EP0698817A1 - Sortiment von photographischen Silberhalogenidfilmen für die industrielle Radiographie und Verfahren zur Verarbeitung dieses Sortiments - Google Patents

Sortiment von photographischen Silberhalogenidfilmen für die industrielle Radiographie und Verfahren zur Verarbeitung dieses Sortiments Download PDF

Info

Publication number
EP0698817A1
EP0698817A1 EP95202199A EP95202199A EP0698817A1 EP 0698817 A1 EP0698817 A1 EP 0698817A1 EP 95202199 A EP95202199 A EP 95202199A EP 95202199 A EP95202199 A EP 95202199A EP 0698817 A1 EP0698817 A1 EP 0698817A1
Authority
EP
European Patent Office
Prior art keywords
assortment
gelatin
materials
silver halide
rinsing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95202199A
Other languages
English (en)
French (fr)
Inventor
Luc C/O Agfa-Gevaert N.V. Heremans
Raymond c/o Agfa-Gevaert N.V. Florens
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP95202199A priority Critical patent/EP0698817A1/de
Publication of EP0698817A1 publication Critical patent/EP0698817A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G03C2007/3025—Silver content

Definitions

  • This invention relates to an assortment of silver halide photographic industrial X-ray films of different speed classes and a method of manufacturing said films.
  • a normal processing cycle is characterised by the following steps: developing at 28°C and fixing at 26°C, rinsing and drying.
  • the developer is normally composed from 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 from 2 concentrated solutions, wherein solution A contains the commonly used highly active ammonium thiosulphate as a fixing agent and solution B contains aluminum sulphate as a hardening agent.
  • Hardening agents are necessary not only to lead the film through the processor without damages, but also to reduce the amount of water absorption and, as a consequence, to reduce the drying time and to enhance the drying capacity. This is especially important for industrial X-ray films as these films are coated with a high amount of gelatin e.g. about 30 g/m2.
  • the said high amount of gelatin is a consequence of the need to have high coated amounts of silver halide crystals capable of absorbing direct X-rays in industrial X-ray applications.
  • an assortment is offered of silver halide industrial X-ray photographic materials, said assortment having at least five films to be processed in the processing cycle of an automatic processing machine following the steps of developing, rinsing, fixing, rinsing and drying, wherein each of said film materials comprises at least one gelatino silver halide emulsion layer and at least one non-sensitive protective antistress coating on at least one side of a support, characterised in that for each of said materials belonging to the assortment the total amount of silver halide, expressed as the equivalent amount of silver nitrate, per square meter and per side is lying in the range from 7.5 to 15 grams, the total amount of gelatin coated in all of the hydrophilic layers present is such and the gelatin is hardened to such an extent that the amount of water absorption is substantially the same for each material and is not more than 2 grams per gram of gelatin after rinsing and before drying each material and that within said assortment the materials are differing in speed.
  • the processing step proceeds in a total processing time from 3 to 12 minutes. It has been found that, depending on said total processing time, two different manufacturing methods can be applied.
  • the method of manufacturing of an assortment of films corresponding to this invention proceeds by the steps of coating gelatin in the emulsion layer in amounts corresponding with amounts of gelatin of at least 2.5 grams and hardening each film belonging to said assortment to such an extent that the amount of water absorption is substantially the same for each material belonging to said assortment and not more than 2 grams per gram of gelatin after rinsing and before drying.
  • the method of manufacturing of an assortment of films corresponding to this invention can also proceed by the use of gelatin in the emulsion layer and in the protective layer in higher amounts, provided each film belonging to said assortment is hardened to such an extent that the amount of water absorption is substantially the same for each material belonging to said assortment and is not more than 2 grams per gram of gelatin after rinsing and before drying.
  • an increasing drying time is obtained if the films of the assortment are coated with more gelatin, resulting in an enhancement of the "gesi".
  • Said enhancement of the "gesi” normally results in a lower film speed for the same processing time. In order to compensate for this loss in speed the processing time is increased.
  • Minimum amounts of a total gelatin content in the emulsion layer(s) at one side the support of at least 4.5 grams per square meter are preferred.
  • Manufacturing an assortment according to this invention for films having a minimum amount of a total gelatin content in the emulsion layer(s) at one side the support of at least 4.5 grams per square meter preferably proceeds by coating more gelatin in the protective antistress layer or by a layer arrangement wherein a gelatin undercoat layer is applied, adjacent to the emulsion layer and situated more closely to the support.
  • the objects of this invention can thus be obtained by providing materials belonging to an assortment of at least five films provided that the amount of water absorption is substantially the same for each material belonging to said assortment and is not more than 2 grams per gram of gelatin after rinsing and before drying. It is preferred to have an amount of water absorption of not less than 0.9 grams per gram of gelatin in order to avoid pressure sensitivity of the materials. Moreover for all materials belonging to an assortment of materials according to this invention having a water absorption that is substantially the same it is preferred that differences in water absorption should be less than 20% of the average amount of water absorption, calculated from the amounts measured for all of the materials belonging to said assortment in order to get materials leaving the processor showing no sticking phenomena,nor deformation.
  • the gelatin binder of the assortment of at least five industrial X-ray film materials according to this invention can be hardened with whatever a hardener
  • the gelatin binder of the silver halide photographic industrial X-ray materials having different speeds is preferably hardened with hardening agents of the vinylsulphone type. Especially di-(vinylsulphonyl)-methane and ethylene di-vinyl-sulphone are preferred.
  • aldehyde type hardeners like e.g.
  • the hardening agent may be added to the coating composition of the emulsion layer(s) and/or to the coating composition of the protective antistress layer(s) before or during the coating procedure applied to prepare the materials differing in speed. If the hardener is added during the coating procedure it is still possible to make corrections for the water absorption of the material that has to be coated further on by controlling the amount of water absorption for the coated material directly after coating.
  • hardening is provided to such an extent that, when the photographic material is rinsed at the end of the processing cycle just before drying, an amount of less than 2 grams of water per gram of gelatin per square meter and per side of said material should be absorbed. For each of the films of the assortment this amount should be the substantially the same.
  • the silver halide emulsions coated in the silver halide emulsion layer(s) of the materials, belonging to the assortment of films according to this invention, comprise silver chloride, silver chlorobromide, silver chlorobromoiodide, silver bromide or silver bromoiodide.
  • Suitable silver chloride and silver chlorobromide emulsions have e.g. been described in EP-A 538 947, filed October 24, 1991, whereas other suitable materials substantially consisting of silver bromoiodide emulsions have been described e.g. in EP-A 555 897, filed February 14, 1992 and in EP-A 0 622 668.
  • Preferred emulsions are silver bromoiodide emulsions comprising at most 10 mole% of iodide, preferably at most 3 mole% and still more preferably 1 mole%. It is preferred to use regular-shaped silver halide crystals and more particularly silver bromoiodide emulsions with a cubic crystal habit which are used in industrial radiographic materials and are known to have good development characteristics with respect to high speed.
  • the precipitation stage of the emulsion making the parameter determining whether cubic or octahedral crystals are formed is the pAg of the solution.
  • the pAg of the solution may be regulated by any of the means known in the art of emulsion making, such as the electronic control apparatus and method disclosed in US-P 3, 821, 002.
  • a preferred embodiment of making the emulsions used according to the present invention involves the preparation of high-sensitive silver bromoiodide emulsions as these X-ray emulsions, by precipitation under double jet conditions.
  • processes for the preparation of homogeneous silver halide emulsions make use of special control devices to regulate the form of the resulting silver halide crystals, said form mainly being determined by the pAg value and temperature in the reaction vessel, the silver ion concentration can be kept constant during the precipitation by the use of a special inlet technique as described in Research Disclosure 10308.
  • iodide ions can be distributed over the crystal volume in whatever a way, as e.g. divided heterogeneously as in so-called core-shell emulsion crystals, it is preferred to prepare crystals with homogenously divided iodide ions over the whole crystal volume.
  • the average grain-size of the silver halide emulsions made for the materials differing in sensitivity according to the present invention are situated between 0.1 and 2.0 ⁇ m and more preferably between 0.1 and 1.0 ⁇ m.
  • Particle size of silver halide grains can be determined using conventional techniques e.g. as described by Trivelli and M.Smith, The Photographic Journal, vol. 69, 1939, p. 330-338, Loveland "ASTM symposium on light microscopy” 1953, p. 94-122 and Mees and James “The Theory of the photographic process” (1977), Chapter II.
  • the temperature and pAg have to be adjusted very carefully.
  • Grain-growth restrainers or accelerators may be added from the start or during the preparation of the emulsion crystals.
  • monodispersed emulsions can be prepared as is preferred for this invention.
  • Monodispersed emulsions in contrast to heterodispersed emulsions have been characterized in the art as emulsions of which at least 95 % by weight or number of the grains have a diameter which is within about 40 %, preferably within about 30 % of the mean grain-diameter and more preferably within about 10% to 20%.
  • Silver halide grains having a very narrow grain-size distribution can thus be obtained by strictly controlling the conditions at which the silver halide grains are prepared using a double jet procedure.
  • the silver halide grains are prepared by simultaneously running an aqueous solution of a water-soluble silver salt, e.g., silver nitrate, and water-soluble halide, e.g., a mixture of potassium bromide and potassium iodide, into a rapidly agitated aqueous solution of a silver halide peptizer, preferably gelatin, a gelatin derivative or some other protein peptizer.
  • a silver halide peptizer preferably gelatin, a gelatin derivative or some other protein peptizer.
  • colloidal silica may be used as a protective colloid as has been described in EP-Applications 392 092; 517 961 and 528 476, as well as in EP-A 0 649 051.
  • the rates of addition of the silver nitrate and the halide salt solutions are steadily increased in such a way that no renucleation appears in the reaction vessel.
  • This procedure is especially recommended, not only to save time but also to avoid physical ripening of the silver halide crystals during precipitation, the so-called Ostwald ripening phenomenon, which gives rise to the broadening of the silver halide crystal distribution.
  • the emulsions are generally washed after being flocculated to remove the by-products of grain formation and grain-growth.
  • washing is applied at a pH value which can vary during washing but remains comprised between 3.7 and 3.0 making use of a flocculating agent like polystyrene sulphonic acid.
  • the emulsion may be washed by diafiltration by means of a semi-permeable 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.
  • a semi-permeable membrane also called ultrafiltration
  • the emulsions are preferably washed by acid-coagulation techniques using acid-coagulable gelatin derivatives or anionic polymeric compounds or, when precipitation occurred in silica medium, by certain polymers capable of forming hydrogen bridges with silica, in an amount sufficient to form coagulable aggregates with the silica particles as has been described in EP Application 517 961.
  • the acid-coagulable gelatin derivatives are reaction products of gelatin with organic carboxylic or sulphonic acid chlorides, carboxylic acid anhydrides, aromatic isocyanates or 1,4-diketones.
  • the use of these acid-coagulable gelatin derivatives generally comprises precipitating the silver halide grains in an aqueous solution of the acid coagulable gelatin derivative or in an aqueous solution of gelatin to which an acid coagulable gelatin derivative has been added in sufficient proportion to impart acid-coagulable properties to the entire mass.
  • the gelatin derivative may be added after the stage of emulsification in normal gelatin, and even after the physical ripening stage, provided it is added in an amount sufficient to render the whole coagulable under acid conditions.
  • acid-coagulable gelatin derivatives suitable for use in accordance with the present invention can be found e.g. in the US-Patents referred to above. Particularly suitable are phthaloyl gelatin and N-phenylcarbamoyl gelatin.
  • the coagulum formed may be removed from the liquid by any suitable means, for example the supernatant liquid is decanted or removed by means of a siphon, where upon the coagulum is washed out once or several times.
  • washing of the coagulum may occur by rinsing with mere cold water.
  • the first wash water is preferably acidified to lower the pH of the water to the pH of the coagulation point.
  • Anionic polymer e.g. polystyrene sulphonic acid may be added to the wash water even when an acid coagulable gelatin derivative has been used e.g. as described in published German Patent Specification (DOS) 2,337,172 mentioned hereinbefore.
  • washing may be effected by redispersing the coagulum in water at elevated temperature using a small amount of alkali, e.g. sodium or ammonium hydroxide, recoagulating by addition of an acid to reduce the pH to the coagulation point and subsequently removing the supernatant liquid. This redispersion and recoagulation operation may be repeated as many times as is necessary.
  • the coagulum is redispersed to form a photographic emulsion suitable for the subsequent finishing and coating operations by treating, preferably at a temperature within the range of 35 to 70°C, with the required quantity of water, gelatin and, if necessary, alkali for a time sufficient to effect a complete redispersal of the coagulum.
  • photographic hydrophilic colloids can also be used for redispersion e.g. a gelatin derivative as referred to above, albumin, agar-agar, sodium alginate, hydrolysed cellulose esters, polyvinyl alcohol, hydrophilic polyvinyl copolymers, colloidal silica etc.
  • the light-sensitive silver halide emulsions are chemically sensitized with a sulphur and gold sensitizer. This can be done as described i.a. 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 Sawe mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968). As described in said literature sulphur sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur e.g.
  • thiosulphate thiocyanate, thioureas, sulphites, mercapto compounds, and rhodamines.
  • Gold sensitization occurs by means of gold compounds.
  • small amounts of compounds of Ir, Rh, Ru, Pb, Cd, Hg, Tl, Pd or Pt can be used.
  • the emulsion can be sensitized in addition by means of reductors e.g. tin compounds as described in GB-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • the said halide emulsions are chemically ripened separately.
  • compounds for preventing the formation of fog or stabilizing the photographic characteristics during the production or storage of photographic elements differing in sensitivity or during the photographic treatment thereof may be supplementary added.
  • stabilizers are heterocyclic nitrogen-containing stabilizing compounds 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 pentaza
  • the weight ratio of gelatin to silver halide (expressed as silver nitrate) in the silver halide emulsion layers of the assortment of photographic materials according to the present invention is comprised between 0.3 and 1.2, and more preferably between 0.4 and 1.0.
  • the silver halide emulsion layer(s) of the materials differing in speed and belonging to said assortment according to this invention comprise total amounts of silver halide, coated per side and per square meter of from 7.5 to 15 g, expressed as the equivalent amounts of silver nitrate.
  • the photographic elements under consideration differing in speed 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 polyoxyalkylene compound reducing dust to an acceptable level are described in EP-A's 0 620 482, 0 620 483 and 0 620 484, which are incorporated herein by reference.
  • Both the polyoxyalkylene compound(s) and the hardener(s) described hereinbefore are preferably present in at least one of the non light-sensitive layers and more preferably both compounds are added to the protective antistress layer which is preferably present as an outermost layer at both sides of the support.
  • Other preferred surface-active coating agents are compounds containing perfluorinated alkyl groups.
  • suitable surface-active agents include non-ionic agents such as saponins, alkylene oxides e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, siliconepolyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; anionic agents comprising an acid group such as a carboxy, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids, aminoalkyl sulphates or phosphates, alkyl betaines, and amine-
  • Such surface-active agents can be used for various purposes e.g. as coating aids, as compounds preventing electric charges, as compounds improving slidability, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving the photographic characteristics e.g higher contrast, sensitization, and development acceleration.
  • Development acceleration can be accomplished with the aid of various compounds, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-P's 3,038,805 ; 4,038,075 and 4,292,400.
  • the photographic elements differing in sensitivity used according to this invention 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.
  • Suitable additives for improving the dimensional stability of the photographic element are i.a. dispersions of a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl (meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters, acrylonitriles, olefins , and styrenes, or copolymers of the above with acrylic acids, methacrylic acids, Alpha-Beta-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulphoalkyl (meth)acrylates, and styrene sulphonic acids.
  • a water-soluble or soluble synthetic polymer e.g. polymers of alkyl (meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters,
  • Suitable UV-absorbers are i.a. aryl-substituted benzotriazole compounds as described in US-P 3,533,794, 4-thiazolidone compounds as described in US-P's 3,314,794 and 3,352,681, benzophenone compounds as described in JP-A 2784/71, cinnamic ester compounds as described in US-P's 3,705,805 and 3,707,375, butadiene compounds as described in US-P 4,045,229, and benzoxazole compounds as described in US-P 3,700,455.
  • the average particle size of spacing agents is comprised between 0.2 and 10 ⁇ m.
  • Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic element, whereas alkali-soluble spacing agents usually are removed therefrom in an alkaline processing bath.
  • Suitable spacing agents can be made i.a. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydrophthalate. Other suitable spacing agents have been described in US-P 4,614,708.
  • the photographic element can comprise an antistatic layer e.g. to avoid static discharges during coating, processing and other handlings of the material.
  • antistatic layer can be an outermost coating or stratum of one or more antistatic agents or a coating applied directly to the film support.
  • Said antistatic layer(s) may be overcoated with a barrier layer of e.g. gelatin.
  • Antistatic compounds suitable for use in such layers are e.g. vanadium pentoxide sols, tin oxide sols or conductive polymers such as polyethylene oxides, polymer latices and the like.
  • the support of the photographic materials used 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 absorption spectrum of the material as obtained after the processing cycle described hereinafter may be obtained by the addition of suitable non-migratory dyes to the subbing layer, the emulsion layer(s) or the protective antistress layer(s) or to the topcoat layer at both sides of the support.
  • suitable non-migratory dyes to the subbing layer, the emulsion layer(s) or the protective antistress layer(s) or to the topcoat layer at both sides of the support.
  • a blue coloured dye is therefore recommended, especially for films having a lower speed.
  • the photographic industrial X-ray materials differing in speed used according to this invention 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 is a radioactive Co60 source.
  • a metal screen usually a lead screen, can be used in combination with the photographic film. The generation of secondary electrons by this metal screen enhances the sensitivity.
  • an automatically operating apparatus is used provided with a system for automatic replenishment of the processing solutions.
  • the processing of the materials exposed as described hereinbefore proceeds by the steps of developing, rinsing, fixing, followed by rinsing and drying in automatic processing machines with drying means in the film-drying station. Infrared lamps are used as drying means.
  • the developer solution according to the 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.
  • the development step is followed by a washing step, a fixing solution and another washing or stabilization step. Finally after the last washing step the photographic material is dried by means of infrared drying means as cited hereinbefore.
  • the assortment of at least five film materials according to this invention includes at least one photographic material which is a single-side coated material having on one side of the film support at least one emulsion layer and at least one protective antistress layer and on the other side of said support at least one backing layer.
  • the assortment according to this invention has at least four silver halide industrial X- ray photographic materials, to be processed in the processing cycle of an automatic processing machine following the steps of developing, rinsing, fixing, rinsing and drying, wherein each of said film materials comprises at least one gelatino silver halide emulsion layer and at least one non-sensitive protective antistress coating on both sides of the film support.
  • Still further applications are related with stored digital information as in CT- and MRI-imaging techniques, where the same method to make a hardcopy as hereinbefore can be applied, but where nowadays laser imagers are used and where films are spectrally sensitive to the laser light of the (red or infrared) laser that has been installed.
  • the whole assortment of films differing in specific application field should be processed in the same automatical processing machine for the same time.
  • a gelatino silver iodobromide X-ray emulsion comprising 99 mole % of silver bromide and 1 mole % of silver iodide was prepared in the following way.
  • An aqueous solution containing 6 grams of ammonia was added to the reaction vessel containing 1550 ml of a 3 % by weight aqueous solution of gelatin at 45°C.
  • a solution of 2000 ml of an aqueous 1.5 molar solution of potassium bromide and a solution of 2000 ml of an aqueous 1.5 molar solution of silver nitrate were introduced at constant rate of 86 ml/min under vigorously stirring conditions.
  • the pAg value was adjusted to and maintained at a value corresponding to an E.M.F. of +20 mV with reference to a silver/saturated calomel electrode. In this way homogeneous and regular silver halide grains having a crystal diameter of 0.80 ⁇ m were obtained.
  • the emulsion was coagulated by adding polystyrene sulphonic acid acting as a flocculating agent after adjustment of the pH value of the emulsion in the reaction vessel to 3.5 with sulphuric acid. After rapid sedimentation of said silver halide emulsion the supernatant liquid was decanted. To remove the water-soluble salts from said flocculate, demineralized water of 11°C was added under controlled stirring conditions followed by a further sedimentation and decantation. This washing procedure was repeated until the emulsion was sufficiently desalted.
  • the coagulum was redispersed at 45°C in water after the addition of a sufficient amount of gelatin to obtain a ratio of gelatin to silver halide expressed as silver nitrate of 0.4.
  • the pH-value was adjusted to 6.5 and pAg to a value of +70 mV with reference to the silver/saturated calomel electrode.
  • Chemical sensitization of said emulsion was performed by the addition of a sulphur and gold sensitizer and digestion at 50°C to the point where the highest sensitivity was reached for a still acceptable fog level.
  • This emulsion was coated at both sides of a blue polyethylene terephtalate support having a thickness of 175 ⁇ m, so that per sq. m. and per side an amount of silver halide corresponding to 20.0 g of silver nitrate and 17.0 g of gelatin were present.
  • G stabilizers such as 5-methyl-7-hydroxy-5-triazolo-[1,5-a]-pyrimidin and 1-phenyl-5-mercaptotetrazol were added to the emulsion.
  • REF Relative Exposure Factor
  • GELTOT total amount of gelatin
  • ABS total amount of water absorption
  • ABS grams per gram of gelatin
  • an emulsion layer B is only coated at one side of the support and that in this case the amount of gelatin coated at the side of the backing layer is equal to that coated normally in the emulsion layer and the protective layer at the emulsion side.
  • the exposed radiographic films were developed, rinsed, fixed, rinsed and dried in an automatic machine processing cycle of 8 minutes.
  • the film was run in a Structurix NDT-1 machine marketed by Agfa-Gevaert and developed at 28°C in a one-part package developer, followed by fixation in a one-part package fixer as described hereinafter.
  • composition of the concentrated one-part package developer (amounts given in grams/liter) is as follows: water 200 ml potassium bromide 6 grams potassium sulphite (65% solution) ethylenediamine tetraacetic acid, 247 grams tetrasodium salt trihydrate 9.6 grams hydroquinone 112.0 grams 5 -methylbenzotriazole 0.076 grams 1-phenyl-5-mercaptotetrazole 0.040 grams sodium tetraborate (decahydrate) 18.0 grams potassium carbonate 38.0 grams potassium hydroxyde 42.0 grams diethylene glycol 100.0 grams potassium iodide 0.088 grams 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone 12.0 grams Water to make 1 liter. pH adjusted to 11.15 at 25°C with potassium hydroxide.
  • composition of the concentrated one-part package fixer ammoniumthiosulphate (59% solution) 552 grams boric acid 20.8 grams sodium sulphite 45 grams sodium acetate.3 aq 58 grams sulphuric acid (99% solution) 48.5 ml Water to make 1 liter. pH adjusted to 4.80 at 25°C with sulphuric acid.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP95202199A 1994-08-22 1995-08-14 Sortiment von photographischen Silberhalogenidfilmen für die industrielle Radiographie und Verfahren zur Verarbeitung dieses Sortiments Withdrawn EP0698817A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP95202199A EP0698817A1 (de) 1994-08-22 1995-08-14 Sortiment von photographischen Silberhalogenidfilmen für die industrielle Radiographie und Verfahren zur Verarbeitung dieses Sortiments

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP94202398 1994-08-22
EP94202398 1994-08-22
EP95202199A EP0698817A1 (de) 1994-08-22 1995-08-14 Sortiment von photographischen Silberhalogenidfilmen für die industrielle Radiographie und Verfahren zur Verarbeitung dieses Sortiments

Publications (1)

Publication Number Publication Date
EP0698817A1 true EP0698817A1 (de) 1996-02-28

Family

ID=26136504

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95202199A Withdrawn EP0698817A1 (de) 1994-08-22 1995-08-14 Sortiment von photographischen Silberhalogenidfilmen für die industrielle Radiographie und Verfahren zur Verarbeitung dieses Sortiments

Country Status (1)

Country Link
EP (1) EP0698817A1 (de)

Citations (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2614929A (en) 1947-08-13 1952-10-21 Eastman Kodak Co Method of preparing photographic emulsions
US2728662A (en) 1947-08-13 1955-12-27 Eastman Kodak Co Method of preparing photographic emulsions
GB789823A (en) 1955-04-29 1958-01-29 Gevaert Photo Prod Nv Improvements in or relating to photographic sensitive emulsions
US3038805A (en) 1959-10-14 1962-06-12 Eastman Kodak Co Non-polymeric open-chain sensitizers
US3314794A (en) 1964-05-13 1967-04-18 Eastman Kodak Co Ultraviolet absorbers
US3352681A (en) 1965-09-13 1967-11-14 Fuji Photo Film Co Ltd Color photographic light-sensitive element containing ultraviolet absorber
GB1203757A (en) 1966-12-08 1970-09-03 Minnesota Mining & Mfg Heterocyclic compounds
US3533794A (en) 1968-03-25 1970-10-13 Fuji Photo Film Co Ltd Color photographic light-sensitive material containing ultraviolet absorbing agents
GB1209146A (en) 1966-12-09 1970-10-21 Minnesota Mining & Mfg Substituted tetraazaindene compounds and their use as stabilizers for photographic silver halide emulsions
US3700455A (en) 1969-09-05 1972-10-24 Konishiroku Photo Ind Color photograph containing fade-preventing agents
US3705805A (en) 1970-11-14 1972-12-12 Agfa Gevaert Ag Photographic layers containing compounds which absorb ultraviolet light
US3707375A (en) 1969-10-07 1972-12-26 Fuji Photo Film Co Ltd Color photographic light sensitive materials having improved light fastness
DE2337172A1 (de) 1972-08-03 1974-02-14 Agfa Gevaert Ag Verfahren zur herstellung von photographischen gelatine-silberhalogenidemulsionen
US3821002A (en) 1972-03-06 1974-06-28 Eastman Kodak Co Process control apparatus and method for silver halide emulsion making
JPS5039537A (de) 1973-08-13 1975-04-11
US4038075A (en) 1975-01-22 1977-07-26 Agfa-Gevaert N.V. Development of photographic silver halide material
US4045229A (en) 1974-09-17 1977-08-30 Eastman Kodak Company Novel UV absorbing compounds and photographic elements containing UV absorbing compounds
GB1500278A (en) 1975-07-24 1978-02-08 Kodak Ltd Photographic silver halide emulsions
JPS562784A (en) 1979-06-22 1981-01-13 Nippon Telegr & Teleph Corp <Ntt> Image pickup device
US4292400A (en) 1979-09-27 1981-09-29 Agfa-Gevaert, N.V. Photographic silver halide development in the presence of thioether development activators
US4334012A (en) 1980-01-30 1982-06-08 Eastman Kodak Company Silver halide precipitation process with deletion of materials
US4614708A (en) 1981-11-23 1986-09-30 Agfa-Gevaert, N.V. Method for the preparation of stable aqueous dispersions of polymer beads and the use of these dispersions in photographic elements
US4727017A (en) 1985-02-04 1988-02-23 Agfa-Gevaert, N.V. Substituted triazolopyrimidines and their use in light-sensitive photographic elements
EP0392092A1 (de) 1989-04-11 1990-10-17 Agfa-Gevaert N.V. Verfahren zur Herstellung von lichtempfindlichen Silberhalogenid Emulsionen
EP0517961A1 (de) 1991-06-11 1992-12-16 Agfa-Gevaert N.V. Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen
EP0528476A1 (de) 1991-08-15 1993-02-24 Agfa-Gevaert N.V. Verfahren zur Herstellung eines photographischen Silberhalogenidmaterials
EP0538947A1 (de) 1991-10-24 1993-04-28 Agfa-Gevaert N.V. Für Schnellverarbeitungssysteme geeignetes photographisches Silberhalogenidröntgenmaterial
EP0555897A1 (de) 1992-02-14 1993-08-18 Agfa-Gevaert N.V. Photographisches Silberhalogenidröntgenmaterial mit passenden Bildton und Oberflächenglanz
EP0620483A1 (de) 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Verarbeitung von photographischen industriellen Silberhalogenid-Röntgenfilmen
EP0620484A1 (de) 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Photographische industrielle Silberhalogenid-Röntgenfilme
EP0620482A1 (de) 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Verfahren zur Verarbeitung von vorgehärteten photographischen industriellen Silberhalogenid-Röntgenfilmen
EP0621506A1 (de) 1993-04-13 1994-10-26 Agfa-Gevaert N.V. Verarbeitung von photographischen, industriellen Silberhalogenid-Röntgenfilmen
EP0622668A1 (de) 1993-04-27 1994-11-02 Agfa-Gevaert N.V. Photographisches Silberhalogenidmaterial für die industrielle Radiographie, das für verschiedene Verarbeitungsanwendungen geeignet ist
EP0649051A1 (de) 1993-09-16 1995-04-19 Agfa-Gevaert N.V. Herstellungsverfahren für lichtempfindliche Silberhalogenidemulsion und diese Emulsionen enthaltendes Material

Patent Citations (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2614928A (en) 1947-08-13 1952-10-21 Eastman Kodak Co Method of preparing photographic emulsions
US2728662A (en) 1947-08-13 1955-12-27 Eastman Kodak Co Method of preparing photographic emulsions
US2614929A (en) 1947-08-13 1952-10-21 Eastman Kodak Co Method of preparing photographic emulsions
GB789823A (en) 1955-04-29 1958-01-29 Gevaert Photo Prod Nv Improvements in or relating to photographic sensitive emulsions
US3038805A (en) 1959-10-14 1962-06-12 Eastman Kodak Co Non-polymeric open-chain sensitizers
US3314794A (en) 1964-05-13 1967-04-18 Eastman Kodak Co Ultraviolet absorbers
US3352681A (en) 1965-09-13 1967-11-14 Fuji Photo Film Co Ltd Color photographic light-sensitive element containing ultraviolet absorber
GB1203757A (en) 1966-12-08 1970-09-03 Minnesota Mining & Mfg Heterocyclic compounds
GB1209146A (en) 1966-12-09 1970-10-21 Minnesota Mining & Mfg Substituted tetraazaindene compounds and their use as stabilizers for photographic silver halide emulsions
US3533794A (en) 1968-03-25 1970-10-13 Fuji Photo Film Co Ltd Color photographic light-sensitive material containing ultraviolet absorbing agents
US3700455A (en) 1969-09-05 1972-10-24 Konishiroku Photo Ind Color photograph containing fade-preventing agents
US3707375A (en) 1969-10-07 1972-12-26 Fuji Photo Film Co Ltd Color photographic light sensitive materials having improved light fastness
US3705805A (en) 1970-11-14 1972-12-12 Agfa Gevaert Ag Photographic layers containing compounds which absorb ultraviolet light
US3821002A (en) 1972-03-06 1974-06-28 Eastman Kodak Co Process control apparatus and method for silver halide emulsion making
DE2337172A1 (de) 1972-08-03 1974-02-14 Agfa Gevaert Ag Verfahren zur herstellung von photographischen gelatine-silberhalogenidemulsionen
JPS5039537A (de) 1973-08-13 1975-04-11
US4045229A (en) 1974-09-17 1977-08-30 Eastman Kodak Company Novel UV absorbing compounds and photographic elements containing UV absorbing compounds
US4038075A (en) 1975-01-22 1977-07-26 Agfa-Gevaert N.V. Development of photographic silver halide material
GB1500278A (en) 1975-07-24 1978-02-08 Kodak Ltd Photographic silver halide emulsions
JPS562784A (en) 1979-06-22 1981-01-13 Nippon Telegr & Teleph Corp <Ntt> Image pickup device
US4292400A (en) 1979-09-27 1981-09-29 Agfa-Gevaert, N.V. Photographic silver halide development in the presence of thioether development activators
US4334012A (en) 1980-01-30 1982-06-08 Eastman Kodak Company Silver halide precipitation process with deletion of materials
US4614708A (en) 1981-11-23 1986-09-30 Agfa-Gevaert, N.V. Method for the preparation of stable aqueous dispersions of polymer beads and the use of these dispersions in photographic elements
US4727017A (en) 1985-02-04 1988-02-23 Agfa-Gevaert, N.V. Substituted triazolopyrimidines and their use in light-sensitive photographic elements
EP0392092A1 (de) 1989-04-11 1990-10-17 Agfa-Gevaert N.V. Verfahren zur Herstellung von lichtempfindlichen Silberhalogenid Emulsionen
EP0517961A1 (de) 1991-06-11 1992-12-16 Agfa-Gevaert N.V. Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen
EP0528476A1 (de) 1991-08-15 1993-02-24 Agfa-Gevaert N.V. Verfahren zur Herstellung eines photographischen Silberhalogenidmaterials
EP0538947A1 (de) 1991-10-24 1993-04-28 Agfa-Gevaert N.V. Für Schnellverarbeitungssysteme geeignetes photographisches Silberhalogenidröntgenmaterial
EP0555897A1 (de) 1992-02-14 1993-08-18 Agfa-Gevaert N.V. Photographisches Silberhalogenidröntgenmaterial mit passenden Bildton und Oberflächenglanz
EP0620483A1 (de) 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Verarbeitung von photographischen industriellen Silberhalogenid-Röntgenfilmen
EP0620484A1 (de) 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Photographische industrielle Silberhalogenid-Röntgenfilme
EP0620482A1 (de) 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Verfahren zur Verarbeitung von vorgehärteten photographischen industriellen Silberhalogenid-Röntgenfilmen
EP0621506A1 (de) 1993-04-13 1994-10-26 Agfa-Gevaert N.V. Verarbeitung von photographischen, industriellen Silberhalogenid-Röntgenfilmen
EP0622668A1 (de) 1993-04-27 1994-11-02 Agfa-Gevaert N.V. Photographisches Silberhalogenidmaterial für die industrielle Radiographie, das für verschiedene Verarbeitungsanwendungen geeignet ist
EP0649051A1 (de) 1993-09-16 1995-04-19 Agfa-Gevaert N.V. Herstellungsverfahren für lichtempfindliche Silberhalogenidemulsion und diese Emulsionen enthaltendes Material

Non-Patent Citations (12)

* Cited by examiner, † Cited by third party
Title
AGFA-GEVAERT: "Industriele Radiografie. Materialen en systemen", ADVERTISING MATERIAL AGFA-GEVAERT 21.5221, no. 78787, MORTSEL, BE, pages 1 - 6 *
AGFA-GEVAERT: "Structurix D3-film", FACTSHEET AGFA-GEVAERT 21.6260 'NDT TECHNISCHE INFORMATIE', MORTSEL, BE *
APPLICATION CONTAINS STILL MORE REFERENCES
B.J.SCOTT, A.R.BRADWELL: "A Comparison of 12 X-Ray films for the Autoradiography of Isotopes Emitting Weak Ÿ-Particles", INTERNATIONAL JOURNAL OF APPLIED RADIATION AND ISOTOPES, vol. 34, no. 4, OXFORD GB, pages 765 - 767, XP024718142, DOI: doi:10.1016/0020-708X(83)90260-0 *
E. MOISAR & E. KLEIN: "The influence of Growth Conditions on the Crystalline Behaviour of Silver halides.", BUNSENGESELLSCHAFT FUER PHYSIKALISCHE CHEMIE, vol. 67, no. 9.10., 1963, pages 949 - 957
H.BÖTTCHER, J.EPPERLEIN: "Moderne photographische Systeme", VEB DEUTSCHER VERLAG FÜR GRUNDSTOFFINDUSTRIE, LEIPZIG,DD *
K.KELLER (ED.): "Science and Technology of Photography", VCH VERLAGSGESELLSCHAFT MBH, WEINHEIM, DE *
LOVELAND: "ASTM symposium on light microscopy", 1953, pages: 94 - 122
MEES & JAMES: "The Theory of the photographic process", 1977
RESEARCH DISCLOSURE, vol. 102, no. 8, October 1972 (1972-10-01)
RESEARCH DISCLOSURE, vol. 131, no. 22
TRIVELLI & M. SMITH, THE PHOTOGRAPHIC JOURNAL, vol. 69, 1939, pages 330 - 338

Similar Documents

Publication Publication Date Title
EP0476521B1 (de) Photographisches Silberhalogenidmaterial und Verfahren zu dessen Verarbeitung
EP0610609B1 (de) Lichtempfindliches, photograhisches Silberhalogenidmaterial mit gesteigerter Bildqualität für Schnellverarbeitung zur Anwendung in der Mammographie
EP0620484B1 (de) Photographische industrielle Silberhalogenid-Röntgenfilme
US5447817A (en) Processing of silver halide photographic industrial x-ray films
US5620836A (en) Assortment of silver halide photographic industrial x-ray films and method of processing said assortment
EP0712034A1 (de) Verfahren zur spektralen Sensibilisierung von tafelförmigen Silberhalogenidkörnern
EP0555897B1 (de) Photographisches Silberhalogenidröntgenmaterial mit passenden Bildton und Oberflächenglanz
US5462831A (en) Processing of silver halide photographic industrial X-ray films
EP0712036B1 (de) Lichtempfindliches photographisches Schirm/Silberhalogenidfilmsystem mit verbesserter Bildqualität für Schnellverarbeitungsanwendungen in der Mammographie
US5015562A (en) Light-sensitive silver halide element containing modant, dye and sonic polymer
EP0622668B1 (de) Photographisches Silberhalogenidmaterial für die industrielle Radiographie, das für verschiedene Verarbeitungsanwendungen geeignet ist
EP0620482A1 (de) Verfahren zur Verarbeitung von vorgehärteten photographischen industriellen Silberhalogenid-Röntgenfilmen
EP0678772A1 (de) Lichtempfindliches Silberchlorobromojodid- oder Silbuchlorojodid-Tafelkörner enthaltendes Material
EP0321948A2 (de) Photographisches Material mit Silberhalogenid
EP0698817A1 (de) Sortiment von photographischen Silberhalogenidfilmen für die industrielle Radiographie und Verfahren zur Verarbeitung dieses Sortiments
US6277552B1 (en) Shallow electron trap dopants in silver halide tabular grain emulsions for use in medical diagnostic imaging materials
EP0610608B1 (de) Photographisches, lichtempfindliches Silberhalogenidmaterial zur Wiedergabe von medizinischen laseraufgezeichneten Bildern und Verfahren zur Verarbeitung
JPH0812387B2 (ja) ハロゲン化銀写真感光材料
US6936411B2 (en) Industrial radiographic silver halide material suitable for rapid processing applications
EP0528480B1 (de) Ein photographisches Silberhalogenidmaterial
EP0890875B1 (de) Mehrschichtiges photographisches Silberhalogenidmaterial und bilderzeugendes Verfahren für Anwendungen in der zerstörungsfreien Prüfung mittels industrieller Radiographie
US5576154A (en) Photographic recording materials for medical radiography
JPH0255351A (ja) ハロゲン化銀写真感光材料
JPS6373244A (ja) 画像形成方法
JPH04147130A (ja) ハロゲン化銀写真感光材料

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB NL

17P Request for examination filed

Effective date: 19960828

17Q First examination report despatched

Effective date: 19961002

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20000426