EP0603686A1 - Method for preparation of a matte light sensitive silver halide recording material - Google Patents
Method for preparation of a matte light sensitive silver halide recording material Download PDFInfo
- Publication number
- EP0603686A1 EP0603686A1 EP93120008A EP93120008A EP0603686A1 EP 0603686 A1 EP0603686 A1 EP 0603686A1 EP 93120008 A EP93120008 A EP 93120008A EP 93120008 A EP93120008 A EP 93120008A EP 0603686 A1 EP0603686 A1 EP 0603686A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver halide
- solid particles
- light
- particles
- recording material
- 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- Withdrawn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
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
-
- 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
- G03C1/32—Matting agents
-
- 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
- Y10S430/151—Matting or other surface reflectivity altering material
-
- 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
- Y10S430/162—Protective or antiabrasion layer
Definitions
- the invention relates to a method for producing a matted light-sensitive silver halide recording material, in which the particles of the matting agent are light-sensitive and are blackened during image recording.
- Photosensitive silver halide recording materials are often provided with a matt surface.
- the roughness of the surface is said to reduce the tendency to electrostatic charge and the susceptibility to scratching by dust grains, and to facilitate the extraction of air between the original and the recording material when reproducing.
- the undesirable starry sky effect can occur.
- the image areas show pinholes like lightening. These are caused by particularly large particles or by agglomerates of the generally polydisperse, finely divided solid, which laterally displace the silver halide emulsion during drying.
- DE 37 00 551-C2 describes a light-sensitive silver halide recording material which contains a light-sensitive matting agent, the particles of which have a size of 1 to 30 ⁇ m, are blackened after exposure and processing of the material and therefore also when they have displaced the silver halide emulsion , cause no brightening.
- the particles of this matting agent contain a chemically and possibly spectrally sensitized silver halide, a binder and a finely divided solid, the particle size of which is significantly below that of the matting agent and which has no permanent intrinsic color.
- the preparation of the light-sensitive matting agents described in the prior art requires several steps.
- part of the silver halide emulsion intended for the light-sensitive layer of the recording material is mixed with a hardening agent and the finely divided solid and then spray-dried.
- the powder thus obtained is then classified if necessary and finally added to one of the coating solutions in the preparation of the light-sensitive material.
- some of these steps which are unusual for the photographic industry, must be carried out under dark room conditions.
- the object of the invention is therefore to provide a process for the production of matted light-sensitive silver halide recording materials which is considerably simplified compared to the prior art.
- the silver halide can be precipitated by known methods, as described, for example, in Research Disclosure 308 119 (December 1989), Chapter I.
- the single-jet or the double-jet method possibly with regulation of the silver ion concentration, can be used.
- Starting solutions are both the solutions fed to the precipitation vessel during the precipitation and a solution which may be presented in the precipitation vessel before the beginning of the precipitation.
- the starting solutions contain either a water-soluble silver salt, usually silver nitrate, or one or more water-soluble halides.
- the hydrophilic colloid, usually gelatin, required to stabilize the silver halide crystal dispersion can be added to one or more of the starting solutions.
- the particle size of the water-insoluble solid is approximately the same as that of the light-sensitive matting agent contained in the finished recording material.
- the light-sensitive matting agent particles are produced during the precipitation of the silver halide for the light-sensitive silver halide emulsion layers of the recording material and remain in the emulsions.
- the particles of the solid and of the light-sensitive matting agent are therefore preferably at least as large as the total thickness of all layers applied to the side of the layer support carrying the light-sensitive layer after drying. The practical range is between 1 and 30 ⁇ m.
- a particularly preferred range of particle size for the water-insoluble solid is between 3 and 15 ⁇ m.
- Particle size is intended to mean the number average of the diameter of spheres with the same volume as the particles.
- a solid with a monodisperse particle size distribution is particularly preferred.
- Monodisperse here means that the quotient between the particle diameter at the 75 percent point and that at the 25 percent point of the cumulative frequency curve is at most 1.5.
- Particles with a rough surface and porous particles are preferably used.
- the surface roughness can be generated, for example, by etching.
- Porous solid particles are commercially available, for example, for purposes of chromatography or as adsorbents, which require a large inner surface.
- a preferred water-insoluble solid is silica. This is available in porous form with a wide variety of dimensions, for example in the form of dried precipitated silicas.
- the solid particles are added to the starting solutions before the beginning of the precipitation. It is advantageous to expose the suspensions to an ultrasound field before use. This avoids the formation of agglomerates and dissolves existing ones.
- a wetting agent in particular of the nonionic or of the anionic type, is particularly preferably added to the suspension. Examples include nonyl or octylphenol ethoxylates with 10 to 20 ethylene oxide units per molecule, sodium lauryl sulfate, sulfonates of bis-ethoxyalkylphenols.
- the emulsions prepared according to the invention are freed from soluble salts in the customary manner, for example by flocculation or reverse osmosis. They will also be in the usual way chemically and optionally also optically sensitized, whereby further gelatin can also be added at any time. Then customary stabilizers, coating aids and, if appropriate, further additives for adjusting certain properties of the recording material are added. Surprisingly, the process steps required to prepare the ready-to-pour emulsion are not hindered by the presence of the solid.
- the invention finds application in the production of light-sensitive recording materials with silver halides, in particular for use in reproduction technology and in medical diagnostics.
- the flock emulsion was redispersed with a further 45 g of gelatin per mole of silver halide and subjected to chemical ripening with thiosulfate and gold salt for optimum sensitivity. Finally, the emulsion was made ready for pouring by adding conventional stabilizers and coating aids and an optical sensitizer for the green spectral range.
- the emulsion was applied together with an aqueous gelatin pouring solution onto a layer carrier made of polyethylene terephthalate provided with an adhesive layer.
- the thickness of the dry layers was 4 ⁇ m for the emulsion layer and 1 ⁇ m for the pouring layer. That so produced recording material is referred to as sample A.
- Example B a material (sample B) was produced in which, instead of the porous silicon dioxide powder, a powder of a dewatered precipitated silica with a particle size of 4.6 ⁇ m was added to the silver nitrate solution before the precipitation.
- sample C For comparison (sample C), a material was produced in the same way as sample A, but in which no solid was added to the starting solutions for the precipitation. Instead, the silica powder used for Sample A was dispersed in the overmolding solution as the matting agent.
- the recording materials were exposed over the entire area with an exposure corresponding to the saturation range of the density curve and processed with a roll developing machine. While sample C showed a pronounced starry sky effect, samples A and B were free from this error.
- the optical density measured with an aperture of 3 mm in diameter was 0.6 greater in samples A and B than in sample C.
- gelatin-containing layers were detached from further samples of the unprocessed materials with a proteolytic enzyme.
- the matting agent particles settled and could be separated, washed and prepared for scanning electron microscopy.
- Particles were covered with cubic silver halide microcrystals.
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung eines mattierten lichtempfindlichen Silberhalogenid-Aufzeichnungsmaterials, bei dem die Teilchen des Mattierungsmittels lichtempfindlich sind und bei der Bildaufzeichnung geschwärzt werden.The invention relates to a method for producing a matted light-sensitive silver halide recording material, in which the particles of the matting agent are light-sensitive and are blackened during image recording.
Lichtempfindliche Silberhalogenid-Aufzeichnungsmaterialien werden häufig mit einer matten Oberfläche ausgerüstet. Die Rauhigkeit der Oberfläche soll die Neigung zu elektrostatischer Aufladung und die Anfälligkeit gegenüber Verkratzen durch Staubkörner vermindern sowie beim reproduktionstechnischen Kopieren das Absaugen der Luft zwischen Vorlage und Aufzeichnungsmaterial erleichtern.Photosensitive silver halide recording materials are often provided with a matt surface. The roughness of the surface is said to reduce the tendency to electrostatic charge and the susceptibility to scratching by dust grains, and to facilitate the extraction of air between the original and the recording material when reproducing.
Die praktisch wichtigste Maßnahme hierzu ist die Zugabe von feinteiligen Feststoffen zu den Beschichtungslösungen.The most important practical measure for this is the addition of finely divided solids to the coating solutions.
Insbesondere wenn die Schicht, welche die Feststoffteilchen enthält, gleichzeitig mit der Silberhalogenidemulsionsschicht auf der gleichen Seite des Schichtträgers aufgetragen und getrocknet wird, kann der unerwünschte Sternhimmeleffekt auftreten. Dabei zeigen die Bildstellen nach Belichtung und Verarbeitung nadelstichartige Aufhellungen. Diese werden durch besonders große Teilchen oder durch Agglomerate des in der Regel polydispersen feinteiligen Feststoffes hervorgerufen, welche beim Trocknen die Silberhalogenidemulsion seitlich verdrängen.In particular, if the layer containing the solid particles is applied and dried simultaneously with the silver halide emulsion layer on the same side of the support, the undesirable starry sky effect can occur. After exposure and processing, the image areas show pinholes like lightening. These are caused by particularly large particles or by agglomerates of the generally polydisperse, finely divided solid, which laterally displace the silver halide emulsion during drying.
Die DE 37 00 551-C2 beschreibt ein lichtempfindliches Silberhalogenid-Aufzeichnungsmaterial, das ein lichtempfindliches Mattierungsmittel enthält, dessen Teilchen eine Größe von 1 bis 30 µm haben, nach Belichtung und Verarbeitung des Materials geschwärzt sind und deshalb auch dann, wenn sie die Silberhalogenidemulsion verdrängt haben, keine Aufhellungen hervorrufen. Die Teilchen dieses Mattierungsmittels enthalten ein chemisch und ggf. spektral sensibilisiertes Silberhalogenid, ein Bindemittel sowie einen feinteiligen Feststoff, dessen Teilchengröße deutlich unter der des Mattierungsmittels liegt und der keine permanente Eigenfärbung besitzt.DE 37 00 551-C2 describes a light-sensitive silver halide recording material which contains a light-sensitive matting agent, the particles of which have a size of 1 to 30 μm, are blackened after exposure and processing of the material and therefore also when they have displaced the silver halide emulsion , cause no brightening. The particles of this matting agent contain a chemically and possibly spectrally sensitized silver halide, a binder and a finely divided solid, the particle size of which is significantly below that of the matting agent and which has no permanent intrinsic color.
Die Herstellung der im Stand der Technik beschriebenen lichtempfindlichen Mattierungsmittel erfordert mehrere Arbeitsschritte. Im einfachsten Falle wird ein Teil der für die lichtempfindliche Schicht des Aufzeichnungsmaterials bestimmten Silberhalogenidemulsion mit einem Härtemittel und dem feinteiligen Feststoff versetzt und danach sprühgetrocknet. Das so erhaltene Pulver wird dann erforderlichenfalls klassiert und schließlich bei der Herstellung des lichtempfindlichen Materials einer der Beschichtungslösungen zugesetzt. Selbstverständlich müssen diese teilweise für die photographische Industrie unüblichen Arbeitsschritte unter Dunkelraumbedingungen durchgeführt werden.The preparation of the light-sensitive matting agents described in the prior art requires several steps. In the simplest case, part of the silver halide emulsion intended for the light-sensitive layer of the recording material is mixed with a hardening agent and the finely divided solid and then spray-dried. The powder thus obtained is then classified if necessary and finally added to one of the coating solutions in the preparation of the light-sensitive material. Of course, some of these steps, which are unusual for the photographic industry, must be carried out under dark room conditions.
Die Erfindung stellt sich daher die Aufgabe, ein Verfahren für die Herstellung mattierter lichtempfindlicher Silberhalogenid-Aufzeichnungsmaterialien anzugeben, welches gegenüber dem Stand der Technik wesentlich vereinfacht ist.The object of the invention is therefore to provide a process for the production of matted light-sensitive silver halide recording materials which is considerably simplified compared to the prior art.
Diese Aufgabe wird durch ein Verfahren nach dem Hauptanspruch gelöst.This object is achieved by a method according to the main claim.
Die Fällung des Silberhalogenids kann nach bekannten Methoden erfolgen, wie sie beispielsweise in der Research Disclosure 308 119 (Dezember 1989), Kapitel I, beschrieben sind. Insbesondere kann das Einstrahl- oder das Doppelstrahlverfahren, ggf. mit Regelung der Silberionenkonzentration, angewendet werden.The silver halide can be precipitated by known methods, as described, for example, in Research Disclosure 308 119 (December 1989), Chapter I. In particular, the single-jet or the double-jet method, possibly with regulation of the silver ion concentration, can be used.
Ausgangslösungen sind sowohl die bei der Fällung dem Fällungsgefäß zugeführten Lösungen als auch eine gegebenenfalls vor Beginn der Fällung im Fällungsgefäß vorgelegte Lösung. Die Ausgangslösungen enthalten entweder ein wasserlösliches Silbersalz, gewöhnlich Silbernitrat, oder ein oder mehrere wasserlösliche Halogenide. Das zur Stabilisierung der Silberhalogenid-Kristalldispersion notwendige hydrophile Kolloid, gewöhnlich Gelatine, kann einer oder mehreren der Ausgangslösungen zugesetzt werden.Starting solutions are both the solutions fed to the precipitation vessel during the precipitation and a solution which may be presented in the precipitation vessel before the beginning of the precipitation. The starting solutions contain either a water-soluble silver salt, usually silver nitrate, or one or more water-soluble halides. The hydrophilic colloid, usually gelatin, required to stabilize the silver halide crystal dispersion can be added to one or more of the starting solutions.
Die Teilchengröße des wasserunlöslichen Feststoffs ist annähernd gleich der des im fertigen Aufzeichnungsmaterial enthaltenen lichtempfindlichen Mattierungsmittels. Beim erfindungsgemäßen Verfahren werden die lichtempfindlichen Mattierungsmittelteilchen während der Fällung des Silberhalogenids für die lichtempfindlichen Silberhalogenid-Emulsionsschichten des Aufzeichnungsmaterials erzeugt und verbleiben in den Emulsionen. Die Teilchen des Feststoffs und des lichtempfindlichen Mattierungsmittels sind daher bevorzugt mindestens so groß wie die Gesamtdicke aller auf der die lichtempfindliche Schicht tragenden Seite des Schichtträgers aufgetragenen Schichten nach der Trocknung. Der praktisch brauchbare Bereich liegt zwischen 1 und 30 µm.The particle size of the water-insoluble solid is approximately the same as that of the light-sensitive matting agent contained in the finished recording material. In the method according to the invention, the light-sensitive matting agent particles are produced during the precipitation of the silver halide for the light-sensitive silver halide emulsion layers of the recording material and remain in the emulsions. The particles of the solid and of the light-sensitive matting agent are therefore preferably at least as large as the total thickness of all layers applied to the side of the layer support carrying the light-sensitive layer after drying. The practical range is between 1 and 30 µm.
Ein besonders bevorzugter Bereich der Teilchengröße für den wasserunlöslichen Feststoff liegt zwischen 3 und 15 µm.A particularly preferred range of particle size for the water-insoluble solid is between 3 and 15 μm.
Der Begriff 
Besonders bevorzugt ist ein Feststoff mit einer monodispersen Teilchengrößenverteilung. Monodispers bedeutet hier, daß der Quotient zwischen dem Teilchendurchmesser beim 75-Prozent-Punkt und dem beim 25-Prozent-Punkt der Summenhäufigkeitskurve höchstens 1,5 beträgt.A solid with a monodisperse particle size distribution is particularly preferred. Monodisperse here means that the quotient between the particle diameter at the 75 percent point and that at the 25 percent point of the cumulative frequency curve is at most 1.5.
Man kann annehmen, daß die Feststoffteilchen infolge ihrer Anwesenheit während der Fällung Silberhalogenid-Mikrokristalle an ihrer Oberfläche bzw. in vorhandenen Poren binden. Hierdurch erhalten sie die Eigenschaft eines lichtempfindlichen Mattierungsmittels.It can be assumed that the solid particles, due to their presence during the precipitation, bind silver halide microcrystals to their surface or in existing pores. This gives them the property of a light-sensitive matting agent.
Bevorzugt verwendet man Teilchen mit einer rauhen Oberfläche und poröse Teilchen. Die Oberflächenrauhigkeit kann beispielsweise durch Anätzen erzeugt werden. Poröse Feststoffteilchen sind beispielsweise für Zwecke der Chromatographie oder als Adsorbentien, bei denen es auf eine große innere Oberfläche ankommt, handelsüblich.Particles with a rough surface and porous particles are preferably used. The surface roughness can be generated, for example, by etching. Porous solid particles are commercially available, for example, for purposes of chromatography or as adsorbents, which require a large inner surface.
Ein bevorzugter wasserunlöslicher Feststoff ist Siliciumdioxid. Dieses steht in poröser Form mit verschiedensten Abmessungen beispielsweise in Form von getrockneten Fällungskieselsäuren zur Verfügung.A preferred water-insoluble solid is silica. This is available in porous form with a wide variety of dimensions, for example in the form of dried precipitated silicas.
Die Feststoffteilchen werden den Ausgangslösungen vor dem Beginn der Fällung zugesetzt. Es ist vorteilhaft, die Suspensionen vor der Verwendung einem Ultraschallfeld auszusetzen. Dadurch wird die Bildung von Agglomeraten vermieden und bestehende aufgelöst. Besonders bevorzugt wird der Suspension noch ein Netzmittel, insbesondere vom nichtionischen oder vom anionischen Typ, zugesetzt. Beispiele dafür sind Nonyl- oder Octylphenolethoxylate mit 10 bis 20 Ethylenoxideinheiten je Molekül, Natriumlaurylsulfat, Sulfonate von Bis-ethoxyalkylphenolen.The solid particles are added to the starting solutions before the beginning of the precipitation. It is advantageous to expose the suspensions to an ultrasound field before use. This avoids the formation of agglomerates and dissolves existing ones. A wetting agent, in particular of the nonionic or of the anionic type, is particularly preferably added to the suspension. Examples include nonyl or octylphenol ethoxylates with 10 to 20 ethylene oxide units per molecule, sodium lauryl sulfate, sulfonates of bis-ethoxyalkylphenols.
Nach der Fällung und ggf. physikalischen Reifung werden die erfindungsgemäß hergestellten Emulsionen auf übliche Weise von löslichen Salzen befreit, beispielsweise durch Flockung oder Umkehrosmose. Ebenfalls auf übliche Art werden sie dann chemisch und ggf. auch optisch sensibilisiert, wobei jederzeit auch noch weitere Gelatine zugefügt werden kann. Danach werden übliche Stabilisatoren, Beschichtungshilfsmittel und ggf. weitere Zusätze zur Einstellung bestimmter Eigenschaften des Aufzeichnungsmaterials zugesetzt. Überraschenderweise werden die zur Herstellung der gießfertigen Emulsion notwendigen Verfahrensschritte durch die Anwesenheit des Feststoffes nicht behindert.After the precipitation and, if appropriate, physical ripening, the emulsions prepared according to the invention are freed from soluble salts in the customary manner, for example by flocculation or reverse osmosis. They will also be in the usual way chemically and optionally also optically sensitized, whereby further gelatin can also be added at any time. Then customary stabilizers, coating aids and, if appropriate, further additives for adjusting certain properties of the recording material are added. Surprisingly, the process steps required to prepare the ready-to-pour emulsion are not hindered by the presence of the solid.
Die Erfindung findet Anwendung bei der Herstellung von lichtempfindlichen Aufzeichnungsmaterialien mit Silberhalogeniden, insbesondere zur Anwendung in der Reproduktionstechnik und in der medizinischen Diagnostik.The invention finds application in the production of light-sensitive recording materials with silver halides, in particular for use in reproduction technology and in medical diagnostics.
In eine Lösung von 1784 g Silbernitrat in 3150 g Wasser wurden 1,5 g eines Pulvers von porösem Siliciumdioxid mit einer Teilchengröße von 7 µm und einer mittleren Porenweite von 0,4 µm eingerührt. Die Suspension wurde 5 min lang einem Ultraschallfeld ausgesetzt und in einem pAg-geregelten Doppelstrahl-Einlaufverfahren zur Herstellung einer Silberchlorobromidemulsion (30 Molprozent Bromid) mit kubischen Mikrokristallen von 0,35 µm Kantenlänge verwendet. Die Emulsion enthielt 16 g Gelatine je mol Silberhalogenid und wurde im Flockverfahren von löslichen Salzen befreit. Die Flockemulsion wurde mit weiteren 45 g Gelatine je mol Silberhalogenid redispergiert und einer chemischen Reifung mit Thiosulfat und Goldsalz zur optimalen Empfindlichkeit unterworfen. Schließlich wurde die Emulsion noch durch Zusatz üblicher Stabilisatoren und Beschichtungshilfsmittel sowie eines optischen Sensibilisators für den grünen Spektralbereich gießfertig gemacht.1.5 g of a powder of porous silicon dioxide with a particle size of 7 μm and an average pore size of 0.4 μm were stirred into a solution of 1784 g of silver nitrate in 3150 g of water. The suspension was exposed to an ultrasonic field for 5 minutes and used in a pAg-controlled double-jet enema process to produce a silver chlorobromide emulsion (30 mole percent bromide) with cubic microcrystals with an edge length of 0.35 μm. The emulsion contained 16 g of gelatin per mole of silver halide and was freed from soluble salts by the flock process. The flock emulsion was redispersed with a further 45 g of gelatin per mole of silver halide and subjected to chemical ripening with thiosulfate and gold salt for optimum sensitivity. Finally, the emulsion was made ready for pouring by adding conventional stabilizers and coating aids and an optical sensitizer for the green spectral range.
Die Emulsion wurde gemeinsam mit einer wäßrigen Gelatine-Übergußlösung auf einen mit einer Haftschicht versehenen Schichtträger aus Polyethylenterephthalat aufgetragen. Die Dicke der trockenen Schichten betrug 4 µm für die Emulsionsschicht und 1 µm für die Übergußschicht. Das so hergestellte Aufzeichnungsmaterial wird als Probe A bezeichnet.The emulsion was applied together with an aqueous gelatin pouring solution onto a layer carrier made of polyethylene terephthalate provided with an adhesive layer. The thickness of the dry layers was 4 µm for the emulsion layer and 1 µm for the pouring layer. That so produced recording material is referred to as sample A.
In gleicher Weise wurde ein Material (Probe B) hergestellt, bei dem anstelle des porösen Siliciumdioxidpulvers der Silbernitratlösung vor der Fällung ein Pulver aus einer entwässerten Fällungskieselsäure mit einer Teilchengröße von 4,6 µm zugesetzt wurde.In the same way, a material (sample B) was produced in which, instead of the porous silicon dioxide powder, a powder of a dewatered precipitated silica with a particle size of 4.6 μm was added to the silver nitrate solution before the precipitation.
Zum Vergleich (Probe C) wurde ein Material in sonst gleicher Weise wie Probe A hergestellt, bei dem jedoch den Ausgangslösungen für die Fällung kein Feststoff zugesetzt wurde. Statt dessen wurde als Mattierungsmittel das für Probe A verwendete Siliciumdioxidpulver in der Übergußlösung dispergiert.For comparison (sample C), a material was produced in the same way as sample A, but in which no solid was added to the starting solutions for the precipitation. Instead, the silica powder used for Sample A was dispersed in the overmolding solution as the matting agent.
Die Aufzeichnungsmaterialien wurden vollflächig mit einer dem Sättigungsbereich der Schwärzungskurve entsprechenden Belichtung exponiert und mit einer Rollenentwicklungsmaschine verarbeitet. Während Probe C einen ausgeprägten Sternhimmeleffekt zeigte, waren die Proben A und B frei von diesem Fehler. Die mit einer Blende von 3 mm Durchmesser gemessene optische Dichte war bei den Proben A und B um 0,6 größer als bei Probe C.The recording materials were exposed over the entire area with an exposure corresponding to the saturation range of the density curve and processed with a roll developing machine. While sample C showed a pronounced starry sky effect, samples A and B were free from this error. The optical density measured with an aperture of 3 mm in diameter was 0.6 greater in samples A and B than in sample C.
Lichtmikroskopische Untersuchung der unverarbeiteten Materialien zeigte bei allen drei Proben Mattierungsmittelteilchen, die aus der Übergußschicht herausragten. Bei den Proben A und B waren diese nach der Belichtung und Entwicklung geschwärzt und lichtundurchlässig; bei der Probe C erschienen sie im durchfallenden Licht hell.Light microscopic examination of the unprocessed materials showed matting agent particles protruding from the pouring layer in all three samples. In samples A and B, after exposure and development, these were blackened and opaque; in sample C they appeared bright in the transmitted light.
Von weiteren Proben der unverarbeiteten Materialien wurden die gelatinehaltigen Schichten mit einem proteolytischen Enzym gelöst. Beim Stehen der Lösungen setzten sich die Mattierungsmittelteilchen ab und konnten abgetrennt, gewaschen und für die rasterelektronenmikroskopische Untersuchung vorbereitet werden. Bei den aus den Proben A und B isolierten Teilchen war die Oberfläche mit kubischen Mikrokristallen aus Silberhalogenid bedeckt.The gelatin-containing layers were detached from further samples of the unprocessed materials with a proteolytic enzyme. When the solutions stood, the matting agent particles settled and could be separated, washed and prepared for scanning electron microscopy. For those isolated from samples A and B. Particles were covered with cubic silver halide microcrystals.
Claims (9)
dadurch gekennzeichnet, daß
man Teilchen eines wasserunlöslichen Feststoffes von zumindest einer der Ausgangslösungen bei der Fällung des Silberhalogenids zusetzt.A process for producing a matted silver halide light-sensitive material which contains a light-sensitive matting agent,
characterized in that
particles of a water-insoluble solid from at least one of the starting solutions are added during the precipitation of the silver halide.
dadurch gekennzeichnet, daß
die Feststoffteilchen eine Teilchengröße zwischen 1 und 30 µm haben.Method according to claim 1,
characterized in that
the solid particles have a particle size between 1 and 30 microns.
dadurch gekennzeichnet, daß
die Feststoffteilchen eine Teilchengröße zwischen 3 und 15 µm haben.The method of claim 1 or 2,
characterized in that
the solid particles have a particle size between 3 and 15 microns.
dadurch gekennzeichnet, daß
die Feststoffteilchen monodispers sind.Method according to claim 1,
characterized in that
the solid particles are monodisperse.
dadurch gekennzeichnet, daß
die Feststoffteilchen eine rauhe Oberfläche und/oder eine poröse Struktur besitzen.Method according to claim 3 or 4,
characterized in that
the solid particles have a rough surface and / or a porous structure.
dadurch gekennzeichnet, daß
die Feststoffteilchen aus Siliciumdioxid bestehen.Method according to one of claims 1 to 5,
characterized in that
the solid particles consist of silicon dioxide.
dadurch gekennzeichnet, daß
man die Suspension der Feststoffteilchen in den Ausgangslösungen vor der Verwendung zur Fällung einem Ultraschallfeld aussetzt.Method according to one of claims 1 to 6,
characterized in that
exposing the suspension of the solid particles in the starting solutions to an ultrasonic field before use for precipitation.
dadurch gekennzeichnet, daß
daß in der Suspension ein Netzmittel vorhanden ist.Method according to claim 7,
characterized in that
that a wetting agent is present in the suspension.
dadurch gekennzeichnet, daß
die Silberhalogenidemulsionen chemisch oder chemisch und optisch sensibilisiert werden.Method according to one of claims 1 to 8,
characterized in that
the silver halide emulsions are chemically or chemically and optically sensitized.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4244065A DE4244065A1 (en) | 1992-12-24 | 1992-12-24 | Process for producing a matt silver halide light-sensitive material |
| DE4244065 | 1992-12-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0603686A1 true EP0603686A1 (en) | 1994-06-29 |
Family
ID=6476529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93120008A Withdrawn EP0603686A1 (en) | 1992-12-24 | 1993-12-11 | Method for preparation of a matte light sensitive silver halide recording material |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5420006A (en) |
| EP (1) | EP0603686A1 (en) |
| JP (1) | JP2786991B2 (en) |
| DE (1) | DE4244065A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4244065A1 (en) | 1992-12-24 | 1994-06-30 | Du Pont Deutschland | Process for producing a matt silver halide light-sensitive material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0275152A2 (en) * | 1987-01-10 | 1988-07-20 | E.I. Du Pont De Nemours And Company | Matted photographic imaging materials |
| EP0298310A1 (en) * | 1987-06-30 | 1989-01-11 | E.I. Du Pont De Nemours And Company | Matted photographic registration material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3854952A (en) * | 1973-09-19 | 1974-12-17 | Western Electric Co | Photosensitive silver halide composition |
| US4419442A (en) * | 1982-11-04 | 1983-12-06 | Polaroid Corporation | Photosensitive silver halide emulsion |
| EP0605408A1 (en) * | 1989-10-18 | 1994-07-13 | Research Corporation Technologies, Inc. | Coated particles and methods of coating particles |
| EP0589868A1 (en) * | 1989-10-18 | 1994-04-06 | Research Corporation Technologies, Inc. | Light-sensitive recording media |
| DE4244065A1 (en) | 1992-12-24 | 1994-06-30 | Du Pont Deutschland | Process for producing a matt silver halide light-sensitive material |
-
1992
- 1992-12-24 DE DE4244065A patent/DE4244065A1/en not_active Withdrawn
-
1993
- 1993-12-11 EP EP93120008A patent/EP0603686A1/en not_active Withdrawn
- 1993-12-21 US US08/170,967 patent/US5420006A/en not_active Expired - Fee Related
- 1993-12-24 JP JP5327093A patent/JP2786991B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0275152A2 (en) * | 1987-01-10 | 1988-07-20 | E.I. Du Pont De Nemours And Company | Matted photographic imaging materials |
| EP0298310A1 (en) * | 1987-06-30 | 1989-01-11 | E.I. Du Pont De Nemours And Company | Matted photographic registration material |
Also Published As
| Publication number | Publication date |
|---|---|
| US5420006A (en) | 1995-05-30 |
| JP2786991B2 (en) | 1998-08-13 |
| DE4244065A1 (en) | 1994-06-30 |
| JPH06282027A (en) | 1994-10-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1547667A1 (en) | Photographic material | |
| DE1547791B2 (en) | Electron beam sensitive photographic recording material | |
| DE2003993C3 (en) | Multilayer photographic material | |
| DE1547686A1 (en) | Photographic material | |
| EP0603686A1 (en) | Method for preparation of a matte light sensitive silver halide recording material | |
| DE3700551C2 (en) | ||
| DE2553127A1 (en) | PROCESS FOR INCREASING THE SENSITIVITY OF A PHOTOGRAPHIC SILVER HALOGENIDE EMULSION, THE PRODUCTS CONTAINED WITH IT AND THEIR USE FOR THE MANUFACTURE OF A PHOTOGRAPHIC MATERIAL | |
| DE2215788C2 (en) | Photographic material for the silver salt diffusion transfer process | |
| DE3347215A1 (en) | LIGHT SENSITIVE, PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL | |
| DE1945409A1 (en) | Process for making photographic images | |
| DE3721481C2 (en) | ||
| DE1547745C3 (en) | Photographic recording material | |
| DE1547822C3 (en) | Process for preparing a silver halide photographic emulsion | |
| DE3709818C2 (en) | ||
| DE2144284A1 (en) | Electron beam recording material | |
| DE1961866A1 (en) | Lippmann emulsions | |
| EP0035235A2 (en) | Process for the manufacture of photographic images; photographic material suitable to this process and photographic images obtained therewith | |
| DE2932185A1 (en) | Photographic emulsion contg. rhombic dodecahedron silver halide - crystals pptd. in presence of divalent cadmium ions and free ammonia | |
| DE3506712C2 (en) | Photographic recording material for forming an image by silver halide diffusion transfer | |
| DE4205450C2 (en) | Photothermographic recording material | |
| EP0706084A1 (en) | Rapid processable photographic recording material for medical radiography | |
| DE2234736A1 (en) | PROCESS FOR MODIFYING THE ELECTROSTATIC CHARGING PROPERTIES OF OBJECTS | |
| DE1772904B2 (en) | Process for preparing a photosensitive silver halide emulsion | |
| DE4311888A1 (en) | Silver halide light-sensitive material with reduced sensitivity to pressure | |
| DE3206342A1 (en) | LIGHT-SENSITIVE COPPER (I) HALOGENID EMULSION AND METHOD FOR THE PRODUCTION THEREOF |
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): DE FR GB IT |
|
| 17P | Request for examination filed |
Effective date: 19941207 |
|
| 17Q | First examination report despatched |
Effective date: 19970404 |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| 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 |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: AGFA-GEVAERT AG |
|
| 18D | Application deemed to be withdrawn |
Effective date: 19980320 |