EP0392092B1 - Méthode pour la préparation d'émulsions à l'halogénure d'argent photosensibles - Google Patents

Méthode pour la préparation d'émulsions à l'halogénure d'argent photosensibles Download PDF

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EP0392092B1
EP0392092B1 EP89200909A EP89200909A EP0392092B1 EP 0392092 B1 EP0392092 B1 EP 0392092B1 EP 89200909 A EP89200909 A EP 89200909A EP 89200909 A EP89200909 A EP 89200909A EP 0392092 B1 EP0392092 B1 EP 0392092B1
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silver halide
silicic acid
onium
light
compound
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EP0392092A1 (fr
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Hubert Vandenabeele
Antonius Albertus Rutges
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions

Definitions

  • This invention relates to methods of preparing light-sensitive silver halide emulsions, 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 is added and the emulsion is subjected to chemical ripening.
  • the most commonly used protective colloid is gelatin.
  • the conventional gelatino-silver halide emulsion layers undergo considerable swelling and subsequent shrinkage consequent upon absorption and release of processing liquids during image processing. This lack of dimensional stability under processing conditions can adversely affect image quality.
  • due to their rather slow absorption and release of the processing liquids such conventional gelatino-silver halide layers cannot meet the rapid processing criteria which are often demanded. This is notwithstanding the fact that rapid processing can to some extent be promoted by using light-sensitive photographic materials which incorporate silver halide developing agents in or in water-permeable relationship to the light-sensitive layer and using a two-step development process comprising an activating and stabilising step instead of the conventional development, fixing and washing steps.
  • colloidal silicic acid Another substance proposed in the prior art as protective colloid binder in silver-halide emulsions is colloidal silicic acid.
  • 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 silicic acid sol as binder have less tendency to swell on treatment with aqeuous processing liquids than conventional gelatino-silver halide emulsion layers of the same thickness.
  • United States Patent 4 001 022 discloses photographic elements which are described as suitable for rapid processing and which comprise a support bearing an acidic developer layer and a basic gelatino-silver halide emulsion layer, both of which layers contain a substantial amount of colloidal silica.
  • the binder in which the silver halide is dispersed comprises by weight about 6 to 40 percent of gelatin, the remainder being colloidal silica.
  • silicic acid sol as a protective colloid reduces swelling of light-sensitive silver halide layers during liquid processing
  • the extent of that advantage has hitherto been limited by the need for the concentration of the silicic acid sol to be restricted in order to avoid making the emulsions physically unstable.
  • the instability of silicic acid sols when used as protective colloid binder for silver halide is recognised in United States Patent 3 637 391. It is disclosed in that patent that if a silicic acid sol of too high a concentration is used, agglomeration occurs when a reaction mixture of alkali metal and silver salts is added to the sol.
  • the patent proposes treatment of the silicic acid sol with ethanol, the addition of a homo or co-polymer of sufficiently water soluble monomer(s) or the polymerisation of such monomer(s) in situ in the silicic acid sol.
  • the patent recommends that the precipitated emulsion be redispersed in gelatin before being chemically ripened and that the concentration of the silicic acid sol in the final emulsion should not be more than 20% and preferably not more than 10% by weight.
  • the necessity to restrict the concentration of the silicic acid sol limits the advantage which can be derived from the use of the sol in terms of for instance improved dimensional stability of photographic layers formed from the emulsion.
  • An object of the present invention is to enable the proportion of silicic acid sol used as a protective colloid in the preparation of silver halide emulsions to be substantially increased without resulting in unacceptable physical instability of the emulsion.
  • a method of preparing a light-sensitive silver halide emulsion by precipitating silver halide in the presence of colloidal silicic acid serving as protective colloid characterised in that the precipitation takes place in the presence of an onium compound, except for ammonium bromide.
  • At least 75% by weight of the protective colloid used in the silver halide precipitation step consists of silicic acid sol.
  • such protective colloid consists entirely of such sol.
  • light-sensitive layers which have the maximum dimensional stability benefit derivable from the use of silicic acid sol as binder can be formed directly from the precipitated emulsion after it has been ripened and washed.
  • the invention is not restricted to methods wherein silicic acid sol is used as the sole protective colloid in the precipitation of the silver halide.
  • the protective colloid used in that precipitation can comprise silicic acid sol and a proportion of some other binder known as such in the photographic art.
  • the protective colloid can comprise silicic acid sol and gelatin.
  • additional silicic acid sol can be added to the emulsion after the precipitation of the silver halide, e.g. during the subsequent redispersion of the emulsion.
  • the invention includes light-sensitive material comprising a support bearing at least one light-sensitive silver halide emulsion layer which incorporates silicic acid sol as a protective colloid binder, characterised in that said layer further comprises an onium compound, except for ammonium bromide.
  • the protective colloid binder of said emulsion layer preferably comprises at least 75% by weight of silicic acid sol, and most preferably it consists entirely of such sol.
  • the preferred onium compounds according to the present invention can be represented by the following general formulae : A + X ⁇ wherein X ⁇ represents an anion and A+ represents an onium ion selected from any of the following general formulae : wherein : each of R1 and R3 (same or different) represents hydrogen, an alkylgroup, a substituted alkyl group, a cycloalkyl group, an aryl group or a substituted aryl group, R2 represents any of the said groups represented by R1 and R3 or the atoms necessary to close a heterocyclic nucleus with either R1 or R3, the said onium ion being linked
  • trialkyl sulfonium salts examples include polysulfonium salts, tetraalkyl quaternary ammonium salts, quaternary ammonium salts in which the quaternary nitrogen atom is a part of a ring system, cationic polyalkylene oxide salts including e.g. quaternary ammonium and phosphonium and bis-quaternary salts.
  • Onium salt polymers whereby the onium group may be e.g. an ammonium, phosphonium or sulphonium group, are disclosed in U.S. Patent 4,525,446.
  • the concentration of onium compound should preferably be not less than 0.5x10 ⁇ 3 mol of onium compound and preferably be not higher than 5x10 ⁇ 3 mol of onium compound per 90g of SiO2.
  • the usual silicic acid sols are suitable for the process according to the invention, regardless of whether the silicic acid has been prepared by a wet decomposition process or a pyrogenic process.
  • Suitable silicic acid sols are commercially available such as the "Syton” silica sols (a trademarked product of Monsanto Inorganic Chemicals Div.), the “Ludox” silica sols (a trademarked product of duPont de Nemours & Co., Inc.), the “Nalco” and “Nalcoag” silica sols (trademarked products of Nalco Chemical Co.), and the "Kieselsol, Types 100, 200, 300 and 600" (trademarked product of Bayer AG).
  • the colloidal silicic acid used has a specific surface area between 200 and 400 m2/g.
  • the specific surface area of the selected type of colloidal silicic acid should be taken into account.
  • silicic acid sols containing up to 20 percent by weight of aluminium oxide related to the solid content are used.
  • the process of the invention is suitable for the preparation of silver halide emulsions, the halide composition of which is not specifically limited and may be any composition selected from i.a. chloride, bromide, iodide, chlorobromide, bromoiodide, and chlorobromoiodide.
  • the content of silver iodide is equal to or less than 20 mol%, preferably equal to or less than 5 mol%, even more preferably equal to or less than 3 mol%.
  • the photographic silver halide emulsions used according to the present invention can be prepared by mixing the halide and silver solutions in partially or fully controlled conditions of temperature, concentrations, sequence of addition, and rates of addition.
  • the silver halide can be precipitated according to the single-jet method, the double-jet method, or the conversion method.
  • the silver halide particles of the photographic emulsions used according to the present invention may have a regular crystalline form such as a cubic or octahedral form or they may have a transition form. They may also have an irregular crystalline form such as a spherical form or a tabular form, or may otherwise have a composite crystal form comprising a mixture of said regular and irregular crystalline forms.
  • the silver halide grains may have a multilayered grain structure. According to a simple embodiment the grains may comprise a core and a shell, which may have different halide compositions and/or may have undergone different modifications such as the addition of dopes.
  • the silver halide crystals can be doped e.g. with Rh3+, Ir4+, Cd2+, Zn2+, Pb2+. Besides having a differently composed core and shell the silver halide grains may also comprise different phases inbetween.
  • Two or more types of silver halide emulsions that have been prepared differently can be mixed for forming a photographic emulsion for use in accordance with the present invention.
  • the average size of the silver halide grains may range from 0,01 to 7 ⁇ m, preferably from 0,01 ⁇ m up to 5 ⁇ m.
  • the size distribution of the silver halide particles of the photographic emulsions to be used according to the present invention can be homodisperse or heterodisperse.
  • a homodisperse size distribution is obtained when 95% of the grains have a size that does not deviate for more than 30% from the average grain size.
  • the emulsion can be desalted by ultra-centrifugal techniques, by dialysis, which is a preferred method for the emulsions prepared in accordance with the present invention, and ultrafiltration, by flocculation and re-dispersing, etc.
  • the light-sensitive silver halide emulsion can be a so-called primitive emulsion, in other words an emulsion that has not been chemically sensitized.
  • the light-sensitive silver halide emulsion 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 rhodamines.
  • the emulsions can be sensitized also by means of gold-sulphur ripeners or by means of reductors e.g. tin compounds as described in GB-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • Chemical sensitization can also be performed with small amounts of Ir, Rh, Ru, Pb, Cd, Hg, Tl, Pd, Pt, or Au.
  • One of these chemical sensitization methods or a combination thereof can be used.
  • the 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.
  • the silver halide emulsion for use in accordance with the present invention may comprise 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 ripening thereof and mixtures of two or more of these compounds can be used.
  • the photographic element of 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, 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.
  • the photographic element of the present invention may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents, hardeners, and plasticizers.
  • additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents, hardeners, and plasticizers.
  • the emulsion has been prepared in accordance with the most preferred mode of application of the invention, i.e. precipitation in the presence of silicic acid sol only, and if the ratio by weight of silicic acid sol over silver halide exceeds 0.5 and preferably exceeds 1.0, the addition of supplemental hardening agents is not required to the emulsion so as to form photographic materials.
  • supplemental silicic acid sol should be added shortly before coating the silver halide emulsion concerned on a suitable substrate such as, preferably, a thermoplastic resin e.g. polyethyleneterephtalate.
  • 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 ⁇ m 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 i.a. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydrophthalate. Other suitable spacing agents have been desribed 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.
  • a photographic emulsion was prepared and coated on a support according to the following procedure : 300 ml of 30 % silica sol, 'Kieselsol 300F' (trademarked product of Bayer A.G.), 100 ml of 1 % solution of a stabilizing sulfonium compound corresponding to the following formula : and demineralised water up to a total volume of 2000 ml were mixed with constant stirring in a 12 l stainless steel vessel. Then the temperature was stabilised at 20°C, the pH adjusted to 3.0 by the addition of a sufficient amount of 6N sulfuric acid and the pAg was adjusted to 9.0.
  • the emulsion contained approximately 110 g of silver nitrate per kg of the dispersion.
  • the dispersion was subject to dialysis in a Holoflow dialysing tube type F60 (trademark producted of Fresenius AG,D6370 Oberursel, F.R. Germany, dialyse-volume of 75 ml) forming part of a closed circuit wherein the dispersion was circulated.
  • a Holoflow dialysing tube type F60 trademark producted of Fresenius AG,D6370 Oberursel, F.R. Germany, dialyse-volume of 75 ml
  • the desalted dispersion then showed an electrical conductivity of approximately 2 mS and contained 225 g of silver nitrate per kg solution.
  • the ratio of silica sol over silver nitrate was then 0.18, whereupon it was increased up to 0.2 by the addition of a sufficient amount of 30 % silica sol.
  • the dispersion was subjected to chemical ripening during 30 min at a constant pH level of 5.0 and pAg value of 9.0 at a stabilised temperature of 20°C by addition of 2.2x10 ⁇ 6 mol of Au3+ per 50 g of silver nitrate and 1.26x10 ⁇ 4 mol of S20 2- 3 per 50 g of silver nitrate.
  • the ratio of silica sol over silver nitrate was increased up to 0.5 by the addition of supplemental silica sol and the dispersion was manually coated in a thermo-stabilised coating table at 50°C, on a support consisting of polyethylene coated paper carrying a gelatine containing substratum layer (comprising 0.4 g of gelatin per square meter) is coated.
  • the light intensity as measured with a MAVOLUX light meter, type 'Electronic' (trademarked product of Gossen GmbH, D8520 Er Weg, F.R. Germany) on the strips amounts to 1350 Lux. Processing took place in a conventional metol hydrochinon developer (buffered at a pH of 10.2 with sodium carbonate) during one minute, followed by fixation during 30 seconds in a 0.9 molar ammonium thiosulfate bath stabilised at a pH of 5, followed by rinsing in water during 30 seconds.
  • a photographic emulsion was prepared according to the procedure described in Example I; however no stabilising compound was used.
  • the stability of the precipitated silver halide was extremely poor and heavy sedimentation occurred.
  • Photographic emulsions were prepared according to the procedure described in Example I, except that the following compounds were used as stabilising compound :
  • Example III same stabilising compound as example I
  • Examples IV and V a monosulfonium compound according to the following structural formula :
  • Examples VI and VII a monosulfonium compound according to the following structural formula :
  • Examples VIII and IX a iodonium compound according to the following structural formula :
  • Examples X and XI a quaternary ammonium compound (pyridine-derivative) according to the following structural formula :
  • Examples XII and XIII a selenonium compound according to the following structural formula :
  • Examples XIV and XV a phosphonium compound according to the following structural formula :
  • Examples XVI and XVII a polyphosphonium compound according to the following structural formula, n being 22 :
  • concentrations of stabilising compound set forth in Table I are all expressed in 10 ⁇ 2 mol of stabilising compound per 90 g of silica sol.
  • the values set forth for stability are the results of measurements resp. calculations in accordance with the following procedure.
  • a 10 ml sample of emulsion is brought into a 10 ml graduated cylinder.
  • the stability of the emulsion is then measured as a function of time by checking the visuability of a sign (e.g. an arrow) which is affixed at the rear of said graduated cylinder.
  • a sign e.g. an arrow
  • the level till which the visuability reaches is noted.
  • the evolution of this level as a function of time is taken as a measure for the stability.
  • the stability is minimal, whereas if the value equals 1, the stability is maximal.
  • a photographic tabular grain emulsion was prepared and coated on a support according to the following procedure : 2000 ml of demineralised water, 83 ml of 30 % Kieselsol 300F (trademarked product of Bayer AG), 18.5 ml of a 1 % solution of the stabilising compound as described in Example I were mixed under constant stirring in a 12 l stainless steel vessel. After heating up to 70°C (under continuous stirring), 1045 ml of demineralised water were added, the pH of the solution was brought to 3.0 by the addition of 6N sulfuric acid, and the pAg was brought to 9.49 by addition of a 2.94 molar solution of potassium bromide.
  • Example II the dispersion was cooled from 70 to 20°C under constant stirring and further washed by dialysis as described in Example I.
  • the aspect ratio was measured and found to be between 2,5 and 6, but if so desired may be increased up to 12.
  • a photographic emulsion was prepared according to the procedure described in Example I; however, instead of the sulfonium compound of said example the following compounds were used (the use of these compounds is suggested for precipitation to take place in the abscence of gelatin and in the presence of silica in the US Patent 3,637,391 cited hereinbefore) : in comparative example II : ethanol (96 %) in comparative example III : polyvinylalcohol in comparative example IV : polyvinylalcohol in comparative example V : polyacrylamide
  • the polyvinylalcohols used in the comparative examples III and IV show an intrinsic viscosity of 5, resp. 28, when measured at 20°C in a 4 % by weight aqueous solution of said polyvinylalcohol.

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Claims (10)

  1. Un procédé pour la préparation d'une émulsion à l'halogénure d'argent sensible à la lumière, y compris la phase de la précipitation d'halogénure d'argent en présence d'acide silicique colloïdal servant de colloïde protecteur, caractérisé en ce que la précipitation d'halogénure d'argent s'effectue en présence d'un composé onium, excepté le bromure d'ammonium.
  2. Le procédé selon la revendication 1, caractérisé en ce que le composé onium correspond à la formule générale suivante:

            A⁺ X⁻

    dans laquelle:
    X⁻ représente un anion, et
    A⁺ représente un ion onium, choisi dans l'une quelconque des formules générales suivantes:
    Figure imgb0018
     dans lesquelles:
    R¹ et R³ (identiques ou différents) représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe alkyle substitué, un groupe cycloalkyle, un groupe aryle ou un groupe aryle substitué,
    R² l'un quelconque des groupes représentés par R¹ et R³, ou les atomes nécessaires pour fermer un noyau hétérocyclique avec R¹ ou R³, l'ion onium étant lié
    1) à une chaîne polymère, ou
    2) via un groupe de liaison organique bivalent à n'importe quelle autre d'une telle structure onium, ou
    3) directement à l'un quelconque des groupes représentés par R¹, excepté l'atome d'hydrogène.
  3. Le procédé selon la revendication 1 ou 2, caractérisé en ce que le composé onium est présent dans un taux correspondant à au moins 0,5 10⁻³ mole par 90 g de sol d'acide silicique.
  4. Le procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'acide silicique colloïdal a une aire de surface spécifique entre 200 et 400 m²/g.
  5. Le procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que, outre l'acide silicique colloïdal, de la gélatine est présente comme colloïde protecteur additionnel.
  6. Le procédé selon la revendication 5, caractérisé en ce qu'au moins 75 % en poids du colloïde protecteur utilisé dans la phase de précipitation d'halogénure d'argent consiste en acide silicique colloïdal.
  7. Le procédé selon l'une quelconque des revendications précédentes comprenant en plus la phase de la redispersion de l'halogénure d'argent précipité en présence d'acide silicique colloïdal.
  8. Un matériau à l'halogénure d'argent sensible à la lumière comprenant un support portant au moins une couche à l'halogénure d'argent sensible à la lumière incorporant un sol d'acide silicique comme liant colloïdal protecteur et un composé onium, à l'exception de bromure d'ammonium.
  9. Un matériau sensible à la lumière selon la revendication 8, caractérisé en ce que le composé onium correspond à la formule générale suivante:

            A⁺ X⁻

    dans laquelle:
    X⁻ représente un anion, et
    A+ représente un ion onium, choisi dans l'une quelconque des formules générales suivantes:
    Figure imgb0019
     dans lesquelles:
    R¹ et R³ (identiques ou différents) représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe alkyle substitué, un groupe cycloalkyle, un groupe aryle ou un groupe aryle substitué,
    R² l'un quelconque des groupes représentés par R¹ et R³ ou les atomes nécessaires pour fermer un noyau hétérocyclique avec R¹ ou R³, l'ion onium étant lié
    1) à une chaîne polymère, ou
    2) via un groupe de liaison organique bivalent à n'importe quelle autre d'une telle structure onium, ou
    3) directement à l'un quelconque des groupes représentés par R¹, excepté l'atome d'hydrogène.
  10. Un matériau sensible à la lumière selon la revendication 8 ou 9, caractérisé en ce que le composé onium est présent dans un taux correspondant à au moins 0,5 10⁻³ mole par 90 g d'acide silicique colloïdal.
EP89200909A 1989-04-11 1989-04-11 Méthode pour la préparation d'émulsions à l'halogénure d'argent photosensibles Expired - Lifetime EP0392092B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE1989618267 DE68918267T2 (de) 1989-04-11 1989-04-11 Verfahren zur Herstellung von lichtempfindlichen Silberhalogenid Emulsionen.
EP89200909A EP0392092B1 (fr) 1989-04-11 1989-04-11 Méthode pour la préparation d'émulsions à l'halogénure d'argent photosensibles
JP2096147A JP2835636B2 (ja) 1989-04-11 1990-04-10 感光性ハロゲン化銀乳剤の製造方法

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EP89200909A EP0392092B1 (fr) 1989-04-11 1989-04-11 Méthode pour la préparation d'émulsions à l'halogénure d'argent photosensibles

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EP0392092A1 EP0392092A1 (fr) 1990-10-17
EP0392092B1 true EP0392092B1 (fr) 1994-09-14

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Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0517961B1 (fr) * 1991-06-11 1998-03-25 Agfa-Gevaert N.V. Méthode pour la préparation d'émulsions à halogénure d'argent photosensibles
EP0528476B1 (fr) * 1991-08-15 1997-03-05 Agfa-Gevaert N.V. Méthode pour préparer un matériau photographique à halogénure d'argent
EP0649051A1 (fr) * 1993-09-16 1995-04-19 Agfa-Gevaert N.V. Méthode de préparation des émulsions à l'halogénure d'argent sensible à la lumière et matériau comprenant ces émulsions
US5476761A (en) * 1993-09-16 1995-12-19 Agfa-Gevaert, N.V. Preparation method of regular silver (halide) bromide or silver bromoiodide light-sensitive emulsions and material comprising said emulsions
US6312882B1 (en) * 1994-04-06 2001-11-06 Agfa-Gevaert Silver halide emulsions comprising tabular crystals, emulsions and the processing thereof
EP0677773A1 (fr) * 1994-04-06 1995-10-18 Agfa-Gevaert N.V. Emulsions à l'halogénure d'argent comprenant des cristaux tabulaires et méthode de traitement de ces émulsions
EP0682287B1 (fr) * 1994-05-09 2000-08-16 Agfa-Gevaert N.V. Méthode de préparation des émulsions à l'halogénure d'argent sensible à la lumière comprenant des cristaux riches en chlorure
EP0698817A1 (fr) 1994-08-22 1996-02-28 Agfa-Gevaert N.V. Assortiment de films photographiques à l'halogénure d'argent pour la radiographie industrielle et procédé de traitement de cet assortiment
EP0754964A1 (fr) * 1995-07-18 1997-01-22 Agfa-Gevaert N.V. Matériaux photographiques à l'halogénure d'argent comprenant des émulsions au bromure ou iodobromure d'argent ayant des cristaux tabulaires triangulaires
US5733715A (en) * 1995-07-18 1998-03-31 Agfa-Gevaert, N.V. Silver halide photographic materials comprising silver bromide or bromoiodide emulsions having triangular tabular crystals
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
EP0767400A1 (fr) * 1995-10-02 1997-04-09 Agfa-Gevaert N.V. Procédé de préparation de grains tabulaires (100) à l'halogénure d'argent riche en chlorure avec sol de silice comme liant
EP0794456B1 (fr) 1996-03-07 2003-01-29 Agfa-Gevaert Procédé de reproduction d'une image médicale mémorisée électroniquement sur matériau photographique sensible à la lumière

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US3637391A (en) * 1968-09-05 1972-01-25 Agfa Gevaert Ag Process for the preparation of silver halide emulsions

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FR1364027A (fr) * 1963-05-06 1964-06-19 Kodak Pathe Procédé pour améliorer la perméabilité aux bains de traitement des émulsions à liant en majeure partie hydrophobe et produits obtenus
US3895950A (en) * 1971-05-12 1975-07-22 Agfa Gevaert Ag Photographic material with improved antistatic properties
US4001022A (en) * 1975-08-13 1977-01-04 Minnesota Mining And Manufacturing Company Photographic materials comprising developer layers and binders comprising silica sol

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
US3637391A (en) * 1968-09-05 1972-01-25 Agfa Gevaert Ag Process for the preparation of silver halide emulsions

Also Published As

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JP2835636B2 (ja) 1998-12-14
DE68918267T2 (de) 1995-03-02
JPH02293838A (ja) 1990-12-05
DE68918267D1 (de) 1994-10-20
EP0392092A1 (fr) 1990-10-17

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