EP0528476A1 - Verfahren zur Herstellung eines photographischen Silberhalogenidmaterials - Google Patents

Verfahren zur Herstellung eines photographischen Silberhalogenidmaterials Download PDF

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Publication number
EP0528476A1
EP0528476A1 EP92202359A EP92202359A EP0528476A1 EP 0528476 A1 EP0528476 A1 EP 0528476A1 EP 92202359 A EP92202359 A EP 92202359A EP 92202359 A EP92202359 A EP 92202359A EP 0528476 A1 EP0528476 A1 EP 0528476A1
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EP
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Prior art keywords
silver halide
silver
emulsion
preparing
photographic material
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EP92202359A
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English (en)
French (fr)
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EP0528476B1 (de
Inventor
Hubert Vandenabeele
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • 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
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • 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

Definitions

  • the present invention relates to a silver halide light-sensitive photographic material which is highly sensitive, rapidly processable, less subjected to pressure phenomena and which has a high coverage power.
  • a photographic material satisfying the above objects and comprising a support and one or more silver halide emulsion layers is prepared by coating a support with one or more hydrophilic colloid layers including at least one layer of a silver halide emulsion prepared by the steps of:
  • the ratio by weight of gelatin over silver nitrate is adjusted by adding an adapted amount of gelatin at the stage of or after redispersing the desalted emulsion.
  • the ratio of silica to silver halide is determined at the stage of precipitation and/or by further addition of silica at the redispersion stage or later.
  • the most remarkable difference between silver halide emulsions being precipitated in colloidal silica and those prepared in gelatineous medium is the fact that colloidal silica is effectively surrounding the silver halide crystal, preventing the adsorption of a competitive protective colloid like gelatin, resulting in a weaker inhibition of the development.
  • a further unexpected effect of the present invention is the better resistance of the coated material to pressure phenomena.
  • Emulsion layers in accordance with the present invention, especially thin emulsion layers are showing remarkable improvements concerning both resistance to stress and rapid processability compared to conventional emulsions prepared in gelatineous medium.
  • the ratio of weight of gelatin to silver halide decreases the effect is more pronounced and is probably a result of the protective action of the adsorbed silica to the silver halide crystal surface.
  • the photographic silver halide can be precipitated by mixing the halide and silver solutions in the colloidal silica medium under partially or fully controlled conditions of temperature, concentrations, sequence of addition, and rates of addition.
  • the silver halide grains to be used in practising this invention may be prepared by applying the orderly mixing, inversely mixing, double jet, conversion, core/shell method or the like. Epitaxial depositions, whether or not directed by so called "site-directors", may be useful.
  • the average size of the silver halide grains used in accordance with the present invention may range from 0.01 to 7 ⁇ m, preferably from 0.3 to 3 ⁇ m.
  • the size distribution of the silver halide particles of the photographic emulsions may be homodisperse or heterodisperse. Homodisperse distributions are obtained when 95 % of the grains have a size that does not deviate for more than 30 % from the average grain size.
  • the supply of silver and halide ions may be so as to have a growth rate of the grains which is gradually and continuously increasing, never exceeding the critical growth rate in order to avoid the production and growth of newly created nuclei, nor being too low, resulting in the dissolution of the existing finest grains. This critical growth rate varies according to a lot of parameters, e.g. temperature, pH, pAg, the grain size, crystal habit and halide composition of the crystals, the dilution of the emulsion in the reaction vessel, etc.
  • the silver halide particles of the photographic emulsions according to the present invention may have a regular crystalline form, e.g. cubic or octahedral or a transition form. Also an irregular crystalline form such as a spherical form or a tabular form may be obtained. Otherwise the emulsion crystals may have a composite crystal form comprising a mixture of said regular and irregular crystalline forms.
  • the silver halide grains may also have a multilayered grain structure.
  • the crystals may be doped with whatever a dope, as e.g. with Rh3+, Ir4+, Cd2+, Zn2+, Pb2+.
  • a dope e.g. with Rh3+, Ir4+, Cd2+, Zn2+, Pb2+.
  • chloride, bromide, iodide and any combination may be used.
  • Two or more different, separately formed silver halide emulsions may be mixed and used in accordance with the present invention.
  • 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 “Ludex” silica sols (a trademarked product of duPont de Nemours & Co., Inc.), the "Nalco” and “Nalcoag” silica sols (trademarked products of Nalco Chemical Co) and the "Kieselsol, Types 100, 200, 300, 500 and 600" (trademarked products of Bayer AG).
  • the light-sensitive silver halide emulsion prepared according to the present invention can be chemically sensitized as described i.a. in the above-mentioned "Chimie et Physique Photographique” by P. Glafkides, in the above-mentioned “Photographic Emulsion Chemistry” by G.F. Duffin, in the above-mentioned “Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in "Die Grundlagen der Photographischen Sawe mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
  • chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur e.g. thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodanines.
  • sulphur e.g. thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodanines.
  • the emulsions can be sensitized also by means of gold-sulphur ripeners or by means of reductors e.g. tin compounds as described in GB-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • Chemical sensitization can also be performed with small amounts of Ir, Rh, Ru, Pb, Cd, Hg, Tl, Pd, Pt, or Au.
  • One of these chemical sensitization methods or a combination thereof can be used.
  • the chemical sensitization is generally carried out under well-defined conditions of pH, pAg, temperature, gelatine, silver halide and sensitizer concentration until sensitivity and fogging are both optimal.
  • the surface has to be chemically sensitized because otherwise the sensitivity is not sufficient in a surface developer.
  • An advantage of this embodiment is that an excess of chemical ripening agents is eliminated so that negative influences on the stability of the material during preservation are substantially reduced.
  • the silver halide crystals are chemically sensitized in the presence of a spectral sensitizer, which results in an improved relationship between fog and sensitivity especially in short development times. So it is specifically recommended in this invention that spectral sensitization should be started concurrently with chemical sensitization, even entirely preceding chemical sensitization as has been mentioned in Research Disclosure 22534, p. 28, including also alternative procedures such as introducing a portion of sensitizing dye prior to chemical sensitization and the remaining portion at the end, being suggested by Locker et al. USP 4225666. In a preferred embodiment a blue spectrally sensitizing dye is added before the addition of the chemical ripening agents and/or during chemical sensitization. Spectral sensitization can be improved by chemical sensitization methods as has been described in U.S. Patent Nos. 3.917.485 and 3.966.476.
  • Spectral sensitizers may be added before or after the addition of the chemical ripening agents and may even portionwise be added at different stages during the process. Besides these compounds, acting as sensitizing aids, compounds as azaindenes, azapyridines or azapyrimidines, the latter compounds being known as stabilizers, are reducing fog and increasing sensitivity in such emulsions as well.
  • the light-sensitive silver halide emulsions of the invention can also be spectrally sensitized prior to coating with methine dyes such as those described by F.M. Hamer in the above-cited "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, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes, complex merocyanine dyes.
  • Suitable supersensitizers are i.a. heterocyclic mercapto compounds containing at least one electronegative substituent as described in e.g. US-A 3,457,078, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds as described in e.g. US-A 2,933,390 and US-A 3,635,721, aromatic organic acid/formaldehyde condensation products as described in e.g. US-A 3,743,510, cadmium salts, and azaindene compounds.
  • To the silver halide emulsion prepared in accordance with the present invention may be added 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.
  • Many known compounds can be added as fog-inhibiting agent or stabilizer to the silver halide emulsion. Suitable examples 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
  • the 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.
  • the light-sensitive material of this invention may contain in the hydrophyllic layer thereof a water-soluble dye as a filter dye, antiirradiation dye or antihalation dye or for various other purposes.
  • a water-soluble dye as a filter dye, antiirradiation dye or antihalation dye or for various other purposes.
  • examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.
  • the dye may be mordanted by a cationic polymer or the like. A description of such dyes is given in "Absorbing and Filter Dyes", Research Disclosure vol. 176, p. 23-26.
  • the silver halide emulsions prepared in accordance with the present invention can be used to form one or more silver halide emulsion layers coated on a support to form a photographic silver halide element according to well known techniques.
  • the photographic element of the present invention may comprise various kinds of surface-active agents in the photographic emulsion layer or in at least one other hydrophilic colloid layer.
  • Suitable surface-active agents include non-ionic agents such as saponins, alkylene oxides e.g, polyethylene glycol, polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, silicone-polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; anionic agents comprising an acid group such as a carboxy, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids, aminoalkyl sulph
  • fluorine-containing surface active agents may be used.
  • Such surface-active agents can be used for various purposes e.g. as coating aids, as compounds preventing electric charges, as compounds improving slidability, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving the photographic characteristics e.g higher contrast, sensitization, and development acceleration.
  • Development acceleration can be accomplished with the aid of various compounds, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-A 3,038,805 - 4,038,075 - 4,292,400.
  • any thickening agent Prior to coating any thickening agent may be used so as to regulate the viscosity of the coating solution, provided that they do not particularly affect the photographic characteristics of the silver halide light-sensitive photographic material.
  • Preferred thickening agents include aqueous polymers such as polystyrene sulphonic acid, dextran, sulphuric acid esters, polysaccharides, polymers having a sulphonic acid group, a carboxylic acid group or a phosphoric acid group.
  • colloidal silicas are especially preferred for applications according to the present invention.
  • Polymeric thickeners well-known from the literature resulting in thickening of the coating solution may be used independently or in combination, even with colloidal silicas.
  • Amounts of it may be suitably selected according to the kinds of silver halide and the kinds of layers or compounds to which these thickening agents are to be added.
  • Patents concerning thickening agents are U.S. Patent No. 3.167.410, Belgian Patent No. 558.143 and JP OPI Nos. 53-18687 and 58-36768. Negative effects on physical stability possibly resulting from the addition of polymeric compounds can be avoided by exclusion of those compounds and restricting extra additions to colloidal silica.
  • the emulsions prepared and coated in accordance with the present invention are particularly advantageous for the formation of very thin emulsion layers, e.g. layers from 0.5 to 1.5 ⁇ m thickness. Such thin coated layers offer besides the rapid processing applicability and the rapid drying of the wet processed material an improvement in sharpness.
  • the photographic element of the present invention may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents, hardeners, and plasticizers as described below.
  • additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents, hardeners, and plasticizers as described below.
  • the gelatin binder of the photographic element 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.
  • 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, glyox
  • dimethylolurea and methyloldimethylhydantoin dioxan derivatives e.g, 2,3-dihydroxy-dioxan, active vinyl compounds e.g. 1,3,5-triacryloyl-hexahydro-s-triazine, active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid.
  • These hardeners can be used alone or in combination.
  • the gelatin binder can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts.
  • the emulsion 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.
  • suitable additives for improving the dimensional stability of the photographic element may be added, i.a. dispersions of a water-soluble or hardly soluble synthetic polymer e.g.
  • Plasticizers suitable for incorporation in the emulsions according to the present invention are 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.
  • Suitable UV-absorbers are 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.
  • Spacing agents the average particle size of which is comprised between 0.2 ⁇ m and 10 ⁇ m can also be used. Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic element, whereas alkali-soluble spacing agents usually are removed therefrom in an alkaline processing bath. Suitable spacing agents can be made i.a. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydrophthalate. Other suitable spacing agents have been described in US-A 4,614,708.
  • the photographic silver halide emulsions can be used 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, etc..
  • the photographic silver halide emulsions are used in X-ray materials.
  • a photographic silver iodobromide emulsion containing 2.0 mole % of silver iodide was prepared by the single jet method in a vessel containing 75 ml of 15 % silica sol 'Kieselsol 500' (trademarked product of Bayer AG), 2.5 g of 3,6-dithio-1,8-octanediol as a grain growth accelerator and 50 ml of a 1 % stabilizing sulfonium compound of the type described in EP 0392092. The temperature was stabilized at 55°C.
  • the obtained emulsion was of an average grain size of 0.50 ⁇ m, containing approximately 60 g of silver nitrate per kg of the dispersion after addition of 3 moles of silver nitrate at a constant rate of 150 ml.min-1.
  • the emulsion was coagulated and after sedimentation the supernatant liquid was removed by means of a siphon.
  • Redispersion was carried out after the addition of demineralized water, quickly stirring the flocculate during 15 minutes, rising the temperature to 45°C and addition of gelatin to get an emulsion with a weight ratio of gelatin to silver nitrate of 0.28.
  • the whole redispersion procedure took 60 minutes and before the emulsion was cooled pH was brought to a value of 6.5.
  • the obtained silver halide crystal was of an average grain size diameter of 0.50 ⁇ m, containing an amount of silver bromoiodide emulsion corresponding to approximately 180 g of silver nitrate pro kg.
  • the silver halide crystals were prepared by a conventional single jet method in a vessel containing 40 g of ftaloyl gelatin.
  • the ammoniacal silver nitrate solution was held at 42°C as well as the emulsion vessel, containing the halide salts.
  • the precipitation time was ended after 10 minutes and followed by a physical ripening time of 40 minutes. After that time an additional amount of 20 g of gelatin was added.
  • the obtained emulsion was of an average grain of 0.62 ⁇ m and contained approximately 90 g of silver nitrate per kg of the dispersion after addition of 3 moles of silver nitrate.
  • the emulsion 150 g of gelatin were added so that the weight ratio of gelatin to silver nitrate was 0.42, the emulsion containing an amount of silver bromoiodide equivalent with 190 g of silver nitrate pro kg.
  • Both emulsions were chemically ripened with sulphur and gold at 47°C for 4 hours to get an optimized relation between fog and sensitivity and were stabilized with 4-hydroxy-6-methyl-1,3,3a-tetrazaindene before coating on both sides of a polyester support of 175 ⁇ m thickness. Amounts of coating solutions were the same in both cases in the emulsion layer as well as in the protective layer.
  • Differences were in coating amounts of silver halide crystals, expressed as the equivalent amount of silver nitrate and of gelatin in the emulsion layer are: 2x4.41 g/m2 for the comparative example and 2x3.34 g/m2 for the silica emulsion, the amount of gelatin 2x1.05 and 2x0.50 g/m2 respectively, so that the ratios of gelatin to silver nitrate for both emulsions were approximately 0.24 (for the comparative example) and 0.15 (for the example corresponding to the invention) respectively.
  • the film was exposed to visible light coming from projection lamps (130V; 250W) for an exposure voltage of 90V during 0.1 s at a distance of 1.8 m from the film, through a continuously varying carbon-coated wedge(wedge constant 0.15), a densitometric filter with a density of 0.30 and a "Corning filter 5850" as a blue filter with a density 2.64 (measured with a Macbeth TR 924 densitometer).
  • the radiographic materials were automatically processed, including the steps of processing (24 s at 34°C), fixing (24 s at 34°C), rinsing (24s at 20 °C) and drying (18s at 40°C).
  • the developing bath used had a pH of 10.1 and comprised the following ingredients per litre hydroquinone 120 g 1-phenyl-3-pyrazolidine-1-one 6 g 5-nitroindazole 1 g methyl-6-benztriazole 0.36 g
  • the same emulsions were prepared as in the first example, except for the fact that the emulsions were prepared at a 3°C higher temperature of the vessel and that the emulsion according to the invention was spectrally sensitized with a blue sensitizer according to the formula which was added to the emulsion after redispersion of the flocculate, before chemical ripening in an amount of 0.6 mg per g AgNO3.
  • the sizes of the silver halide crystals were 0.69 and 0.50 ⁇ m respectively with an increase of the heterogeneity of both distributions with 15% versus the emulsions being precipitated at lower temperatures.
  • Total amounts of the silver halide emulsions coated were 7.96 g/m2 and 6.96 g/m2 expressed as the equivalent amount of AgNO3 respectively for the comparative emulsion and for the emulsion according to the present invention.
  • Total amounts of gelatin coated in the emulsion layer were 1.70 and 1.02 g/m2 .
  • the protective layer was the same as in the first example, as well as the polyester undercoat layer.
  • Tables 3 and 4 an identical evaluation as in the previous tables 1 and 2 is given.
  • Table 3 S GRAD DMAX CP SPS DPDS DRLS comparative example 1.30 3.09 3.68 46 comp. -0.17 0.66 invention 1.29 2.95 3.62 52 better -0.15 0.50
  • a material is obtained that has better pressure characteristics and a comparative scratch resistance even when the emulsion layer is containing only one half of the gelatin of the emulsion layer with a "conventional" emulsion containing gelatin as a protective colloid in the precipitation.
  • a "conventional" emulsion containing gelatin as a protective colloid in the precipitation is remarkably advantageous for the material containing the "silica emulsion",allowing a lower coating amount of the silver halide.
  • the thinner emulsion layer combined with the smaller coating amount of the silver halide makes the material especially suitable for rapid processing purposes.
EP19920202359 1991-08-15 1992-07-30 Verfahren zur Herstellung eines photographischen Silberhalogenidmaterials Expired - Lifetime EP0528476B1 (de)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0644455A1 (de) * 1993-09-17 1995-03-22 Agfa-Gevaert N.V. Photographisches lichtempfindliches Material zur Verwendung für schnelle Verarbeitung
EP0649051A1 (de) * 1993-09-16 1995-04-19 Agfa-Gevaert N.V. Herstellungsverfahren für lichtempfindliche Silberhalogenidemulsion und diese Emulsionen enthaltendes Material
EP0670517A2 (de) * 1994-02-28 1995-09-06 Konica Corporation Verarbeitungsverfahren eines photographischen lichtempfindlichen Silberhalogenidmaterials
EP0682287A1 (de) * 1994-05-09 1995-11-15 Agfa-Gevaert N.V. Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen, die chloridreiche Kristalle enthalten; und diese Emulsionen enthaltendes Material
US5476761A (en) * 1993-09-16 1995-12-19 Agfa-Gevaert, N.V. Preparation method of regular silver (halide) bromide or silver bromoiodide light-sensitive emulsions and material comprising said emulsions
EP0698817A1 (de) 1994-08-22 1996-02-28 Agfa-Gevaert N.V. Sortiment von photographischen Silberhalogenidfilmen für die industrielle Radiographie und Verfahren zur Verarbeitung dieses Sortiments
EP0794456A1 (de) 1996-03-07 1997-09-10 Agfa-Gevaert N.V. Verfahren zur Wiedergabe eines elektronisch gespeicherten medizinischen Bildes auf lichtempfindlichen photographischem Material
EP0831362A1 (de) * 1996-09-18 1998-03-25 Agfa-Gevaert N.V. Lichtempfindliches Silberhalogenidmaterial mit Kieselsäure-Schutzkolloid, das Schichten enthält, die kein oder ein Minimum an Gelatine als Bindemittel enthalten
US5840474A (en) * 1995-10-02 1998-11-24 Agfa-Gevaert, N.V. Preparation method for (100) tabular silver halide grains rich in chloride in silica sol as binder
US6312882B1 (en) * 1994-04-06 2001-11-06 Agfa-Gevaert Silver halide emulsions comprising tabular crystals, emulsions and the processing thereof

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GB2085180A (en) * 1980-10-03 1982-04-21 Agfa Gevaert Ag A silver halide emulsion a photographic material and a process for producing photographic images
EP0264788A2 (de) * 1986-10-18 1988-04-27 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial mit einer einzigen Oberfläche
EP0391405A2 (de) * 1989-04-06 1990-10-10 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial und Verarbeitungsmethode dafür
EP0392092A1 (de) * 1989-04-11 1990-10-17 Agfa-Gevaert N.V. Verfahren zur Herstellung von lichtempfindlichen Silberhalogenid Emulsionen

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FR2017463A1 (de) * 1968-09-05 1970-05-22 Agfa Gevaert Ag
US4001022A (en) * 1975-08-13 1977-01-04 Minnesota Mining And Manufacturing Company Photographic materials comprising developer layers and binders comprising silica sol
GB2085180A (en) * 1980-10-03 1982-04-21 Agfa Gevaert Ag A silver halide emulsion a photographic material and a process for producing photographic images
EP0264788A2 (de) * 1986-10-18 1988-04-27 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial mit einer einzigen Oberfläche
EP0391405A2 (de) * 1989-04-06 1990-10-10 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial und Verarbeitungsmethode dafür
EP0392092A1 (de) * 1989-04-11 1990-10-17 Agfa-Gevaert N.V. Verfahren zur Herstellung von lichtempfindlichen Silberhalogenid Emulsionen

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EP0649051A1 (de) * 1993-09-16 1995-04-19 Agfa-Gevaert N.V. Herstellungsverfahren für lichtempfindliche Silberhalogenidemulsion und diese Emulsionen enthaltendes Material
US5476761A (en) * 1993-09-16 1995-12-19 Agfa-Gevaert, N.V. Preparation method of regular silver (halide) bromide or silver bromoiodide light-sensitive emulsions and material comprising said emulsions
EP0644455A1 (de) * 1993-09-17 1995-03-22 Agfa-Gevaert N.V. Photographisches lichtempfindliches Material zur Verwendung für schnelle Verarbeitung
EP0670517A2 (de) * 1994-02-28 1995-09-06 Konica Corporation Verarbeitungsverfahren eines photographischen lichtempfindlichen Silberhalogenidmaterials
EP0670517A3 (de) * 1994-02-28 1995-11-02 Konishiroku Photo Ind Verarbeitungsverfahren eines photographischen lichtempfindlichen Silberhalogenidmaterials.
US5516627A (en) * 1994-02-28 1996-05-14 Konica Corporation Method of processing silver halide light-sensitive photographic material
US6312882B1 (en) * 1994-04-06 2001-11-06 Agfa-Gevaert Silver halide emulsions comprising tabular crystals, emulsions and the processing thereof
EP0682287A1 (de) * 1994-05-09 1995-11-15 Agfa-Gevaert N.V. Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen, die chloridreiche Kristalle enthalten; und diese Emulsionen enthaltendes Material
US5543284A (en) * 1994-05-09 1996-08-06 Agfa-Gevaert, N.V. Preparation method of regular silver halide light-sensitive emulsions comprising silver halide crystals rich in chloride and material comprising said emulsions
EP0698817A1 (de) 1994-08-22 1996-02-28 Agfa-Gevaert N.V. Sortiment von photographischen Silberhalogenidfilmen für die industrielle Radiographie und Verfahren zur Verarbeitung dieses Sortiments
US5840474A (en) * 1995-10-02 1998-11-24 Agfa-Gevaert, N.V. Preparation method for (100) tabular silver halide grains rich in chloride in silica sol as binder
EP0794456A1 (de) 1996-03-07 1997-09-10 Agfa-Gevaert N.V. Verfahren zur Wiedergabe eines elektronisch gespeicherten medizinischen Bildes auf lichtempfindlichen photographischem Material
EP0831362A1 (de) * 1996-09-18 1998-03-25 Agfa-Gevaert N.V. Lichtempfindliches Silberhalogenidmaterial mit Kieselsäure-Schutzkolloid, das Schichten enthält, die kein oder ein Minimum an Gelatine als Bindemittel enthalten

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