EP0517961B1 - Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen - Google Patents

Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen Download PDF

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Publication number
EP0517961B1
EP0517961B1 EP19910201426 EP91201426A EP0517961B1 EP 0517961 B1 EP0517961 B1 EP 0517961B1 EP 19910201426 EP19910201426 EP 19910201426 EP 91201426 A EP91201426 A EP 91201426A EP 0517961 B1 EP0517961 B1 EP 0517961B1
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EP
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Prior art keywords
silver halide
emulsion
value
silica
gelatin
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Expired - Lifetime
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EP19910201426
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English (en)
French (fr)
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EP0517961A1 (de
Inventor
Hubert Vandenabeele
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to DE1991629148 priority Critical patent/DE69129148T2/de
Priority to EP19910201426 priority patent/EP0517961B1/de
Priority to JP17607592A priority patent/JPH05204068A/ja
Publication of EP0517961A1 publication Critical patent/EP0517961A1/de
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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
    • G03C1/015—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
    • 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

Definitions

  • This invention relates to methods of coagulating, washing and redispersing light-sensitive silver halide emulsions, the silver halide of which has been precipitated in a colloid medium of silica and to photographic materials incorporating layers of such emulsions.
  • Light-sensitive silver halide emulsions are conventionally prepared by reacting an aqueous silver salt solution, e.g. silver nitrate, with an aqueous alkali metal halide solution to cause precipitation of silver halide in the presence of a protective colloid. After physical ripening to the desired average grain size and washing, a further amount of protective colloid may be added so that the emulsion may be subjected to chemical ripening.
  • gelatin which is a thermoreversible polymer, showing a sufficient gel strength after coating.
  • gelatino-silver halide emulsion layers undergo considerable swelling and subsequent shrinkage upon absorption and release of processing liquids during image processing. This lack of dimensional stability under processing conditions can adversely affect image quality.
  • colloidal silica Another substance proposed in the prior art as protective colloid binder in silver-halide emulsions is colloidal silica. This colloid has no or less adverse effects on light-sensitivity and as disclosed in UK Patent 1276894 silver halide emulsions comprising gelatin together with various proportions of silica sol as a binder have less tendency to swell on treatment with aqeuous processing liquids than conventional gelatino-silver halide emulsion layers of the same thickness.
  • a method of preparing a light-sensitive silver halide emulsion by precipitating silver halide in the presence of colloidal silica serving as protective colloid characterized in that the precipitation takes place in the presence of an onium compound having an emulsion-stabilising effect.
  • Coagulation in gelatineous medium can e.g. be effected by an alcohol or a salt or if the emulsion contains a sufficient amount of acid-coagulable gelatin derivatives or hydrogen bridge forming anionic polymeric compounds by addition of an acid to lower the pH value to the isoelectric point.
  • Hydro bridge forming anionic polymeric compounds are polystyrene sulphonic acid and sulphonated copolymers of styrene, which are commonly used.
  • Acid coagulable gelatin derivatives as phtaloyl or N-phenyl carbamoyl gelatin can be used, requiring only adjustment of the pH to the right value to cause the emulsion to coagulate.
  • Coagulation techniques have been described e.g. in U.S. Patent Specifications 2,614,928; 2,614,929 and 2,728,662.
  • a method of preparing a light-sensitive silver halide emulsion comprising the steps of precipitating the silver halide in the presence of an onium compound and colloidal silica having a specific surface area between 200 and 600 g/m 2 serving as the sole protective colloid, coagulation washing the formed precipitate and redispersing the silver halide, characterised in that the coagulation proceeds in the presence of a polymer capable of forming hydrogen-bridge s with the silica in an amount of 1 to 40 % by weight verus silica sol.
  • a variety of hydrogen bridge forming polymers can be used as a flocculating agent, e.g. gelatin, polyethylene oxyde, polyethylene imide, polyacrylic acid, polyvinylalcohol, etc. and a combination of two or more of these agents.
  • gelatin is used as flocculating agent.
  • the quantity of flocculating agent can be optimized for each particular case. The amount should not be such that redispersion occurs.
  • Amounts of e.g. 1 to 40%, preferably 10 to 40% by weight of flocculating agent versus silica sol generally give rise to qualitatively good flocculates, which are transportable in a handsome way through e.g. conduct-pipes as they have a "sandy" structure, never showing sticking phenomena.
  • the amount of silica normally used at the stage of precipitation is comprised between 2 and 20 parts by weight with respect to 100 parts by weight of silver nitrate used. This procedure is offering quite a lot of advantages e.g. it is even possible to produce powdery silver halide crystals by dry-freezing of this sandy flocculate.
  • silver halide emulsions are prepared by the following steps :
  • protective colloid at the stage of redispersion is determined by further treatment conditions as e.g. chemical ripening, spectral sensitization, stabilization and preparation to coating.
  • an excess of the original flocculating agents can be used in whatever an amount, which depends on the coating requirements.
  • other colloids than the hydrogen bridge forming polymers mentioned as flocculating agent, can be used in redispersing the coagulate.
  • the temperature of the reaction vessel can be lowered without risking a jelly structure and unprotected silver halide crystals.
  • silica sol may be added at the stage of redispersion and the ratio by weight of silica sol over silver halide can be regulated. So in EP 0392092 even a value exceeding 1.0 is described to be the most preferable one if one wants to avoid the addition of supplemental hardening agents to the emulsion before or during the coating procedure. Any combination of ingredients, being compatible to form a stable colloid system before and during coating, may be used.
  • the ratio by weight of gelatin over silver nitrate can be adjusted by adding an adapted amount of gelatin, silica and/or suitable polymers at the stage of or after redispersing the coagulation washed emulsion. Even coating without gelatin is possible, especially on a paper undercoat or substrate.
  • the average size of the silver halide grains may range from 0.01 to 7 ⁇ m.
  • the size distribution of the silver halide particles of the photographic emulsions prepared according to the present invention 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 photographic silver halide can be precipitated by mixing the halide and silver solutions in the 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.
  • 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 Rh 3+ , Ir 4+ , Cd 2+ , Zn 2+ , Pb 2+ .
  • Rh 3+ , Ir 4+ , Cd 2+ , Zn 2+ , Pb 2+ There are no restrictions concerning the halide composition : chloride, bromide, iodide and any combination may be used.
  • 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 200, 300, 500 and 600" (trademarked products of Bayer AG).
  • the light-sensitive silver halide emulsion prepared in accordance with the present invention is, after redispersion, a so-called primitive emulsion.
  • 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 mit Silberhalogeniden” edited by H.
  • 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.
  • a mixture can also be made of two or more separately precipitated emulsions being chemically sensitized before mixing them.
  • the light-sensitive silver halide emulsions can be spectrally sensitized with methine dyes such as those 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, 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 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.
  • 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 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.
  • a photographic element comprising a light-sensitive silver halide emulsion prepared by the method 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 sulphates 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
  • 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.
  • a photographic element comprising a light-sensitive silver halide emulsion prepared by the method 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.
  • the binders 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. 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
  • 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.
  • active vinyl compounds e.g. 1,3,5-triacryloyl-hexahydro-s-triazine
  • active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine
  • mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid.
  • 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.
  • the average particle size of spacing agents is comprised between 0.2 um and 10 um.
  • 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..
  • 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. 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.
  • a photographic emulsion was prepared according to the procedure described in Example 1; however no flocculating agent was added.
  • Photographic emulsions were prepared according to the procedure described in Example 1, except that the following compounds were used as flocculating agents.
  • Gelatin in an amount as in example 1 was replaced by another inert type of gelatin, the viscosity being lower in this case (19.4 mPas instead of 32.8 mPas for a 10% solution at 40°C, measured with a Haake Rotavisco RV2 apparatus).
  • silica Per 100 g of silica a mixture was used of 6.6 g of polyethylene imine (see example 6) and 32 g of
  • Table II is illustrating clearly that silica is quantitatively adsorbed at the silver halide crystal surface, the losses of silica being limited to between 1 and 2 % in the mother lye and even less than 0.5 % after washing.
  • the flocculation procedure can thus be considered to be quantitative and reliable.

Claims (9)

  1. Ein Verfahren zur Herstellung einer lichtempfindlichen Silberhalogenidemulsion, in dem das Silberhalogenid in Gegenwart einer Oniumverbindung und als einziges Schutzkolloid dienender kolloidaler Kieselerde mit einem spezifischen Oberflächeninhalt zwischen 200 und 600 g/m2 gefällt, der gebildete Niederschlag durch Koagulation gewaschen und die Silberhalogenidemulsion redispergiert wird, dadurch gekennzeichnet, daß die Koagulation in Gegenwart eines Polymeren, das mit der Kieselerde Wasserstoffbrücken zu bilden vermag und in einer Menge zwischen 1 und 40 Gew.-% bezogen auf Kieselsol enthalten ist, erfolgt.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Wasserstoffbrücken bildende, als Ausflockungsmittel dienende Polymere Gelatine, Polyethylenoxid, Polyethylenimid, Polyacrylsäure, Polyvinylalkohol oder Polystyrolsulfonsäure oder eine Kombination von zwei oder mehr derselben ist.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Ausflockungsmittel Gelatine ist und in einer Menge zwischen 10 und 40 Gew.-% bezogen auf das Kieselsol benutzt wird.
  4. Verfahren nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der pH-Wert vor und nach der Zugabe des Ausflockungsmittels und nach jedem Waschvorgang auf einen Wert zwischen 1,0 und 4,0 gebracht wird.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß der pH-Wert auf einen Wert zwischen 2,5 und 3,0 gebracht wird.
  6. Verfahren nach irgendeinem der Ansprüche 1 bis 5, das weiterhin die Stufe der Redispergierung des gefällten Silberhalogenids durch Zugabe von kolloidaler Kieselerde umfaßt.
  7. Verfahren nach irgendeinem der Ansprüche 1 bis 6, das weiterhin die Stufe der Redispergierung des gefällten Silberhalogenids durch Zugabe von Gelatine umfaßt.
  8. Verfahren zur Herstellung einer lichtempfindlichen Silberhalogenidemulsion nach Anspruch 1, das die folgenden Stufen umfaßt :
    a. die Fällung von Silberhalogenid in einem wäßrigen, als einziges Schutzkolloid dienenden, eine Oniumverbindung enthaltenden Kieselerdemedium mit dem obengenannten spezifischen Oberflächeninhalt, wobei das wäßrige Medium einen pH-Wert von mehr als 4 aufweist,
    b. das Anpassen des pH-Wertes der Silberhalogenidemulsion auf einen Wert zwischen 1,0 und 4,0,
    c. die Zugabe im Emulsionsgefäß, in der obenerwähnten Menge, eines Wasserstoffbrücken bildenden Polymeren als Ausflockungsmittel,
    d. das Erlauben der Bildung von Aggregaten nach der Bildung von Wasserstoffbrücken,
    e. die Entfernung der klaren überschwimmenden Flüssigkeit,
    f. das Waschen der Ausflockung,
    g. das Wiederanpassen des pH-Wertes auf einen Wert zwischen 1,0 und 4,0,
    h. die Entfernung der klaren überschwimmenden Flüssigkeit,
    i. wenn nötig die Wiederholung der Stufen f bis h, um den erwünschten pAg-Werterfordernissen entgegenzukommen,
    j. das Auslösen der Redispergierung der Ausflockung durch Zugabe eines Überschusses von Schutzkolloid oder einem Wasserstoffbrücken bildenden Polymeren.
  9. Verfahren nach irgendeinem der Ansprüche 1 bis 8, das weiterhin die Stufen der chemischen und/oder spektralen Sensibilisierung und des Auftrags der Emulsion auf einen Träger zur Bildung eines fotografischen Materials umfaßt.
EP19910201426 1991-06-11 1991-06-11 Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen Expired - Lifetime EP0517961B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE1991629148 DE69129148T2 (de) 1991-06-11 1991-06-11 Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen
EP19910201426 EP0517961B1 (de) 1991-06-11 1991-06-11 Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen
JP17607592A JPH05204068A (ja) 1991-06-11 1992-06-09 感光性ハロゲン化銀乳剤の製造方法

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EP19910201426 EP0517961B1 (de) 1991-06-11 1991-06-11 Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen

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EP0517961A1 EP0517961A1 (de) 1992-12-16
EP0517961B1 true EP0517961B1 (de) 1998-03-25

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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
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DE69425557T2 (de) * 1994-05-09 2001-05-23 Agfa Gevaert Nv Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen, die chloridreiche Kristalle enthalten
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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
EP0794456B1 (de) 1996-03-07 2003-01-29 Agfa-Gevaert Verfahren zur Wiedergabe eines elektronisch gespeicherten medizinischen Bildes auf lichtempfindlichen photographischem Material
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US5994049A (en) * 1997-08-28 1999-11-30 Eastman Kodak Company Water-soluble non-interactive polymers and surfactant micelles for desalting and concentrating silver halide photographic emulsions
KR100477912B1 (ko) * 2002-02-20 2005-03-17 (주)엔피텍 에탄올을 포함한 유기 용매하에서의 콜로이드 실버의 제조방법

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HU201612B (en) * 1985-12-23 1990-11-28 Forte Fotokemiai Ipar Method for making silver halogenide photoemulsio
DE68918267T2 (de) * 1989-04-11 1995-03-02 Agfa Gevaert Nv Verfahren zur Herstellung von lichtempfindlichen Silberhalogenid Emulsionen.

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JPH05204068A (ja) 1993-08-13
DE69129148D1 (de) 1998-04-30
DE69129148T2 (de) 1998-10-08
EP0517961A1 (de) 1992-12-16

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