EP0569074B1 - Verfahren zur Herstellung einer wässrigen Dispersion von festen Teilchen einer photographisch verwendbaren Verbindung - Google Patents

Verfahren zur Herstellung einer wässrigen Dispersion von festen Teilchen einer photographisch verwendbaren Verbindung Download PDF

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EP0569074B1
EP0569074B1 EP19930201135 EP93201135A EP0569074B1 EP 0569074 B1 EP0569074 B1 EP 0569074B1 EP 19930201135 EP19930201135 EP 19930201135 EP 93201135 A EP93201135 A EP 93201135A EP 0569074 B1 EP0569074 B1 EP 0569074B1
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Prior art keywords
silica
dispersion
compound
aqueous
present
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French (fr)
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EP0569074A1 (de
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Hubert C/O Agfa-Gevaert N.V. Vandenabeele
Hendrik c/o Agfa-Gevaert N.V. Lambrecht
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images

Definitions

  • This invention relates to dispersion methods for chemical compounds which are intended for incorporation in photographic silver halide materials and to photographic materials with coated layers incorporating dispersions prepared by such dispersion methods.
  • One general suitable dispersion method consists of ball-milling the compound in gelatinous medium. It is also possible to disperse an organic solution of the compound in an aqueous gelatinous medium followed by removal of the solvent e.g. by evaporation under vacuum.
  • Alkaline-soluble compounds can be incorporated by a dispersion method based on decreasing the pH (pH shift) of an aqueous alkaline gelatin solution.
  • the coarse particle size dispersions also have disadvantageous effects on the photographic characteristics as the physical and chemical properties are the better the finer the particle sizes are.
  • colour couplers have improved coupling activity and dyes have improved light absorption.
  • aqueous gelatin compositions comprising dispersed ingredients, which are stored as such before being incorporated in the actual coating composition for forming the photographic layers, represent an extra amount of gelatin that is combined with the gelatin coating composition thus increasing the binder content of the photographic material and reducing the capability of rapid access processing after exposure due to the increased drying times necessary.
  • a method for the preparation of an aqueous solid particle dispersion of a photographically useful compound, for being incorporated in one of the layers of a photographic silver halide material comprising the steps of
  • lowering of the pH of the alkaline solution occurs by neutralizing with an aqueous acidic solution.
  • the silica may be present in the aqueous alkaline solution and/or in the aqueous acidic solution or it may be present in a separate aqueous alkaline solution into which both the aqueous alkaline solution and the aqueous acidic solution are added.
  • fine, homogeneous and reproducible dispersions can be made with a relatively simple apparatus and within a reasonable preparation time of about one hour by the adsorption of finely divided silica particles onto flocculated or coagulated particles prepared by neutralization of an alkaline solution of a photographically useful compound in the presence of said silica particles and preferably, in the presence of a surfactant.
  • fine silica dispersions of dyes can be prepared for incorporation in at least one of the layers of a photographic material e.g. as filter, screening or antihalation dye, thereby showing an increased efficiency of light absorption, requiring a reduced coating amount of a dye and showing a high decolouration speed in the processing of said photographic material, making it particularly suitable for rapid processing applications.
  • a photographic material e.g. as filter, screening or antihalation dye
  • Silica is well-known as suitable hydrophilic binder for replacing gelatin in hydrophilic layers and more particularly in silver-halide emulsion layers. As has been disclosed in EP-A 0 528 476 an increased amount of silica sol used as a protective colloid in the preparation of silver halide emulsions results in an acceptable physical stability of the emulsion after coating.
  • aqueous alkaline-soluble compounds as e.g. dyes dissolved in an aqueous alkaline solution having a pH value of at least 8.0, are precipitated by mixing the alkaline solution with an aqueous acidic solution in an aqueous silica medium under partially or fully controlled conditions of temperature, concentration, sequence of addition, and rates of addition.
  • this precipitation may be performed in the presence of a dispersing agent which is an ionizable polymer and/or an amphoteric and/or a surface active agent present in the alkaline solution and/or in the reaction vessel to get a finely dispersed compound in a stable colloidal medium.
  • silica and/or dispersing agent(s) may be divided partially between the reaction vessel and the solution(s) to be added to said vessel.
  • pH-stat it is possible to measure the pH value in the vessel continuously with a glass electrode and to derive the rate of addition of the acidic aqueous solution therefrom electronically so that it is possible to conduct this acidifying step in perfectly controlled conditions.
  • This preferably constant value should be low enough to get a quantitative flocculate of the compound e.g. dye, a pH value lower than 6.0 being recommended and a value of about 3.0 being particularly preferred.
  • the rate of addition of the alkaline solution strongly depends on the concentration of the alkaline solution, of the stirring rate and of the constant pH value to be maintained in the reaction vessel. The rate of addition of the alkaline solution to the reaction vessel and/or the stirring rate in the vessel may be increased during the precipitation procedure.
  • the pH precipitation value can be chosen beforehand. It is clear that the preferred rate of addition of the aqueous alkaline solution also depends on the pH value of the aqueous alkaline solution of the compound or compounds and on the stirring rate in the vessel. Amounts of silica present in the reaction vessel with relation to the amount of compound may vary from weight ratios of 5/1 to 1/5.
  • the precipitated compound(s) prepared in accordance with the present invention is(are) very finely divided by using this technique and is(are) covered with a protective layer of silica particles, adsorbed onto the compound or coprecipitated with the compound. It is possible to store the very stable and concentrated particle dispersions at room temperature for at least some weeks and even months before the ingredient is used in a coated layer of a photographic material.
  • the ultrafiltration technique is preferred: in about half an hour it is possible to get a stable silica dispersion concentrated to about 6% and even to about 10% by weight for the compound although these higher values are not recommended as the viscosity may rise and as afterwards a dilution may become necessary before addition to coating compositions.
  • Any compound that is normally used in photographic materials can be dispersed in accordance with the present invention, provided that their chemical structure allows the essential condition of having a water-solubility depending on pH.
  • aqueous-insoluble compounds as e.g. colour couplers without an ionizable soluble group are dissolved in a minimum amount of an organic solvent and added to an aqueous alkaline solution.
  • the solution is slowly added, simultaneously with a neutralizing acidic solution to a reaction vessel containing a stirred aqueous dispersion of silica particles wherein preferably a suitable dispersing agent is present.
  • These additions are preferably performed under partially or fully controlled stirring conditions of temperature, concentration, sequence of addition, and rates of addition. It should be recommended to perform this precipitation in the presence of at least one polymer and/or surfactant present in the reaction vessel to get a finely dispersed compound in a stable colloidal medium.
  • silica sols are suitable for the process according to the invention.
  • Suitable silica sols are commercially available such as the "Syton” silica sols (a trademarked product of Monsanto Inorganic Chemicals Div.), the “Ludox” silica sols (a trademarked product of du Pont de Nemours & Co., Inc.), the "Nalco” and “Nalcoag” silica sols (trademarked products of Nalco Chemical Co), the "Snowtex” silica sols of Nissan Kagaku K.K. and the "Kieselsol, Types 100, 200, 300, 500 and 600" (trademarked products of Bayer AG).
  • Especially colloidal silicas having a specific surface area between 100 and 600 m 2 /g are preferred.
  • Said dispersing agent may be chosen from the classes of chemical compounds known as partially ionizable polymers and surfactants and may act as a synergetically working co-stabilizer. Any combination may be used to optimize the stabilization of the silica particle dispersion of the organic compound obtained.
  • Suitable co-stabilizing agents are surface-active agents which as is known have a hydrophobic moiety e.g. a long-chain aliphatic group or an aliphatic-aromatic group and a hydrophilic moiety e.g. an anionic or cationic group, an amphoteric group or a non-ionic group as ethylene oxide groups.
  • agents include surface anionic agents comprising an acid group such as a carboxy, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids, aminoalsulphates or phosphates, alkyl betaines, and amine-N-oxides; and cationic agents such as alkylamine salts, aliphatic, aromatic, or heterocyclic quaternary ammonium salts, aliphatic or heterocyclic ring-containing phosphonium or sulphonium salts.
  • said agents especially have the function of facilitating the dispersive emulsification of ingredients in silicic acid during the preparation procedure.
  • These surface-active compounds may e.g.
  • ampholytic compounds as 2-N,N,N-trialkylamino acetic acid compounds.
  • the dispersing agents are preferably present in amounts from 1 to 20 % by weight versus the photographically useful compound.
  • the preparation procedure described hereinbefore may be applied to prepare fine, stable and homogeneous silica dispersions for all organic compounds that are normally used in dissolved or finely divided state in the coated layers of photographic materials as e.g. spectrally sensitizing or desensitizing dyes, stabilizers, developers or developer accelerators, coupler compounds as DIR-couplers, coloured mask couplers and couplers, being coloured or uncoloured after coupling reactions with oxidised developer compounds as those used in colour photographic materials, coupler precursors etc.
  • auxiliary organic solvents may be used to dissolve said organic compound before addition to an aqueous alkaline solution containing colloidal silica particles and preferably containing an auxiliary co-stabilizing dispersing agent.
  • Preferred organic solvents are methyl alcohol, ethyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethylformamide, dioxane, N-methyl-pyrrolidone, acetonitrile, ethylene glycol, ethyl acetate etc.
  • the aqueous solution is made alkaline with a base as sodium hydroxide.
  • a base as sodium hydroxide.
  • organic acids as acetic acid, propionic acid and the like are used or diluted anorganic acids as hydrochloric acid, sulphuric acid or phosphourous acid.
  • silica dispersability of an aqueous-insoluble ingredient in silica strongly depends on the degree of partition obtained as a function of the relative amounts of the said ingredient, of silica and of ionizable polymer(s) and/or surfactant(s) present in the reaction vessel and of the stirring rate applied during the neutralization step. Accordingly it is possible to get very finely dispersed ingredients with a high quantitative yield and neglectable losses when the procedure is fully optimized.
  • the silica dispersion obtained may be concentrated making use of the techniques as have been described hereinbefore. It is clear that these very finely divided photographically useful compounds are characterized by a very high photographic activity, if compared with the compounds in a gelatinous dispersion prepared from ball-mill techniques and the like.
  • Spectral sensitizers with methine groups may be used in accordance with this invention. Examples are e.g. described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons. Dyes that can be used for the purpose of spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly valuable dyes that can be dispersed in silica are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • Suitable supersensitizers that can be added as silica dispersions are i.a. heterocyclic mercapto compounds containing at least one electronegative substituent as described e.g. in US-A 3,457,078, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds as described e.g. in US-A 2,933,390 and US-A 3,635,721, aromatic organic acid/formaldehyde condensation products as described e.g. in US-A 3,743,510, cadmium salts, and azaindene compounds.
  • Compounds preventing the formation of fog or stabilizing the photographic characteristics during the production or storage of photographic elements or during the photographic treatment thereof may be added as dispersions of fog-inhibiting agent or stabilizer to the silver halide emulsion.
  • Making use of silica dispersions of such ingredients avoids the otherwise required addition of pH buffers.
  • Suitable examples of stabilizers of which silica dispersions can be made are i.a.
  • heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles (preferably 5-methyl-benzotriazole), nitrobenzotriazoles, mercaptotetrazoles, in particular 1-phenyl-5-mercapto-tetrazole, mercaptopyrimidines, mercaptotriazines, benzothiazoline-2-thione, oxazoline-thione, triazaindenes, tetrazaindenes and pentazaindenes, especially those described by Birr in Z.
  • benzothiazolium salts such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlor
  • fog-inhibiting agents or stabilizers can be added to the silver halide emulsion prior to, during, or after the chemical ripening thereof and mixtures of two or more of these compounds can be used.
  • additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, hardeners, plasticizers, coating aids, compounds preventing electric charges, compounds improving slidability, compounds preventing or reducing adhesion, compounds improving the photographic characteristics e.g higher contrast, sensitization, and development acceleration.
  • Preferred development accelerators are e.g. polyalkylene derivatives having a molecular weight of at least 400.
  • silica dispersions in hydrophilic layers are e.g. developing agents as dihydroxy benzene or derivatives, phenidones and the like, whether or not in combination with other organic compounds used in developers as e.g. stabilizers as benztriazole and/or indazole or benzimidazole derivatives.
  • silica dispersions of UV-absorbers may be added such as i.a. aryl-substituted benzotriazole compounds as described in US-A 3,533,794, 4-thiazolidone compounds as described in US-A 3,314,794 and 3,352,681, benzophenone compounds as described in JP-A 2784/71, cinnamic ester compounds as described in US-A 3,705,805 and 3,707,375, butadiene compounds as described in US-A 4,045,229, and benzoxazole compounds as described in US-A 3,700,455.
  • benzotriazole compounds as described in US-A 3,533,794, 4-thiazolidone compounds as described in US-A 3,314,794 and 3,352,681
  • benzophenone compounds as described in JP-A 2784/71
  • cinnamic ester compounds as described in US-A 3,705,805 and 3,707,375
  • butadiene compounds as described in US-A 4,
  • silica dispersions of photographically useful compounds made in accordance with the present invention can be added to the coating composition of light-sensitive silver halide emulsion layers or of light-insensitive auxiliary layers known in the art of silver halide photography.
  • Suitable further additives for improving the dimensional stability of the photographic element comprising silica dispersions of ingredients according to the description given hereinbefore may be added, i.a. dispersions of a water-soluble or hardly soluble synthetic polymer e.g.
  • plasticizers suitable for incorporation in the emulsion layers according to the present invention e.g. glycol, glycerine, or the latexes of neutral film forming polymers including polyvinylacetate, acrylates and methacrylates of lower alkanols, e.g. polyethylacrylate and polybutylmethacrylate.
  • the light-sensitive silver halide emulsion can be a conventional emulsion or an emulsion made with silica as protective colloid according to the published EP Application 392,092.
  • said binder can be hardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol , chromium salts e.g. chromium acetate and chromium alum, aldehydes e.g. formaldehyde, glyoxal and glutaraldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives e.g.
  • appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol , chromium salts e.g. chromium acetate and chromium
  • the dispersion technique according to the present invention is particularly suitable for ingredients that should be non-migratory during coating and drying as migration from one layer to another in the usually multi-layered photographic coatings would mutually disturb the photographic properties.
  • These ingredients include non-spectrally sensitizing dyes which are used in a photosensitive silver halide emulsion layer as screening dyes, in an undercoat adjacent to the photosensitive layer and/or in a backing layer on the side of the support opposite to the photosensitive layer(s) to absorb reflected and scattered light thereby serving as antihalation dye or in an overcoat or interlayer to shield a particular photosensitive layer against undesired exposure being therefore referred to as filter or absorber dye, thereby adjusting the sensitivity of a photographic element as required in the manufacturing.
  • Such an absorber dye can e.g. be present in one or more filter layers between silver halide emulsion layers that are coated at opposite sides of a transparent film support of a duplitized X-ray recording material in order to improve image sharpness.
  • the imagewise exposure of said recording material proceeds in a cassette between a pair of X-ray intensifying screens that each are held in contact with an adjacent silver halide emulsion layer.
  • the dye absorption spectrum should spectrally be approximately equal to the sensitivity spectrum of the corresponding silver halide emulsion in the layer of which a sharp image has to be reproduced.
  • the amount of very fine, homogeneously divided silica dispersed dye can be reduced due to its enhanced photographic activity., The non-migratory dye dispersion is completely removed in rapid processing conditions as no colour stain is observed on the film afterwards.
  • Hydrophilic layers containing silica dispersions in accordance with the present invention may be coated on any suitable substrate such as, preferably, a thermoplastic resin e.g. polyethyelenterephtalate or a polyethylene coated paper support.
  • a thermoplastic resin e.g. polyethyelenterephtalate or a polyethylene coated paper support.
  • ingredients prepared in accordance with the present invention may be added in silica dispersed form in various types of photographic elements such as i.a. in photographic elements for graphic arts and for so-called amateur and professional photography, diffusion transfer reversal photographic elements, low-speed and high-speed photographic elements, X-ray materials, colour materials etc..
  • a gelatinous dispersion was made by the ball mill technique using glass beads of zirconium oxide to pulverize the dye. After a total milling time of 6 hours a dispersion was obtained with 10 g of dye for a total weight of the aqueous dispersion of 40 g containing 15 g of gelatin, from which 12.5 g was added after the mechanical procedure was ended. As a result a very heterogeneous dispersion was obtained for particles with an average size of about 650 nm. Said dispersion was called the comparative dispersion GEL COMP.
  • a silica dispersion was made from dye 1, in a vessel containing an aqueous silica sol 'Kieselsol 500' (product of Bayer AG). Therefore an alkaline solution of dye 1 in demineralized water the pH value of which had been adjusted at 8.0 was added at a constant rate to said silica sol together with a solution of sulphuric acid which was added at a controlled rate of addition determined by the starting pH of 3.0 which was initially set up in the reaction vessel.
  • the procedure was carried out at room temperature for the reaction vessel, the acidic and alkaline solutions. During the double-jet addition the reaction mixture was stirred. After the end of the precipitation the ultrafiltration procedure was started. The resulting silica dispersion of dye 1 was called "SILICA A”. With a nanosizer measuring instrument "Coulter Nano-Sizer TM” an average particle size diameter of 330 nm was measured.
  • Dispersion of dye 1 in a mixture of silica sol and surfactant 1 in the reaction vessel Dispersion of dye 1 in a mixture of silica sol and surfactant 1 in the reaction vessel.
  • SILICA B The dispersion called SILICA B was made in the presence of an amphoteric surfactant corresponding to the formula given hereinafter (surfactant 1). During the preparation of said dispersion the procedure was followed as for SILICA A except for the further presence of surfactant 1 in the reaction vessel. Nanosizer measurements gave an average particle diameter of 320 nm.
  • This dispersion called SURF COMP was made in the same way as SILICA A except for the presence of surfactant 1 in the reaction vessel instead of silica sol, surfactant 1 being present in an amount of 1g, added from an aqueous 1% solution of said surfactant.
  • a silica dispersion was made from dye 2, the formula of which is given hereinafter, in a vessel containing aqueous silica sol 'Kieselsol 500' (product of Bayer AG) by the addition of an alkaline solution of dye 2 the pH value of which was adjusted at 11.5 at a constant rate of addition and the simultaneous addition of a citric acid solution at a constant pH value of 3.0.
  • the dispersion called SILICA C had an average particle diameter of 175 nm.
  • Dispersion of dye 2 in a mixture of silica and surfactant 1 in the reaction vessel Dispersion of dye 2 in a mixture of silica and surfactant 1 in the reaction vessel.
  • SILICA D The dispersion called SILICA D was made in the presence of the amphoteric surfactant 1. During the preparation of said dispersion the procedure was followed as for SILICA C except for the further presence of surfactant 1 in the reaction vessel added from an aqueous solution of 1% by weight of said surfactant to the reaction vessel. An average particle diameter of 250 nm was obtained.
  • Dispersion of dye 2 from an alkaline solution containing silica sol in a mixture of silica and surfactant 1 in the reaction vessel Dispersion of dye 2 from an alkaline solution containing silica sol in a mixture of silica and surfactant 1 in the reaction vessel.
  • This dispersion was prepared in the same way as dispersion SILICA D, the only difference being the use of a ten times diluted silica sol.
  • the pH value of this alkaline solution was adjusted at 11.5.
  • the homogeneity was qualitatively determined by observation of photographs of the dispersion particles with a "scanning electron microscope” and qualitatively expressed as being “very homogeneous”, “homogeneous”, “heterogeneous” or “very heterogeneous”. Evaluation of the different dispersions.
  • Table I clearly illustrates that it is possible to get very fine, very stable and very homogeneous dispersion particles in the absence of any organic solvent by the formation of a "solid silica dispersion" in accordance with the present invention whether or not in the presence of a surfactant added to the silica sol.
  • Table II clearly illustrates that it is possible to get very fine, very stable and very homogeneous dispersion particles in the presence of silica sol and a surfactant being present as a co-stabilizer.
  • SILICA D The dispersion called SILICA D, the preparation of which has been described in example 4 and the evaluation of which has been given in Table I, being in accordance with this invention was incorporated in a filter layer of an X-ray material and compared with the incorporated GEL COMP2 dispersion.
  • the preparation and coating procedure is given hereinafter.
  • Chromium (III) acetate as hardening agent and additional gelatin in amounts to obtain the same total amounts of gelatin in the filter dye layers were added to the above prepared dye dispersions kept at a temperature of 36 °C and pH 6.1.
  • Said dispersions were double-side coated and dried on a polyethylene terephthalate film support of 175 ⁇ m. thickness in order to obtain at each side a dye coverage of 0.025 g/m 2 for the SILICA D dispersion and of 0.075 g/m 2 for the GEL COMP2 dispersion respectively, a gelatin coverage of 1 g/m 2 and coverage of hardening agent of 0.016 g/m 2 .
  • Said dyes being coated on both sides of a polyethylene terephthalate film support in an anti cross-over layer were overcoated with an emulsion and a protective layer, the silver halide emulsion being spectrally unsensitized.
  • Samples of these coatings were illuminated using a continuous wedge with blue light during 0.1 seconds and were processed under a 38 seconds processing cycle applied in rapid processing applications of X-ray materials and the cross-over was determined as described hereinafter.
  • the density as a function of the light dose was measured and therefrom were determined the following sensitometric characteristics: fog level (with an accuracy of 0.001 density), the relative speed S at a density of 1 above fog (the sample with the gelatinous dispersion GEL COMP2 was set to a speed of 100), maximum density DMAX and the contrast calculated between the densities 0.25 and 2.0 above fog.
  • the gelatin binder can be successfully replaced by other non gelatinous layers allowing lower swelling degree and faster drying e.g. a polyvinyl alcohol binder.

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Claims (10)

  1. Ein Verfahren zur Herstellung einer wäßrigen Dispersion von festen Teilchen einer fotografisch verwendbaren Verbindung zur Einarbeitung in eine der Schichten eines fotografischen Silberhalogenidmaterials, wobei das Verfahren die nachstehenden Schritte umfaßt :
    das Lösen einer nicht-wasserlöslichen aber alkalilöslichen Verbindung in einer wäßrigen alkalischen Lösung, wenn nötig unter Anwendung eines organischen wasserlöslichen Lösungsmittels,
    das Fällen der Verbindung aus der Lösung, in Gegenwart von kolloidalem Kieselsol, durch gleichzeitige Zugabe einer wäßrigen alkalischen, die alkalilösliche Verbindung enthaltenden Lösung und einer wäßrigen sauren Lösung in einer gerührten Lösung, die die Gesamtmenge oder einen Teil des kolloidalen Kieselsols und eines Dispersionsmittels enthält, wobei der pH konstant behalten wird und die eventuelle Restmenge in wenigstens einer der Lösungen enthalten ist,
    die Abtrennung der durch die Fällung gebildeten wasserlöslichen Salze und jegliches gegebenenfalls benutzten organischen Lösungsmittels, und
    das Konzentrieren der Dispersion - entweder während oder nach der Fällung - durch Dialyse oder Ultrafiltration oder nach der Fällung durch Ausflockung und Dekantierung, gefolgt durch einen Waschsschritt und eine weitere Dekantierung.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der konstante pH-Wert auf einen Wert von weniger als 6,0 gebracht wird.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Dispersionsmittel ein teilweise ionisierbares Polymeres oder ein Tensid oder eine Kombination beider ist.
  4. Verfahren nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die fotografisch nutzbare Verbindung in einem Gewichtsverhältnis zwischen 1:5 und 5:1 bezogen auf das kolloidale Kieselsol enthalten ist.
  5. Verfahren nach irgendeinem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das gegebenenfalls benutzte Dispersionsmittel in einer Menge zwischen 1 und 20 Gew.-% bezogen auf die Verbindung enthalten ist.
  6. Verfahren nach irgendeinem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die kolloidale Kieselerde einen Flächeninhalt zwischen 200 und 600 m2/g aufweist.
  7. Verfahren nach irgendeinem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die fotografisch nutzbare Verbindung ein Farbstoff, ein Stabilisator, ein gefärbter oder ungefärbter Kuppler, ein Farbkupplervorläufer, ein Entwickler, ein Entwicklungsbeschleuniger, ein Härter oder ein Desensibilisator ist.
  8. Verfahren nach irgendeinem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das gegebenenfalls benutzte Dispersionsmittel eine 2-N,N,N-Trialkylaminoessigsäure ist.
  9. Fotografisches Material, wobei eine nach dem in irgendeinem der Ansprüche 1 bis 8 beschriebenen Verfahren hergestellte Dispersion von festen Teilchen vor oder während dem Auftrag einer hydrophilen Schicht auf wenigstens eine Schicht eines Trägers in die hydrophile Schicht eingearbeitet wird.
  10. Fotografisches Material nach Anspruch 9, dadurch gekennzeichnet, daß das fotografische Material ein doppelseitig emulsioniertes Röntgenmaterial und die fotografisch nutzbare Verbindung ein in einer Filterschicht zwischen der Silberhalogenid-Emulsionsschicht und einem Filmträger enthaltener Filterfarbstoff ist.
EP19930201135 1992-05-04 1993-04-20 Verfahren zur Herstellung einer wässrigen Dispersion von festen Teilchen einer photographisch verwendbaren Verbindung Expired - Lifetime EP0569074B1 (de)

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EP92201228 1992-05-04
EP92201228 1992-05-04

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EP0569074B1 true EP0569074B1 (de) 1998-10-14

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Publication number Priority date Publication date Assignee Title
US5994041A (en) * 1985-04-06 1999-11-30 Eastman Kodak Company Process for buffering concentrated aqueous slurries
DE69422624T2 (de) * 1994-09-27 2000-07-13 Agfa-Gevaert N.V., Mortsel Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen und Dispersionen von photographisch verwendbaren Verbindungen
US5609998A (en) * 1994-12-29 1997-03-11 Eastman Kodak Company Process for dispersing concentrated aqueous slurries
JP2835711B2 (ja) * 1995-07-24 1998-12-14 アグファ・ゲヴェルト・ナームロゼ・ベンノートチャップ 写真材料の親水性層の被覆溶液にすぐ使用できる写真的に有用な化合物の分散体の製造方法
EP0790526B1 (de) 1996-02-19 2002-07-24 Agfa-Gevaert System von Film und Schirm zur Herstellung radiographischen Bildes

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JPH035748A (ja) * 1989-06-01 1991-01-11 Fuji Photo Film Co Ltd Ｘ―レイ用写真感光材料

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DE69321514T2 (de) 1999-05-27
JP3222266B2 (ja) 2001-10-22
JPH06194763A (ja) 1994-07-15
EP0569074A1 (de) 1993-11-10
DE69321514D1 (de) 1998-11-19

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