system (Structurix D4p film with G135 as developer and G335 as fixer) to amounts of 400 ml/m 2 , respectively 600 ml/m 2 for developer PQ2 and fixer F, said amounts to be added to compartments each containing 6.5 liters of developing, respectively fixing solution.
  • Table II Material Exposure Developer Total processing time Fog log K local G2 gradient G4 automatic machine processing NDT-M D4p (comp.) B G135 8 min. 0.14 1.96 5.51 6.49 2 B PQ2 2 min. 0.15 1.96 5.14 7.05 2 B PQ2 3 min. 0.18 1.90 6.12 7.26 D4p (comp.) A G135 8 min.
  • Noise values ( ⁇ D ) for the automatically processed materials at a density of 2.0 are 0.020; 0.020; 0.021; 0.019 and 0.020 respectively, indicating only small, neglectable differences.
  • the materials according to the present invention for non-destructive testing purposes can be developed in automatic machine processing as well as in manual processing in a hardener-free 1-phenyl-3-pyrazolidinone-hydroquinone developer during a remarkably shorter time (2 min. vs. 8 min.) than the comparative D4p material and can be fixed without making use of ammonium ions in the fixer.
  • manual processing conditions it is even possible to reach an equivalent sensitometry as the comparitive example after 30 s, the comparitive example having a standard development time of 3 min. in this particular case. Nevertheless it should be stated that the automatic machine processing stays the most preferred.
  • the drying conditions are not a problem either.
  • the non-destructive test film material 2 from example 1 was processed in 4 different developers the composition of which is given in table III, differing in the amount of potassium iodide and potassium thiocyanate added to the developer.
  • Table III Solutions Ingredients A B C D hydroquinone 20 g 20 g 20 g 20 g 4-methyl,4-hydroxymethyl-1-phenyl-3-pyrazolidinone 0.8 g 0.8 g 0.8 g 0.8 g potassium bromide 10 g 10 g 10 g 10 g 10 g potassium iodide -- 1 g -- 1 g potassium thiocyanate -- -- 2.5 g 2.5 g phenylmercaptotetrazole 0.03 g 0.03 g 0.03 g 0.03 g 0.03 g g g g aqueous potassium sulphite (655 g/l) 100 ml 100 ml 100 ml 100 ml 100 ml aqueous potassium carbonate (765 g/l) 40 m
  • Emulsion X Emulsion X .
  • a AgCl-emulsion (100 mole % chloride) with an average crystal diameter of 0.64 ⁇ m was prepared in two steps.
  • the sodium chloride solution was added at the same rate as the silver nitrate solution (3 ml/min.) into a vessel containing 900 ml of demineralised water, 38 mmoles of sodium chloride and 46 g of inert gelatin.
  • the crystal growth step proceeded with an increasing flow rate starting at 5 ml/min. and ending after 55 minutes at 30 ml/min., the pAg value being maintained during the whole procedure at a value of 75 mV at 60°C by variation of the flow rate of the halide solution.
  • Emulsion Y Emulsion Y .
  • Emulsion Y was prepared as emulsion X, the difference with the previous emulsion being realised by a reduction in flow rate in the nucleation step to 1.8 ml/min and adding a halide solution of a different composition (90 mol % sodium chloride; 10 mol % potassium bromide) after 5 minutes.
  • a halide solution of a different composition 90 mol % sodium chloride; 10 mol % potassium bromide
  • the emulsion according to this preparation method had a core-shell structure characterised in that the core representing a crystal volume of 60 % by weight had a local bromide concentration of 10 mol %, with an average value of 6 mol % calculated over the whole crystal volume.
  • the average crystal diameter was exactly the same as for Emulsion X: 0.64 ⁇ m.
  • Emulsion Z Emulsion Z .
  • Emulsion Z was prepared in the same way as emulsion Y the differences being related to the composition of the second halide composition viz. 85 mole % of sodiumchloride and 15 mole % of potassium bromide and to the flow rate in the growing step increasing from 5 ml/min. to 13.9 ml/min. in 20 min 12 s. Further increase of the flow rate up to 30 ml/min. in 36 min 25 s occurred with the 100 % chloride solution.
  • the average crystal diameter of this core-shell emulsion was 0.62 ⁇ m, with an average bromide concentration of 3 mole %, locally concentrated in the core up to 15 mole % for a volume % of 20 of the whole crystal volume.
  • the emulsions were coated at both sides of a substrated blue polyester undercoat, being 175 ⁇ m thick, making use of the slide hopper technique, the emulsion layers containing silver halide, expressed as AgNO 3 , in an amount of 14.5 g/m 2 and and gelatin in an amount of 7.24 g/m 2 . Both emulsion layers were covered with a protective layer coated at 1.40 g/m 2 of gelatin and hardened with formaldehyd and resorcinol to such an extent that the amount of demineralised water of 25°C absorbed by the film pro g of gelatin was about 2.1 g after 3 minutes.
  • Sensitometric results obtained after applying exposure B and manual processing in developer PQ1 or PQ2 and fixing in fixer F, free of ammonium ions are given in Table V.
  • STRUCTURIX D7p was chosen, commercially available from Agfa-Gevaert. This material was manually developed in its common processing solutions G128 developer and G335 fixer marketed by Agfa-Gevaert. Table V. Material g H 2 O/g gelatin Developer Development time Fog log K local gradient G2 G4 manual processing 25°C D7p (comp.) 2.93 G128 3 min.
  • the materials of the invention for non-destructive testing purposes can be developed in manual processing in a hardener-free 1-phenyl-3-pyrazolidinone-hydroquinone developer during a remarkably shorter time (3 s vs. 3 min.) than the comparative STRUCTURIX D7p material. They can be fixed without making use of ammonium ions in the fixer.
  • the materials of the invention can be chlorobromide core-shell emulsions as well as emulsions of pure silver chloride crystals. Core-shell emulsions with silver chlorobromide cores and silver chloride shells, with a limited amount of bromide ions, are preferred with regard to the lower fog values and higher local gradients.
  • Non-destructive testing material 2 of example 1 was developed after exposure in a developer containing ascorbic acid (developer PA) having the composition given in example 1.
  • developer PA ascorbic acid
  • the fixer of example 1 was used in both manual processing cycles at 25°C.
  • the sensitometric results obtained are summarized in Table VI.
  • Table VI. Material Exposure Developer Development time Fog log K local gradient G2 G4 2 B PA 35 s 0.15 1.87 4.29 7.74 2 B PQ2 35 s 0.13 1.92 4.34 7.77

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Claims (13)

  1. Ein in der industriellen Radiografie eingesetztes photographisches Silberhalogenidmaterial mit einem Filmträger, der einseitig oder beidseitig wenigstens eine Silberhalogenidemulsionsschicht enthält, wobei jede Silberhalogenidemulsionsschicht als Silberhalogenid Silberchlorid oder Silberchloridbromid mit einer maximalen Bromidmenge von 25 mol-% enthält, ein Verhältnis von Gelatine zu (als Silbernitrat ausgedrücktem) Silberhalogenid zwischen 3:10 und 6:10 aufweist und eine Menge Silberhalogenid entsprechend 5 g bis 15 g als Silbernitrat ausgedrücktes Silber/m2 enthält, und das photographische Material im voraus in einem solchen Maße gehärtet wird, daß bei einem 3minütigen Eintauchen dieses photographischen Materials in entmineralisiertes Wasser von 25°C höchstens 2,5 g Wasser pro g Gelatine absorbiert wird.
  2. Ein photographisches Material nach Anspruch 1, dadurch gekennzeichnet, daß das Material ein doppelseitig emulsioniertes radiografisches Material mit einem beidseitig mit einer Silberhalogenidemulsionsschicht überzogenen Träger ist.
  3. Ein photographisches Material nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Material in einem solchen Maße gehärtet ist, daß bei einem 3minütigen Eintauchen dieses photographischen Materials in entmineralisiertes Wasser von 25°C höchstens 2,0 g Wasser pro g Gelatine absorbiert wird.
  4. Ein photographisches Material nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Silberhalogenidemulsion(en) (eine) Silberchloridbromid-Emulsion(en) mit einer Kern-Hülle- oder Mehrfachstruktur ist (sind), bei der (denen) die Hülle aus 100 mol-% Silberchlorid besteht.
  5. Ein photographisches Material nach irgendeinem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Korngrößenverteilung der Silberhalogenidkristalle homogen ist.
  6. Verfahren zur Verarbeitung eines in irgendeinem der Ansprüche 1 bis 5 definierten belichteten vorgehärteten photographischen Materials für die industrielle Radiografie, das die Stufen Entwicklung, Fixierung, Waschen und Trocknung umfaßt, wobei die Gesamtverarbeitungszeit weniger als 5 Minuten beträgt.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß der Entwickler und/oder das Fixiermittel wesentlich keine Härtungsmittel enthält.
  8. Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, daß das Fixiermittel wesentlich keine Ammoniumionen enthält.
  9. Verfahren nach irgendeinem der Ansprüche 6 bis 8, dadurch gekennzeichnet, daß der Entwickler Hydrochchinon und einen 1-Phenyl-3-pyrazolidinon-Entwickler enthält.
  10. Verfahren nach irgendeinem der Ansprüche 6 bis 8, dadurch gekennzeichnet, daß der Entwickler Ascorbinsäure und 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinon enthält.
  11. Verfahren nach irgendeinem der Ansprüche 6 bis 10, dadurch gekennzeichnet, daß der Entwickler Thiocyanationen in einer Menge von 0,1 bis 10 g/l enthält.
  12. Verfahren nach irgendeinem der Ansprüche 6 bis 11, dadurch gekennzeichnet, daß der Entwickler Iodidionen in einer Menge von 250 mg/l enthält.
  13. Verfahren nach irgendeinem der Ansprüche 6 bis 12, dadurch gekennzeichnet, daß das Fixiermittel als Fixiermittel Natriumthiosulfat enthält.
EP92203210A 1991-10-24 1992-10-20 Für Schnellverarbeitungssysteme geeignetes photographisches Silberhalogenidröntgenmaterial Expired - Lifetime EP0538947B1 (de)

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EP91202761 1991-10-24
EP91202761 1991-10-24
EP92203210A EP0538947B1 (de) 1991-10-24 1992-10-20 Für Schnellverarbeitungssysteme geeignetes photographisches Silberhalogenidröntgenmaterial

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EP0538947B1 true EP0538947B1 (de) 1997-04-09

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Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0621506A1 (de) * 1993-04-13 1994-10-26 Agfa-Gevaert N.V. Verarbeitung von photographischen, industriellen Silberhalogenid-Röntgenfilmen
EP0620483A1 (de) * 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Verarbeitung von photographischen industriellen Silberhalogenid-Röntgenfilmen
EP0622668B1 (de) * 1993-04-27 1999-03-03 Agfa-Gevaert N.V. Photographisches Silberhalogenidmaterial für die industrielle Radiographie, das für verschiedene Verarbeitungsanwendungen geeignet ist
EP0698817A1 (de) 1994-08-22 1996-02-28 Agfa-Gevaert N.V. Sortiment von photographischen Silberhalogenidfilmen für die industrielle Radiographie und Verfahren zur Verarbeitung dieses Sortiments
EP0709730B1 (de) * 1994-10-24 2000-01-12 Agfa-Gevaert N.V. Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials
EP0726491B1 (de) * 1995-02-10 2003-04-16 Eastman Kodak Company Photographische Fixierzusammensetzung mit herabgesetztem Schwefeldioxidausstoss
EP0731382A1 (de) * 1995-02-21 1996-09-11 Agfa-Gevaert N.V. Verfahren zur Verarbeitung eines photographischen, belichteten Silberhalogenidmaterials
EP0732619A1 (de) * 1995-02-21 1996-09-18 Agfa-Gevaert N.V. Entwicklerlösung und Verfahren zum Entwickeln eines belichteten photographischen Silberhalogenidmaterials
DE69528640D1 (de) * 1995-07-18 2002-11-28 Agfa Gevaert Nv Photographisches Silberhalogenidröntgenmaterial das zur Verwendung in hellem Dunkelkammerlicht geeignet ist
EP0754971A1 (de) 1995-07-18 1997-01-22 Agfa-Gevaert N.V. Material für die industrielle Radiographie und Entwicklungsverfahren dafür
FR2737587A1 (fr) * 1995-08-01 1997-02-07 Kodak Pathe Nouveau produit pour radiographie industrielle
FR2737588B1 (fr) * 1995-08-01 2001-11-02 Kodak Pathe Nouveau produit pour radiographie industrielle
FR2757280B1 (fr) * 1996-12-13 2003-03-21 Kodak Pathe Nouveau produit pour radiographie industrielle ayant un contraste ameliore

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US3841872A (en) * 1972-09-29 1974-10-15 Eastman Kodak Co Hydrophilic-colloid silver halide emulsion hardened with a bisvinylsulfonyl compound
US4414304A (en) * 1981-11-12 1983-11-08 Eastman Kodak Company Forehardened high aspect ratio silver halide photographic elements and processes for their use

Non-Patent Citations (1)

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Title
PATENTS ABSTRACTS OF JAPAN Vol. 13, no. 324 (P-903)(3672) 21 July 1989 *

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