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EP0503700B1 - Verfahren zur Herstellung von Jodobromid-Emulsionen, die monodisperse tabulare Körner enthalten - Google Patents

Verfahren zur Herstellung von Jodobromid-Emulsionen, die monodisperse tabulare Körner enthalten Download PDF

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Publication number
EP0503700B1
EP0503700B1 EP19920200498 EP92200498A EP0503700B1 EP 0503700 B1 EP0503700 B1 EP 0503700B1 EP 19920200498 EP19920200498 EP 19920200498 EP 92200498 A EP92200498 A EP 92200498A EP 0503700 B1 EP0503700 B1 EP 0503700B1
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Prior art keywords
emulsion
tabular grains
grains
silver
aminoazaindene
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EP19920200498
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French (fr)
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EP0503700A1 (de
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Ann Leni Verbeeck
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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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/07—Substances influencing grain growth during silver salt formation
    • 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
    • G03C1/0051—Tabular grain emulsions

Definitions

  • the present invention relates to silver halide emulsion technology and more particularely to a method for the preparation of silver bromide or silver iodobromide emulsions containing tabular grains which show a monodisperse grain size distribution.
  • monodisperse emulsions show some interesting photographic properties.
  • Monodispersity is characterized by a low coefficient of variation (or variance), defined as the quotient of the standard deviation on the size distribution divided by the average grain size. This value is often expressed as a percentage. Because of the influence of the specific grain surface on the chemical reactions occuring during chemical sensitization the latter process leads in the case of heterodisperse emulsions to a heterogeneously distributed degree of progress of said sensitization. In this way only a fraction of the total grain population is optimally sensitized. On the contrary chemical ripening of monodisperse emulsions leads to a homogeneous distribution of sensitivity specks resulting in a homogeneous photographic response.
  • monodisperse emulsions favourably influence overall picture quality. Fine grain populations which contribute disproportionately to light scattering resulting in sharpness reduction are restricted; populations of relative larger grains which contribute mainly to image granularity are restricted too.
  • tabular grains with a high diameter to thickness ratio exhibit several pronounced photographic advantages.
  • aspect ratio exhibit several pronounced photographic advantages.
  • tabular grains are known for quite some time the early publications cannot be regarded as dealing with high aspect ratio tabular grains.
  • So Wilgus US 4,434,226 discloses tabular silver bromoiodide grains having a thickness less than 0.3 ⁇ m, a diameter of at least 0.6 ⁇ m and an average aspect ratio greater than 8:1 and accounting for at least 50 percent of the total projected area of all the emulsion grains.
  • Kofron US 4,439,520 discloses similar grains which are spectrally sensitized.
  • Abbott US 4,425,425 describes radiographic materials containing tabular grains with aspect ratio of at least 8:1 and Abbott US 4,425,426 discloses similar grains with an aspect ratio between 5:1 and 8:1.
  • Solberg US 4,433,048 protects tabular silver bromoiodide grains with inhomogeneously distributed iodide.
  • a survey on high aspect ratio silver halide emulsions appeared in Research Disclosure, Vol 225, Jan 1983, Item 22534.
  • Zola EP 0 362 699 describes silver bromoiodide grains with an average aspect ratio greater than 12 characterized in that the quotient of the average aspect ratio of the tabular grains divided by the coefficient of variation of the total grain population is greater than 0.7. In this way the monodispersity is correlated with the aspect ratio because of the greater difficulty of preparing monodisperse tabular grains with very high aspect ratios.
  • An essential feature of the preparation method consists in a nucleation stage characterized by a very high flow rate and concentrated solutions.
  • the object of the present invention of preparing emulsions containing tabular silver iodobromide or silver bromide grains showing a coefficient of variation of at most 15 % is realized by adding an aminoazaindene to the reaction vessel at any stage of the emulsion preparation before 50 % of the total silver halide is precipitated.
  • said aminoazaindene is an adenine derivative according to formula Ia or a 4-amino-pyrazolo-pyrimidine derivative according to formula Ib : wherein each of R 1 and R 2 which may be the same or different represents hydrogen, alkyl , alkenyl, aryl, alkoxy, hydroxy, mercapto, carboxy, amino or halogen, and each of R 3 and R 4 which may be the same or different represents hydrogen or alkyl;
  • aminoazaindenes in general or particular classes thereof were known in the prior art in connection with the preparation of tabular grains rich in chloride, e.g. as disclosed in Maskasky US 4,400,463, Maskasky US 4,713,323 and Tufano US 4,804,621, it is the first time that their use in the preparation of tabular (iodo)bromide is disclosed. Further it is the first time that their surprising effect on the homogenisation of the size distribution of said tabular silver (iodo)bromide grains is recognized.
  • the new method of the present invention is particularly suited for the preparation of tabular silver (iodo)bromide grains with an average aspect ratio comprised between 2 and 12.
  • the aminoazaindenes used in connection with the present invention can be added at any stage of the silver halide precipitation procedure e.g. before the start of the precipitation, during the nucleation step, during a physical ripening stage or during one or more of the growth steps with the proviso that the total amount of aminoazaindene is added before 50 % of the total silver amount is precipitated.
  • the substance can be added to the. dispersion medium itself as a solid or as a predissolved aqueous solution; alternatively the substance can be dissolved in one or more of the solutions which are entered into the dispersion medium, e.g. in one or more of the halide or silver salt solutions.
  • aminoazaindenes used in connection with the present invention are preferably present in a concentration ranging from 10 -4 to 10 -3 moles per mole silver halide.
  • the aminoazaindene is an adenine derivative or a 4-amino-pyrazolo-pyrimidine derivative. More preferably the aminoazaindene is adenine (formula Ia-1); the 4-amino-pyrazolo-pyrimidine derivative preferably is 4-aminopyrazolo[3,4]pyrimidine (formula Ib-1) :
  • the emulsion precipitation can be principally performed by one double jet step it is preferred to perform a sequence of a nucleation step and at least one growth step.
  • a nucleation step preferably 0.5 % to 5.0 % is precipitated during said nucleation step which consists preferably of an approximately equimolecular addition of silver and halide salts.
  • the rest of the silver and halide salts is added during one or more consecutive double jet growth steps.
  • the different steps of the precipitation can be alternated by physical ripening steps.
  • an increasing flow rate of silver and halide solutions is preferably established, e.g. a linearly increasing flow rate.
  • the flow rate at the end is about 3 to 5 times greater then at the start of the growth step.
  • These flow rates can be monitored by e.g. magnetic valves.
  • the pAg is preferably maintained at a constant value corresponding to a silver potential preferably at least -30 milli-Volt measured by a silver versus calomel electrode.
  • the pH is preferably established at a value of at least 4.0.
  • gelatin concentration from 0.05 % to 5.0 % by weight in the dispersion medium. Additional gelatin is added in a later stage of the emulsion preparation, e.g. after washing, to establish optimal coating conditions and/or to establish the required thickness of the coated emulsion layer. Preferably a gelatin / silver halide ratio ranging from 0.3 to 1.0 is then obtained, wherein silver halide is expressed as silver nitrate.
  • Conventional lime-treated or acid treated gelatin can be used, preferably of the inert type. The preparation of such gelatin types has been described in e.g. "The Science and Technology of Gelatin", edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 and next pages.
  • the gelatin can also be an enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan, N° 16, page 30 (1966).
  • wash technique in order to remove the excess of soluble salts is applied.
  • Any conventional wash technique can be used e.g. washing with several water portions after flocculation by an inorganic salt or by a polymeric flocculating agent like polystyrene sulphonic acid.
  • the emulsions containing tabular grains prepared according to the method of the present invention can be used in various types of photographic elements. However because of their (iodo)bromide composition they are preferably used in those applications for which high sensitivity is required.
  • Preferred embodiments include black-and-white or colour negative recording materials for still photography or for cinematographic application, black-and-white or colour reversal materials, graphic arts camera sensitive films and materials for radiographic recording.
  • the photographic element containing one or more emulsions prepared in accordance with the present invention can be composed of one single emulsion layer, as is the case for many applications, or it can be built up by two or even more emulsion layers.
  • the material contains blue, green and red sensitive layers each of which can be single or multiple.
  • the photographic material can contain several non-light sensitive layers, e.g. a protective layer, one or more backing layers, one or more subbing layers, and one or more intermediate layers e.g. filter layers.
  • the emulsions containing tabular silver (iodo)bromide grains prepared in accordance with the present invention can be chemically sensitized as described e.g. in "Chimie et Physique Photographique” by P. Glafkides, in “Photographic Emulsion Chemistry” by G.F. Duffin, in “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.
  • emulsions can be sensitized also by means of gold-sulphur ripeners or by means of reductors e.g. tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • reductors e.g. tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • the silver halide emulsions under consideration 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, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • the silver halide emulsion layer(s) in accordance with the present invention or the non-light-sensitive layers may comprise compounds preventing the formation of fog or stabilizing the photographic characteristics during the production or storage of the 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 e.g.
  • 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
  • colour negative or colour reversal photographic material the usual ingredients specific for colour materials can be present e.g. colour couplers, couplers bearing a releasable photographic useful group and scavengers for oxidized developer.
  • These typical ingredients for colour materials can be soluble or added in dispersed form, e.g. with the aid of so-called oilformers or they can be added in polymeric latex form.
  • the gelatin binder of the photographic elements 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
  • the photographic element used in connection with the present invention may further 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 and as compounds preventing or reducing adhesion.
  • Preferred surface-active coating agents are compounds containing perfluorinated alkyl groups.
  • 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 3,038,805 - 4,038,075 - 4,292,400.
  • the photographic element in connection with 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 and plasticizers.
  • Suitable additives for improving the dimensional stability of the photographic element are e.g. dispersions of a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl(meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters, acrylonitriles, olefins, and styrenes, or copolymers of the above with acrylic acids, methacrylic acids, Alpha-Beta-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulphoalkyl (meth)acrylates, and styrene sulphonic acids.
  • a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl(meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters,
  • UV-absorbers are e.g. aryl-substituted benzotriazole compounds as described in US 3,533,794, 4-thiazolidone compounds as described in US 3,314,794 and 3,352,681, benzophenone compounds as described in JP-A 2784/71, cinnamic ester compounds as described in US 3,705,805 and 3,707,375, butadiene compounds as described in US 4,045,229, and benzoxazole compounds as described in US 3,700,455.
  • UV-absorbers are especially useful in colour recording materials where they prevent the fading by light of the colour images formed after processing.
  • spacing agents can be present of which, in general, the average particle size is comprised between 0.2 and 10 ⁇ m. 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 e.g. 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 4,614,708.
  • the photographic material can contain several non light sensitive layers, e.g. an anti-stress top layer, one or more backing layers, and one or more intermediate layers eventually containing filter- or or antihalation dyes that absorb scattering light and thus promote the image sharpness.
  • Suitable light-absorbing dyes are described in e.g. US 4,092,168, US 4,311,787, DE 2,453,217, and GB 7 907 440.
  • One or more backing layers can be provided at the non-light sensitive side of the support.
  • These layers which can serve as anti-curl layer can contain e.g. matting agents like silica particles, lubricants, antistatic agents, light absorbing dyes, opacifying agents, e.g. titanium oxide and the usual ingredients like hardeners and wetting agents.
  • the support of the photographic material may be opaque or transparent, e.g. a paper support or resin support.
  • a paper support preference is given to one coated at one or both sides with an Alpha-olefin polymer, e.g. a polyethylene layer which optionally contains an anti-halation dye or pigment.
  • an organic resin support e.g. cellulose nitrate film, cellulose acetate film, polyvinylacetal) film, polystyrene film, polyethylene terephthalate film, polycarbonate film, polyvinylchloride film or poly-Alpha-olefin films such as polyethylene or polypropylene film.
  • the thickness of such organic resin film is preferably comprised between 0.07 and 0.35 mm.
  • These organic resin supports are preferably coated with a subbing layer which can contain water insoluble particles such as silica or titanium dioxide.
  • the photographic material containing tabular grains prepared according to the present invention can be image-wise exposed by any convenient radiation source in accordance with its specific application.
  • processing conditions and composition of processing solutions are dependent from the specific type of photographic material in which the tabular grains containing emulsions prepared according to the present invention are applied.
  • an automatically operating processing apparatus is used provided with a system for automatic regeneration of the processing solutions.
  • control emulsion 1 A pure silver bromide emulsion (control emulsion 1) was prepared as described hereafter.
  • a nucleation step was performed by introducing solution A and solution B simultaneously into dispersion medium C both at a flow rate of 25 ml/min during 28 seconds. During the following physical ripening stage of 15 min the temperature was raised to 70 °C and 532 ml of water and 48 g of inert gelatin were added; the mixture was stirred for an additional 5 minutes. Then a first growth step was performed by introducing by a double jet during 564 seconds solution A at a constant flow rate of 5.0 ml/min and solution B as to maintain a constant silver potential, measured by a silver electrode versus calomel , of -3 milli-Volt.
  • a second growth step was performed by introducing by a double jet during 3764 seconds solution A starting at a flow rate of 5.0 ml/min and linearly increasing the flow rate to an end value of 25 ml/min and solution B at an increasing flow rate as to maintain a constant silver potential of -3 mV.
  • a second pure silver bromide emulsion in accordance with the present invention (emulsion 2) was prepared in a way similar to control emulsion 1 with the following modification : during the physical ripening stage 0.18 g of adenine was added simultaneously with the water and the gelatin.
  • control emulsion 3 A third emulsion containing 99 % of bromide and 1 % of iodide (control emulsion 3) was prepared by a method similar to control emulsion 1 with following modifications :
  • a fourth emulsion containing 99 % of bromide and 1 % of iodide in accordance with the present invention (emulsion 4) was prepared in a way similar to control emulsion 3 with the following modification : during the physical ripening stage 0.18 g of adenine was added simultaneously with the water and the gelatin.
  • the emulsion samples were chemically ripened to an optimal fog-sensitivity relationship using conventional sulfur-gold sensitization. Then they were sensitized to the green spectral region by the addition of a green sensitizer with following chemical formula :
  • the coated emulsion samples were image-wise exposed through a continuous tone wedge using a conventional white light source. Then they were developed on one hand in a active radiographic developer containing per liter 40 g of hydroquinone, 1.5 g of Phenidone and a polyoxyalkylene development accelerator at pH 10.3, and on the other hand in a rather weak developer containing per liter a.o. 26.7 g of hydroquinone and 1.6 g of Phenidone at pH 10.4. Finally the coated samples were fixed in a conventional ammonium thiosulphate containing fixing solution and dried.
  • Table 2 presents the sensitometric results in the active developer and the difference in speed and in gradation between development in the weak and in the strong developer; a low difference is considered to be an indication of a good developability of the emulsion sample under consideration.
  • Table 2 illustrates the better developability of the emulsions in connection with the invention.
  • a pure silver bromide emulsion (emulsion 5) was prepared in a way similar to emulsion 2 with the modification that 0.09 g of 4-aminopyrazolo[3,4d]pyrimidine was added during physical ripening instead of 0.18 g of adenine;
  • Table 3 compares the grain size characteristics of emulsion 5 with those of control emulsion 1; the sensitometric characteristics are given in table 4.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Claims (10)

  1. Verfahren zur Herstellung einer Silberbromid- oder Silberjodobromid-Emulsion mit monodispersen tabularen Körnern, die wenigstens 50% der projizierten Gesamtoberfläche aller Körner bilden, wobei der Streuungskoeffizient der Korngrößenverteilung der tabularen Körner höchstens 15% beträgt, dadurch gekennzeichnet, daß in einer beliebigen Stufe während der Herstellung der Emulsion, ehe sich 50% der Gesamtmenge Silberhalogenid niedergeschlagen hat, ein Aminoazainden zugesetzt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Aspektverhältnis der tabularen Körner zwischen 2 und 12 liegt.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Aminoazainden ein Adeninderivat nach der Formel Ia oder ein 4-Amino-pyrazolo-pyrimidin-Derivat nach der Formel Ib ist :
    Figure imgb0009
     in denen bedeuten :
    R1 und R2 (gleich oder verschieden) je Wasserstoff, eine Alkyl-, Alkenyl-, Aryl-, Alkoxy-, Hydroxy-, Mercapto-, Carboxy-, Amino- oder Halogengruppe, und
    R3 und R4 (gleich oder verschieden) Wasserstoff oder eine Alkylgruppe.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß das Aminoazainden gemäß Formel Ia Adenin ist.
  5. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß das 4-Amino-pyrazolo-pyrimidin-Derivat gemäß Formel Ib 4-Aminopyrazolo[3,4]pyrimidin ist.
  6. Verfahren nach irgendeinem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Aminoazainden in einem Verhältnis zwischen 10-4 und 10-3 Mol pro Mol Silberhalogenid enthalten ist.
  7. Verfahren nach irgendeinem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Aminoazainden während einer physikalischen Reifungsstufe zugesetzt wird.
  8. Verfahren nach irgendeinem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die tabularen Körner wenigstens 70% der projizierten Gesamtoberfläche aller Körner bilden.
  9. Verfahren nach irgendeinem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß der Streuungskoeffizient der Korngrößenverteilung der tabularen Körner höchstens 10% beträgt.
  10. Photographisches Material mit einem Träger und wenigstens einer Emulsionsschicht, die eine gemäß irgendeinem der Ansprüche 1 bis 9 entsprechenden Verfahren hergestellte Emulsion enthält.
EP19920200498 1991-03-08 1992-02-20 Verfahren zur Herstellung von Jodobromid-Emulsionen, die monodisperse tabulare Körner enthalten Expired - Lifetime EP0503700B1 (de)

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US5411851A (en) * 1994-02-14 1995-05-02 Eastman Kodak Company Grain growth process for the preparation of high bromide ultrathin tabular grain emulsions
US5411853A (en) * 1994-09-08 1995-05-02 Eastman Kodak Company Grain growth process for the preparation of high bromide ultrathin tabular grain emulsions
US5418125A (en) * 1994-09-08 1995-05-23 Eastman Kodak Company Grain growth process for the preparation of high bromide ultrathin tabular grain emulsions
DE69518502T2 (de) * 1995-03-29 2001-04-19 Tulalip Consultoria Comercial Sociedade Unipessoal S.A., Funchal Verfahren zur Herstellung von Emulsionen mit monodispersen Silberhalogenidtafelkörnern
EP0735413B1 (de) * 1995-03-29 2000-10-18 Minnesota Mining And Manufacturing Company Verfahren zur Herstellung von Emulsionen mit monodispersen Silberhalogenidtafelkörnern
US5750326A (en) * 1995-09-29 1998-05-12 Eastman Kodak Company Process for the preparation of high bromide tabular grain emulsions
US6228573B1 (en) 1999-12-15 2001-05-08 Eastman Kodak Company Process for the preparation of high bromide ultrathin tabular grain emulsions
JP4262401B2 (ja) * 2000-09-28 2009-05-13 富士フイルム株式会社 ハロゲン化銀写真感光材料

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US4804621A (en) * 1987-04-27 1989-02-14 E. I. Du Pont De Nemours And Company Process for the preparation of tabular silver chloride emulsions using a grain growth modifier

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