EP0517053B1 - Emulsion photographique à l'halogénure d'argent - Google Patents

Emulsion photographique à l'halogénure d'argent Download PDF

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Publication number
EP0517053B1
EP0517053B1 EP92108735A EP92108735A EP0517053B1 EP 0517053 B1 EP0517053 B1 EP 0517053B1 EP 92108735 A EP92108735 A EP 92108735A EP 92108735 A EP92108735 A EP 92108735A EP 0517053 B1 EP0517053 B1 EP 0517053B1
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EP
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Prior art keywords
silver halide
emulsion
mol
halide emulsion
photographic
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EP92108735A
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German (de)
English (en)
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EP0517053A1 (fr
Inventor
Walter Dr. Pätzold
Bruno Dr. Mücke
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising

Definitions

  • the invention relates to a photographic silver halide emulsion which is distinguished by a high maximum density, steep gradation, great sensitivity and rapid developability.
  • a flat threshold gradation can occur with these emulsions, which can lead to a flattening of the gradation and a rise in fog. Furthermore, due to the necessary strong maturation, a further increase in the haze, especially after storage at normal or elevated temperature, is observed.
  • the object of the invention was to avoid the disadvantages described, that is to say to produce a rapidly developing and highly sensitive silver halide emulsion which is distinguished by a steep gradation with a slight increase in fog of the material during storage.
  • Another goal was to improve threshold gradation and decrease sensitivity to subliminal pre-exposure, e.g. Darkroom light.
  • This object was achieved in that a diindolyl disulfide was added to the silver halide emulsion before the chemical ripening began.
  • the silver halide emulsion according to the invention is preferably doped with 10 ⁇ 9 to 10 ⁇ 4 mol / mol Ag Rh3+ and / or Ir4+ ions.
  • the emulsion is preferably ripened with gold and sulfur compounds, in particular in a concentration of 2 ⁇ 10 ⁇ 6 to 2 ⁇ 10 ⁇ 4 mol of gold compound / mol of Ag and 10 ⁇ 6 to 10 ⁇ 4 mol of sulfur compound / mol of Ag.
  • AgCl, AgBr, AgBrCl, AgBrI and AgBrClI are suitable as silver halides.
  • the silver halide emulsion according to the invention preferably has a composition of AgCl 0.15 Br 0.85 to AgCl 0.999 Br 0.001 .
  • Particularly clear effects are achieved with so-called chloride emulsions, ie silver chloride bromide emulsions with chloride proportions above 80, preferably above 95 mol%.
  • the silver halide emulsion according to the invention can be used for photographic materials, in particular for color negative paper and black and white negative paper.
  • Another object of the invention is therefore a photographic material with a support and at least one light-sensitive silver halide emulsion layer, characterized in that the silver halide emulsion of the silver halide emulsion layer contains a compound of formula (I) in an amount of 10 ⁇ 7 to 10 ⁇ 3 mol / mol Ag.
  • the photographic material of the invention can be color photographic material, e.g. a color negative film, a color negative paper, a color reversal film or a color reversal paper or a black and white material, e.g. a black and white film or black and white paper.
  • color photographic material e.g. a color negative film, a color negative paper, a color reversal film or a color reversal paper or a black and white material, e.g. a black and white film or black and white paper.
  • Suitable compounds for doping the silver halide emulsion according to the invention are, for example, Na3RhCl6 and Na2IrCl6.
  • Other suitable compounds are described in European Patents 336 425, 336 426 and 336 427.
  • Suitable gold ripening agents are e.g. H (AuCl4) + KSCN, Na3 [Au (S2O3) 2] ⁇ 2H2O and gold rhodanine. Further gold ripening agents are known from German patents 854 883 and 848 910.
  • Suitable compounds for sulfur ripening are e.g. Thiosulfates and thioureas such as N, N-dimethylthiourea and N-allylthiourea as well as thioacetamide.
  • the diindolyl disulfides according to the invention and their preparation are described in Chem. Pharm. Bull. 21 (1973), 2739.
  • the diindolyl disulfides can be added during the preparation of the emulsion.
  • the compounds according to the invention are added at any time after the end of crystal formation and before the end of chemical ripening. In a particularly preferred embodiment, the addition takes place directly before the start of chemical ripening.
  • the silver halide can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms.
  • platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably less than 8: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
  • the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is greater than 8: 1.
  • the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as doping of the individual grain areas, being different.
  • the average grain size of the emulsion is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be either homodisperse or heterodisperse.
  • the emulsions can also contain organic silver salts, for example silver benzotriazolate or silver behenate.
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al., Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • various methods e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al., Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
  • the silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used.
  • the latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
  • the water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded.
  • the pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation.
  • so-called inverse precipitation with excess silver ions is also possible.
  • the silver halide crystals can also grow by physical ripening (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent.
  • the growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.
  • Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Fe can also be present during the precipitation and / or physical ripening of the silver halide grains.
  • the precipitation can also be carried out in the presence of sensitizing dyes.
  • Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.
  • Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
  • Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers.
  • Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates.
  • Semi-synthetic gelatin substitutes are usually modified natural products.
  • Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives, which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers, are examples of this.
  • the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
  • functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
  • the gelatin which is preferably used can be obtained by acidic or alkaline digestion.
  • the gelatin can be oxidized.
  • the preparation of such gelatins is described, for example, in The Science and Technology of Gelatine, edited by AG Ward and A. Courts, Academic Press 1977, page 295 ff.
  • the gelatin used in each case should have the lowest possible photographic content contain active impurities (inert gelatine). High viscosity, low swelling gelatins are particularly advantageous.
  • the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.
  • the photographic emulsions can contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
  • Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, (subst.) Benzotriazoles or benzothiazolium salts can also be used as antifoggants.
  • metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, (subst.) Benzotriazoles or benzothiazolium salts can also be used as
  • Heterocycles containing mercapto groups for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • mercaptobenzthiazoles for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptopyrimidines
  • water-solubilizing group for example a carboxyl group or sulfo group.
  • Other suitable compounds are published in Research Disclosure No. 17643 (1978), Section VI.
  • the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
  • the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
  • the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
  • Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromide.
  • Suitable supports for the production of color photographic materials are e.g. Films and foils of semi-synthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or ⁇ -olefin polymer layer (e.g. polyethylene).
  • These carriers can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light.
  • the surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.
  • Color photographic materials usually contain at least one red sensitive, green sensitive and blue sensitive emulsion layer each. These emulsion layers are assigned non-diffusing monomeric or polymeric color couplers that are in the same layer or in an adjacent one Layer. Usually, cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.
  • Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type; suitable examples of this are known in the literature.
  • Color couplers for producing the yellow partial color image are generally couplers with an open-chain catomethylene group, in particular couplers of the ⁇ -acylacetamide type; Suitable examples are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers, which are also known from the literature.
  • Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; Suitable examples of this are described in large numbers in the literature.
  • the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
  • the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off during the coupling.
  • the 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products.
  • the 2-equivalent couplers also include those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), exhibits a certain desired photographic effectiveness, eg as a development inhibitor or accelerator.
  • Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.
  • DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also important suitable, which give essentially colorless products on coupling (DE-A-1 547 640).
  • the cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
  • High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
  • the high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
  • the couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion from the compound in question and then adding the casting solution for the layer in question.
  • the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
  • Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-0 043 037.
  • oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
  • the compounds can also be introduced into the casting solution in the form of loaded latices.
  • anionic water-soluble compounds e.g. dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers are e.g. Alkyl phthalates, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters and trimesic acid esters.
  • Color photographic material typically comprises at least one red sensitive emulsion layer, at least one green sensitive emulsion layer and at least one blue sensitive emulsion layer on the support.
  • the order of these layers can be varied as desired. Couplers that form blue-green, purple and yellow dyes are usually incorporated into the red, green or blue-sensitive emulsion layers. However, different combinations can also be used.
  • Each of the light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
  • red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers, which in turn are closer than blue-sensitive layers there is generally a non-light-sensitive yellow filter layer between green-sensitive layers and blue-sensitive layers.
  • green or red sensitive layers are suitably low in their own sensitivity, other layer arrangements can be selected without the yellow filter layer, in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.
  • the non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
  • sub-layers of the same spectral sensitization can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains.
  • the sub-layer with higher sensitivity will be arranged further away from the support than the sub-layer with lower sensitivity.
  • Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, e.g. be separated by layers of other spectral sensitization.
  • all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-1 958 709, DE-A-2 530 645, DE-A-2 622 922).
  • the photographic material may further contain UV light absorbing compounds, whites, spacers, filter dyes, formalin scavengers and others.
  • Examples are aryl-substituted Benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3 707 375), butadiene compounds (US-A-4 015 229) or benzoxazole compounds (US-A-3 700 455).
  • Ultraviolet absorbing couplers such as ⁇ -naphthol type cyan couplers
  • ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
  • Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styrene dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
  • Suitable whiteners are e.g. in Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter V.
  • binder layers in particular the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A-3 331 542, DE-A-3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17643, Chapter XVI).
  • photographically inert particles of inorganic or organic nature e.g. as a matting agent or as a spacer (DE-A-3 331 542, DE-A-3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17643, Chapter XVI).
  • the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
  • the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
  • suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
  • binders of the material according to the invention are hardened with suitable hardeners, for example with hardeners of the epoxy type, the ethyleneium type, the acryloyl type or the vinylsulfone type.
  • suitable hardeners for example with hardeners of the epoxy type, the ethyleneium type, the acryloyl type or the vinylsulfone type.
  • suitable hardeners for example with hardeners of the epoxy type, the ethyleneium type, the acryloyl type or the vinylsulfone type.
  • dizine, triazine or 1,2-dihydroquinoline series hardeners are also suitable.
  • the binders of the material according to the invention are preferably hardened with instant hardeners.
  • Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction .
  • Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
  • hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.
  • Suitable examples of instant hardeners are e.g. in European Patent 313,949.
  • the materials according to the invention are processed in the usual manner according to the processes recommended for this.
  • Solutions 2 and 3 are simultaneously added to solution 1 at 50 ° C. in the course of 120 minutes at a pAg of 7.7 with vigorous stirring.
  • a silver chloride emulsion with an average particle diameter of 0.8 ⁇ m is obtained.
  • the gelatin / AgNO3 weight ratio is 0.18.
  • the emulsion is flocked in a known manner, washed and redispersed with so much gelatin that the gelatin / AgNO3 weight ratio is 1.0.
  • the emulsion contains 1 mol of silver halide per kg. It is then optimally ripened at a pH of 4.5 with 3.5 ⁇ mol gold chloride / mol Ag and 1.5 ⁇ mol Na2S2O3 / MolAg. After chemical ripening, the emulsion (silver halide composition: AgCl 0.99 Br 0.01 ) is stabilized and sensitized to the blue spectral range.
  • the layer contains per m2 0.63 g AgNO3 1.38 g gelatin 0.95 g yellow coupler 0.2 g white coupler 0.29 g tricresyl phosphate.
  • a protective layer of 0.2 g of gelatin and 0.3 g of hardening agent of the formula is applied over this layer cast per m2.
  • the material is exposed imagewise and processed using the Ektacolor RA 4 process.
  • the emulsion is prepared and processed as described in Example 1, but with the difference that during chemical ripening, 4.5 mg of diphenylindolyl disulfide are added as a 0.1% by weight acetone solution before the thiosulfate is added.
  • the emulsion is prepared and processed as described in Example 1, but with the difference that 225 mg of diphenylindolyl disulfide are added during chemical ripening before the addition of thiosulfate.
  • Solutions 2 and 3 are simultaneously added to solution 1 at 55 ° C. in the course of 60 minutes at a pAg of 7.8 with vigorous stirring.
  • the emulsion is flocculated in a known manner, washed and redispersed with the addition of gelatin, phenol (as a preservative) and water.
  • the emulsion contains 0.9 mol of silver halide per kg. Subsequently, with the addition of 10 ⁇ mol HAuCl4 / mol Ag and 20 ⁇ mol Na2S2O3 / mol Ag 120 minutes at 52 ° C.
  • the emulsion (silver halide composition: AgCl 0.5 Br 0.5 ) is then poured onto a paper support coated on both sides with polyethylene with the addition of sensitizers, stabilizers, plasticizer latex, optical brighteners, developer substances and hardening agents.
  • the material is exposed imagewise and processed according to the AGFA 100 recipe.
  • the emulsion is prepared and processed as described in Example 4, but with the difference that in chemical ripening, 160 mg of diphenylindolyl disulfide are added before the ripening substances are added.
  • the emulsion is prepared and processed as described in Example 4. However, the sensitometric data are only measured after a two-day storage at 60 ° C.
  • the emulsion is prepared and processed as described in Example 5. However, the sensitometric data are only measured after a two-day storage at 60 ° C.
  • the emulsion is produced and processed as described in Example 4, but after image-wise exposure, an additional diffuse exposure was carried out using amber filters (corresponds to the draft standard ISO / DIS 8374).
  • the emulsion is produced and processed as described in Example 5, but after image-wise exposure, an additional diffuse exposure was carried out using amber filters (corresponds to the draft standard ISO / DIS 8374).

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • General Physics & Mathematics (AREA)
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Claims (5)

  1. Emulsion photographique à l'halogénure d'argent, caractérisée en ce qu'elle contient 10⁻⁷ à 10⁻³ mole, par mole d'argent, d'un composé de formule (I)
    Figure imgb0010
     dans laquelle
    R₁   représente H ou un groupe alkyle,
    R₂   est un groupe alkyle, benzyle, phényle ou phényle substitué,
    R³, R₄   représentent H, un groupe alkyle, alkoxy, un halogène ou un groupe nitro.
  2. Emulsion photographique à l'halogénure d'argent suivant la revendication 1, caractérisée en ce qu'elle est dopée avec 10⁻⁹ à 10⁻⁴ mole, par mole d'argent, d'ions Rh³⁺ et/ou Ir⁴⁺.
  3. Emulsion photographique à l'halogénure d'argent suivant la revendication 1, caractérisée en ce qu'on utilise 2.10⁻⁶ à 2.10⁻⁴ mole de composé d'or et 10⁻⁶ à 10⁻⁴ mole de composé de soufre par mole d'argent pour sa maturation.
  4. Emulsion photographique à l'halogénure d'argent suivant la revendication 1, caractérisée en ce que sa composition va de AgCl0,15Br0,85 à AgCl0,999Br0,001.
  5. Matériel photographique comportant un support et au moins une couche photosensible d'émulsion à l'halogénure d'argent, caractérisé en ce que la couche d'émulsion à l'halogénure d'argent contient une émulsion à l'halogénure d'argent suivant la revendication 1.
EP92108735A 1991-06-06 1992-05-23 Emulsion photographique à l'halogénure d'argent Expired - Lifetime EP0517053B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4118542A DE4118542A1 (de) 1991-06-06 1991-06-06 Fotografische silberhalogenidemulsion
DE4118542 1991-06-06

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EP0517053A1 EP0517053A1 (fr) 1992-12-09
EP0517053B1 true EP0517053B1 (fr) 1994-03-23

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Publication number Priority date Publication date Assignee Title
US5219721A (en) * 1992-04-16 1993-06-15 Eastman Kodak Company Silver halide photographic emulsions sensitized in the presence of organic dichalcogenides
US5364754A (en) * 1992-04-16 1994-11-15 Eastman Kodak Company Silver halide photographic emulsions precipitated in the presence of organic dichalcogenides
DE19507914A1 (de) * 1995-03-07 1996-09-12 Agfa Gevaert Ag Farbfotografisches Silberhalogenidmaterial
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DE59200097D1 (de) 1994-04-28
JPH05181224A (ja) 1993-07-23
EP0517053A1 (fr) 1992-12-09
US5229264A (en) 1993-07-20
DE4118542A1 (de) 1992-12-10

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