EP0706084A1 - Rapid processable photographic recording material for medical radiography - Google Patents
Rapid processable photographic recording material for medical radiography Download PDFInfo
- Publication number
- EP0706084A1 EP0706084A1 EP95115494A EP95115494A EP0706084A1 EP 0706084 A1 EP0706084 A1 EP 0706084A1 EP 95115494 A EP95115494 A EP 95115494A EP 95115494 A EP95115494 A EP 95115494A EP 0706084 A1 EP0706084 A1 EP 0706084A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver halide
- recording material
- silver
- photographic
- material according
- 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- Withdrawn
Links
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
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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
- G03C1/035—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
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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
- 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
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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
- G03C2200/00—Details
- G03C2200/27—Gelatine content
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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
- G03C2200/00—Details
- G03C2200/52—Rapid processing
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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
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/164—Rapid access processing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/167—X-ray
Definitions
- the invention relates to a rapidly processable photographic recording material for medical radiography, which is characterized by rapid processability with very good photographic and physical properties.
- photographic recording materials which contain at least one radiation-sensitive silver halide emulsion layer (hereinafter referred to as X-ray films) on both sides of a support are used in combination with intensifying screens.
- X-ray films radiation-sensitive silver halide emulsion layer
- the physical and photographic properties of the X-ray films determine their suitability for the safe diagnosis of diseases by the radiologist.
- the processing time of a photographic film depends crucially on the composition of the respective film, the structure and mode of operation of the respective film processor and the developer solution and fixer used in the film processor. All parameters, such as the dryer geometry and drying time of the film processor or the process water absorption of the corresponding photographic film, which influence the drying of the photographic films in the film processor, are of particular importance.
- the processing time is defined as the time that an X-ray film in the standard format of 0.35 X 0.35 m edge length requires for the passage through a film processor, starting with the start of the X-ray film and ending with the complete release of the developed X-ray image. This period is also referred to in the literature as "nose to drop".
- a silver halide photographic material is said to be rapidly processable if it can be processed in a film processor within 30 to 60 seconds.
- Another way of reducing the processing time of X-ray films has been to reduce the swelling of the binder by means of stronger crosslinking.
- this measure leads to a deterioration in photographic properties such as gradation, sensitivity and maximum image blackness.
- a simultaneous reduction in the application of binder and silver halide in the recording material leads to a lower maximum image blackness and increased through-exposure and thus to a poorer image sharpness of the image produced thereby.
- This can only be compensated for insufficiently by using filter dyes, since the filter dyes cannot be completely washed out with the desired short processing time and thus have a negative influence on the image color of the x-ray image produced in this way.
- washable polymers contaminate the processor fluids and are therefore disadvantageous. Furthermore, such films with a low weight ratio of non-washable binder to silver have poor wet printing properties.
- the object of the invention is to provide a photographic recording material for medical radiography which has very good photographic and physical properties and can be processed in a roll developing machine in less than 60 seconds.
- the object is achieved by a rapidly processable photographic silver halide recording material for medical radiography according to claim 1.
- Binder application or silver application is understood to mean the weight of the sum of the binders or the weight of silver in the form of its ions in the layers containing the silver halide crystals, based on the unit area of the silver halide photographic material.
- the binder that is contained in the auxiliary layers of the silver halide photographic material is therefore not taken into account in the calculation of the binder application.
- the values for the application of binder or silver are given in grams / square meter and, unless stated otherwise, relate to the totality of all layers of the recording material containing silver halide.
- a silver coating of at least 5 g / m 2 is suitable for the rapidly processable silver halide photographic material according to the invention.
- a silver coating of at least 5.2 g / m2 is preferably used. The range from 5.2 to 6.0 g / m 2 is particularly preferred.
- the recording material according to the invention contains at least one silver halide emulsion layer on each side of the support.
- a recording material which contains at least one silver halide emulsion layer on each side of the substrate and the silver halide emulsion layers on both sides of the substrate are largely the same.
- the silver application can be set, for example, via the silver halide concentration in the silver halide emulsion and the layer thickness of the silver halide emulsion layer or silver halide emulsion layers.
- synthetic polymers such as polymers or copolymers of vinyl alcohol, N-vinylpyrrolidone, acrylamide, acrylic acid, methacrylic acid, vinylimidazole, vinylpyrazole and natural polymers such as casein
- binder mixtures can also be used in the individual layers.
- a preferred main constituent of a binder mixture or the sole binder in the layers of photographic recording materials can be, for example, gelatin.
- Alkaline digested bovine bone gelatin is preferably used as the protective colloid for the silver halide crystals and binder in the emulsion layer. This can be ion-exchanged or not ion-exchanged.
- a weight ratio of binder or binder mixture to silver of at least 1.1 is preferably used in the silver halide emulsion.
- a ratio between 1.1 and 1.4 is particularly preferred.
- This ratio is set, for example, during the preparation of the silver halide emulsion via the amount of binder to be added relative to the amount of silver.
- the grain volume of a silver halide emulsion is understood to mean the mean volume of the column. This allows different grain shapes such as spheres, cubes, octahedra or plates to be compared with one another.
- essentially silver halide emulsions are used, the average grain volume of which is below 0.35 ⁇ m3.
- the preferred range is between 0.05 and 0.35 ⁇ m3
- the grain size or the grain volume can be determined with the aid of various methods, for example with the aid of electron microscope images of the corresponding emulsion or by the method described in DE 20 25 147.
- the process water absorption PWP of a photographic silver halide recording material can be determined, for example, by the method described in the exemplary embodiments. Another method is described in European Patent EP-A 03 08 193. Recording materials according to the invention have a process water absorption of less than 20 g of water per square meter of recording material. However, it is preferred to use a recording material which has a PWP of less than 18 g water / m 2.
- the process water absorption of a photographic recording material can be adjusted, for example, via the amount of hardening agents used to harden the layers in the recording material.
- the amount of hardener required for this can be determined, for example, with the aid of series tests with different amounts of hardener.
- the silver halide grains in the silver halide emulsion can have a regular crystal shape such as cubes, octahedra, cubo-octahedra or tetrahedron, an irregular shape such as plates or spheres or mixtures of at least two of these shapes.
- Silver halide emulsions are preferably used which essentially contain grains with a regular crystal shape and / or spherical silver halide grains. Silver halide emulsions which contain essentially spherical silver halide grains are particularly preferred.
- Cubes, octahedra, cuboctahedra and single twins with (111) and / or (100) boundary surfaces have an average ratio of the smallest to the largest dimension (aspect ratio) between 1.0: 1.1 and 2.0 and can be regarded as approximately spherical become.
- Spherical silver halide crystals have a ratio of smallest to largest dimension between 1.0: 1.1 and 1.0: 1.0.
- Plate-shaped silver halide crystals have an aspect ratio of at least 1.0: 2.0.
- the photographic silver halide recording material can contain auxiliary layers such as, for example, adhesion-promoting layers, protective layers, intermediate layers, antistatic layers and layers containing colorants on both sides of the substrate in addition to emulsion layers.
- auxiliary layers such as, for example, adhesion-promoting layers, protective layers, intermediate layers, antistatic layers and layers containing colorants on both sides of the substrate in addition to emulsion layers.
- the protective layer is the layer which is furthest away from the base and usually does not contain any silver halide.
- such protective layers may also contain other substances which influence the chemical, physical and mechanical properties of photographic silver halide recording materials. These substances include, for example, lubricants, surface-active substances containing perfluoroalkyl groups, latexes (polymeric organic particles), finely divided crystalline SiO 2 dispersions, matting agents (spacers), curing agents, antistatic substances and preservatives.
- the binder application for emulsion layers is usually between 0.5 g / m2 and 10.0 g / m2 for protective layers between 0.5 g / m2 and 5.0 g / m2 and for intermediate layers between 0.1 g / m2 and 5.5 g / m2.
- the photographic emulsions can be prepared from soluble silver salts and soluble halides by various methods.
- Metal ions such as cadmium, zinc, thallium, mercury, iridium, rhodium and iron or their complexes may be present during the production and / or physical ripening of the silver halide emulsion.
- the silver halide emulsion can contain silver halide crystals consisting of silver bromide, silver bromoiodide, silver chlorobromoiodide or silver chlorobromide.
- a silver halide emulsion is preferably used which contains silver bromoiodide with a maximum of 5% iodide based on the halide content.
- the soluble salts are removed from the emulsion, for example by pasta and washing, by flaking and washing, by ultrafiltration or with the aid of ion exchangers.
- the silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached.
- chemical sensitizers such as active gelatin, sulfur, selenium or tellurium compounds, salts or complexes of gold, platinum, rhodium, palladium, iridium, osmium, rhenium, ruthenium can be used alone or in combination. Procedures are described, for example, by H.
- the layers containing hydrophilic binders can contain organic or inorganic hardening agents.
- the hardening of a layer can also be effected by covering the layer to be hardened with a layer which contains a diffusible hardening agent, as is described, for example, in DE-A 38 36 945.
- the curing agent can be added in the course of the preparation of emulsion solutions and / or casting solution for auxiliary layers. Another possible form of addition is to inject a solution of the hardening agent into at least one emulsion or casting solution while it is being transported from the storage kettle to the casting device.
- chromium salts such as chromium alum
- aldehydes such as formaldehy
- Spectral sensitizers such as cyanine dyes, merocyanine dyes, hemicyanine dyes, styryl dyes can be contained in the silver halide emulsion.
- a spectral sensitizer alone or a combination can be used.
- substances for stabilizing the emulsion against fog or for stabilizing other photographic properties such as, for example, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazole, chlorobenzimidazole, benzobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidozole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, brom
- the silver halide emulsion and in the mixtures for producing the auxiliary layers there can be surface-active substances for various purposes, such as coating aids, to prevent electrostatic charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve photographic characteristics (e.g. acceleration of development, high contrast, sensitization).
- coating aids to prevent electrostatic charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve photographic characteristics (e.g. acceleration of development, high contrast, sensitization).
- non-ionic surfactants which contain oligo- or polyoxyalkylene groups, glycerol compounds and glycidol compounds, cationic surfactants, for example higher alkylamines, quaternary ammonium salts, pyridine compounds, and other heterocyclic compounds, Sulphonium compounds or phosphonium compounds, anionic surfactants containing an acid group, for example carboxylic acid, phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants such as amino acid and aminosulphonic acid compounds and sulfur and phosphoric acid esters of an amino alcohol.
- the various layers of the photographic material can contain filter dyes such as oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, cyanine dyes, azomethine dyes, triarylmethane dyes, phthalocyanines and azo dyes.
- filter dyes such as oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, cyanine dyes, azomethine dyes, triarylmethane dyes, phthalocyanines and azo dyes.
- the support of the photographic recording material can consist of a transparent and optionally blue-colored plastic film which has been produced from polyethylene terephthalate, cellulose acetate, cellulose acetate butyrate, polystyrene or polycarbonate.
- the surface of the carrier is preferably treated by a coronary discharge before a first coating to improve the adhesion properties.
- Various casting methods can be used to make the photographic material. Examples of this are curtain casting, cascade casting, dip casting, wash-on casting, slot casting. If necessary, several layers can be applied simultaneously.
- Another advantage of the rapidly processable photographic recording material according to the invention is the property of having a comparable sensitometry both with a processing time of 90 seconds and with a processing time of less than 60 seconds.
- the rapidly processable silver halide photographic material according to the invention also has an improved visual resolution, an improved silver color, a particularly good wet scratch resistance and improved wet printing properties.
- a silver halide emulsion A was prepared using spherical silver bromide iodide grains (2% iodide content) with an average grain volume of 0.09 ⁇ m3, the ratio of the weight proportions of binder to silver being 1.4.
- the emulsion and a mixture for producing a protective layer were applied uniformly on both sides to a polyester base provided with an adhesive layer on both sides and dried.
- the mixture for the preparation of a protective layer consisted essentially of an aqueous gelatin solution and also contained wetting agents and formaldehyde as hardening agents.
- the layers on both sides of a film sample each had the same silver and binder application and were each hardened with the same amount of hardener.
- the amount of hardener used and the wet application of the two layers were chosen so that the silver applications and process water absorption values PWP of the two film samples A1 and A2 described in Table 1 and a gelatin application of the protective layer of 1.2 g / m 2 each were achieved.
- a silver halide emulsion B was prepared using spherical silver bromide iodide grains (2% iodide content) with an average grain volume of 0.22 ⁇ m3, the ratio of the weight proportions of binders to silver being 1.15.
- the emulsion was applied to a film B1 and B2 as described for film samples A1 and A2 together with a mixture for producing a protective layer located above the emulsion layer, essentially containing gelatin, and using formaldehyde as a hardening agent and dried so that the in Silver applications and process water absorption values PWP described in Table 1 were achieved and the gelatin application of the protective layer was 1.36 g / m2 on each side.
- the mean grain volume was determined in each case using the method described in German patent DE 20 25 147.
- the process water absorption values PWP of the film samples were determined by first exposing a sheet of the recording material to be examined without pouring margins or non-cast areas over its entire area with an exposure corresponding to the saturation range of the density curve, using a Kodak processor M8 roll developing machine with the rear cover and the upper deflection shaft behind the Was removed, charged with a developer solution and a fixing bath of the following composition: Developer: Fixing bath: Hydroquinone 24.0 g / l Ammonium thiosulfate 130.0 g / l Phenylpyrazolidone 0.75 g / l Sodium sulfite, anhydrous 10.0 g / l Sodium sulfite, anhydrous 60.0 g / l Boric acid 7.0 g / l Sodium metaborate 33.0 g / l Acetic acid (90% by weight) 5.5 g / l Sodium hydroxide 19.0 g / l Sodium acetate trihydrate 25.0
- the sensitometric data for the sensitivity, maximum image blackness (D-Max) and medium gradient were obtained by standardized exposure and processing and are shown in Tables 2 and 3. Numerical values in brackets mean that the film has not left the film processor sufficiently dry and that the measured data are therefore unsuitable for direct comparison.
- film samples A2 and B2 leave the film processor after a processing time of 53 seconds and each have a sensitometry suitable for radiological use. After processing in the two processing times used, the two film samples A2 and B2 each have comparable sensitometric values for sensitivity, maximum image blackness and gradation. Both film samples A2 and B2 also have, compared to film samples A1 and B1, an improved wet printing property, an improved image silver color, that is to say more neutral, improved pressure sensitization properties, improved noise and improved image sharpness.
Abstract
Description
Gegenstand der Erfindung ist ein schnellverarbeitbares photographisches Aufzeichnungsmaterial für die medizinische Radiographie, das sich durch eine schnelle Verarbeitbarkeit bei sehr guten photographischen und physikalischen Eigenschaften auszeichnet.The invention relates to a rapidly processable photographic recording material for medical radiography, which is characterized by rapid processability with very good photographic and physical properties.
In der medizinischen Radiologie werden photographische Aufzeichnungsmaterialien die auf beiden Seiten eines Trägers jeweils mindestens eine strahlungsempfindliche Silberhalogenidemulsionsschicht enthalten (nachfolgend als Röntgenfilme bezeichnet) in Kombination mit Verstärkerfolien verwendet. Physikalische und photographische Eigenschaften der Röntgenfilme bestimmen dabei deren Eignung zur sicheren Diagnose von Erkrankungen durch den Radiologen.In medical radiology, photographic recording materials which contain at least one radiation-sensitive silver halide emulsion layer (hereinafter referred to as X-ray films) on both sides of a support are used in combination with intensifying screens. The physical and photographic properties of the X-ray films determine their suitability for the safe diagnosis of diseases by the radiologist.
Neben gleichbleibend hohen Qualitätsanforderungen an moderne Röntgenfilme ist auch die schnelle Verfügbarkeit der daraus entwickelten Röntgenbilder von Bedeutung, beispielsweise von Aufnahmen, die während Operationen aufgenommen werden und Hinweise auf den weiteren Verlauf von Operationen gehen sollen.In addition to the consistently high quality requirements for modern X-ray films, the rapid availability of the X-ray images developed from them is also important, for example images that are taken during operations and are intended to provide information on the further course of operations.
Desweiteren werden in Krankenhäusern oder großen Arztpraxen häufig Bildaufnahmen von mehreren Aufnahmegeräten wie beispielsweise Röntgenapparat, Laserkamera, Gerät für Monitorphotographie und Kopiergerät für Röntgenfilme in der gleichen Filmentwicklungsmaschine verarbeitet. Daher ist eine möglichst kurze Verarbeitungszeit der Filmentwicklungsmaschine für Röntgenfilme sowie andere in den entsprechenden Krankenhäusern und Arztpraxen von weniger als 60 Sekunden erwünscht.Furthermore, in hospitals or large medical practices, image recordings from multiple recording devices such as, for example, X-ray apparatus, laser camera, device for monitor photography and copier for X-ray films are often processed in the same film processor. Therefore, the shortest possible processing time of the film processing machine for X-ray films and others in the corresponding hospitals and medical practices of less than 60 seconds is desirable.
Die Verarbeitungszeit eines photographischen Filmes hängt entscheidend von der Zusammensetzung des jeweiligen Filmes, dem Aufbau und der Betriebsweise der jeweiligen Filmentwicklungsmaschine und der in der Filmentwicklungsmaschine verwendeten Entwicklerlösung sowie Fixierbad ab. Alle Parameter wie beispielsweise die Trocknergeometrie und Trocknungszeit der Filmentwicklungsmaschine oder die Prozeßwasseraufnahme des entsprechenden photographischen Filmes, welche die Trocknung der photographischen Filme in der Filmentwicklungsmaschine beeinflussen, sind dabei von besonderer Bedeutung.The processing time of a photographic film depends crucially on the composition of the respective film, the structure and mode of operation of the respective film processor and the developer solution and fixer used in the film processor. All parameters, such as the dryer geometry and drying time of the film processor or the process water absorption of the corresponding photographic film, which influence the drying of the photographic films in the film processor, are of particular importance.
Die Verarbeitungszeit ist hierbei definiert als die Zeit, die ein Röntgenfilm im Standardformat von 0,35 X 0,35 m Kantenlänge für den Durchlauf durch eine Filmentwicklungsmaschine benötigt, beginnend mit dem Einzugsbegin des Röntgenfilmes und endend mit der vollständigen Freigabe des entwickelten Röntgenbildes. Diese Zeitspanne wird in der Literatur auch als "nose to drop" bezeichnet.The processing time is defined as the time that an X-ray film in the standard format of 0.35 X 0.35 m edge length requires for the passage through a film processor, starting with the start of the X-ray film and ending with the complete release of the developed X-ray image. This period is also referred to in the literature as "nose to drop".
Ein photographisches Silberhalogenid-Aufzeichnungsmaterial gilt als schnellverarbeitbar, wenn es innerhalb von 30 bis 60 Sekunden in einer Filmentwicklungsmaschine verarbeitbar ist.A silver halide photographic material is said to be rapidly processable if it can be processed in a film processor within 30 to 60 seconds.
Ein Beispiel für eine für diese Verarbeitung geeignete Rollenentwicklungsmaschine sowie eine Rezeptur für einen darin verwendbaren Entwickler sowie ein Fixierbad ist in EP-A 02 38 271 beschrieben.An example of a roll developing machine suitable for this processing, as well as a recipe for a developer which can be used therein, and a fixing bath is described in EP-A 02 38 271.
Zur Verringerung der Verarbeitungszeit von photographischen Filmen wurde die Verminderung des Gesamtgelatineauftrags in EP-A 02 48 390 auf einen Bereich von 2,2 bis 3,1 g/m² pro Seite vorgeschlagen. Dadurch werden aber bestimmte Eigenschaften von Röntgenfilmen wie beispielsweise Naßdruck, Kratzsensibilisierung, Körnigkeit und Druckdesensibilisierung sowie die Bildqualität des mit diesem Material hergestellten Bildes verschlechtert.In order to reduce the processing time of photographic films, the reduction of the total gelatin application in EP-A 02 48 390 to a range of 2.2 to 3.1 g / m² per side has been proposed. As a result, however, certain properties of X-ray films, such as, for example, wet printing, scratch sensitization, granularity and pressure desensitization, and the image quality of the image produced using this material are impaired.
Als weiterer Weg zur Reduktion der Verarbeitungszeit von Röntgenfilmen wurde die Verminderung der Quellung des Bindemittels durch stärkere Vernetzung vorgeschlagen. Diese Maßnahme hat aber eine Verschlechterung von photographischen Eigenschaften wie Gradation, Empfindlichkeit und maximale Bildschwärze zur Folge.Another way of reducing the processing time of X-ray films has been to reduce the swelling of the binder by means of stronger crosslinking. However, this measure leads to a deterioration in photographic properties such as gradation, sensitivity and maximum image blackness.
Eine gleichzeitige Verminderung von Bindemittel- und Silberhalogenidauftrag im Aufzeichnungsmaterial führt zu einer niedrigeren maximalen Bildschwärze und einer verstärkten Durchbelichtung und damit zu einer schlechteren Bildschärfe des damit hergestellten Bildes. Dies kann durch die Verwendung von Filterfarbstoffen nur ungenügend kompensiert werden, da die Filterfarbstoffe bei der angestrebten kurzen Verarbeitungszeit nicht vollständig auswaschbar sind und somit die Bildfarbe des so hergestellten Röntgenbildes negativ beeinflussen.A simultaneous reduction in the application of binder and silver halide in the recording material leads to a lower maximum image blackness and increased through-exposure and thus to a poorer image sharpness of the image produced thereby. This can only be compensated for insufficiently by using filter dyes, since the filter dyes cannot be completely washed out with the desired short processing time and thus have a negative influence on the image color of the x-ray image produced in this way.
Als weiterer Weg zur schnelleren Verarbeitung von Röntgenfilmen wurde der Einsatz von während des Entwicklungsprozesses auswaschbaren Polymeren wie Polyacrylamid und/oder Saccharose in der Silberhalogenid- bzw. Schutzschicht in EP-A 02 59 855 vorgeschlagen.The use of polymers that can be washed out during the development process, such as polyacrylamide and / or sucrose, in the silver halide or protective layer in EP-A 02 59 855 has been proposed as a further route for faster processing of X-ray films.
Die auswaschbaren Polymere verschmutzen aber die Prozessorflüssigkeiten und sind daher von Nachteil. Weiterhin besitzen solche Filme mit einem niedrigem gewichtsmäßigen Verhältnis von nichtauswaschbaren Bindemittel zu Silber schlechte Naßdruckeigenschaften.However, the washable polymers contaminate the processor fluids and are therefore disadvantageous. Furthermore, such films with a low weight ratio of non-washable binder to silver have poor wet printing properties.
Bisher wurde kein photographisches Aufzeichnungsmaterial für die medizinische Radiologie gefunden, das sowohl innerhalb von 60 Sekunden mit einer Rollenentwicklungsmaschine verarbeitbar ist und auch sehr gute physikalischen und photographischen Eigenschaften sowie eine hohe Bildqualität besitzt.No photographic recording material for medical radiology has hitherto been found which can be processed with a roll developing machine within 60 seconds and also has very good physical and photographic properties and high image quality.
Die bisher vorgeschlagenen photographischen Aufzeichnungsmaterialien für die medizinische Radiologie, welche innerhalb von 60 Sekunden verarbeitbar sind, weisen zudem unterschiedliche sensitometrische Daten in Abhängigkeit von der Verarbeitungszeit auf. Dies ist in der Anwendung unerwünscht, da für unterschiedliche Verarbeitungsgeschwindigkeiten verschiedene Aufnahmeparameter notwendig werden.The previously proposed photographic recording materials for medical radiology, which can be processed within 60 seconds, also have different sensitometric data depending on the processing time. This is undesirable in the application, since different recording parameters are necessary for different processing speeds.
Aufgabe der Erfindung ist die Bereitstellung eines photographischen Aufzeichnungsmaterials für die medizinische Radiographie, welches sehr gute photographische und physikalische Eigenschaften besitzt und in weniger als 60 Sekunden in einer Rollenentwicklungsmaschine verarbeitbar ist.The object of the invention is to provide a photographic recording material for medical radiography which has very good photographic and physical properties and can be processed in a roll developing machine in less than 60 seconds.
Die Aufgabe wird gelöst durch ein schnellverarbeitbares photographisches Silberhalogenid-Aufzeichnungsmaterial für die medizinische Radiographie gemäß Anspruch 1.The object is achieved by a rapidly processable photographic silver halide recording material for medical radiography according to claim 1.
Unter Bindemittelauftrag bzw. Silberauftrag wird das Gewicht der Summe der Bindemittel bzw. das Gewicht an Silber in Form seiner Ionen in den die Silberhalogenidkristalle enthaltenden Schichten, bezogen auf die Flächeneinheit des photographischen Silberhalogenidmaterials verstanden. Unberücksichtigt bleiben bei der Berechnung des Bindemittelauftrags also die Bindemittel, die in den Hilfsschichten des photographischen Silberhalogenidmaterials enthalten sind. Die Werte für den Bindemittel- oder Silberauftrag sind in Gramm/Quadratmeter angegeben und beziehen sich, sofern nicht anders angegeben, auf die Gesamtheit aller Silberhalogenid enthaltenden Schichten des Aufzeichnungsmaterials.Binder application or silver application is understood to mean the weight of the sum of the binders or the weight of silver in the form of its ions in the layers containing the silver halide crystals, based on the unit area of the silver halide photographic material. The binder that is contained in the auxiliary layers of the silver halide photographic material is therefore not taken into account in the calculation of the binder application. The values for the application of binder or silver are given in grams / square meter and, unless stated otherwise, relate to the totality of all layers of the recording material containing silver halide.
Geeignet für das erfindungsgemäße schnellverarbeitbare photographische Silberhalogenid-Aufzeichnungsmaterial ist ein Silberauftrag von mindestens 5g/m². Bevorzugt wird ein Silberauftrag von mindestens 5,2 g/m² verwendet. Besonders bevorzugt ist der Bereich von 5,2 bis 6,0 g/m².A silver coating of at least 5 g / m 2 is suitable for the rapidly processable silver halide photographic material according to the invention. A silver coating of at least 5.2 g / m² is preferably used. The range from 5.2 to 6.0 g / m 2 is particularly preferred.
In einer bevorzugten Ausführung enthält des erfindungsgemäße Aufzeichnungsmaterial auf jeder Seite des Trägers mindestens eine Silberhalogenidemulsionsschicht. Besonders bevorzugt ist dabei ein Aufzeichnungsmaterial, welches auf jeder Seite des Substrates mindestens eine Silberhalogenidemulsionsschicht enthält und die Silberhalogenidemulsionsschichten auf beiden Seiten des Substrats sich weitgehend gleichen.In a preferred embodiment, the recording material according to the invention contains at least one silver halide emulsion layer on each side of the support. Particularly preferred is a recording material which contains at least one silver halide emulsion layer on each side of the substrate and the silver halide emulsion layers on both sides of the substrate are largely the same.
Der Silberauftrag kann beispielsweise über die Silberhalogenidkonzentration in der Silberhalogenidemulsion und die Schichtdicke der Silberhalogenidemulsionsschicht beziehungsweise Silberhalogenidemulsionsschichten eingestellt werden.The silver application can be set, for example, via the silver halide concentration in the silver halide emulsion and the layer thickness of the silver halide emulsion layer or silver halide emulsion layers.
Beispiele für Bindemittel, welche in den verschiedenen Schichten des Silberhalogenid-Aufzeichnungsmaterials Verwendung finden können, sind synthetische Polymere wie Polymerisate oder Copolymerisate aus Vinylalkohol, N-Vinylpyrrolidon, Acrylamid, Acrylsäure, Methacrylsäure, Vinylimidazol, Vinylpyrazol sowie natürliche Polymere wie Casein, Gelatine(sauer oder alkalisch aufgeschlossen, aus Rinderknochen oder Schweinehäuten hergestellt), Cellulose und Cellulosederivate, Alginate, Albumin, Stärke, sowie modifizierte Polymere wie Hydroxyethylcellulose, hydrolysierte Gelatine, chemisch modifizierte Gelatine wie beispielsweise beschrieben in EP-A 03 75 522, chemisch modifizierte und hydrolysierte Gelatine wie beispielsweise beschrieben in DE-B 21 66 605 und U.S. 3,837,861.Examples of binders which can be used in the different layers of the silver halide recording material are synthetic polymers such as polymers or copolymers of vinyl alcohol, N-vinylpyrrolidone, acrylamide, acrylic acid, methacrylic acid, vinylimidazole, vinylpyrazole and natural polymers such as casein, gelatin (acidic or alkaline digested, made from bovine bones or pig skin), cellulose and cellulose derivatives, alginates, albumin, starch, and modified polymers such as hydroxyethyl cellulose, hydrolyzed gelatin, chemically modified gelatin as described for example in EP-A 03 75 522, chemically modified and hydrolyzed gelatin such as, for example described in DE-B 21 66 605 and US 3,837,861.
In den einzelnen Schichten können auch Mischungen von Bindemitteln Verwendung finden. Bevorzugter Hauptbestandteil einer Bindemittelmischung oder alleiniges Bindemittel in den Schichten von photographischen Aufzeichnungsmaterialien kann beispielsweise Gelatine sein.Mixtures of binders can also be used in the individual layers. A preferred main constituent of a binder mixture or the sole binder in the layers of photographic recording materials can be, for example, gelatin.
Als Schutzkolloid für die Silberhalogenidkristalle und Bindemittel in der Emulsionsschicht wird bevorzugt alkalisch aufgeschlossene Rinderknochengelatine verwendet. Diese kann ionenausgetauscht oder auch nicht ionenausgetauscht sein.Alkaline digested bovine bone gelatin is preferably used as the protective colloid for the silver halide crystals and binder in the emulsion layer. This can be ion-exchanged or not ion-exchanged.
Bevorzugt wird in der Silberhalogenidemulsion ein gewichtsmäßiges Verhältnis von Bindemittel oder Bindemittelmischung zu Silber von mindestens 1,1 verwendet. Besonders bevorzugt ist dabei ein Verhältnis zwischen 1,1 und 1,4.A weight ratio of binder or binder mixture to silver of at least 1.1 is preferably used in the silver halide emulsion. A ratio between 1.1 and 1.4 is particularly preferred.
Dieses Verhältnis wird beispielsweise während der Herstellung der Silberhalogenidemulsion über die zuzugebende Menge an Bindemittel relativ zur Silbermenge eingestellt.This ratio is set, for example, during the preparation of the silver halide emulsion via the amount of binder to be added relative to the amount of silver.
Unter Kornvolumen einer Silberhalogenidemulsion wird das mittlere Kolnvolumen verstanden. Damit lassen sich auch unterschiedliche Kornformen wie Sphären, Kuben, Oktaeder oder Platten geeignet miteinander vergleichen.The grain volume of a silver halide emulsion is understood to mean the mean volume of the column. This allows different grain shapes such as spheres, cubes, octahedra or plates to be compared with one another.
Erfindungsgemäß werden im wesentlichen Silberhalogenidemulsionen verwendet, deren mittleres Kornvolumen unter 0,35 µm³ liegt. Der bevorzugter Bereich liegt dabei zwischen 0,05 und 0,35 µm³According to the invention, essentially silver halide emulsions are used, the average grain volume of which is below 0.35 µm³. The preferred range is between 0.05 and 0.35 µm³
Die Korngröße oder das Kornvolumen kann mit Hilfe von verschiedenen Methoden wie beispielsweise mit Hilfe von Elektronenmikroskopaufnahmen der entsprechenden Emulsion oder nach dem in DE 20 25 147 beschriebenen Verfahren bestimmt werden.The grain size or the grain volume can be determined with the aid of various methods, for example with the aid of electron microscope images of the corresponding emulsion or by the method described in DE 20 25 147.
Die Prozesswasseraufnahme PWP eines photographischen Silberhalogenid-Aufzeichnungsmaterials kann beispielsweise nach dem in den Ausführungsbeispielen beschriebenen Verfahren bestimmt werden. Eine weitere Methode ist in der Europäischen Patentschrift EP-A 03 08 193 beschrieben. Erfindungsgemäße Aufzeichnungsmaterialien weisen eine Prozesswasseraufnahme von weniger als 20 g Wasser pro Quadratmeter Aufzeichnungsmaterial auf. Bevorzugt wird jedoch ein Aufzeichnungsmaterial verwendet, welches einen PWP von weniger als 18 g Wasser /m² aufweist.The process water absorption PWP of a photographic silver halide recording material can be determined, for example, by the method described in the exemplary embodiments. Another method is described in European Patent EP-A 03 08 193. Recording materials according to the invention have a process water absorption of less than 20 g of water per square meter of recording material. However, it is preferred to use a recording material which has a PWP of less than 18 g water / m 2.
Die Prozesswasseraufnahme eines photographischen Aufzeichnungsmaterials kann beispielsweise über die zur Härtung der in dem Aufzeichnungsmaterial befindlichen Schichten verwendeten Menge von Härtungsmitteln eingestellt werden. Die dazu erforderliche Härtermittelmenge kann beispielsweise mit Hilfe von Reihenversuchen mit unterschiedlichen Härtermittelmengen ermittelt werden.The process water absorption of a photographic recording material can be adjusted, for example, via the amount of hardening agents used to harden the layers in the recording material. The amount of hardener required for this can be determined, for example, with the aid of series tests with different amounts of hardener.
Die Silberhalogenidkörner in der Silberhalogenidemulsion können eine regelmäßige Kristallform wie Kuben, Oktaeder, Kubooktaeder oder Tetraeder, eine unregelmäßige Form wie Platten oder Sphären oder Mischungen aus mindestens zwei dieser Formen aufweisen. Bevorzugt werden Silberhalogenidemulsionen verwendet, welche im wesentlichen Körner mit einer regelmäßigen Kristallform und/oder sphärenförmige Silberhalogenidkörner enthalten. Besonders bevorzugt sind dabei Silberhalogenidemulsionen welche im wesentlichen sphärenförmige Silberhalogenidkörner enthalten.The silver halide grains in the silver halide emulsion can have a regular crystal shape such as cubes, octahedra, cubo-octahedra or tetrahedron, an irregular shape such as plates or spheres or mixtures of at least two of these shapes. Silver halide emulsions are preferably used which essentially contain grains with a regular crystal shape and / or spherical silver halide grains. Silver halide emulsions which contain essentially spherical silver halide grains are particularly preferred.
Kuben, Oktaeder, Kubooktaeder und Einfachzwillinge mit (111) und/oder (100) Begrenzungsflächen weisen ein durchschnittliches Verhältnis von kleinster zu größter Abmessung (Aspektverhältnis) zwischen 1,0 : 1,1 und zu 2,0 auf und können als angenähert sphärisch betrachtet werden.Cubes, octahedra, cuboctahedra and single twins with (111) and / or (100) boundary surfaces have an average ratio of the smallest to the largest dimension (aspect ratio) between 1.0: 1.1 and 2.0 and can be regarded as approximately spherical become.
Sphärische Silberhalogenidkristalle weisen ein Verhältnis von kleinster zu größter Abmessung zwischen 1,0 : 1,1 und 1,0 : 1,0 auf. Plattenförmigen Silberhalogenidkristallen weisen ein Aspektverhältnis von mindestens 1,0 : 2,0 auf.Spherical silver halide crystals have a ratio of smallest to largest dimension between 1.0: 1.1 and 1.0: 1.0. Plate-shaped silver halide crystals have an aspect ratio of at least 1.0: 2.0.
Das photographische Silberhalogenid-Aufzeichnungsmaterial kann auf beiden Seiten des Substrates neben Emulsionsschichten Hilfsschichten wie beispielsweise haftvermittelnde Schichten, Schutzschichten, Zwischenschichten, Antistatikschichten sowie Farbmittel enthaltende Schichten enthalten.The photographic silver halide recording material can contain auxiliary layers such as, for example, adhesion-promoting layers, protective layers, intermediate layers, antistatic layers and layers containing colorants on both sides of the substrate in addition to emulsion layers.
Als Schutzschicht wird die am weitesten von der Unterlage entfernte, üblicherweise kein Silberhalogenid enthaltende Schicht bezeichnet. Solche Schutzschichten enthalten neben Bindemitteln und oberflächenaktiven Stoffen gegebenenfalls auch andere Stoffe, welche die chemischen, physikalischen und mechanischen Eigenschaften von photographischen Silberhalogenid-Aufzeichnungsmaterialien beeinflussen. Zu diesen Stoffen gehören beispielsweise Gleitmittel, Perfluoralkygruppen enthaltende oberflächenaktive Stoffe, Latizes (polymere organische Teilchen), feinteilige kristalline SiO₂-Dispersionen, Mattierungsmittel (Abstandhalter), Härtungsmittel, antistatisch wirkende Stoffe sowie Konservierungsmittel.The protective layer is the layer which is furthest away from the base and usually does not contain any silver halide. In addition to binders and surface-active substances, such protective layers may also contain other substances which influence the chemical, physical and mechanical properties of photographic silver halide recording materials. These substances include, for example, lubricants, surface-active substances containing perfluoroalkyl groups, latexes (polymeric organic particles), finely divided crystalline SiO 2 dispersions, matting agents (spacers), curing agents, antistatic substances and preservatives.
Der Bindemittelauftrag liegt für Emulsionsschichten üblicherweise zwischen 0,5 g/m² und 10,0 g/m² für Schutzschichten zwischen 0,5 g/m² und 5,0 g/m² und für Zwischenschichten zwischen 0,1 g/m² und 5,5 g/m².The binder application for emulsion layers is usually between 0.5 g / m² and 10.0 g / m² for protective layers between 0.5 g / m² and 5.0 g / m² and for intermediate layers between 0.1 g / m² and 5.5 g / m².
Die photographischen Emulsionen können nach verschiedenen Methoden aus löslichen Silbersalzen und löslichen Halogeniden hergestellt werden.The photographic emulsions can be prepared from soluble silver salts and soluble halides by various methods.
Während der Herstellung und/oder physikalischen Reifung der Silberhalogenidemulsion können Metallionen wie beispielsweise solche von Cadmium, Zink, Thallium, Quecksilber, Iridium, Rhodium sowie Eisen oder deren Komplexe zugegen sein.Metal ions such as cadmium, zinc, thallium, mercury, iridium, rhodium and iron or their complexes may be present during the production and / or physical ripening of the silver halide emulsion.
Die Silberhalogenidemulsion kann Silberhalogenidkristalle bestehend aus Silberbromid, Silberbromojodid, Silberchlorobromojodid oder Silberchlorobromid enthalten. Bevorzugt wird eine Silberhalogenidemulsion verwendet, welche Silberbromojodid mit einem Anteil von maximal 5% Jodid bezogen auf den Halogenidanteil enthält.The silver halide emulsion can contain silver halide crystals consisting of silver bromide, silver bromoiodide, silver chlorobromoiodide or silver chlorobromide. A silver halide emulsion is preferably used which contains silver bromoiodide with a maximum of 5% iodide based on the halide content.
Nach abgeschlossener Kristallbildung oder auch schon zu einem früheren Zeitpunkt werden die löslichen Salze aus der Emulsion entfernt, zum Beispiel durch Nudeln und Waschen, durch Flocken und Waschen, durch Ultrafiltration oder mit Hilfe von Ionenaustauschern.After crystal formation has been completed or at an earlier point in time, the soluble salts are removed from the emulsion, for example by pasta and washing, by flaking and washing, by ultrafiltration or with the aid of ion exchangers.
Die Silberhalogenidemulsion wird im allgemeinen einer chemischen Sensibilisierung unter definierten Bedingungen - pH, pAg, Temperatur, Gelatine-, Silberhalogenid-, und Sensibilisatorkonzentration - bis zum Erreichen des Empfindlichkeits- und Schleieroptimums unterworfen. Bei der chemischen Sensibilisierung können chemische Sensibilisatoren wie beispielsweise aktive Gelatine, Schwefel-, Selen- oder Tellurverbindungen, Salze oder Komplexe von Gold, Platin, Rhodium, Palladium, Iridium, Osmium, Rhenium, Ruthenium alleine oder in Kombination Verwendung finden. Verfahrensweisen sind zum Beispiel bei H. Frieser "Die Grundlagen der Photographischen Prozesse mit Silberhalogeniden" Seite 675-734, Akademische Verlagsgesellschaft (1968) oder in T. H. James, The theory of the photographic process, 4th ed., Macmillan Publishing C., Inc., New York, S. 149-160 und den darin zitierten Publikationen beschrieben.The silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached. In chemical sensitization, chemical sensitizers such as active gelatin, sulfur, selenium or tellurium compounds, salts or complexes of gold, platinum, rhodium, palladium, iridium, osmium, rhenium, ruthenium can be used alone or in combination. Procedures are described, for example, by H. Frieser "The Basics of Photographic Processes with Silver Halides" page 675-734, Akademische Verlagsgesellschaft (1968) or in TH James, The theory of the photographic process, 4th ed., Macmillan Publishing C., Inc. , New York, pp. 149-160 and the publications cited therein.
Zur Herstellung der erfindungsgemäßen photographischen Silberhalogenid-Aufzeichnungsmaterialien können die hydrophile Bindemittel enthaltenden Schichten organische oder anorganische Härtungsmittel enthalten. Die Härtung einer Schicht kann auch bewirkt werden, indem die zu härtende Schicht mit einer Schicht überschichtet wird, die ein diffusionsfähiges Härtungsmittel enthält, wie es beispielsweise in DE-A 38 36 945 beschrieben ist. Das Härtungsmittel kann im Verlauf der Herstellung von Emulsionslösungen und/oder Gießlösung für Hilfsschichten zugesetzt werden. Eine weitere mögliche Zugabeform ist das Injizieren einer Lösung des Härtungsmittels in mindestens eine Emulsions- oder Gießlösung während dessen Transports vom Vorratskessel zur Gießeinrichtung.To produce the photographic silver halide recording materials according to the invention, the layers containing hydrophilic binders can contain organic or inorganic hardening agents. The hardening of a layer can also be effected by covering the layer to be hardened with a layer which contains a diffusible hardening agent, as is described, for example, in DE-A 38 36 945. The curing agent can be added in the course of the preparation of emulsion solutions and / or casting solution for auxiliary layers. Another possible form of addition is to inject a solution of the hardening agent into at least one emulsion or casting solution while it is being transported from the storage kettle to the casting device.
Beispiele für solche in photographischenAufzeichnungsmitteln verwendbaren Härtungsmittel sind Chromsalze wie Chromalaun, Aldehyde wie Formaldehyd, Glyoxal und Glutardialdehyd, N-Methylolverbindungen wie N,N'-Dimethylolharnstoff, reaktive Vinylgruppen tragende Verbindungen wie 1,3-Bis-(vinylsulfonyl)-2-propanol, Bis-(vinylsulfonyl)methylether, N,N',N''-trisacryloylhexahydrotriazin, polymere Härtungsmittel wie beispielsweise in DE-C 32 23 621 beschrieben, 1,3-Bis-carbamoylimidazoliumverbindungen wie in DE-B 41 19 982 beschrieben oder Carbamoylpyrimidiniumverbindungen wie beispielsweise in DE-C 23 17 677 beschrieben.Examples of such hardening agents which can be used in photographic recording media are chromium salts such as chromium alum, aldehydes such as formaldehyde, glyoxal and glutardialdehyde, N-methylol compounds such as N, N'-dimethylolurea, compounds bearing reactive vinyl groups such as 1,3-bis- (vinylsulfonyl) -2-propanol, Bis- (vinylsulfonyl) methyl ether, N, N ', N' '- trisacryloylhexahydrotriazine, polymeric curing agents as described for example in DE-C 32 23 621, 1,3-bis-carbamoylimidazolium compounds as described in DE-B 41 19 982 or carbamoylpyrimidinium compounds as described for example in DE-C 23 17 677.
In der Silberhalogenidemulsion können spektrale Sensibilisatoren wie beispielsweise Cyaninfarbstoffe, Merocyaninfarbstoffe, Hemicyaninfarbstoffe, Styrylfarbstoffe enthalten sein. Es kann ein spektraler Sensibilisator alleine oder eine Kombination verwendet werden.Spectral sensitizers such as cyanine dyes, merocyanine dyes, hemicyanine dyes, styryl dyes can be contained in the silver halide emulsion. A spectral sensitizer alone or a combination can be used.
In der Silberhalogenidemulsion können Stoffe zur Stabilisierung der Emulsion gegen Schleierbildung oder zur Stabilisierung anderer photographischen Eigenschaften wie beispielsweise Benzothiazoliumsalze, Nitroindazole, Nitrobenzimidazole, Mercaptothiazole, Mercaptobenzothiazole, Mercaptobenzimidazole, Mercaptothiadiazole, Chlorobenzimidazole, Bromobenzimidazole, Aminotriazole, Benzotriazole, Nitrobenzotriazole, Mercaptopyrimidine, Mercaptotriazine, Thioketoverbindungen wie zum Beispiel Oxazolinthion, Azaindene wie Triazainen und Tetraazainden wie das besonders bevorzugte 5-Hydroxy-7-methyl-1,3,3a,4,-tetraazainden, und Mercaptotetrazole wie zum Beispiel 1-Phenyl-5-mercaptotetrazol für sich alleine oder in Kombination mit anderen Stoffen dieser Gruppe Verwendung finden.In the silver halide emulsion, substances for stabilizing the emulsion against fog or for stabilizing other photographic properties such as, for example, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazole, chlorobenzimidazole, benzobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidozole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole, bromobenzotrimidazole Example oxazolinthione, azaindenes such as triazaines and tetraazaindens such as the particularly preferred 5-hydroxy-7-methyl-1,3,3a, 4, -tetraazaindene, and mercaptotetrazoles such as 1-phenyl-5-mercaptotetrazole alone or in combination with other substances in this group are used.
In der Silberhalogenidemulsion sowie in den Gemischen zur Herstellung der Hilfsschichten können sich oberflächenaktive Stoffe für verschiedene Zwecke befinden, wie Überzugshilfen, zur Verhinderung der elektrostatischen Aufladung, zur Verbesserung der Gleiteigenschaften, zum Emulgieren der Dispersion, zur Verhinderung der Adhäsion und zur Verbesserung von photographischen Charakteristika (zum Beispiel Entwicklungsbeschleunigung, hoher Kontrast, Sensibilisierung). Neben natürlichen oberflächenaktiven Verbindungen wie beispielsweise Saponin finden hauptsächlich synthetische oberflächenaktive Verbindungen (Tenside) Verwendung: nicht-ionische Tenside welche Oligo- oder Polyoxyalkylengruppen enthalten, Glycerinverbindungen und Glycidolverbindungen, kationische Tenside, zum Beispiel höhere Alkylamine, quartäre Ammoniumsalze, Pyridinverbindungen, und andere heterozyklische Verbindungen, Sulphoniumverbindungen oder Phosphoniumverbindungen, anionische Tenside , enthaltend eine Säuregruppe , zum Beispiel Karbonsäure-, Phosphorsäure-, Schwefelsäureester- oder Phosphorsäureestergruppe, ampholytische Tenside wie zum Beispiel Aminosäure- und Aminosulphonsäureverbindungen sowie Schwefel- und Phosphorsäureester eines Aminoalkohols.In the silver halide emulsion and in the mixtures for producing the auxiliary layers, there can be surface-active substances for various purposes, such as coating aids, to prevent electrostatic charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve photographic characteristics ( e.g. acceleration of development, high contrast, sensitization). In addition to natural surface-active compounds such as saponin, synthetic surface-active compounds (surfactants) are mainly used: non-ionic surfactants which contain oligo- or polyoxyalkylene groups, glycerol compounds and glycidol compounds, cationic surfactants, for example higher alkylamines, quaternary ammonium salts, pyridine compounds, and other heterocyclic compounds, Sulphonium compounds or phosphonium compounds, anionic surfactants containing an acid group, for example carboxylic acid, phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants such as amino acid and aminosulphonic acid compounds and sulfur and phosphoric acid esters of an amino alcohol.
Die verschiedenen Schichten des photographischen Aufzeichnungsmaterials können Filterfarbstoffe wie Oxonolfarbstoffe, Hemioxonolfarbstoffe, Styrylfarbstoffe, Merocyaninfarbstoffe, Anthrachinonfarbstoffe, Cyaninfarbstoffe, Azomethinfarbstoffe, Triarylmethanfarbstoffe, Phtalocyanine und Azofarbstoffe enthalten.The various layers of the photographic material can contain filter dyes such as oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, cyanine dyes, azomethine dyes, triarylmethane dyes, phthalocyanines and azo dyes.
Der Träger des photographischen Aufzeichnungsmaterials kann aus einer transparenten und gegebenenfalls blau eingefärbten Kunststoffolie bestehen, die aus Polyethylenterephthalat, Celluloseacetat, Celluloseacetatbutyrat, Polystyrol, oder Polycarbonat hergestellt wurde.The support of the photographic recording material can consist of a transparent and optionally blue-colored plastic film which has been produced from polyethylene terephthalate, cellulose acetate, cellulose acetate butyrate, polystyrene or polycarbonate.
Die Oberfläche des Träger wird bevorzugt vor einer ersten Beschichtung zur Verbesserung der Adhäsionseigenschaften durch Coronarentladung behandelt.The surface of the carrier is preferably treated by a coronary discharge before a first coating to improve the adhesion properties.
Verschiedene Gießverfahren können zur Herstellung des photographischen Aufzeichnungsmaterials Verwendung finden. Beispiele hierfür sind Vorhanggießen, Kaskadengießen, Tauchgießen, Anspülgießen, Schlitzgießen. Es können gegebenenfalls mehrere Schichten gleichzeitig aufgebracht werden.Various casting methods can be used to make the photographic material. Examples of this are curtain casting, cascade casting, dip casting, wash-on casting, slot casting. If necessary, several layers can be applied simultaneously.
Eine generelle Übersicht über photographische Silberhalogenidemulsionen, deren Herstellung, Zusätze, Verarbeitung und Verwendung ist in Research Disclosure, Vol. 308, Nummer 308119, 1989 sowie in "Ullmann's Encyclopedia of Industrial Chemistry", Band 20A, Seiten 1 bis 159, VCH Verlagsgesellschaft Weinheim 1992 und in den jeweils aufgeführten Zitaten gegeben. Research Disclosure wird von Kenneth Mason Publications Ltd., Dudley Annex, 21a North Street, Elmsworth, Hampshire P010 7DQ, England herausgegeben.A general overview of photographic silver halide emulsions, their preparation, additions, processing and use can be found in Research Disclosure, Vol. 308, number 308119, 1989 and in "Ullmann's Encyclopedia of Industrial Chemistry", volume 20A, pages 1 to 159, VCH Verlagsgesellschaft Weinheim 1992 and given in the quotations listed in each case. Research Disclosure is published by Kenneth Mason Publications Ltd., Dudley Annex, 21a North Street, Elmsworth, Hampshire P010 7DQ, England.
Standardverfahren zur Belichtung und Verarbeitung sowie zur Qualitätssicherung in der radiologischen Praxis sind in "Bildqualität in der Röntgendiagnostik", herausgegeben von H.-S. Stender und F.-E. Stieve, Deutscher Ärzte-Verlag Köln, 1990 beschrieben.Standard procedures for exposure and processing as well as for quality assurance in radiological practice are published in "Image quality in X-ray diagnostics", published by H.-S. Stender and F.-E. Stieve, Deutscher Ärzte-Verlag Cologne, 1990.
Ein weiterer Vorteil des erfindungsgemäßen schnellverarbeitbaren photographischen Aufzeichnungsmaterials besteht in der Eigenschaft, sowohl bei einer Verarbeitungszeit von 90 Sekunden als auch bei einer Verarbeitungszeit von weniger als 60 Sekunden eine vergleichbare Sensitometrie aufzuweisen.Another advantage of the rapidly processable photographic recording material according to the invention is the property of having a comparable sensitometry both with a processing time of 90 seconds and with a processing time of less than 60 seconds.
Das erfindungsgemäße schnellverarbeitbare photographische Silberhalogenid-Aufzeichnungsmaterial weist zudem eine verbesserte visuelle Auflösung, eine verbesserte Bildsilberfarbe, eine besonders gute Naßkratzfestigkeit sowie verbesserte Naßdruckeigenschaften auf.The rapidly processable silver halide photographic material according to the invention also has an improved visual resolution, an improved silver color, a particularly good wet scratch resistance and improved wet printing properties.
Es wurde eine Silberhalogenidemulsion A unter Verwendung von sphärischen Silberbromidjodidkörnern (2% Jodidanteil) mit einem mittleren Kornvolumen von 0,09 µm³ hergestellt, wobei das Verhältnis der gewichtsmäßigen Anteile von Bindemitteln zu Silber 1,4 betrug. Die Emulsion und eine Mischung zur Herstellung einer Schutzschicht wurde gleichmäßig beidseitig auf einer beidseitig mit einer Haftschicht versehenen Polyesterunterlage aufgebracht und getrocknet. Die Mischung zur Herstellung einer Schutzschicht bestand im wesentlichen aus einer wäßrigen Gelatinelösung und enthielt weiterhin Netzmittel und Formaldehyd als Härtungsmittel. Die Schichten auf beiden Seiten einer Filmprobe wiesen jeweils den gleichen Silber- und Bindemittelauftrag auf und wurden jeweils mit der jeweils gleichen Härtermittelmenge gehärtet. Dabei wurde die verwendete Härtungsmittelmenge und der Naßauftrag der beiden Schichten so gewählt, daß die in Tabelle 1 beschriebenen Silberaufträge und Prozesswasseraufnahmewerte PWP der beiden Filmproben A1 und A2 sowie ein Gelatineauftrag der Schutzschicht jeweils pro Seite von 1,2 g/m² erzielt wurden.A silver halide emulsion A was prepared using spherical silver bromide iodide grains (2% iodide content) with an average grain volume of 0.09 µm³, the ratio of the weight proportions of binder to silver being 1.4. The emulsion and a mixture for producing a protective layer were applied uniformly on both sides to a polyester base provided with an adhesive layer on both sides and dried. The mixture for the preparation of a protective layer consisted essentially of an aqueous gelatin solution and also contained wetting agents and formaldehyde as hardening agents. The layers on both sides of a film sample each had the same silver and binder application and were each hardened with the same amount of hardener. The amount of hardener used and the wet application of the two layers were chosen so that the silver applications and process water absorption values PWP of the two film samples A1 and A2 described in Table 1 and a gelatin application of the protective layer of 1.2 g / m 2 each were achieved.
Weiterhin wurde eine Silberhalogenidemulsion B unter Verwendung von sphärischen Silberbromidjodidkörnern (2% Jodidanteil) mit einem mittleren Kornvolumen von 0,22 µm³ hergestellt, wobei das Verhältnis der gewichtsmäßigen Anteile von Bindemitteln zu Silber 1,15 betrug. Die Emulsion wurde zusammen mit einer Mischung zur Herstellung einer über der Emulsionsschicht befindlichen, im wesentlichen Gelatine enthaltenden Schutzschicht und unter Verwendung von Formaldehyd als Härtungsmittel zu den Filmproben B1 und B2 so wie für die Filmproben A1 und A2 beschrieben aufgebracht und getrocknet, so daß die in Tabelle 1 beschriebenen Silberaufträge und Prozesswasseraufnahmewerte PWP erzielt wurden und der Gelatineauftrag der Schutzschicht jeweils pro Seite 1,36 g/m² betrug.Furthermore, a silver halide emulsion B was prepared using spherical silver bromide iodide grains (2% iodide content) with an average grain volume of 0.22 μm³, the ratio of the weight proportions of binders to silver being 1.15. The emulsion was applied to a film B1 and B2 as described for film samples A1 and A2 together with a mixture for producing a protective layer located above the emulsion layer, essentially containing gelatin, and using formaldehyde as a hardening agent and dried so that the in Silver applications and process water absorption values PWP described in Table 1 were achieved and the gelatin application of the protective layer was 1.36 g / m² on each side.
Das mittlere Kornvolumen wurde jeweils mit dem in der deutschen Patentschrift DE 20 25 147 beschriebenen Verfahren bestimmt.The mean grain volume was determined in each case using the method described in German patent DE 20 25 147.
Die Prozesswasseraufnahmewerte PWP der Filmproben wurde bestimmt, indem ein Blatt des zu untersuchenden Aufzeichnungsmaterials ohne Gießränder oder unbegossenen Stellen zuerst vollflächig mit einer dem Sättigungsbereich der Schwärzungskurve entsprechenden Belichtung exponiert, mit einer Rollenentwicklungsmaschine Kodak Prozessor M8, bei der die hintere Abdeckung und das obere Umlenkwelle hinter der Wässerung entfernt wurde, beschickt mit einer Entwicklerlösung und einem Fixierbad folgender Zusammensetzung:
im RP-Prozess (90 Sekunden Durchlaufzeit; Entwicklerbadtemperatur 34°) verarbeitet und direkt nach der Wässerung entnommen, im nassen Zustand gewogen, getrocknet und im trockenen Zustand erneut gewogen wurde. Die Gewichtsdifferenz, dividiert durch die Fläche ist als Prozesswasseraufnahme PWP des Aufzeichnungsmaterials in Gramm Wasser pro Quadratmeter Film angegeben.
Die sensitometrischen Daten für die Empfindlichkeit, maximale Bildschwärze (D-Max) und Mittelgradient wurden durch standardisierte Belichtung und Verarbeitung erhalten und sind in den Tabellen 2 und 3 dargestellt. Zahlenwerte in Klammern bedeuten dabei daß der Film die Filmentwicklungsmaschine nicht hinreichend trocken verlassen hat und damit die gemessenen Daten für einen direkten Vergleich nicht geeignet sind.
Vergleich wichtiger sensitometrischen Daten bei Verarbeitungszyklen von 90 und 53 Sekunden der zwei Filmproben A1 und A2.
Vergleich wichtiger sensitometrischen Daten bei Verarbeitungszyklen von 90 und 53 Sekunden der beiden Filmproben B1 und B2.Comparison of important sensitometric data with processing cycles of 90 and 53 seconds of the two film samples B1 and B2.
Die Filmproben A2 und B2 verlassen die Filmentwicklungsmaschine nach einer Verarbeitungszeit von 53 Sekunden im Gegensatz zu den Filmproben A1 und B1 trocken und weisen jeweils eine für die radiologische Verwendung geeignete Sensitometrie auf. Nach der Verarbeitung in den zwei verwendeten Verarbeitungszeiten weisen die beiden Filmproben A2 und B2 jeweils vergleichbare sensitometrische Werte für Empfindlichkeit, maximalen Bildschwärze und Gradation auf. Beide Filmproben A2 und B2 weisen zudem verglichen mit den Filmproben A1 beziehungsweise B1 eine verbesserte Naßdruckeigenschaft, eine verbesserte, also mehr in das Neutrale gehende Bildsilberfarbe, verbesserte Drucksensibilisierungseigenschaften, ein verbessertes Rauschen und eine verbesserte Bildschärfe auf.In contrast to film samples A1 and B1, film samples A2 and B2 leave the film processor after a processing time of 53 seconds and each have a sensitometry suitable for radiological use. After processing in the two processing times used, the two film samples A2 and B2 each have comparable sensitometric values for sensitivity, maximum image blackness and gradation. Both film samples A2 and B2 also have, compared to film samples A1 and B1, an improved wet printing property, an improved image silver color, that is to say more neutral, improved pressure sensitization properties, improved noise and improved image sharpness.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4435876A DE4435876A1 (en) | 1994-10-07 | 1994-10-07 | Rapidly processable photographic material for medical radiography |
| DE4435876 | 1994-10-07 |
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| Publication Number | Publication Date |
|---|---|
| EP0706084A1 true EP0706084A1 (en) | 1996-04-10 |
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ID=6530205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95115494A Withdrawn EP0706084A1 (en) | 1994-10-07 | 1995-09-30 | Rapid processable photographic recording material for medical radiography |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5576155A (en) |
| EP (1) | EP0706084A1 (en) |
| JP (1) | JPH08211520A (en) |
| DE (1) | DE4435876A1 (en) |
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| US5994039A (en) * | 1998-08-24 | 1999-11-30 | Eastman Kodak Company | Black-and-white photographic developing composition and a method for its use |
| US6573036B2 (en) * | 2000-04-10 | 2003-06-03 | Afga-Gevaert | Single-side coated silver halide photographic film material having reduced tendency to curl |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0308193A2 (en) * | 1987-09-14 | 1989-03-22 | Konica Corporation | Silver halide photographic light-sensitive material |
| EP0559061A2 (en) * | 1992-03-06 | 1993-09-08 | Minnesota Mining And Manufacturing Company | Method of processing a silver halide radiographic element |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3880665A (en) * | 1972-05-24 | 1975-04-29 | Agfa Gevaert Ag | Hardening with a heterocyclic carbamoyl ammonium compound of a photographic material containing a silver halide layer |
| JPS57212427A (en) * | 1981-06-24 | 1982-12-27 | Fuji Photo Film Co Ltd | Silver halide photosensitive material |
| JP2530145B2 (en) * | 1986-03-13 | 1996-09-04 | コニカ株式会社 | Silver halide photographic material and processing method thereof |
| EP0259855A3 (en) * | 1986-09-10 | 1990-04-18 | Fuji Photo Film Co., Ltd. | Method of developing silver halide photographic materials |
| USH674H (en) * | 1986-11-04 | 1989-09-05 | Konica Corporation | Silver halide photographic light-sensitive material capable of super-rapid processing |
| DE3789208T2 (en) * | 1986-12-08 | 1994-09-01 | Konishiroku Photo Ind | Silver halide photographic light-sensitive material for quick treatment and its treatment. |
| US5081007A (en) * | 1987-09-15 | 1992-01-14 | Konica Corporation | Method for processing a silver halide light-sensitive photographic material and an automatic processor therefor |
| JPH01213642A (en) * | 1988-02-20 | 1989-08-28 | Konica Corp | Method for processing silver halide photographic sensitive material |
| FR2640634B1 (en) * | 1988-12-16 | 1991-04-05 | Sanofi Sa | FLUORINATED GELATIN AND PROCESS FOR OBTAINING IT |
| JPH0466934A (en) * | 1990-07-04 | 1992-03-03 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
| US5310636A (en) * | 1990-10-31 | 1994-05-10 | Fuji Photo Film Co., Ltd. | Silver halide photographic material and the development processing method |
-
1994
- 1994-10-07 DE DE4435876A patent/DE4435876A1/en not_active Withdrawn
-
1995
- 1995-09-27 US US08/534,363 patent/US5576155A/en not_active Expired - Fee Related
- 1995-09-30 EP EP95115494A patent/EP0706084A1/en not_active Withdrawn
- 1995-10-06 JP JP7294637A patent/JPH08211520A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0308193A2 (en) * | 1987-09-14 | 1989-03-22 | Konica Corporation | Silver halide photographic light-sensitive material |
| EP0559061A2 (en) * | 1992-03-06 | 1993-09-08 | Minnesota Mining And Manufacturing Company | Method of processing a silver halide radiographic element |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4435876A1 (en) | 1996-04-11 |
| JPH08211520A (en) | 1996-08-20 |
| US5576155A (en) | 1996-11-19 |
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