EP0503700B1 - Méthode pour la préparation d'émulsions d'iodobromure contenant des grains tabulaires monodispersés - Google Patents

Méthode pour la préparation d'émulsions d'iodobromure contenant des grains tabulaires monodispersés Download PDF

Info

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
Authority
EP
European Patent Office
Prior art keywords
emulsion
tabular grains
grains
silver
aminoazaindene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19920200498
Other languages
German (de)
English (en)
Other versions
EP0503700A1 (fr
Inventor
Ann Leni Verbeeck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP19920200498 priority Critical patent/EP0503700B1/fr
Publication of EP0503700A1 publication Critical patent/EP0503700A1/fr
Application granted granted Critical
Publication of EP0503700B1 publication Critical patent/EP0503700B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (10)

  1. Une méthode pour la préparation d'une émulsion à base du bromure ou de l'iodobromure d'argent comprenant des grains tabulaires monodispersés représentant au moins 50 % de la totalité de la surface de projection de tous les grains, dans laquelle le coefficient de variation de la distribution granulométrique des grains tabulaires a une valeur maximale de 15 %, caractérisée en ce qu'on ajoute de l'aminoazaïndène à n'importe quel stade de la préparation de l'émulsion mais avant que 50 % de la totalité de l'halogénure d'argent soit précipité.
  2. Méthode suivant la revendication 1, caractérisée en ce que le rapport d'aspect de ces grains tabulaires est compris entre 2 et 12.
  3. Méthode selon la revendication 1 ou 2, caractérisée en ce que cet aminoazaindène est un dérivé de l'adénine répondant à la formule Ia ou un dérivé de la 4-amino-pyrazolo-pyrimidine suivant la formule Ib:
    Figure imgb0010
     dans lesquelles
    R1 et R2, identiques ou différents, représentent chacun l'hydrogène, un groupe alkyle, alcényle, aryle, alkoxy, hydroxy, mercapto, carboxy, amino ou halogène, et R3 et R4, identiques ou différents, représentent chacun l'hydrogène ou un groupe alkyle.
  4. Méthode selon la revendication 3, caractérisée en ce que cet aminoazaïndène suivant la formule Ia est l'adénine.
  5. Méthode selon la revendication 3, caractérisée en ce que ce dérivé de la 4-amino-pyrazolo-pyrimidine suivant la formule Ib est la 4-aminopyrazolo[3,4d]pyrimidine.
  6. Méthode selon l'une quelconque des revendications de 1 à 5, caractérisée en ce que cet aminoazaïndène est présent à une concentration qui varie de 10-4 10-3 moles par mole d'halogénure d'argent.
  7. Méthode selon l'une quelconque des revendications de 1 à 6, caractérisée en ce que cet aminoazaïndène est ajouté durant un stade de la maturation physique.
  8. Méthode selon l'une quelconque des revendications de 1 à 7, caractérisée en ce que les grains tabulaires représentent au moins 70 % de la totalité de la surface de projection de tous les grains.
  9. Méthode selon l'une quelconque des revendications de 1 à 8, caractérisée en ce que le coefficient de variation de la distribution granulométrique de ces grains tabulaires est au plus 10 %.
  10. Un matériau photographique comprenant un support et au moins une couche d'émulsion qui contient une émulsion préparée suivant la méthode de l'une quelconque des revendications de 1 à 9.
EP19920200498 1991-03-08 1992-02-20 Méthode pour la préparation d'émulsions d'iodobromure contenant des grains tabulaires monodispersés Expired - Lifetime EP0503700B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19920200498 EP0503700B1 (fr) 1991-03-08 1992-02-20 Méthode pour la préparation d'émulsions d'iodobromure contenant des grains tabulaires monodispersés

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP91200508 1991-03-08
EP91200508 1991-03-08
EP19920200498 EP0503700B1 (fr) 1991-03-08 1992-02-20 Méthode pour la préparation d'émulsions d'iodobromure contenant des grains tabulaires monodispersés

Publications (2)

Publication Number Publication Date
EP0503700A1 EP0503700A1 (fr) 1992-09-16
EP0503700B1 true EP0503700B1 (fr) 1996-10-16

Family

ID=26129189

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920200498 Expired - Lifetime EP0503700B1 (fr) 1991-03-08 1992-02-20 Méthode pour la préparation d'émulsions d'iodobromure contenant des grains tabulaires monodispersés

Country Status (1)

Country Link
EP (1) EP0503700B1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5411851A (en) * 1994-02-14 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
US5411853A (en) * 1994-09-08 1995-05-02 Eastman Kodak Company Grain growth process for the preparation of high bromide ultrathin tabular grain emulsions
EP0735413B1 (fr) * 1995-03-29 2000-10-18 Minnesota Mining And Manufacturing Company Procédé de préparation d'une émulsion à grain tabulaire à l'halogénure d'argent monodispersé
DE69518502T2 (de) * 1995-03-29 2001-04-19 Tulalip Consultoria Comercial Sociedade Unipessoal S.A., Funchal 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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
EP0503700A1 (fr) 1992-09-16

Similar Documents

Publication Publication Date Title
US5595864A (en) Method for making tabular silver halide grains
EP0503700B1 (fr) Méthode pour la préparation d'émulsions d'iodobromure contenant des grains tabulaires monodispersés
US5601969A (en) Preparation of tabular emulsion grains rich in chloride
EP0528476B1 (fr) Méthode pour préparer un matériau photographique à halogénure d'argent
US5286621A (en) Method for the preparation of tabular emulsion grains rich in chloride
EP0653669B1 (fr) Emulsion à grains tabulaire riche en chlorire avec des faces majeures (100)
EP0577886B1 (fr) Préparation des émulsions à grains tabulaires avec un indice de forme intermé- diaires
EP0678772A1 (fr) Matériau sensible à la lumière comprenant des grains tabulaires à chlorobromoiodure ou chloroiodure d'argent
EP0569075B1 (fr) Procédé pour la fabrication de grains d'halogénure d'argent tabulaires
EP0555897B1 (fr) Matériau photographique à l'halogénure d'argent sensible aux rayons X avec tonalité et brillance appropriés
EP0651284A1 (fr) Précipitation de cristaux à l'halogénure d'argent comprenant de l'iodure
US5733715A (en) Silver halide photographic materials comprising silver bromide or bromoiodide emulsions having triangular tabular crystals
EP0843207B1 (fr) Procédé de préparation d'une émulsion photographique améliorée à grains tabulaires riches en chlorure
EP0843208A1 (fr) Procédé pour la préparation de grains tubulaires riches en bromure d'argent en présence de gélatines spécifiques
EP0770909A1 (fr) Matériau photographique multicouche à halogénure d'argent et son procédé de préparation
US6436621B1 (en) Multilayer silver halide photographic material and process for preparing the same
EP0465728A1 (fr) Stabilisation de grains tabulaires par des dérivés de pyrimidine
US6136524A (en) Light-sensitive emulsion having (100) tabular grains rich in silver chloride and method for preparing said grains
EP0610608B1 (fr) Matériau photographique sensible à la lumière, à base d'halogénure d'argent, pour la restitution d'images médicales enregistrées par laser et méthode de traitement
US6280915B1 (en) Spectrally sensitized tabular grain photographic materials
US6080536A (en) Method of preparing (100) tabular grains rich in silver bromide
EP0809135A1 (fr) Procédé de préparation d'une émulsion photographique à grains tabulaires riches en chlorure
US6083678A (en) Method for preparing a light-sensitive emulsion having (100) tabular grains rich in silver chloride
EP0647877A1 (fr) Préparation d'une émulsion argentique ayant des grains tabulaires riches en chlorure
EP0590715B1 (fr) Préparation d'une emulsion utilisant simultanément sensibilisation chimique et spectrale en présence d'un sel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB

17P Request for examination filed

Effective date: 19930204

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

17Q First examination report despatched

Effective date: 19960402

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19961016

REF Corresponds to:

Ref document number: 69214486

Country of ref document: DE

Date of ref document: 19961121

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: 746

Effective date: 19990204

REG Reference to a national code

Ref country code: FR

Ref legal event code: D6

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20021210

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20021212

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041029

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20050124

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060220

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20060220